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

International Nuclear Information System (INIS)

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

2005-01-01

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

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

NARCIS (Netherlands)

Meindersma, G.W.; Podt, J.G.; de Haan, A.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

Gas hydrate phase equilibria measurement techniques and phase rule considerations

International Nuclear Information System (INIS)

Beltran, Juan G.; Bruusgaard, Hallvard; Servio, Phillip

2012-01-01

Highlights: → Inconsistencies found in hydrate literature. → Clarification to the number of variables needed to satisfy and justify equilibrium data. → Application of phase rule to mixed hydrate systems. → Thermodynamically consistent format to present data. - Abstract: A brief review of the Gibbs phase rule for non-reacting systems and its correct application to clathrate hydrates is presented. Clarification is provided for a common mistake found in hydrate phase-equilibria literature, whereby initial compositions are used as intensive variables to satisfy the Gibbs phase rule instead of the equilibrium values. The system of (methane + carbon dioxide + water) under (hydrate + liquid + vapor) equilibrium is used as a case study to illustrate key points and suggestions to improve experimental techniques are proposed.

Modeling of liquid phases

CERN Document Server

Soustelle, Michel

2015-01-01

This book is part of a set of books which offers advanced students successive characterization tool phases, the study of all types of phase (liquid, gas and solid, pure or multi-component), process engineering, chemical and electrochemical equilibria, and the properties of surfaces and phases of small sizes. Macroscopic and microscopic models are in turn covered with a constant correlation between the two scales. Particular attention has been given to the rigor of mathematical developments. This second volume in the set is devoted to the study of liquid phases.

Measurement and modeling of high-pressure (vapor + liquid) equilibria of (CO2 + alkanol) binary systems

International Nuclear Information System (INIS)

Bejarano, Arturo; Gutierrez, Jorge E.; Araus, Karina A.; Fuente, Juan C. de la

2011-01-01

Research highlights: → (Vapor + liquid) equilibria of three (CO 2 + C 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 2 + 3-methyl-2-butanol), (CO 2 + 2-pentanol), and (CO 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 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.

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.

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 system. On the basis of quasi-equilibrium solid-fat content (SFC) measurements, a new approach to the estimation of the interaction parameters, needed for the activity-coefficient model, has been developed. The parameters are fitted by matching the SFC of two oils at various degrees of dilution...... and isothermal temperatures. Subsequently, the parameters are successfully validated against three oils, rich in asymmetric and symmetric triacylglycerols (TAG), respectively. The new approach developed is shown to be very flexible, allowing incorporation of additional TAG and polymorphic states. It thereby...

Experimental investigation of phase equilibria in the Ni-Nb-V ternary system

Energy Technology Data Exchange (ETDEWEB)

Liu, Xingjun; Yang, Shuiyuan; Wang, Cuiping [Xiamen Univ. (China). Dept. of Materials Science and Engineering; Xiamen Univ. (China). Fujian Provincial Key Lab. of Materials Genome; Zhang, Xianjie; Jiang, Hengxing; Shi, Zhan [Xiamen Univ. (China). Dept. of Materials Science and Engineering

2017-09-15

The phase equilibria of the Ni-Nb-V ternary system at 1000 C and 1200 C were established using electron probe microanalysis, X-ray diffraction and differential scanning calorimetry. The results of the investigation revealed that: (1) The Nb solubility in (Ni) and σ{sup '} phases was less than 10 at.%; (2) A ternary compound τ (NiNbV) was confirmed, in which V had a large solubility; (3) A new liquid region was evident at 1200 C, but was absent at 1000 C; (4) The lattice constants of Ni{sub 3}Nb and Ni{sub 6}Nb{sub 7} phase decreased with increase in V content in the Ni{sub 3}Nb and Ni{sub 6}Nb{sub 7}. The phase equilibria of the Ni-Nb-V ternary system will contribute to its thermodynamic assessment.

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.

Liquids - vapor and liquids - solids equilibria in the system Th(NO3)4 - UO2(NO3)2 - HNO3 - H2O

International Nuclear Information System (INIS)

Volk, V.I.; Vakhrushin, A.Yu.; Mamaev, S.L.; Zhirnov, Yu.P.

1999-01-01

Liquids - vapor and liquids - solids equilibria in the system Th(NO 3 ) 4 - UO 2 (NO 3 ) 2 - HNO 3 - H 2 O were investigated. It was established that in this system thorium nitrate hexahydrate and uranyl nitrate hexa- and trihydrate are formed. Empiric equations of solubility isotherm at 25 deg C were found. Densities of liquid phases of the system were determined. It was established that uranyl nitrates and thorium nitrates salt out nitric acid in vapor phase just as separately so in the case of mutual presence. Empiric equation fixing relationship between nitric acid concentration in condensed phase and concentrations of all components in liquid phase was found

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

Energy Technology Data Exchange (ETDEWEB)

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

1991-12-01

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

Séparations par changement de phase. Etude et représentation des équilibres liquide-vapeur Separation by Phase Hange. Study and Computing Liquid-Vapor Equilibria

Directory of Open Access Journals (Sweden)

Asselineau L.

2006-11-01

Full Text Available Pour concevoir et optimiser les principales opérations de séparation (particulièrement les distillations avec ou sans solvant et l'extraction liquide-liquide on doit disposer de méthodes de corrélation ou, mieux, de prédiction des équilibres entre phases. A basse pression, et pour les mélanges d'hydrocarbures, les résultats présentés permettent la prévision des coefficients d'équilibre, même pour les séparations les plus délicates. En présence de constituants polaires, les données expérimentales d'équilibre liquide-liquide et liquide-vapeur de mélanges binaires et ternaires peuvent être simultanément corrélées dans le but de simuler et d'optimiser les distillations azéotropiques ou extractives. Sous haute pression, et particulièrement aux abords immédiats du point critique, le choix d'une équation d'état conduit à un traitement unitaire des phases en présence et permet, en particulier, la prédiction du lieu des points critiques des mélanges d'hydrocarbures et la corrélation de ce lieu en présence de solvants polaires. To determine and optimize the main separation operations (in particular distillations with or without a solvent, and liquid-liquid extraction correlation methods must be available or, better yet, methods of predicting phase equilibria. At low pressure and for hydrocarbon mixtures, the results described make the prediction of equilibrium coefficients possible, even for the most delicate separation. In the presence of polar constituents, the experimental data for the liquid-liquid and liquid-vapor equilibrium of binary and ternary mixtures can be simultaneously correlaten so as to simulate and optimize azeotropic or extractive distillations. Under high pressure and especially in the immediate vicinityof the critical point, the choice of an equation of state leads ta a unit treatment of the phases present and, in particular, makes it possible to predict the location of critical points in hydrocarbon

Phase equilibria for mixtures containing very many components. development and application of continuous thermodynamics for chemical process design

International Nuclear Information System (INIS)

Cotterman, R.L.; Bender, R.; Prausnitz, J.M.

1984-01-01

For some multicomponent mixtures, where detailed chemical analysis is not feasible, the compositio of the mixture may be described by a continuous distribution function of some convenient macroscopic property suc as normal boiling point or molecular weight. To attain a quantitative description of phase equilibria for such mixtures, this work has developed thermodynamic procedures for continuous systems; that procedure is called continuous thermodynamics. To illustrate, continuous thermodynamics is used to calculate dew points for natural-gas mixtures, solvent loss in a high-pressure absorber, and liquid-liquid phase equilibria in a polymer fractionation process. Continuous thermodynamics provides a rational method for calculating phase equilibria for those mixtures where complete chemical analysis is not available but where composition can be given by some statistical description. While continuous thermodynamics is only the logical limit of the well-known pseudo-component method, it is more efficient than that method because it is less arbitrary and it often requires less computer time

Experimental investigation of phase equilibria in the Zr-Cu-Ni ternary system

International Nuclear Information System (INIS)

Yang, Mujin; Wang, Cuiping; Yang, Shuiyuan; Shi, Zhan; Han, Jiajia; Liu, Xingjun

2017-01-01

The phase equilibria in the Zr-Cu-Ni ternary system are investigated combined with X-ray diffraction, electron probe micro-analysis and differential scanning calorimetry. Two isothermal sections of the Zr-Cu-Ni ternary system at 1 000 C and 1 100 C are experimentally established. Most of the binary intermetallic compounds, e.g. Zr 7 Ni 10 , ZrNi, ZrNi 5 , Zr 14 Cu 51 , and Zr 2 Cu 9 , show a remarkable ternary solubility. A new ternary compound named τ 3 (Zr 31.1-30.7 . Cu 28.5-40.3 Ni 40.4-29.0 ) is detected at 1 000 C and dissolved at 1 020 C because the nearby large liquid phase field further expands. The newly determined phase equilibria will provide important information for both thermodynamic assessment and alloy design of Zr-based metallic glass.

Measurement and modeling of high-pressure (vapour + liquid) equilibria of (CO2 + alcohol) binary systems

International Nuclear Information System (INIS)

Gutierrez, Jorge E.; Bejarano, Arturo; Fuente, Juan C. de la

2010-01-01

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 2 + 1-propanol), (CO 2 + 2-methyl-1-propanol), (CO 2 + 3-methyl-1-butanol), and (CO 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 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.

The calculation of phase equilibria of oxide core-concrete systems

International Nuclear Information System (INIS)

Ball, R.G.J.; Mignanelli, M.A.; Barry, T.I.; Gisby, J.A.

1993-01-01

Thermodynamic models have been developed to describe the phase equilibria of oxide solutions appropriate for the understanding of the chemical interactions between nuclear reactor core debris and concrete. For this purpose, the Gibbs energy of the liquid phase is described by the inclusion of associate species and nonideal interactions between the components and associate species. Assessments of the thermodynamic and phase equilibrium data for the subsystems of the CaO-Al 2 O 3 -SiO 2 -UO 2 -ZrO 2 system have been used to obtain a thermodynamic description of the crystalline and liquid phases in good agreement with published data. The data for the subsystems have then been combined, using well established principles, to predict the phase relationships in the ternary and quaternary sytsems and in the overall quinary system. The results show that he overall system cannot properly be treated as a pseudo-ideal liquid and solid solution, as used in some computer codes which attempt to model the physics and chemistry of core-concrete interactions. The limitations of the current model are discussed. (orig.)

High-pressure fluid phase equilibria phenomenology and computation

CERN Document Server

Deiters, Ulrich K

2012-01-01

The book begins with an overview of the phase diagrams of fluid mixtures (fluid = liquid, gas, or supercritical state), which can show an astonishing variety when elevated pressures are taken into account; phenomena like retrograde condensation (single and double) and azeotropy (normal and double) are discussed. It then gives an introduction into the relevant thermodynamic equations for fluid mixtures, including some that are rarely found in modern textbooks, and shows how they can they be used to compute phase diagrams and related properties. This chapter gives a consistent and axiomatic approach to fluid thermodynamics; it avoids using activity coefficients. Further chapters are dedicated to solid-fluid phase equilibria and global phase diagrams (systematic search for phase diagram classes). The appendix contains numerical algorithms needed for the computations. The book thus enables the reader to create or improve computer programs for the calculation of fluid phase diagrams. introduces phase diagram class...

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Quaternary (liquid + liquid) equilibria of aqueous two-phase polyethylene glycol, poly-N-vinylcaprolactam, and KH{sub 2}PO{sub 4}: Experimental and the generalized Flory-Huggins theory

Energy Technology Data Exchange (ETDEWEB)

Foroutan, Masumeh [Department of Physical Chemistry, Faculty of Chemistry, College of Science, University of Tehran, Enghelab Ave., Tehran 14155-6455 (Iran, Islamic Republic of)], E-mail: foroutan@khayam.ut.ac.ir; Zarrabi, Mona [Department of Physical Chemistry, Faculty of Chemistry, College of Science, University of Tehran, Enghelab Ave., Tehran 14155-6455 (Iran, Islamic Republic of)

2008-06-15

A quaternary (liquid + liquid) equilibrium study was performed to focus attention on the interaction parameters between poly-N-vinylcaprolactam (PVCL) and poly-ethylene glycol (PEG) as well as between other species. At first, the new experimental data of (liquid + liquid) equilibria for aqueous two-phase systems containing PEG, KH{sub 2}PO{sub 4}, and PVCL at T = 303.15 K have been determined. Then the Flory-Huggins theory with two electrostatic terms (the Debye-Huckel and the Pitzer-Debye-Huckel equations) has been generalized to correlate the phase behavior of the quaternary system. Good agreement has been found between experimental and calculated data from both models especially from the Pitzer-Debye-Huckel equation. Also an effort was done to compare the effect of temperature as well as addition of PVCL on the binodal curves of PEG, KH{sub 2}PO{sub 4}, and water. The effect of the type of salt on the binodals has been also studied, and the salting out power of the salts has been determined.

Experimental investigation of phase equilibria in the Zr-Cu-Ni ternary system

Energy Technology Data Exchange (ETDEWEB)

Yang, Mujin; Wang, Cuiping; Yang, Shuiyuan; Shi, Zhan; Han, Jiajia; Liu, Xingjun [Xiamen Univ. (China). College of Materials and Fujian Provincial Key Lab. of Materials Genome

2017-08-15

The phase equilibria in the Zr-Cu-Ni ternary system are investigated combined with X-ray diffraction, electron probe micro-analysis and differential scanning calorimetry. Two isothermal sections of the Zr-Cu-Ni ternary system at 1 000 C and 1 100 C are experimentally established. Most of the binary intermetallic compounds, e.g. Zr{sub 7}Ni{sub 10}, ZrNi, ZrNi{sub 5}, Zr{sub 14}Cu{sub 51}, and Zr{sub 2}Cu{sub 9}, show a remarkable ternary solubility. A new ternary compound named τ{sub 3} (Zr{sub 31.1-30.7} . Cu{sub 28.5-40.3}Ni{sub 40.4-29.0}) is detected at 1 000 C and dissolved at 1 020 C because the nearby large liquid phase field further expands. The newly determined phase equilibria will provide important information for both thermodynamic assessment and alloy design of Zr-based metallic glass.

Modeling Phase Equilibria for Acid Gas Mixtures using the Cubic-Plus-Association Equation of State. 3. Applications Relevant to Liquid or Supercritical CO2 Transport

DEFF Research Database (Denmark)

Tsivintzelis, Ioannis; Ali, Shahid; Kontogeorgis, Georgios

2014-01-01

density data for both CO2 and CO2–water and for vapor–liquid equilibrium for mixtures of CO2 with various compounds present in transport systems. In all of these cases we consider various possibilities for modeling CO2 (inert, self-associating using two-, three-, and four sites) and the possibility......The CPA (cubic-plus-association) equation of state is applied in this work to a wide range of systems of relevance to CO2 transport. Both phase equilibria and densities over extensive temperature and pressure ranges are considered. More specifically in this study we first evaluate CPA against......” for applying CPA to acid gas mixtures. The overall conclusion is that CPA performs satisfactorily; the model in most cases correlates well binary data and predicts with good accuracy multicomponent vapor–liquid equilibria. Among the various approaches investigated, the best ones are when cross association...

Phase equilibria at low temperature for light hydrocarbons-methanol-water-acid gases mixtures: measurements and modelling; Equilibres de phases a basse temperature de systemes complexes CO{sub 2} - hydrocarbures legers - methanol - eau: mesures et modelisation

Energy Technology Data Exchange (ETDEWEB)

Ruffine, L.

2005-10-15

The need to develop and improve natural gas treatment processes is real. The petroleum industry usually uses separation processes which require phase equilibrium phenomena. Yet, the complexity of the phase equilibria involved results in a lack of data, which in turn limits the development of thermodynamic models. The first part of this work is devoted to experimental investigations for systems containing light hydrocarbons, methanol, water and acid gases. We present a new apparatus that was developed to measure vapor-liquid and vapor-liquid-liquid equilibria. It allowed us to obtain new phase composition data for the methanol-ethane binary system and different mixtures, and also to determine a part of the three phases equilibrium envelope of the same systems. In the second part of this work, we have developed a thermodynamic model based on the CPA equation of state. This choice may be justified by the presence of associating components like methanol, hydrogen sulfide and water in the systems. Such model is necessary for the design of gas treatment plants. Our model provides good results for phase equilibrium calculations for binaries systems without binary interaction parameter in many cases, and describes correctly the vapour-liquid and vapor-liquid-liquid equilibria for complex mixtures. (author)

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...

Prediction of vapour-liquid and vapour-liquid-liquid equilibria of nitrogen-hydrocarbon mixtures used in J-T refrigerators

Science.gov (United States)

Narayanan, Vineed; Venkatarathnam, G.

2018-03-01

Nitrogen-hydrocarbon mixtures are widely used as refrigerants in J-T refrigerators operating with mixtures, as well as in natural gas liquefiers. The Peng-Robinson equation of state has traditionally been used to simulate the above cryogenic process. Multi parameter Helmholtz energy equations are now preferred for determining the properties of natural gas. They have, however, been used only to predict vapour-liquid equilibria, and not vapour-liquid-liquid equilibria that can occur in mixtures used in cryogenic mixed refrigerant processes. In this paper the vapour-liquid equilibrium of binary mixtures of nitrogen-methane, nitrogen-ethane, nitrogen-propane, nitrogen-isobutane and three component mixtures of nitrogen-methane-ethane and nitrogen-methane-propane have been studied with the Peng-Robinson and the Helmholtz energy equations of state of NIST REFPROP and compared with experimental data available in the literature.

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

International Nuclear Information System (INIS)

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

2011-01-01

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

Phase equilibria and phase structures of polymer blends

International Nuclear Information System (INIS)

Chalykh, Anatolii E; Gerasimov, Vladimir K

2004-01-01

Experimental, methodical and theoretical studies dealing with phase equilibria and phase structures of polymer blends are generalised. The general and specific features of the change in solubility of polymers with changes in the molecular mass and copolymer composition and upon the formation of three-dimensional cross-linked networks are described. The results of the effect of the prehistory on the phase structure and the non-equilibrium state of polymer blends are considered in detail.

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

(Vapour + liquid) equilibria for (2,2-dimethoxypropane + methanol) and (2,2-dimethoxypropane + acetone)

International Nuclear Information System (INIS)

Jiang Hui; Li Haoran; Wang Congmin; Tan Taijun; Han Shijun

2003-01-01

The isothermal and isobaric (vapour + liquid) equilibria for (2,2-dimethoxypropane + methanol) and (2,2-dimethoxypropane + acetone) measured with an inclined ebulliometer are presented. The experimental results are analysed using the UNIQUAC equation with the temperature-dependent binary parameters with satisfactory results. Isobaric (vapour + liquid) equilibria data for these systems at p=99.99 kPa are compared with the literature data. Experimental vapour pressure of 2,2-dimethoxypropane are also included

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

International Nuclear Information System (INIS)

Alvarez, Victor H.; Mattedi, Silvana; Aznar, Martin

2011-01-01

Research highlights: → We report density, refraction index, and VLE for (propionaldehyde or valeraldehyde) + [emim][EtSO 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 {aldehyde + 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO 4 ])}: {propionaldehyde + [emim][EtSO 4 ]} and {valeraldehyde + [emim][EtSO 4 ]}. 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.

Experimental investigation of phase equilibria in the Cu–Ni–Si ternary system

Energy Technology Data Exchange (ETDEWEB)

Liu, Xingjun; Xiang, Shulin; Yang, Shuiyuan; Shi, Rongpei; Wang, Cuiping, E-mail: wangcp@xmu.edu.cn

2013-11-25

Highlights: •Three isothermal sections of the Cu–Ni–Si system have been investigated. •The ternary compound τ{sub 1} and the liquid phase are confirmed at 1073 K. •The γ (Cu{sub 5}Si) and θ (Ni{sub 2}Si) phases can be stabilized at higher or lower temperatures. -- Abstract: The phase equilibria in the Cu–Ni–Si ternary system have been investigated experimentally by means of electron probe microanalysis (EPMA), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analysis on equilibrated ternary alloys. Three isothermal sections at 1073, 1173 and 1273 K are determined in the whole composition range. The existence of liquid phase and the ternary compound τ{sub 1} is confirmed at 1073 K. The binary γ (Cu{sub 5}Si), γ (Ni{sub 31}Si{sub 12}), δ (Ni{sub 2}Si) and θ (Ni{sub 2}Si) phases exhibit a considerable solubility of a third element. In addition, the γ (Cu{sub 5}Si) and θ (Ni{sub 2}Si) phases can be stabilized by the addition of Ni and Cu, respectively.

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)

Modelling (vapour + liquid) and (vapour + liquid + liquid) equilibria of {water (H2O) + methanol (MeOH) + dimethyl ether (DME) + carbon dioxide (CO2)} quaternary system using the Peng-Robinson EoS with Wong-Sandler mixing rule

International Nuclear Information System (INIS)

Ye Kongmeng; Freund, Hannsjoerg; Sundmacher, Kai

2011-01-01

Highlights: → Phase behaviour modelling of H 2 O-MeOH-DME under pressurized CO 2 (anti-solvent) using PRWS. → PRWS-UNIFAC-PSRK has better performance than PRWS-UNIFAC-Lby in general. → Reliable to extend the VLE and VLLE phase behaviour from binary to multicomponent systems. → Successful prediction of the VLE and VLLE of binary, ternary, and quaternary systems. → Potential to apply the model for designing new DME separation process. - Abstract: The (vapour + liquid) equilibria (VLE) and (vapour + liquid + liquid) equilibria (VLLE) binary data from literature were correlated using the Peng-Robinson (PR) equation of state (EoS) with the Wong-Sandler mixing rule (WS). Two group contribution activity models were used in the PRWS: UNIFAC-PSRK and UNIFAC-Lby. The systems were successfully extrapolated from the binary systems to ternary and quaternary systems. Results indicate that the PRWS-UNIFAC-PSRK generally displays a better performance than the PRWS-UNIFAC-Lby.

Phase equilibria among α-Fe(Al, Cr, Ti), liquid and TiC and the formation of TiC in Fe3Al-based alloys

International Nuclear Information System (INIS)

Kobayashi, Satoru; Schneider, Andre; Zaefferer, Stefan; Frommeyer, Georg; Raabe, Dierk

2005-01-01

In the context of the development of high-strength Fe 3 Al-based alloys, phase equilibria among α-Fe(Al, Cr, Ti), liquid and TiC phases in the Fe-Al-Cr-Ti-C quinary system and the formation of TiC were determined. A pseudo-eutectic trough (L α + L + TiC) exists at 1470 deg C at around Fe-26Al-5Cr-2Ti-1.7C on the vertical section between Fe-26Al-5Cr (α) and Ti-46C (TiC) in at.%. Large faceted TiC precipitates form from the melt after the formation of primary α phase even in hypoeutectic alloys. The TiC formation is thought to be due to the composition change of the liquid towards the hypereutectic compositions by solidification of the primary α. In order to remove the faceted TiC, which are unfavourable for strengthening the material, two different processing routes have been successfully tested: (i) solidification with an increased rate to reduce the composition variation of the liquid during solidification, and (ii) unidirectional solidification to separate the light TiC precipitates from the melt

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–liqu...

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.

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...

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 ...

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

Indian Academy of Sciences (India)

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 ...

Evaluation of the polysubstituted pyridinium ionic liquid [hmmpy][Ntf2] as a suitable solvent for desulfurization: Phase equilibria

International Nuclear Information System (INIS)

Arce, Alberto; Francisco, Maria; Soto, Ana

2010-01-01

Suitability of a pyridinium ionic liquid as a solvent in desulfurization has been analyzed. (Liquid + liquid) equilibria for ternary systems composed by 1-hexyl-3,5-dimethyl pyridinium {bis[trifluoromethylsulfonyl]imide, thiophene, and three hydrocarbons representative of fuel (n-heptane, 2,2,4 trimethylpentane, and toluene) have been determined at T = 298.15 K and atmospheric pressure. High solubility of thiophene in the ionic liquid and also of toluene have been found, being this solvent practically immiscible with 2,2,4 trimethylpentane and heptane. Equilibrium data of these systems have been well correlated with UNIQUAC equations finding the highest deviations for the ternary system involving toluene. NRTL model drove to worse results being considered as not suitable model to correlate the experimental results.

The prediction and representation of phase equilibria and physicochemical properties in complex coal ash slag systems

Energy Technology Data Exchange (ETDEWEB)

E. Jak; A. Kondratiev; S. Christie; P.C. Hayes [Centre for Coal in Sustainable Development (CCSD), Brisbane (Australia)

2003-07-01

A range of problems in coal utilisation technologies, including ash slag flow in slagging gasifiers, deposit formation, slagging, fouling, fusibility tests, fluxing, blending etc, are related to the melting behaviour of the mineral matter in the coal. To assist with solving these practical issues i) thermodynamic modelling of phase equilibria, and ii) viscosity modelling studies are being undertaken at the Pyrometallurgy Research Centre (The University of Queensland, Australia) with support from the Collaborative Research Centre for Coal in Sustainable Development (CCSD). The thermodynamic modelling has been carried out using the computer system FactSage, which is used for the calculation of multi-phase slag / solid / gas / matte / alloy / salt equilibria in multi-component systems of industrial interest. A modified quasi-chemical solution model is used for the liquid slag phase. New model optimisations have been carried out, which have significantly improved the accuracy of the thermodynamic models for coal combustion processes. Viscosity modelling, using a modified Urbain formalism, is carried out in conjunction with FactSage calculations to predict the viscosities of fully liquid as well as heterogeneous, partly crystallised slags. Custom designed software packages are developed using these fundamental models for wider use by industrial researchers and engineers, and for incorporation as process control modules. The new custom-designed computer software package can be used to produce limiting operability diagrams for slag systems. These diagrams are used to describe phase equilibria and physico-chemical properties in complex slag systems. The approach is illustrated with calculations on the system SiO{sub 2}-Al{sub 2}O{sub 3}-FeO-Fe{sub 2}O{sub 3}-CaO at metallic iron saturation, slags produced in coal slagging gasifiers. 28 refs., 7 figs., 1 tab.

Phase equilibria and critical phenomena in the cesium nitrate-water-diethylamine ternary system

International Nuclear Information System (INIS)

Il'in, K.K.; Kurskij, V.F.; Cherkasov, D.G.

2008-01-01

Phase equilibria and critical events in ternary cesium nitrate-water-diethylamine system, where border binary liquid system is characterized by aliquation with lower critical temperature of solution (LCTS), have been investigated by visual-polythermal method in the 60-150 Deg C range. Interaction of cesium nitrate in the water-diethylamine system leads to lowering of its LCTS from 146.1 to 69.3 Deg C and decrease of mutual solubility. Distribution ratios of diethylamine between water and organic phases of monotectic equilibrium are calculated at different temperatures. Diethylamine salting out from aqueous solutions by cesium nitrates becomes stronger with rising temperature. Plotted isotherms of phase confirms generalized scheme of topological transformations of ternary systems phase diagrams: salt-binary solvent with salting out

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

Experimental determination of the phase equilibria in the Co-Fe-Zr ternary system

International Nuclear Information System (INIS)

Wang, C.P.; Yu, Y.; Zhang, H.H.; Hu, H.F.; Liu, X.J.

2011-01-01

Research highlights: → We determined four isothermal sections of the Co-Fe-Zr system from 1000 o C to 1300 o C. → No ternary compound was found in the Co-Fe-Zr ternary system. → The solubility of Fe in the liquid phase at 1300 o C is extremely large. → The (Co, Fe) 2 Zr phase form the continuous solution from Co-Zr side to Fe-Zr side. → The solubility of Zr in the fcc (Co, Fe) phase is extremely small. - Abstract: The phase equilibria in the Co-Fe-Zr ternary system were investigated by means of optical microscopy (OM), electron probe microanalysis (EPMA), X-ray diffraction (XRD), and differential scanning calorimetry (DSC) on equilibrated ternary alloys. Four isothermal sections of the Co-Fe-Zr ternary system at 1300 o C, 1200 o C, 1100 o C and 1000 o C were experimentally established. The experimental results indicate that (1) no ternary compound was found in this system; (2) the solubility of Fe in the liquid phase of the Co-rich corner at 1300 o C is extremely large; (3) the liquid phase in the Zr-rich corner and the (Co,Fe) 2 Zr phase form the continuous solid solutions from the Co-Zr side to the Fe-Zr side; (4) the solubility of Zr in the fcc (Co, Fe) phase is extremely small.

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.

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

International Nuclear Information System (INIS)

Li Xiaoli; Tamura, Kazuhiro

2010-01-01

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

Solid-Liquid Equilibria in Systems [Cxmim][Tf2N] with Diethylamine

Czech Academy of Sciences Publication Activity Database

Rotrekl, Jan; Vrbka, P.; Sedláková, Zuzana; Wagner, Zdeněk; Jacquemin, J.; Bendová, Magdalena

2015-01-01

Roč. 87, č. 5 (2015), s. 453-460 ISSN 0033-4545. [International Symposium on Solubility Phenomena 2014. Karlsruhe, 20.07.2014-24.07.2014] R&D Projects: GA MŠk(CZ) LD14094; GA MŠk LG13060 Institutional support: RVO:67985858 Keywords : ionic liquids * solid-liquid equilibria * COSMO-RS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.615, year: 2015

Phase equilibria in the MgMoO4-Ln2(MoO4)3 (Ln=La,Gd) systems

International Nuclear Information System (INIS)

Fedorov, N.F.; Ipatov, V.V.; Kvyatkovskij, O.V.

1980-01-01

Phase equilibria in the MgMoO 4 -Ln 2 (MoO 4 ) 3 systems (Ln=La, Gd) have been studied by static and dynamic methods of the physico-chemical analysis, using differential thermal, visual-polythermal, crystal-optical, X-ray phase, and infrared spectroscopic methods, and their phase diagrams have been constructed. Phase equilibria in the systems studied are characterized by limited solubility of components in the liquid state, formation of solid solutions on the base of α- and β-forms of Gd 2 (MoO 4 ) 3 . Eutectics in the MgMoO 4 -Ln 2 (MoO 4 ) 3 (Ln=La, Gd) systems corresponds to the composition of 71 mode % La 2 (MoO 4 ) 3 -29 mole % MgMoO 4 , tsub(melt)--935+-5 deg C and 57 mole % Gd 2 (MoO 4 ) 3 -43 mole % MgMoO 4 , tsub(melt)=1020+-5 deg C. The region of glass formation has been established [ru

High temperature interdiffusion and phase equilibria in U-Mo

International Nuclear Information System (INIS)

Lundberg, L.B.

1988-01-01

Experimental data for interdiffusion and phase equilibria in the U-Mo system have been obtained over the temperature range 1400 to 1525 K as a fallout from compatibility experiments in which UO 2 was decomposed by lithium in closed molybdenum capsules. Composition-position, x-ray diffraction and microstructural data from the interdiffusion zones indicate that the intermediate phase U 2 Mo is found in this temperature range, contrary to the currently accepted equilibrium U-Mo phase diagram. The U-Mo interdiffusion data are in good agreement with published values. Inclusion of the U 2 Mo phase in a theoretical correlation of interdiffusion and phase equilibria data using Darken's equation indicate that high temperature interdiffusion of uranium and molybdenum follows the usual thermodynamic rules. Significant changes in the value of the thermodynamic based Darken factor near the U 2 Mo phase boundary on the high uranium side are indicated from both the new and published interdiffusion data. 9 refs., 10 figs., 3 tabs

Phase equilibria in TlX-Cd(Zn)X (X-S, Se, Te) systems

International Nuclear Information System (INIS)

Gusejnov, F.Kh.; Babanly, M.B.; Kuliev, A.A.

1982-01-01

The methods of DTA, RPA and measurement of the alloys microhardness have been used to investigate the phase equilibria in the TlX-Zn(Cd)X systems. It is established that the TlZn(Cd)X 2 compounds, the presence of which is mentioned in the literature earlier, do not form in these systems. The TlSe-Zn(Cd)Se systems apply to the simple eutectic type and characterized by digenerated eutectic near the TlSe. Thermodynamical analysis of the liquidus of the TlSe-CdSe and TlTe-Zn(Cd)Te systems in approximation of the regular solutions, taking into account the dissociation of tallium chalcogenides in liquid phase, is made

(Liquid plus liquid) equilibria of binary polymer solutions using a free-volume UNIQUAC-NRF model

DEFF Research Database (Denmark)

Radfarnia, H.R.; Ghotbi, C.; Taghikhani, V.

2006-01-01

+ liquid) equilibria (LLE) for a number of binary polymer solutions at various temperatures. The values for the binary characteristic energy parameters for the proposed model and the FV-UNIQUAC model along with their average relative deviations from the experimental data were reported. It should be stated...

Thermodynamics and phase equilibria of ternary systems relevant to contact materials for compound semiconductors

International Nuclear Information System (INIS)

Ipser, H.; Richter, K.; Micke, K.

1997-01-01

In order to investigate the stability of ohmic contacts to compound semiconductors, it is necessary to know the phase equilibria in the corresponding multi-component systems. We are currently studying the phase equilibria and thermophysical properties of several ternary systems which are of interest in view of the use of nickel, palladium and platinum as contact materials for GaSb and InSb compound semiconductors: Ga-Ni-Sb, In-Ni-Sb, Ga-Pd-Sb and Ga-Pt-Sb. Phase equilibria are investigated by thermal analyses, X-ray powder diffraction methods as well as electron microprobe analysis. Thermodynamic properties are derived from vapour pressure measurements using an isopiestic method. It is planned to combine all information on phase equilibria and thermochemistry for the ternary and the limiting binary systems to perform an optimization of the ternary systems by computer calculations using standard software. (author)

Solid-phase equilibria on Pluto's surface

Science.gov (United States)

Tan, Sugata P.; Kargel, Jeffrey S.

2018-03-01

Pluto's surface is covered by volatile ices that are in equilibrium with the atmosphere. Multicomponent phase equilibria may be calculated using a thermodynamic equation of state and, without additional assumptions, result in methane-rich and nitrogen-rich solid phases. The former is formed at temperature range between the atmospheric pressure-dependent sublimation and condensation points, while the latter is formed at temperatures lower than the sublimation point. The results, calculated for the observed 11 μbar atmospheric pressure and composition, are consistent with recent work derived from observations by New Horizons.

Phase equilibria of the Mo-Al-Ho ternary system

Energy Technology Data Exchange (ETDEWEB)

Li, Yitai; Chen, Xiaoxian; Liu, Hao [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials; Zhan, Yongzhong [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials; Guangxi Univ., Nanning (China). Center of Ecological Collaborative Innovation for Aluminum Industry

2017-08-15

Investigation into the reactions and phase equilibria of transition metal elements (i.e. Mo, Zr, Cr, V and Ti), Al and rare earths is academically and industrially important for the development of both refractory alloys and lightweight high-temperature materials. In this work, the equilibria of the Mo-Al-Ho ternary system at 773 K have been determined by using X-ray powder diffraction and scanning electron microscopy equipped with energy dispersive X-ray analysis. A new ternary phase Al{sub 4}Mo{sub 2}Ho has been found and the other ternary phase Al{sub 43}Mo{sub 4}Ho{sub 6} is observed. Ten binary phases in the Al-Mo and Al-Ho systems, including Al{sub 17}Mo{sub 4} rather than Al{sub 4}Mo, have been determined to exist at 773 K. The homogeneity ranges of AlMo{sub 3} and Al{sub 8}Mo{sub 3} phase are 7.5 at.% and 1 at.%, respectively. According to the phase-disappearing method, the maximum solubility of Al in Mo is about 16 at.%.

Phase separation and structure formation in gadolinium based liquid and glassy metallic alloys

International Nuclear Information System (INIS)

Han, Junhee

2014-01-01

In this PhD research the liquid-liquid phase separation phenomena in Gd-based alloys was investigated in terms of phase equilibria, microstructure formation upon quenching the melt and corresponding magnetic properties of phase-separated metallic glasses. The phase diagrams of the binary subsystems Gd-Zr and Gd-Ti were experimentally reassessed. Especially the phase equilibria with the liquid phase could be determined directly by combining in situ high energy synchrotron X-ray diffraction with electrostatic levitation of the melt. The Gd-Zr system is of eutectic type with a metastable miscibility gap. The eutectic composition at 18 ± 2 at.% Zr, the liquidus line and the coexistence of bcc-Zr and bcc-Gd at elevated temperature could be determined. The Gd-Ti system is a monotectic system. The experimental observations in this work led to improved new Gd-Zr and Gd-Ti phase diagrams. The phase equilibria of the ternary Gd-Ti-Co system were analyzed for two alloy compositions. The XRD patterns for molten Gd 35 Ti 35 Co 30 gave direct evidence for the coexistence of two liquid phases formed by liquid-liquid phase separation. The first experimental and thermodynamic assessment of the ternary Gd-Ti-Co system revealed that the stable miscibility gap of binary Gd-Ti extends into the ternary Gd-Ti-Co system (up to about 30 at.% Co). New phase-separated metallic glasses were synthesized in Gd-TM-Co-Al (TM = Hf, Ti or Zr) alloys. The microstructure was characterized in terms of composition and cooling rate dependence of phase separation. Due to large positive enthalpy of mixing between Gd on the one side and Hf, Ti or Zr on the other side, the alloys undergo liquid-liquid phase separation during rapid quenching the melt. The parameters determining the microstructure development during phase separation are the thermodynamic properties of the liquid phase, kinetic parameters and quenching conditions. By controlling these parameters and conditions the microstructure can be

Phase equilibria in the niobium-vanadium-hydrogen system

Energy Technology Data Exchange (ETDEWEB)

Bethin, J. (Grumman Aerospace Corp., Bethpage, NY (USA)); Welch, D.O. (Brookhaven National Lab., Upton, NY (USA)); Pick, M.A. (Commission of the European Communities, Abingdon (UK). JET Joint Undertaking)

1990-01-01

The effect of vanadium additions to niobium on the metal-hydrogen phase equilibria has been studied. Measurements of the equilibrium H{sub 2}(D{sub 2}) pressure-composition-temperature isotherms for Nb{sub 1-x}V{sub x} alloys with 0{le}x<0.2 were used to determine the depression of the {alpha} - {alpha}' critical temperature with increasing vanadium concentration. A simple lattice-fluid model guided reduction of the data. Changes in the triple point temperature as well as the shift of the {zeta} {yields} {epsilon} phase transition were determined by differential scanning calorimetry measurements. A rapid overall depression was found, of the order of 7 K (at.% substituted V){sup -1}, for the metal-hydrogen (deuterium) phase boundary structure when compared with the Nb-H system in the hydrogen concentration range of interest. The results explain the enhanced terminal solubility of hydrogen in this system found previously by other authors. The changes in the phase equilibria are discussed in terms of the effect of hydrogen trapping and compared with the results of a cluster-variation calculation for random-field systems of previous authors, taking into account a distribution of H-site energies due to alloying. (author).

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Phase Equilibria Relationships of High-Tc Superconductors

International Nuclear Information System (INIS)

Wong-Ng, Winnie

2011-01-01

As an integral part of a R and D program partially supported by the Electricity Delivery and Energy Reliability Office of DOE, we have determined phase equilibria data and phase diagrams for the three generations of superconductor materials: 1st generation, (Bi,Pb)-Sr-Ca- Cu-O systems; 2nd generation, Ba-R-Cu-O systems (R=lanthanides and yttrium); and 3rd generation, MgB2 systems. Our studies involved bulk materials, single crystals and thin films. This report gives a summary of our accomplishments, a list of publications, and 15 selected journal publications.

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.

Isobaric vapor-liquid equilibria for the extractive distillation of 2-propanol + water mixtures using 1-ethyl-3-methylimidazolium dicyanamide ionic liquid

International Nuclear Information System (INIS)

Orchillés, A. Vicent; Miguel, Pablo J.; González-Alfaro, Vicenta; Llopis, Francisco J.; Vercher, Ernesto; Martínez-Andreu, Antoni

2017-01-01

Highlights: • VLE of binary and ternary systems of 2-propanol, water and [emim][DCA] at 100 kPa. • The e-NRTL model fits the VLE data of 2-propanol + water + [emim][DCA] system. • [emim][DCA] breaks the 2-propanol + water azeotrope at an IL mole fraction >0.085. - Abstract: Isobaric vapor–liquid equilibria for the binary systems 2-propanol + water, 2-propanol + 1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]), and water + [emim][DCA] as well as the vapor–liquid equilibria for the 2-propanol + water + [emim][DCA] ternary system have been obtained at 100 kPa using a recirculating still. The electrolyte nonrandom two-liquid (e-NRTL) model was used for fitting successfully the experimental data. The effect of [emim][DCA] on the 2-propanol + water system has been compared with that produced by other ionic liquids reported in the literature. From the results, [emim][DCA] appears as a good entrainer for the extractive distillation of this solvent mixture, causing the azeotrope to disappear at 100 kPa when the ionic liquid mole fraction is greater than 0.085.

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Stability of equilibria for a two-phase osmosis model

NARCIS (Netherlands)

Lippoth, F.; Prokert, G.

2012-01-01

For a two-phase moving boundary problem modelling the motion of a semipermeable membrane by osmotic pressure and surface tension, we prove that the manifold of equilibria is locally exponentially attractive. Our method relies on maximal regularity results for parabolic systems with relaxation type

Electronic structure and phase equilibria in ternary substitutional alloys

International Nuclear Information System (INIS)

Traiber, A.J.S.; Allen, S.M.; Waterstrat, R.M.

1996-01-01

A reliable, consistent scheme to study phase equilibria in ternary substitutional alloys based on the tight-binding approximation is presented. With electronic parameters from linear muffin-tin orbital calculations, the computed density of states and band structures compare well with those from more accurate abinitio calculations. Disordered alloys are studied within the tight-binding coherent-potential approximation extended to alloys; energetics of ordered systems are obtained through effective pair interactions computed with the general perturbation method; and partially ordered alloys are studied with a novel simplification of the molecular coherent-potential approximation combined with the general perturbation method. The formalism is applied to bcc-based Zr-Ru-Pd alloys which are promising candidates for medical implant devices. Using energetics obtained from the above scheme, we apply the cluster- variation method to study phase equilibria for particular pseudo- binary alloys and show that results are consistent with observed behavior of electronic specific heat coefficient with composition for Zr 0.5 (Ru, Pd) 0.5

Generalized method for calculation and prediction of vapour-liquid equilibria at high pressures

Energy Technology Data Exchange (ETDEWEB)

Drahos, J; Wichterle, I; Hala, E

1978-02-01

Following the approaches of K.C. Chao and J.D. Seader (see Gas Abstr. 18,24 (1962) Jan.) and B.I. Lee, J.H. Erbar, and W.C. Edmister (see Gas Abst. 29, 73-0331), the Czechoslovak Academy of Sciences developed a generalized method for prediction of vapor-liquid equilibria in hydrocarbon mixtures containing some nonhydrocarbon gases at high pressures. The method proposed is based on three equations: (1) a generalized equation of state for vapor-phase calculations; (2) a generalized expression for the pure-liquid fugacity coefficient; and (3) an activity coefficient expression based on a surface modification of the regular solution model. The equations used contain only one partially generalized binary parameter, which was evaluated from experimental K-value data. Researchers tested the proposed method by computing K-values and pressures in binary and multicomponent systems consisting of 13 hydrocarbons and 3 nonhydrocarbon gases. The results show that the method is applicable over a wide range of conditions with a degree of accuracy comparable with that of more complicated methods.

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, at tem...

Prediction of high pressure vapor-liquid equilibria with mixing rule using ASOG group contribution method

Energy Technology Data Exchange (ETDEWEB)

Tochigi, K.; Kojima, K.; Kurihara, K.

1985-02-01

To develop a widely applicable method for predicting high-pressure vapor-liquid equilibria by the equation of state, a mixing rule is proposed in which mixture energy parameter ''..cap alpha..'' of theSoave-RedlichKwong, Peng-Robinson, and Martin cubic equations of state is expressed by using the ASOG group contribution method. The group pair parameters are then determined for 14 group pairs constituted by six groups, i.e. CH/sub 4/, CH/sub 3/, CH/sub 2/, N/sub 2/, H/sub 2/, and CO/sub 2/ groups. By using the group pair parameters determined, high-pressure vapor-liquid equilibria are predicted with good accuracy for binary and ternary systems constituted by n-paraffins, nitrogen, hydrogen, and carbon dioxide in the temperature range of 100 - 450K.

Experimental Phase Equilibria Studies of the Pb-Fe-O System in Air, in Equilibrium with Metallic Lead and at Intermediate Oxygen Potentials

Science.gov (United States)

Shevchenko, M.; Jak, E.

2017-12-01

The phase equilibria information on the Pb-Fe-O system is of practical importance for the improvement of the existing thermodynamic database of lead-containing slag systems (Pb-Zn-Fe-Cu-Si-Ca-Al-Mg-O). Phase equilibria of the Pb-Fe-O system have been investigated: (a) in air at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); (b) in equilibrium with metallic lead at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); and (c) at intermediate oxidation conditions for the liquid slag in equilibrium with two solids (spinel + magnetoplumbite), at temperatures between 1093 K and 1373 K (820 °C and 1100 °C). The high-temperature equilibration/quenching/electron probe X-ray microanalysis technique has been used to accurately determine the compositions of the phases in equilibrium in the system. The Pb and Fe concentrations in the phases were determined directly; preliminary thermodynamic modeling with FactSage was used to estimate the ferrous-to-ferric ratios and to present the results in the ternary diagram.

Phase equilibrium in systems with ionic liquids: An example for the downstream process of the Biphasic Acid Scavenging utilizing Ionic Liquids (BASIL) process. Part I: Experimental data

International Nuclear Information System (INIS)

Sahandzhieva, Katya; Maurer, Gerd

2012-01-01

Highlights: ► Phase equilibrium for a downstream process in sustainable chemical technology. ► Biphasic Acid Scavenging Utilizing Ionic Liquids (BASIL) Process. ► SLE, LLE, and SLLE of (NaCl + water + 1-propanol + 1-MIM) and its ternary subsystems. ► Experimental phase equilibrium data at temperatures between 298 K and 333 K. - Abstract: Experimental results are presented for the (liquid + liquid), (solid + liquid) and (solid + liquid + liquid) equilibria occurring in the downstream process of a typical example for the Biphasic Acid Scavenging Utilizing Ionic Liquids (BASIL)-processes. In a BASIL process an organic base is used to catalyze a chemical reaction and, at the same time, to scavenge an acid that is an undesired side product of that reaction. The particular example of a BASIL process treated here is the reaction of 1-butanol and acetylchloride to butylacetate and hydrochloric acid, where the acid is scavenged by the organic base 1-methyl imidazole (1-MIM) resulting in the ionic liquid 1-methyl imidazolium chloride. The reaction results in a two-phase system as butylacetate and the ionic liquid reveal a large liquid–liquid miscibility gap. The organic base has to be recovered. This is commonly achieved by treating the ionic liquid–rich liquid phase with an aqueous solution of sodium hydroxide (i.e., converting the ionic liquid to the organic base) and extracting the organic base by an appropriate organic solvent (e.g., 1-propanol). The work presented here deals in experimental work with the (liquid + liquid), (solid + liquid) and (solid + liquid + liquid) phase equilibria that are encountered in such extraction processes. Experimental results are reported for temperatures between about 298 K and 333 K: for the solubility of NaCl in several solvents (1-propanol, 1-MIM), (water + 1-MIM), (1-propanol + 1-MIM), (water + 1-propanol), and (water + 1-propanol + 1-MIM) and for the (liquid + liquid) equilibrium as well as for the (solid + liquid

Phase equilibria constraints on models of subduction zone magmatism

Science.gov (United States)

Myers, James D.; Johnston, Dana A.

Petrologic models of subduction zone magmatism can be grouped into three broad classes: (1) predominantly slab-derived, (2) mainly mantle-derived, and (3) multi-source. Slab-derived models assume high-alumina basalt (HAB) approximates primary magma and is derived by partial fusion of the subducting slab. Such melts must, therefore, be saturated with some combination of eclogite phases, e.g. cpx, garnet, qtz, at the pressures, temperatures and water contents of magma generation. In contrast, mantle-dominated models suggest partial melting of the mantle wedge produces primary high-magnesia basalts (HMB) which fractionate to yield derivative HAB magmas. In this context, HMB melts should be saturated with a combination of peridotite phases, i.e. ol, cpx and opx, and have liquid-lines-of-descent that produce high-alumina basalts. HAB generated in this manner must be saturated with a mafic phase assemblage at the intensive conditions of fractionation. Multi-source models combine slab and mantle components in varying proportions to generate the four main lava types (HMB, HAB, high-magnesia andesites (HMA) and evolved lavas) characteristic of subduction zones. The mechanism of mass transfer from slab to wedge as well as the nature and fate of primary magmas vary considerably among these models. Because of their complexity, these models imply a wide range of phase equilibria. Although the experiments conducted on calc-alkaline lavas are limited, they place the following limitations on arc petrologic models: (1) HAB cannot be derived from HMB by crystal fractionation at the intensive conditions thus far investigated, (2) HAB could be produced by anhydrous partial fusion of eclogite at high pressure, (3) HMB liquids can be produced by peridotite partial fusion 50-60 km above the slab-mantle interface, (4) HMA cannot be primary magmas derived by partial melting of the subducted slab, but could have formed by slab melt-peridotite interaction, and (5) many evolved calc

Vapor-liquid Phase Equilibria for CO2+Tertpentanol Binary System at Elevated Pressures

Institute of Scientific and Technical Information of China (English)

WANG Lin; LUO Jian-cheng; YANG Hao; CHEN Kai-xun

2011-01-01

Vapor-liquid phase equilibrium data of tertpentanol in carbon dioxide were measured at temperatures of 313.4,323.4,333.5 and 343.5 K and in the pressure range of 4.56-11.44 MPa.The phase equilibium apparatus used in the work was a variable-volume high-pressure cell.The experimental data were reasonably correlated with Peng-Robinson equation of state(PR-EOS) together with van der Waals-2 two-parameter mixing rules.Henry's Law constants and partial molar volumes of CO2 at infinite dilution were estimated with Krichevsky-Kasarnovsky equation,and Henry's Law constants increase with increasing temperature,however,partial molar volumes of CO2 at infinite dilution are negative whose magnitudes decrease with temperature.Partial molar volumes of CO2 and tertpentanol in liquid phase at equilibrium were calculated.

Thermophysical properties and phase equilibria study of the binary systems {l_brace}N-hexylquinolinium bis(trifluoromethylsulfonyl)imide + aromatic hydrocarbons, or an alcohol{r_brace}

Energy Technology Data Exchange (ETDEWEB)

Domanska, Urszula, E-mail: ula@ch.pw.edu.p [Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland); Thermodynamic Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4001 (South Africa); Zawadzki, Maciej [Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland); Zwolinska, Magdalena [Department of Ergonomics, Laboratory of Thermal Loads, Central Institute for Labour Protection-National Research Institute, Czerniakowska 16, 00-701 Warsaw (Poland)

2011-05-15

Research highlights: We synthesized new ionic liquid, [HQuin][NTf{sub 2}] with low viscosity, and low density. We found high heat capacity, high enthalpy of melting and low melting temperature. HQuin][NTf{sub 2}] is proposed for possible use in the phase change materials (PCM). We examine phase equilibrium changes, SLE and LLE with hydrocarbons and alcohols. [HQuin][NTf{sub 2}] may be proposed as entrainer for the separation proceses. - Abstract: The new quinolinium ionic liquid has been synthesised as a continuation of our work with quinolinium-based ionic liquids (ILs). The work includes specific basic characterisation of synthesized compounds: N-hexylquinolinium bromide, [HQuin][Br] and N-hexylquinolinium bis{l_brace}(trifluoromethyl)sulfonyl{r_brace}imide [HQuin][NTf{sub 2}] by NMR spectra, elementary analysis and water content. The basic thermal properties of the pure [HQuin][NTf{sub 2}] i.e. melting and glass-transition temperatures, the enthalpy of fusion as well as heat capacity have been measured using a differential scanning microcalorimetry technique (DSC) and thermal analysis instrument (TA). Densities and viscosities were determined as a function of temperature. Phase equilibria for the binary systems: {l_brace}[HQuin][NTf{sub 2}]) + aromatic hydrocarbon (benzene, or toluene, or ethylbenzene, or n-propylbenzene), or an alcohol (1-butanol, or 1-hexanol, or 1-octanol, or 1-decanol){r_brace} have been determined at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from (270 to 320) K. For all the binary systems with benzene and alkylbenzenes, the eutectic diagrams were observed with immiscibility gap in the liquid phase beginning from (0.13 to 0.28) mole fraction of the IL with very high an upper critical solution temperature (UCST). For mixtures with alcohols, the complete miscibility was observed for 1-butanol and immiscibility with UCST in the liquid phase for the remaining alcohols. The typical

Phase equilibria, phases and compounds in the Ti-C system

International Nuclear Information System (INIS)

Gusev, Aleksandr I

2002-01-01

The results of experimental and theoretical investigations of the phase equilibria in the titanium-carbon system are generalised. The generalised thermodynamic characteristics of disordered titanium carbide TiC y , are reported. Peculiarities of the crystal structures of all the known and hypothetical compounds of titanium with carbon are considered in detail. The X-ray diffraction patterns which allow identification of all these compounds are presented. The phase diagrams of the Ti-C system constructed with allowance for atomic ordering of non-stoichio metric carbide, TiC y , and for the existence of the molecular cluster-like compounds Ti 8 C 12 and Ti 13 C 22 (TiC 2 ) are discussed. The bibliography includes 142 references.

Phase equilibria, phases and compounds in the Ti-C system

International Nuclear Information System (INIS)

Gusev, A.I.

2002-01-01

The results of experimental and theoretical investigations related to the phase equilibria in the titanium-carbon system are generalized. The generalized thermodynamic characteristics of the disordered titanium carbide TiC y are given. The crystal structure of all the discovered and hypothetical compounds of titanium with carbon are considered in detail. The x-ray diffraction patterns which allow one to identify all these compounds are given. The phase diagrams of the Ti-C system constructed with allowance for atomic ordering of non-stoichiometric TiC y carbide and for the existence of the compounds Ti 8 C 12 and Ti 13 C 22 (TiC 2 ) of the molecule cluster type are discussed [ru

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

, and water. Furthermore, the predictive capabilities of the models are investigated for four ternary systems composed of these components, which exhibit complex liquid-liquid(-liquid) equilibria (LLLE). Various aspects of association models which have an influence in the results are studied for the PC......, both models perform overall similarly for the binary systems, although ESD shows a remarkably good behavior despite its simplicity and the use of only the two-site scheme for all associating compounds. The prediction of the LLE in the ternary systems water + octane + aniline and water + CHA + aniline......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...

Melt-gas phase equilibria and state diagrams of the selenium-tellurium system

Science.gov (United States)

Volodin, V. N.; Trebukhov, S. A.; Burabaeva, N. M.; Nitsenko, A. V.

2017-05-01

The partial pressures of saturated vapor of the components in the Se-Te system are determined and presented in the form of temperature-concentration dependences from which the boundaries of the melt-gas phase transition are calculated at atmospheric pressure and vacuums of 2000 and 100 Pa. The existence of azeotropic mixtures is revealed. It is found that the points of inseparably boiling melts correspond to 7.5 at % of Se and 995°C at 101325 Pa, 10.9 at % at 673°C and 19.5 at % at 522°C in vacuums of 2000 and 100 Pa, respectively. A complete state diagram is constructed, including the fields of gas-liquid equilibria at atmospheric and low pressures, the boundaries of which allow us to assess the behavior of selenium and tellurium upon distillation fractionation.

Calculation of ethanol refining by means of extractive distillation with water using simulated data on phase equilibria

Energy Technology Data Exchange (ETDEWEB)

Rosak, J; Mertl, I; Huml, M; Wichterle, I

1980-01-01

Available data on phase equilibria in binary mixtures pertaining to the system ethanol - water - impurities (7 compounds that represent the main impurities present in raw synthetic or fermentation ethanol) have been gathered for the computer calculation of a column to be used for the refining of ethanol. Missing experimental data on phase equilibria were supplied by simulation using the increment method UNIFAC which predicts phase equilibria on the basis of the chemical structure. All data about the behavior of binary mixtures were correlated by means of the NRTL method and the sets of constants thus obtained were then used in calculations of the column for the refining of ethanol. The results were compared with reality verified on industrial scale.

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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

International Nuclear Information System (INIS)

Li Hengde; Tamura, Kazuhiro

2006-01-01

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

Liquid–liquid equilibria in the quinary aqueous two-phase system of poly(ethylene glycol) 6000 + sodium sulfate + water in the presence of glucose and ethanol: Experimental investigation and thermodynamic modeling

Energy Technology Data Exchange (ETDEWEB)

Hekayati, Javad; Roosta, Aliakbar, E-mail: aa.roosta@sutech.ac.ir; Javanmardi, Jafar

2016-02-10

Highlights: • Quinary LLE phase equilibria involving PEG 6000 + Na{sub 2}SO{sub 4} + H{sub 2}O + glucose + ethanol. • Favorable partition coefficients of ethanol and glucose. • Satisfactory correlation of the LLE experimental data with the original NRTL model. • Root mean squared deviations (RMSDs) of less than 0.6%. - Abstract: Extractive fermentation processes involving aqueous two-phase systems (ATPSs) are considered as viable means of overcoming the problems associated with product inhibition. Practical development of these processes requires accurate knowledge of the liquid–liquid equilibrium (LLE) of the ATPS forming components alongside the substrate and product of the fermentation process. In this work, the quinary aqueous two-phase LLE of poly(ethylene glycol) 6000 + sodium sulfate + water in the presence of glucose and ethanol have been experimentally determined at 298.15 K using spectrophotometric methods. The resulting LLE data were then satisfactorily correlated by the non-random two-liquid (NRTL) activity coefficient model based on mass fractions. In doing so, the binary energy interaction parameters of the NRTL activity coefficient model were obtained and reported. Calculated RMS deviations below 0.6% demonstrate that the original NRTL activity coefficient model can accurately correlate the LLE data of the quinary aqueous biphasic system of interest.

Liquid–liquid equilibria in the quinary aqueous two-phase system of poly(ethylene glycol) 6000 + sodium sulfate + water in the presence of glucose and ethanol: Experimental investigation and thermodynamic modeling

International Nuclear Information System (INIS)

Hekayati, Javad; Roosta, Aliakbar; Javanmardi, Jafar

2016-01-01

Highlights: • Quinary LLE phase equilibria involving PEG 6000 + Na_2SO_4 + H_2O + glucose + ethanol. • Favorable partition coefficients of ethanol and glucose. • Satisfactory correlation of the LLE experimental data with the original NRTL model. • Root mean squared deviations (RMSDs) of less than 0.6%. - Abstract: Extractive fermentation processes involving aqueous two-phase systems (ATPSs) are considered as viable means of overcoming the problems associated with product inhibition. Practical development of these processes requires accurate knowledge of the liquid–liquid equilibrium (LLE) of the ATPS forming components alongside the substrate and product of the fermentation process. In this work, the quinary aqueous two-phase LLE of poly(ethylene glycol) 6000 + sodium sulfate + water in the presence of glucose and ethanol have been experimentally determined at 298.15 K using spectrophotometric methods. The resulting LLE data were then satisfactorily correlated by the non-random two-liquid (NRTL) activity coefficient model based on mass fractions. In doing so, the binary energy interaction parameters of the NRTL activity coefficient model were obtained and reported. Calculated RMS deviations below 0.6% demonstrate that the original NRTL activity coefficient model can accurately correlate the LLE data of the quinary aqueous biphasic system of interest.

The impact of uni-univalent electrolytes on (water + acetic acid + toluene) equilibria: Representation with electrolyte-NRTL model

International Nuclear Information System (INIS)

Saien, Javad; Fattahi, Mahdi; Mozafarvandi, Maryam

2014-01-01

Highlights: • Experimental LLE data for water + acetic acid + toluene + NaCl or KCl were reported. • The salting-out effect was detected; indicating the stronger effect of NaCl. • The electrolyte-NRTL model was adequately used to correlate the phase equilibria. • A good agreement was observed between calculated and experimental tie-lines. - Abstract: The presence of salts can significantly alter the (liquid + liquid) equilibrium and extraction process. In this work, a study was conducted on the (liquid + liquid) equilibria of (water + acetic acid + toluene + sodium chloride or potassium chloride) at temperatures (288.2, 298.2 and 313.2) K. This chemical system, irrespective of salt, is frequently used in (liquid + liquid) extraction investigations. The selected salt concentrations in initial aqueous solutions were (0.9 and 1.7) mol · L −1 . The results show that salting-out effect of the salts was significant, so that an enhancement in the acetic acid distribution coefficient was achieved within (15.6 to 66.8)% with NaCl and within (2.5 to 37.6)% with KCl. Meantime, high separation factors were found at low temperatures and low solute concentrations. The electrolyte-NRTL model was satisfactorily used to correlate the phase equilibria. In this regard for each salt, the temperature dependent binary interaction parameters between components were calculated. The predicted tie-line mole fractions give root-mean square deviation (RMSD) values of only 0.0038 and 0.0045 for the systems containing NaCl and KCl, respectively

Physico-Chemical Properties and Phase Behaviour of Pyrrolidinium-Based Ionic Liquids

Directory of Open Access Journals (Sweden)

Urszula Domańska

2010-04-01

Full Text Available A review of the relevant literature on 1-alkyl-1-methylpyrrolidinium-based ionic liquids has been presented. The phase diagrams for the binary systems of {1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate [EMPYR][CF3SO3] + water, or + 1-butanol} and for the binary systems of {1-propyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate [PMPYR][CF3SO3] + water, or + an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol} have been determined at atmospheric pressure using a dynamic method. The influence of alcohol chain length was discussed for the [PMPYR][CF3SO3]. A systematic decrease in the solubility was observed with an increase of the alkyl chain length of an alcohol. (Solid + liquid phase equilibria with complete miscibility in the liquid phase region were observed for the systems involving water and alcohols. The solubility of the ionic liquid increases as the alkyl chain length on the pyrrolidinium cation increases. The correlation of the experimental data has been carried out using the Wilson, UNIQUAC and the NRTL equations. The phase diagrams reported here have been compared to the systems published earlier with the 1-alkyl-1-methylpyrrolidinium-based ionic liquids. The influence of the cation and anion on the phase behaviour has been discussed. The basic thermal properties of pure ILs, i.e., melting temperature and the enthalpy of fusion, the solid-solid phase transition temperature and enthalpy have been measured using a differential scanning microcalorimetry technique.

Dynamic data evaluation for solid-liquid equilibria

DEFF Research Database (Denmark)

Cunico, Larissa; Ceriani, Roberta; Kang, Jeong Won

The accuracy and reliability of the measured data sets to be used in regression of model parameters is an important issue related to modeling of phase equilibria. It is clear that good parameters for any model cannot be obtained from low quality data. A thermodynamic consistency test for solid...... and parameter regression. The paper will highlight the data collection, the data analysis for SLE data and the thermodynamic model performance (such as NRTL, UNIQUAC and original UNIFAC)....... studies considering the methodology proposed for SLE thermodynamic consistency tests and data from open literature and databases such as NIST-TDE®, DIPPR® and DECHEMA® are presented. The SLE consistency test and data evaluation is performed in a software containing option for data analysis, model analysis...

Phase equilibria and thermodynamics of the Fe–Al–C system: Critical evaluation, experiment and thermodynamic optimization

International Nuclear Information System (INIS)

Phan, Anh Thu; Paek, Min-Kyu; Kang, Youn-Bae

2014-01-01

In order to provide an efficient tool to design alloy chemistry and processing conditions for high-strength, lightweight steel, an investigation of the Fe–Al–C ternary system was carried out by experimental phase diagram measurement and a CALPHAD thermodynamic analysis. Discrepancies between previously available experimental results and thermodynamic calculations were identified. The Fe–Al sub-binary system was re-optimized in order to obtain an accurate description of the liquid phase, while Gibbs energies of solid phases were mainly taken from a previous thermodynamic modeling. Phase equilibria among face-centered cubic (fcc)/body-centered cubic (bcc)/graphite/κ-carbide/liquid phases in the Fe–Al–C system in the temperature range from 1000 to 1400 °C were obtained by chemical equilibration followed by quenching, and subsequent composition analysis using electron probe microanalysis/inductively coupled plasma spectroscopy. By merging the revised Fe–Al binary description with existing Fe–C and Al–C binary descriptions, a complete thermodynamic description of the Fe–Al–C system was obtained in the present study. The modified quasi-chemical model in the pair approximation was used to model the liquid phase, while solid solutions were modeled using compound energy formalism. A2/B2 order/disorder transition in the bcc phase was taken into account. Compared with previously known experiments/thermodynamic modeling, a better agreement was obtained in the present study, regarding the stable region of fcc and the solidification thermal peak of a ternary alloy near the liquidus temperature. The obtained thermodynamic description also reproduced various types of experimental data in the Fe–Al–C system such as isothermal sections, vertical sections, liquidus projection, etc. The solidification of various steel grades was predicted and discussed

Liquid-liquid phase equilibria for ternary systems of several polyethers with NaCl and H2O

NARCIS (Netherlands)

Milosevic, M.; Staal, K.J.J.; Schuur, Boelo; de Haan, A.B.

2014-01-01

Liquid–liquid extraction using polymers followed by induced phase separation is a potential energy reducing technology for water–salt separation. Ternary equilibrium data have been determined and reported for the (block co)poly ethers–sodium chloride–water systems at two different temperatures at

Prediction of phase equilibria in the In–Sb–Pb system

Directory of Open Access Journals (Sweden)

DUSKO MINIC

2008-03-01

Full Text Available Binary thermodynamic data, successfully used for phase diagram calculations of the binary systems In–Sb, Pb–Sb and In–Pb, were used for the prediction of the phase equilibria in the ternary In–Sb–Pb system. The predicted equilibrium phase diagram of the vertical Pb–InSb section was compared with the results of differential thermal analysis DTA and optical microscopy. The calculated phase diagram of the isothermal section at 300 °C was compared with the experimentally (SEM, EDX determined composition of phases in the chosen alloys after annealing. Very good agreement between the binary-based thermodynamic prediction and the experimental data was found in all cases. The calculated liquidus projection of the ternary In–Sb–Pb system is also presented.

Measurement and correlation of vapor-liquid equilibria for a binary system containing 1-butyl-3-methylimidazolium tridecafluorohexyl sulfonate and carbon dioxide

Energy Technology Data Exchange (ETDEWEB)

Hong, Soon Kang; Park, Yoon Kook [Hongik University, Sejong (Korea, Republic of)

2016-01-15

Using a high-pressure variable-volume view cell, the vapor-liquid equilibria of the binary system CO{sub 2} and 1-butyl-3-methylimidazolium tridecafluorohexylsulfonate ([BMIM][TDfO]) were determined. The CO{sub 2} mole fraction ranged from 0.104 to 0.952 over a temperature range of 298.2-323.2 K. Both the Peng-Robinson and Soave-Redlich- Kwong equations of state were applied with two different mixing rules to correlate with the experimentally obtained results. Increasing the alkyl chain length in perfluorinated sulfonate anion mother structure from methyl to hexyl markedly increased the CO{sub 2} solubility. To investigate the effect of the number of fluorine atoms in the anion on the phase behavior of imidazolium-based ionic liquid, these experimental results were then compared with those reported in previous experimental studies of 1-alkyl-3-methylimidazolium cations-including ionic liquid+CO{sub 2} binary system.

Measurement and correlation of vapor-liquid equilibria for a binary system containing 1-butyl-3-methylimidazolium tridecafluorohexyl sulfonate and carbon dioxide

International Nuclear Information System (INIS)

Hong, Soon Kang; Park, Yoon Kook

2016-01-01

Using a high-pressure variable-volume view cell, the vapor-liquid equilibria of the binary system CO 2 and 1-butyl-3-methylimidazolium tridecafluorohexylsulfonate ([BMIM][TDfO]) were determined. The CO 2 mole fraction ranged from 0.104 to 0.952 over a temperature range of 298.2-323.2 K. Both the Peng-Robinson and Soave-Redlich- Kwong equations of state were applied with two different mixing rules to correlate with the experimentally obtained results. Increasing the alkyl chain length in perfluorinated sulfonate anion mother structure from methyl to hexyl markedly increased the CO 2 solubility. To investigate the effect of the number of fluorine atoms in the anion on the phase behavior of imidazolium-based ionic liquid, these experimental results were then compared with those reported in previous experimental studies of 1-alkyl-3-methylimidazolium cations-including ionic liquid+CO 2 binary system.

Another dimension to metamorphic phase equilibria: the power of interactive movies for understanding complex phase diagram sections

Science.gov (United States)

Moulas, E.; Caddick, M. J.; Tisato, N.; Burg, J.-P.

2012-04-01

The investigation of metamorphic phase equilibria, using software packages that perform thermodynamic calculations, involves a series of important assumptions whose validity can often be questioned but are difficult to test. For example, potential influences of deformation on phase relations, and modification of effective reactant composition (X) at successive stages of equilibrium may both introduce significant uncertainty into phase diagram calculations. This is generally difficult to model with currently available techniques, and is typically not well quantified. We present here a method to investigate such phenomena along pre-defined Pressure-Temperature (P-T) paths, calculating local equilibrium via Gibbs energy minimization. An automated strategy to investigate complex changes in the effective equilibration composition has been developed. This demonstrates the consequences of specified X modification and, more importantly, permits automated calculation of X changes that are likely along the requested path if considering several specified processes. Here we describe calculations considering two such processes and show an additional example of a metamorphic texture that is difficult to model with current techniques. Firstly, we explore the assumption that although water saturation and bulk-rock equilibrium are generally considered to be valid assumptions in the calculation of phase equilibria, the saturation of thermodynamic components ignores mechanical effects that the fluid/melt phase can impose on the rock, which in turn can modify the effective equilibrium composition. Secondly, we examine how mass fractionation caused by porphyroblast growth at low temperatures or progressive melt extraction at high temperatures successively modifies X out of the plane of the initial diagram, complicating the process of determining best-fit P-T paths for natural samples. In particular, retrograde processes are poorly modeled without careful consideration of prograde

Ternary equilibria in bismuth--indium--lead alloys

International Nuclear Information System (INIS)

Liao, K.C.; Johnson, D.L.; Nelson, R.C.

1975-01-01

The liquidus surface is characterized by three binary equilibria. One binary extends from the Pb--Bi peritectic to the Pb--In peritectic. The other two extend from In--Bi eutectics, merge at 50 at. percent Bi and 30 at. percent Pb, and end at the Bi--Pb eutectic. Based on analysis of ternary liquidus contours and vertical sections, it is suggested that solidification for high lead and very high indium alloys occurs from two-phase equilibria. Solidification from all other alloys occurs from three-phase equilibria. Four-phase solidification does not occur in this system

Phase equilibria and stability of the B2 phase in the Ni-Mn-Al and Co-Mn-Al systems

International Nuclear Information System (INIS)

Kainuma, R.; Ise, M.; Ishikawa, K.; Ohnuma, I.; Ishida, K.

1998-01-01

The phase equilibria and ordering reactions in the composition region up to 50 at.% Al have been investigated in the Ni-Mn-Al and Co-Mn-Al systems at temperatures in the interval 850-1200 C mainly by the diffusion couple method. The compositions of the γ (A1: fcc-Ni, -Co, γ-Mn), γ' (L1 2 : Ni 3 Al), β (B2: NiAl, CoAl, NiMn), β-Mn (A13: β-Mn type), δ-Mn (A2: bcc-Mn) and ε (A3: hcp-(Mn, Al)) phases in equilibrium and the critical boundaries of the A2/B2 continuous ordering transition in the bcc phase region have been determined. It is shown that in the Mn-rich portion of the ternary systems both continuous and discontinuous A2 to B2 ordering transitions exist. The A2+B2 two-phase region in the isothermal sections has a lenticular shape and exists over a wide temperature range. The phase equilibria between the γ, γ', β, β-Mn, δ-Mn and ε phases are presented and the stability of the ordered bcc aluminides is discussed. (orig.)

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

Czech Academy of Sciences Publication Activity Database

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

2006-01-01

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

(Vapour + liquid) equilibria for the binary mixtures (1-propanol + dibromomethane, or + bromochloromethane, or + 1,2-dichloroethane or + 1-bromo-2-chloroethane) at T = 313.15 K

International Nuclear Information System (INIS)

Gil-Hernandez, V.; Garcia-Gimenez, P.; Otin, S.; Artal, M.; Velasco, I.

2005-01-01

Isothermal (vapour + liquid) equilibria (VLE) at 313.15 K have been measured for liquid 1-propanol + dibromomethane, or + bromochloromethane or + 1,2-dichloroethane or + 1-bromo-2-chloroethane mixtures. The VLE data were reduced using the Redlich-Kister equation taking into consideration the vapour phase imperfection in terms of the 2nd molar virial coefficients. The excess molar Gibbs free energies of all the studied mixtures are positive and ranging from 794 J·mol -1 for (1-propanol + bromochloromethane) and 1052 J·mol -1 for (1-propanol + 1-bromo-2-chloroethane), at x = 0.5. The experimental results are compared with modified UNIFAC predictions

Systematic identification method for data analysis and phase equilibria modelling for lipids systems

DEFF Research Database (Denmark)

Perederic, Olivia A.; Cunico, Larissa P.; Kalakul, Sawitree

2018-01-01

Industrial use of lipids has been increasing as a consequence of increased developments related to biobased economies. In addition to applications in food-products, lipids are used by many industrial sectors, for example, biodiesel, edible oil, health, and personal care. Phase equilibria...

Phase diagram of nanoscale alloy particles used for vapor-liquid-solid growth of semiconductor nanowires.

Science.gov (United States)

Sutter, Eli; Sutter, Peter

2008-02-01

We use transmission electron microscopy observations to establish the parts of the phase diagram of nanometer sized Au-Ge alloy drops at the tips of Ge nanowires (NWs) that determine their temperature-dependent equilibrium composition and, hence, their exchange of semiconductor material with the NWs. We find that the phase diagram of the nanoscale drop deviates significantly from that of the bulk alloy, which explains discrepancies between actual growth results and predictions on the basis of the bulk-phase equilibria. Our findings provide the basis for tailoring vapor-liquid-solid growth to achieve complex one-dimensional materials geometries.

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

Science.gov (United States)

Circone, S.; Kirby, S.H.; Stern, L.A.

2006-01-01

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Phase Equilibria of Sn-Co-Cu Ternary System

Science.gov (United States)

Chen, Yu-Kai; Hsu, Chia-Ming; Chen, Sinn-Wen; Chen, Chih-Ming; Huang, Yu-Chih

2012-10-01

Sn-Co-Cu ternary alloys are promising lead-free solders, and isothermal sections of Sn-Co-Cu phase equilibria are fundamentally important for the alloys' development and applications. Sn-Co-Cu ternary alloys were prepared and equilibrated at 523 K, 1073 K, and 1273 K (250 °C, 800 °C, and 1000 °C), and the equilibrium phases were experimentally determined. In addition to the terminal solid solutions and binary intermetallic compounds, a new ternary compound, Sn3Co2Cu8, was found. The solubilities of Cu in the α-CoSn3 and CoSn2 phases at 523 K (250 °C) are 4.2 and 1.6 at. pct, respectively, while the Cu solubility in the α-Co3Sn2 phase is as high as 20.0 at. pct. The Cu solubility increases with temperature and is around 30.0 at. pct in the β-Co3Sn2 at 1073 K (800 °C). The Co solubility in the η-Cu6Sn5 phase is also significant and is 15.5 at. pct at 523 K (250 °C).

Survey of the calculation of phase equilibria with the aid of the UNIFAC-method

Energy Technology Data Exchange (ETDEWEB)

Gmehling, J.; Rasmussen, P.; Fredenslund, A.

1981-09-01

In the design of diffusional separation processes and for many other practical purposes one needs quantitative estimates of phase equilibrium compositions. These compositions can today be predicted with good results using modern, two-parameter models for the excess Gibbs energy. However, since the number of different multicomponent mixtures of interest in chemical technology is very large, it is in practise often not possible to find experimental data in the literature for all the possible binary combinations. In these cases it is necessary to use a predictive approach. Today, group-contribution methods such as ASOG and UNIFAC may be used with confidence to predict liquid phase excess Gibbs energies. In these methods, the mixture is assumed to consist not of molecules but of the functional groups which, when added form the parent molecules. This has the advantage that a large number of mixtures of interest in chemical technology can be described in terms of relatively few parameters characterizing the interactions between the groups. This review article demonstrates the application of the UNIFAC method to various practical problems within phase equilibria. The UNIFAC method applies to mixtures of nonelectrolytes in the temperature range of 275-425 K and at pressures up to 10 bar.

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.

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

Science.gov (United States)

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

2012-05-14

We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [C(n)mim] [NTf(2)] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory-Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C(2)mim] [NTf(2)]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C(2)mim][NTf(2)]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase equilibria and molecular interaction studies on (naphthols + vanillin) systems

International Nuclear Information System (INIS)

Gupta, Preeti; Agrawal, Tanvi; Das, Shiva Saran; Singh, Nakshatra Bahadur

2012-01-01

Highlights: ► Phase equilibria of (naphthol + vanillin) systems have been studied for the first time. ► Eutectic type phase diagrams are obtained. ► Eutectic mixtures show nonideal behaviour. ► There is a weak molecular interaction between the components in the eutectic mixtures. ► α-Naphthol–vanillin eutectic is more stable as compared to β-naphthol–vanillin. - Abstract: Phase equilibria between (α-naphthol + vanillin) and (β-naphthol + vanillin) systems have been studied by thaw-melt method and the results show the formation of simple eutectic mixtures. Crystallization velocities of components and eutectic mixtures were determined at different stages under cooling. With the help of differential scanning calorimeter (DSC), the enthalpy of fusion of components and eutectic mixtures was determined and from the values excess thermodynamic functions viz., excess Gibbs free energy (G E ), excess entropy (S E ), excess enthalpy (H E ) of hypo-, hyper- and eutectic mixtures were calculated. Flexural strength measurements were made in order to understand the non-ideal nature of eutectics. FT-IR spectral studies indicate the formation of hydrogen bond in the eutectic mixture. Anisotropic and isotropic microstructural studies of components, hypo-, hyper- and eutectic mixtures were made. Jackson’s roughness parameter was calculated and found to be greater than 2 suggesting the faceted morphology with irregular structures. The overall results have shown that there is a weak molecular interaction between the components in the eutectic mixtures and the (α-naphthol + vanillin) eutectic is more stable as compared to the (β-naphthol + vanillin) eutectic system.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

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 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 volumetric rate of evolved magma production

Phase Equilibria of the Ternary Sn-Pb-Co System at 250°C and Interfacial Reactions of Co with Sn-Pb Alloys

Science.gov (United States)

Wang, Chao-hong; Kuo, Chun-yi; Yang, Nian-cih

2015-11-01

The isothermal section of the ternary Sn-Pb-Co system at 250°C was experimentally determined through a series of the equilibrated Sn-Pb-Co alloys of various compositions. The equilibrium phases were identified on the basis of compositional analysis. For the Sn-Co intermetallic compounds (IMCs), CoSn3, CoSn2, CoSn and Co3Sn2, the Pb solubility was very limited. There exist five tie-triangle regions. The Co-Pb system involves one monotectic reaction, so the phase separation of liquid alloys near the Co-Pb side occurred prior to solidification. The immiscibility field was also determined. Additionally, interfacial reactions between Co and Sn-Pb alloys were conducted. The reaction phase for the Sn-48 at.%Pb and Sn-58 at.%Pb at 250°C was CoSn3 and CoSn2, respectively. Both of them were simultaneously formed in the Sn-53 at.%Pb/Co. The formed IMCs were closely associated to the phase equilibria relationship of the liquid-CoSn3-CoSn2 tie-triangle. Furthermore, with increasing temperatures, the phase formed in equilibrium with Sn-37 wt.%Pb was found to transit from CoSn3 to CoSn2 at 275°C. We propose a simple method of examining the phase transition temperature in the interfacial reactions to determine the boundaries of the liquid-CoSn3-CoSn2 tie-triangles at different temperatures.

Metamorphism and partial melting of ordinary chondrites: Calculated phase equilibria

Science.gov (United States)

Johnson, T. E.; Benedix, G. K.; Bland, P. A.

2016-01-01

Constraining the metamorphic pressures (P) and temperatures (T) recorded by meteorites is key to understanding the size and thermal history of their asteroid parent bodies. New thermodynamic models calibrated to very low P for minerals and melt in terrestrial mantle peridotite permit quantitative investigation of high-T metamorphism in ordinary chondrites using phase equilibria modelling. Isochemical P-T phase diagrams based on the average composition of H, L and LL chondrite falls and contoured for the composition and abundance of olivine, ortho- and clinopyroxene, plagioclase and chromite provide a good match with values measured in so-called equilibrated (petrologic type 4-6) samples. Some compositional variables, in particular Al in orthopyroxene and Na in clinopyroxene, exhibit a strong pressure dependence when considered over a range of several kilobars, providing a means of recognising meteorites derived from the cores of asteroids with radii of several hundred kilometres, if such bodies existed at that time. At the low pressures (recorders of peak conditions. The intersection of isopleths of these variables may allow pressures to be quantified, even at low P, permitting constraints on the minimum size of parent asteroid bodies. The phase diagrams predict the onset of partial melting at 1050-1100 °C by incongruent reactions consuming plagioclase, clinopyroxene and orthopyroxene, whose compositions change abruptly as melting proceeds. These predictions match natural observations well and support the view that type 7 chondrites represent a suprasolidus continuation of the established petrologic types at the extremes of thermal metamorphism. The results suggest phase equilibria modelling has potential as a powerful quantitative tool in investigating, for example, progressive oxidation during metamorphism, the degree of melting and melt loss or accumulation required to produce the spectrum of differentiated meteorites, and whether the onion shell or rubble pile

High-pressure (vapour + liquid) equilibria for ternary systems composed by {(E)-2-hexenal or hexanal + carbon dioxide + water}: Partition coefficient measurement

International Nuclear Information System (INIS)

Bejarano, Arturo; López, Pablo I.; Valle, José M. del; Fuente, Juan C. de la

2015-01-01

Highlights: • A new apparatus based on a static–analytic method was assembled in this work. • This work reports high-pressure VLE data of (E)-2-hexenal or hexanal + CO 2 + water. • Data includes (CO 2 + water) partition coefficients of (E)-2-hexenal and hexanal. • High separation factors from water (∼10 4 ) were found especially for (E)-2-hexenal. • The data were obtained at T = (313, 323, and 333) K and pressures from (8 to 19) MPa. - Abstract: A new apparatus based on a static–analytic method assembled in this work was utilised to perform high-pressure (vapour + liquid) equilibria measurements of aqueous ternary systems. This work includes values of isothermal partition coefficients between CO 2 and water of two apple aroma constituents, (E)-2-hexenal and hexanal. Additionally, this work reports new experimental (vapour + liquid) equilibria measurements for the ternary systems (CO 2 + (E)-2-hexenal + water) and (CO 2 + hexanal + water), at fixed liquid phase composition (600 mg · kg −1 ), at temperatures of (313, 323 and 333) K and at pressures from (8 to 19) MPa. Vapour liquid interphase was checked and monitored visually for all the systems studied in this work. No liquid immiscibility was observed at the composition, temperatures and pressures studied. In order to suggest reasonable operation conditions for fractionation of aromas with dense carbon dioxide, partition coefficients of the aroma compounds between CO 2 and water along with their separation factors from water were calculated. Partition coefficients of (E)-2-hexenal between CO 2 and water were in the range of (6 to 91) and where found to be near six times higher than those of hexanal (9 to 17). Very high separation factors from water were observed (∼10 4 ) especially for (E)-2-hexenal. The highest separation factor, for both compounds, was found at a temperature of 313 K and pressures from (12 to 14) MPa

Sn-In-Ag phase equilibria and Sn-In-(Ag)/Ag interfacial reactions

International Nuclear Information System (INIS)

Chen Sinnwen; Lee Wanyu; Hsu Chiaming; Yang Chingfeng; Hsu Hsinyun; Wu Hsinjay

2011-01-01

Research highlights: → Thermodynamic models of Sn-In and Sn-In-Ag are developed using the CALPHAD approach. → Reaction layer in the Sn-In-(Ag)/Ag couples at 100 deg. C is thinner than those at 25 deg. C, 50 deg. C, and 75 deg. C. → Reactions in the Sn-20 wt%In-2.8 wt%Ag/Ag couples are faster than those in the Sn-20 wt%In/Ag couples. - Abstract: Experimental verifications of the Sn-In and Sn-In-Ag phase equilibria have been conducted. The experimental measurements of phase equilibria and thermodynamic properties are used for thermodynamic modeling by the CALPHAD approach. The calculated results are in good agreement with experimental results. Interfacial reactions in the Sn-In-(Ag)/Ag couples have been examined. Both Ag 2 In and AgIn 2 phases are formed in the Sn-51.0 wt%In/Ag couples reacted at 100 and 150 deg. C, and only the Ag 2 In phase is formed when reacted at 25, 50 and 75 deg. C. Due to the different growth rates of different reaction phases, the reaction layer at 100 deg. C is thinner than those at 25 deg. C, 50 deg. C, and 75 deg. C. In the Sn-20.0 wt%In/Ag couples, the ζ phase is formed at 250 deg. C and ζ/AgIn 2 phases are formed at 125 deg. C. Compared with the Sn-20 wt%In/Ag couples, faster interfacial reactions are observed in the Sn-20.0 wt%In-2.8 wt%Ag/Ag couples, and minor Ag addition to Sn-20 wt%In solder increases the growth rates of the reaction phases.

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…

(Liquid + liquid) equilibria for the ternary mixtures (alkane + toluene + ionic liquid) at T = 298.15 K: Influence of the anion on the phase equilibria

International Nuclear Information System (INIS)

Seoane, Raquel G.; Gómez, Elena; González, Emilio J.; Domínguez, Ángeles

2012-01-01

Highlights: ► [BMpyr][NTF 2 ] and [BMpyr][TFO] were studied as solvents to extract aromatics from alkanes. ► (Liquid + liquid) equilibrium data were measured at 298.15 K for six ternary systems. ► Selectivity and solute distribution ratio were calculated and compared. ► The influence of the structure of anion of the ionic liquid was analyzed. ► Experimental data were satisfactorily correlated using NRTL model. - Abstract: (Liquid + liquid) equilibrium data for the ionic liquids 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMpyr][NTf 2 ], and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, [BMpyr][TFO], with toluene, and heptane or cyclohexane were determined at T = 298.15 K and atmospheric pressure. In order to check if these ILs can be used as potential solvents for the extraction of toluene from aliphatic compounds, the ability of the ILs as solvents was evaluated in terms of selectivity and solute distribution ratio. The experimental data were correlated accurately with the Non Random Two-Liquid model.

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.

Using a Differential Scanning Calorimeter to Teach Phase Equilibria to Students of Igneous and Metamorphic Petrology

Science.gov (United States)

Maria, Anton H.; Millam, Evan L.; Wright, Carrie L.

2011-01-01

As an aid for teaching phase equilibria to undergraduate students of igneous and metamorphic petrology, we have designed a laboratory exercise that allows them to create a phase diagram from data produced by differential scanning calorimetry. By preparing and analyzing samples of naphthalene and phenanthrene, students acquire hands-on insight into…

Effect of alkanolammonium formates ionic liquids on vapour liquid equilibria of binary systems containing water, methanol, and ethanol

International Nuclear Information System (INIS)

Li Xuemei; Shen Chong; Li Chunxi

2012-01-01

Highlights ► Vapour pressures for six ternary systems containing an IL were measured. ► Components studied were water, ethanol, methanol, and alkanolammonium formates. ► The isobaric VLE were predicted using the fitted binary NRTL parameters. ► The ILs studied can generate a promising salt effect on VLE of azeotrope. ► [HMEA][HCOO] might be used as a potential entrainer in extractive distillation. - Abstract: Vapour pressures were measured using a quasi-static ebulliometer for the pseudo-binary mixtures of (water + ethanol), (water + methanol), and (methanol + ethanol) containing an alkanolammonium-based ionic liquid (IL), namely, mono-ethanolammonium formate ([HMEA][HCOO]) and di-ethanolammonium formate ([HDEA][HCOO]), respectively, with fixed IL mass fraction of 0.30 and over the temperature ranges of (292.12 to 371.13) K. The vapour pressures of the IL-containing ternary systems were favourably correlated using the NRTL model with an overall average absolute relative deviation (AARD) of 0.0082. Further, the salt effects of [HMEA][HCOO] and [HDEA][HCOO] on isobaric vapour liquid equilibria (VLE) of azeotrope and close boiling mixture, especially for the mixtures of (water + ethanol) and (methanol + ethanol), were investigated and compared with other ILs in terms of the x′–y phase diagrams predicted with the binary NRTL parameters. It is demonstrated that the relative volatilities of ethanol to water and ethanol to methanol are enhanced, and [HMEA][HCOO] might be used as a promising entrainer for the efficient separation of ethanol aqueous solution by special rectification.

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.

Experimental determination and prediction of liquid-solid equilibria for binary (methyl palimitate + naphthalene mixture

Directory of Open Access Journals (Sweden)

Benziane M.

2013-07-01

Full Text Available Solid-liquid equilibria for binary mixtures of {Methyl palmitate (1 + Naphthalene (2} were measured using differential scanning calorimeter (DSC. Simple eutectic behaviours for this system are observed. The experimental results were correlated by means of the NRTL, Wilson, UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.5477 K (for UNIQUAC model to 3.34K; the deviation depend on the model used. The best solubility correlation was obtained with UNIQUAC model and this observation confirms previous results.

Vapor-Liquid Phase Equilibria for Carbon Dioxide-I- Isopentanol Binary System at Elevated Pressure%Vapor-Liquid Phase Equilibria for Carbon Dioxide-I- Isopentanol Binary System at Elevated Pressure

Institute of Scientific and Technical Information of China (English)

王琳; 曹丰璞; 刘珊珊; 杨浩

2011-01-01

High-pressure vapor-liquid phase equilibrium data for carbon dioxide＋ isopentanol were measured at tempera- tures of 313.2, 323.1, 333.5 and 343.4 K in the pressure range of 4.64 to 12.71 MPa in a variable-volume high-pressure visual cell. The experimental data were well correlated with Peng-Robinson equation of state （PR-EOS） together with van der Waals-2 two-parameter mixing rule, and the binary interaction parameters were obtained. Henry coefficients and partial molar volumes of CO2 at infinite dilution were estimated based on Krichevsky-Kasarnovsky equation, and Henry coefficients increase with increasing temperature, however, partial molar volumes of CO2 at infinite dilution are negative and the magnitudes decrease with temperature.

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.

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

International Nuclear Information System (INIS)

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

2011-01-01

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

Thermodynamic calculation of phase equilibria of the U-Ga and U-W systems

International Nuclear Information System (INIS)

Wang, J.; Liu, X.J.; Wang, C.P.

2008-01-01

The thermodynamic assessments of the U-Ga and U-W systems have been carried out by using the CALPHAD (calculation of phase diagrams) method using experimental data including thermodynamic properties and phase equilibria. Gibbs free energies of the solution phases were described by the subregular solution models with the Redlich-Kister equation, and those of the intermetallic compounds were described by the sublattice models. A consistent set of thermodynamic parameters has been derived for the Gibbs free energy of each phase in the U-Ga and U-W binary systems, respectively. The calculated phase diagrams and thermodynamic properties in the U-Ga and U-W systems are in good agreement with experimental data

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.

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 usin...... 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....

The phase equilibria and thermal stability of the long-period stacking ordered phase in the Mg–Cu–Y system

International Nuclear Information System (INIS)

Jiang, Min; Su, Xiulan; Li, Hongxiao; Ren, Yuping; Qin, Gaowu

2014-01-01

Highlights: • 14H LPSO structure has been confirmed to be stable in the Mg–Cu–Y system. • Partial isothermal sections of the Mg–Cu–Y system from 300 to 450 °C have been established. • Reaction L + α-Mg ↔ 14H + Mg 2 Cu has been determined in the Mg–Cu–Y system. • The thermal stability of the 14H phase in the Mg–Cu–Y system has been well studied. - Abstract: Phase equilibria in the Mg-rich Mg–Cu–Y system at 300, 400 and 450 °C have been experimentally investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), electron probe micro-analyzer (EPMA) and transmission electron microscope (TEM). The results show that a long-period stacking ordered (LPSO) phase 14H is stable in the Mg–Cu–Y system, which is the only one ternary intermetallic compound that gets a thermodynamic equilibrium with the a-Mg phase. The equilibrium 14H phase has a very limited solid solution range, and can be nearly regarded as a ternary stoichiometric compound with a formulae as Mg 91 Cu 4 Y 5 . The thermal stability of the 14H phase in the Mg–Cu–Y system has been well studied, which shows that the 14H phase disappears varying from 442 °C to 490 °C depending on the alloy composition. The isothermal sections of the Mg-rich Mg–Cu–Y system at 300, 400 and 450 °C have been finally established, and moreover, a quasi-peritectic reaction L + α-Mg ↔ 14H + Mg 2 Cu has been determined occurring at 442 °C with an estimated liquid composition of Mg 77 Cu 18 Y 5

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.

Phase equilibria in Dy-Cu-Al system at 500 deg C

International Nuclear Information System (INIS)

Kuz'ma, Yu.B.; Milyan, V.V.

1989-01-01

Using the methods of X-ray diffraction analysis a diagram of phase equilibria in Dy-Cu-Al system at 500 deg C is plotted. Boundaries of solid solutions on the basis of DyCu 2 , DyCu and DyAl 2 compounds are determined and homogeneity regions of ternary compounds Dy 2 (Cu, Al) 7 and Dy(CuAl) 5 are ascertained. Compounds DyCuAl 3 , Dy 4 Cu 4 Al 11 and Dy 5 Cu 6 Al 9 have been detected for the first time

Evaluation of ΔGsub(f) values for unstable compounds: a Fortran program for the calculation of ternary phase equilibria

International Nuclear Information System (INIS)

Throop, G.J.; Rogl, P.; Rudy, E.

1978-01-01

A Fortran IV program was set up for the calculation of phase equilibria and tieline distributions in ternary systems of the type: transition metal-transition metal-nonmetal (interstitial type of solid solutions). The method offers the possibility of determining the thermodynamic values for unstable compounds through their influence upon ternary phase equilibria. The variation of the free enthalpy of formation of ternary solid solutions is calculated as a function of nonmetal content, thus describing the actual curvature of the phase boundaries. The integral and partial molar free enthalpies of formation of binary nonstoichiometric compounds and of phase solutions are expressed as analytical functions of the nonmetal content within their homogeneity range. The coefficient of these analytical expressions are obtained by the use either of the Wagner-Schottky vacancy model or polynomials second order in composition (parabolic approach). The free energy of formation, ΔGsub(f) has been calculated for the systems Ti-C, Zr-C, and Ta-C. Calculations of the ternary phase equilibria yielded the values for ΔGsub(f) for the unstable compounds Ti 2 C at 1500 0 C and Zr 2 C at 1775 0 C of -22.3 and 22.7 kcal g atom metal respectively. These values were used for the calculation of isothermal sections within the ternary systems Ti-Ta-C (at 1500 0 C) and Zr-Ta-C (at 1775 0 C). The ideal case of ternary phase solutions is extended to regular solutions. (author)

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Solid-Liquid and Liquid-Liquid Equilibrium in the Ternary System Acetic Acid-Propanoic Acid-Formamide.

Czech Academy of Sciences Publication Activity Database

Sedláková, Zuzana; Malijevská, I.

2007-01-01

Roč. 261, 1-2 (2007) , s. 129-132 ISSN 0378-3812. [International Conference on Properties and Phase Equilibria for Product and Process Design PPEPPD 2007 /11./. Hersonissos, Crete, 20.05.2007-25.05.2007] Institutional research plan: CEZ:AV0Z40720504 Keywords : solid-liquid equilibrium * ternary system * solid adduct Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.506, year: 2007

Phase equilibria and crystalline structure of compounds in the Lu-Al and Lu-Cu-Al systems

International Nuclear Information System (INIS)

Kuz'ma, Yu.B.; Stel'makhovich, B.M.; Galamushka, L.I.

1992-01-01

Phase equilibria and crystal structure of compounds in Lu-Al and Lu-Cu-Al systems were studied. Existence of Lu 2 Al compound having the structure of the PbCl 2 type is ascertained. Diagram of phase equilibria of Lu-Cu-Al system at 870 K is plotted. Compounds Lu 2 (Cu,Al) 17 (the Th 2 Zn 17 type structure), Lu(Cu,Al) 5 (CaCu 5 type structure), Lu 6 (Cu,Al) 23 (Th 6 Mn 23 type structure) and ∼ LuCuAl 2 have been prepared for the first time. Investigation of component interaction in Lu-Cu-Al system shows that the system is similar to previously studied systems Dy-Cu-Al and Er-Cu-Al. The main difference consists in the absence of LuCuAl 3 compound with rhombic structure of the CeNi 2+x Sb 2-x type in the system investigated

Liquid phase and supercooled liquid phase welding of bulk metallic glasses

International Nuclear Information System (INIS)

Kawamura, Y.

2004-01-01

Recent progress on welding in bulk metallic glasses (BMGs) has been reviewed. BMGs have been successfully welded to BMGs or crystalline metals by liquid phase welding using explosion, pulse-current and electron-beam methods, and by supercooled liquid phase welding using friction method. Successful welding of the liquid phase methods was due to the high glass-forming ability of the BMGs and the high concentration of welding energy in these methods. In contrast, the supercooled liquid phase welding was successful due to the thermally stable supercooled liquid state of the BMGs and the superplasticity and viscous flow of the supercooled liquid. The successful welding of BMGs to BMGs and crystalline materials is promising for the future development of BMGs as engineering materials

The liquid metastable miscibility gap in Cu-based systems

DEFF Research Database (Denmark)

Curiotto, S.; Greco, R.; Pryds, Nini

2007-01-01

Some Cu-based alloys, like Cu–Co, Cu–Fe and Cu–Co–Fe, display a liquid metastable miscibility gap. When the melt is undercooled below a certain temperature depending on the alloy composition, they present a separation in two liquid phases, followed by coagulation before dendritic solidification....... In order to predict the phase equilibria and the mechanisms of microstructure formation, a determination of the metastable monotectics in the phase diagrams is essential. This paper focuses on the up-to-date findings on the Cu–Co, Cu–Fe and Cu–Co–Fe metastable miscibility gap in the liquid phase...

Studies on the liquid-liquid phase distribution equilibria of selenium and its measurement in water using extraction plant with a pulsation column

International Nuclear Information System (INIS)

Iskanderani, F.; Sobhi, K.M.; Ejaz, M.

1989-01-01

Normal heptane, xylene and a 0.01 molar solution of 4-(5-nonyl)pyridine in toluene were investigated as extractants for selenium(IV) from nitric acid media in potassium iodide. Various parameters affecting the distribution of the element are investigated. Extraction at high aqueous to organic phase volume ratio was studied, using a liquid-liquid extraction plant with a pulsation column. The results were employed to measure selenium in spiked water samples. (author) 24 refs.; 8 figs

Phase-field simulation of solidification in multicomponent alloys coupled with thermodynamic and diffusion mobility databases

International Nuclear Information System (INIS)

Zhang Ruijie; Jing Tao; Jie Wanqi; Liu Baicheng

2006-01-01

To simulate quantitatively the microstructural evolution in the solidification process of multicomponent alloys, we extend the phase-field model for binary alloys to multicomponent alloys with consideration of the solute interactions between different species. These interactions have a great influence not only on the phase equilibria but also on the solute diffusion behaviors. In the model, the interface region is assumed to be a mixture of solid and liquid with the same chemical potential, but with different compositions. The simulation presented is coupled with thermodynamic and diffusion mobility databases, which can accurately predict the phase equilibria and the solute diffusion transportation in the whole system. The phase equilibria in the interface and other thermodynamic quantities are obtained using Thermo-Calc through the TQ interface. As an example, two-dimensional computations for the dendritic growth in Al-Cu-Mg ternary alloy are performed. The quantitative solute distributions and diffusion matrix are obtained in both solid and liquid phases

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. Th....... The results from the binary mixtures are used to predict SLE behaviour in ternary mixtures (methane + ethane + heptane, methane + ethane + CO2). Our results are compared with experimental data found in the literature....

Experimental study of the Cu-Al-Sn phase equilibria, close to the copper zone

Directory of Open Access Journals (Sweden)

Soares D.F.

2017-01-01

Full Text Available The ternary Cu-Al-Sn phase diagram is the base for several important types of alloys, with relevant industrial interest and applications. The knowledge of the melting/solidification alloys characteristics are determinant for their preparation and properties control. However, there is a lack of experimental information on the ternary phase diagram, at high temperature. In this work, several alloys, with high copper content and additions of Al, up to 10%, and Sn, up to 14% (in wt%, were studied by thermal analysis and by isothermal phase equilibria determination. The alloys liquidus and solidus lines and the binary α + β phase field, at 800°C, are presented for the studied range of compositions.

Phase equilibria of the Al-Pr-Zr ternary system at 773 K

International Nuclear Information System (INIS)

She, Jia; Zhan, Yongzhong; Li, Chunliu; Du, Yong; Xu, Honghui; He, Yuehui

2010-01-01

The phase equilibria of the Al-Pr-Zr ternary system at 773 K have been investigated mainly by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and differential thermal analysis (DTA). The 14 binary compounds, i.e. AlZr 3 , AlZr 2 , Al 2 Zr 3 , Al 3 Zr 4 , AlZr, Al 3 Zr 2 , Al 2 Zr, Al 3 Zr, α-Al 11 Pr 3 , Al 3 Pr, Al 2 Pr, β-AlPr, AlPr 2 and β-AlPr 3 were confirmed. No binary compound was found in the Pr-Zr binary system. The result shows that the isothermal section of the Al-Pr-Zr ternary system at 773 K consists of 17 single-phase regions, 31 two-phase regions and 15 three-phase regions. All the intermediate compounds phases in this system have not a remarkable solid solution at 773 K. No ternary compound is found in this work.

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

KAUST Repository

Kou, Jisheng; Sun, Shuyu; Wang, Xiuhua

2016-01-01

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

Thermodynamic modelling of phase equilibrium for water + poly(Ethylene glycol + salt aqueous two-phase systems

Directory of Open Access Journals (Sweden)

R.A.G. Sé

2002-04-01

Full Text Available The NRTL (nonrandom, two-liquid model, expressed in mass fraction instead of mole fraction, was used to correlate liquid-liquid equilibria for aqueous two-phase polymer-salt solutions. New interaction energy parameters for this model were determined using reported data on the water + poly(ethylene glycol + salt systems, with different molecular masses for PEG and the salts potassium phosphate, sodium sulfate, sodium carbonate and magnesium sulfate. The correlation of liquid-liquid equilibrium is quite satisfactory.

Phase equilibria, crystal structure and oxygen content of intermediate phases in the Y-Ba-Co-O system

OpenAIRE

Urusova, A. S.; 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...

Evaluation of Thermodynamic Models for Predicting Phase Equilibria of CO2 + Impurity Binary Mixture

Science.gov (United States)

Shin, Byeong Soo; Rho, Won Gu; You, Seong-Sik; Kang, Jeong Won; Lee, Chul Soo

2018-03-01

For the design and operation of CO2 capture and storage (CCS) processes, equation of state (EoS) models are used for phase equilibrium calculations. Reliability of an EoS model plays a crucial role, and many variations of EoS models have been reported and continue to be published. The prediction of phase equilibria for CO2 mixtures containing SO2, N2, NO, H2, O2, CH4, H2S, Ar, and H2O is important for CO2 transportation because the captured gas normally contains small amounts of impurities even though it is purified in advance. For the design of pipelines in deep sea or arctic conditions, flow assurance and safety are considered priority issues, and highly reliable calculations are required. In this work, predictive Soave-Redlich-Kwong, cubic plus association, Groupe Européen de Recherches Gazières (GERG-2008), perturbed-chain statistical associating fluid theory, and non-random lattice fluids hydrogen bond EoS models were compared regarding performance in calculating phase equilibria of CO2-impurity binary mixtures and with the collected literature data. No single EoS could cover the entire range of systems considered in this study. Weaknesses and strong points of each EoS model were analyzed, and recommendations are given as guidelines for safe design and operation of CCS processes.

Prediction of multiphase equilibria in associating fluids by a contact-site quasichemical equation of state

International Nuclear Information System (INIS)

Prikhodko, I.V.; Victorov, A.I.; Loos, Th.W.de

1995-01-01

A contract-site quasichemical equation of state has been used for the modeling of different kinds of fluid phase equilibria (between a gas phase and one or more liquids) over a wide range of conditions. Among the systems of interest are the ternary mixtures water + alkanols + hydrocarbons (alkanes or alkynes), water + alkanols (or acetone) + CO 2 , water + polyoxyethyleneglycol ethers + heavy alkanes. The model has been applied to describing the thermodynamic properties of the binary subsystems and to predict the phase behavior of the ternary systems. For longer-chain alkanols and hydrocarbons a group-contribution approach is implemented, which allows the modeling when no experimental data are available. The model gives reasonable predictions of phase behavior and the correct trends in the calculated phase diagrams in most cases. The concentrations of associates in liquid and gas phases are estimated by the model and compared with some experimental and computer simulation data. The predictive abilities of the model, its limitations, and possible ways of its improvement are discussed

Assessment of solid/liquid equilibria in the (U, Zr)O2+y system

Science.gov (United States)

Mastromarino, S.; Seibert, A.; Hashem, E.; Ciccioli, A.; Prieur, D.; Scheinost, A.; Stohr, S.; Lajarge, P.; Boshoven, J.; Robba, D.; Ernstberger, M.; Bottomley, D.; Manara, D.

2017-10-01

Solid/liquid equilibria in the system UO2sbnd ZrO2 are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the only study available in the literature on the whole pseudo-binary system. In addition, a minimum melting point is identified here for compositions near (U0.6Zr0.4)O2+y, around 2800 K. The solidus line is rather flat on a broad range of compositions around the minimum. It increases for compositions closer to the pure end members, up to the melting point of pure UO2 (3130 K) on one side and pure ZrO2 (2970 K) on the other. Solid state phase transitions (cubic-tetragonal-monoclinic) have also been observed in the ZrO2-rich compositions X-ray diffraction. Investigations under 0.3 MPa air (0.063 MPa O2) revealed a significant decrease in the melting points down to 2500 K-2600 K for increasing uranium content (x(UO2)> 0.2). This was found to be related to further oxidation of uranium dioxide, confirmed by X-ray absorption spectroscopy. For example, a typical oxidised corium composition U0.6Zr0.4O2.13 was observed to solidify at a temperature as low as 2493 K. The current results are important for assessing the thermal stability of the system fuel - cladding in an oxide based nuclear reactor, and for simulating the system behaviour during a hypothetical severe accident.

In situ studies of uranium-plutonium mixed oxides. Influence of composition on phase equilibria and thermodynamic properties

International Nuclear Information System (INIS)

Strach, Michal

2015-01-01

Due to their physical and chemical properties, mixed uranium-plutonium oxides are considered for fuel in 4. generation nuclear reactors. In this frame, complementary experimental studies are necessary to develop a better understanding of the phenomena that take place during fabrication and operation in the reactor. The focus of this work was to study the U-Pu-O phase diagram in a wide range of compositions and temperatures to ameliorate our knowledge of the phase equilibria in this system. Most of experiments were done using in situ X-ray diffraction at elevated temperatures. The control of the oxygen partial pressure during the treatments made it possible to change the oxygen stoichiometry of the sample, which gave us an opportunity to study rapidly different compositions and the processes involved. The experimental approach was coupled with thermodynamic modeling using the CALPHAD method, to precisely plan the experiments and interpret the obtained results. This approach enabled us to enhance the knowledge of phase equilibria in the U-Pu-O system. (author) [fr

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.

Deterpenation of eucalyptus essential oil by liquid + liquid extraction: Phase equilibrium and physical properties for model systems at T = 298.2 K

International Nuclear Information System (INIS)

Gonçalves, Daniel; Koshima, Cristina Chiyoda; Nakamoto, Karina Thiemi; Umeda, Thayla Karla; Aracava, Keila Kazue; Gonçalves, Cintia Bernardo; Rodrigues, Christianne Elisabete da Costa

2014-01-01

Highlights: • Fractionation of essential oil compounds. • Liquid + liquid equilibria of limonene, citronellal, ethanol and water were studied. • Distribution coefficients of limonene and citronellal were evaluated. • Densities and viscosities of the phases were experimentally determined. • Solvent selectivities and physical properties were dependent on citronellal and water mass fractions. -- Abstract: As the principal source in Brazil of eucalyptus essential oil extracts, Eucalyptus citriodora contains citronellal, an oxygenated compound responsible for the flavour characteristics. Deterpenation processes, consisting of the removal of terpenic hydrocarbons with the subsequent concentration of the oxygenated compounds, can be used to improve the aromatic characteristics of this essential oil. The purpose of this work was to perform a study of the technical feasibility of using a liquid + liquid extraction process to deterpenate eucalyptus essential oil. Model systems with various mixtures of limonene and citronellal (representing eucalyptus essential oil) as well as solvent (ethanol with various water mass fractions) were used to obtain liquid + liquid equilibrium data. The raffinate and extract phases were also analyzed to characterize the physical properties (density and viscosity). The equilibrium data were used to adjust the NRTL and UNIQUAC parameters. Two empirical models, the simple mixing rule and the Grunberg–Nissan model, were evaluated for use in the descriptions of the densities and viscosities, respectively, of the samples. Increasing the water content in the solvent resulted in decreases in the limonene and citronellal distribution coefficients, with consequential increases in the solvent selectivity values. Increasing values of the densities and viscosities, especially for the solvent-rich phases, were associated with systems using high amounts of hydrated ethanolic solvents

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 ...

Phase equilibria and thermodynamic functions for Ag–Hg and Cu–Hg binary systems

International Nuclear Information System (INIS)

Liu, Yajun; Wang, Guan; Wang, Jiang; Chen, Yang; Long, Zhaohui

2012-01-01

Highlights: ► The thermodynamic properties of Ag–Hg and Cu–Hg are explored in order to facilitate dental materials design. ► A self-consistent set of thermodynamic parameters is obtained. ► The experimental information can be well reproduced by the optimized thermodynamic data. - Abstract: In order to facilitate the computational design of new amalgams for novel dental alloys, the phase equilibria, phase diagrams and thermodynamic functions for Ag–Hg and Cu–Hg binary systems are explored in this work, based on the CALPHAD framework and experimental characterizations. The Gibbs free energies of the solution phases as well as the stoichiometric phases are calculated, with the aid of enthalpies of mixing, activities, enthalpies of formation, and phase equilibrium data. The thermodynamic descriptions provided in this work enable the stabilities of each phase at various temperatures and compositions to be well described, which contribute to the establishment of a general database to design novel metallic dental materials.

Phase equilibria and thermodynamic functions for Ag-Hg and Cu-Hg binary systems

Energy Technology Data Exchange (ETDEWEB)

Liu, Yajun, E-mail: yajunliu@gatech.edu [School of Materials and Energy, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Wang, Guan [School of Electromechanical Engineering, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Wang, Jiang [School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Chen, Yang [Mining, Metallurgy and Materials Research Department, General Research Institute for Nonferrous Metals, Beijing 100088 (China); Long, Zhaohui [School of Mechanical Engineering, Xiangtan University, Xiangtan, Hunan 411105 (China)

2012-11-10

Highlights: Black-Right-Pointing-Pointer The thermodynamic properties of Ag-Hg and Cu-Hg are explored in order to facilitate dental materials design. Black-Right-Pointing-Pointer A self-consistent set of thermodynamic parameters is obtained. Black-Right-Pointing-Pointer The experimental information can be well reproduced by the optimized thermodynamic data. - Abstract: In order to facilitate the computational design of new amalgams for novel dental alloys, the phase equilibria, phase diagrams and thermodynamic functions for Ag-Hg and Cu-Hg binary systems are explored in this work, based on the CALPHAD framework and experimental characterizations. The Gibbs free energies of the solution phases as well as the stoichiometric phases are calculated, with the aid of enthalpies of mixing, activities, enthalpies of formation, and phase equilibrium data. The thermodynamic descriptions provided in this work enable the stabilities of each phase at various temperatures and compositions to be well described, which contribute to the establishment of a general database to design novel metallic dental materials.

Prediction of phase equilibria and thermal analysis in the Bi-Cu-Pb ternary system

Energy Technology Data Exchange (ETDEWEB)

Manasijevic, Dragan [University of Belgrade, Technical Faculty, VJ 12, 19210 Bor (Serbia); Mitovski, Aleksandra, E-mail: amitovski@tf.bor.ac.rs [University of Belgrade, Technical Faculty, VJ 12, 19210 Bor (Serbia); Minic, Dusko [University of Pristina, Faculty of Technical Sciences, 38220 Kosovska Mitrovica (Serbia); Zivkovic, Dragana; Marjanovic, Sasa [University of Belgrade, Technical Faculty, VJ 12, 19210 Bor (Serbia); Todorovic, Radisa [Institute of Mining and Metallurgy, Zeleni Bulevar 35, 19210 Bor (Serbia); Balanovic, Ljubisa [University of Belgrade, Technical Faculty, VJ 12, 19210 Bor (Serbia)

2010-05-20

The knowledge about phase diagram of the Bi-Cu-Pb ternary system is of importance in development of copper-lead based bearing materials, soldering and in refining of copper and lead. In this work, the phase diagram of the Bi-Cu-Pb ternary system was calculated by the CALPHAD method using binary thermodynamic parameters included in the COST 531 database. The results include liquidus projection, invariant equilibria and three vertical sections with molar ratio Cu:Pb = 1, Cu:Pb = 1:3 and Bi:Cu = 1. Alloys, with compositions along three predicted vertical sections, were measured using differential scanning calorimetry (DSC). The experimentally determined phase transition temperatures were compared with calculated results and good mutual agreement was noticed.

Prediction of phase equilibria and thermal analysis in the Bi-Cu-Pb ternary system

International Nuclear Information System (INIS)

Manasijevic, Dragan; Mitovski, Aleksandra; Minic, Dusko; Zivkovic, Dragana; Marjanovic, Sasa; Todorovic, Radisa; Balanovic, Ljubisa

2010-01-01

The knowledge about phase diagram of the Bi-Cu-Pb ternary system is of importance in development of copper-lead based bearing materials, soldering and in refining of copper and lead. In this work, the phase diagram of the Bi-Cu-Pb ternary system was calculated by the CALPHAD method using binary thermodynamic parameters included in the COST 531 database. The results include liquidus projection, invariant equilibria and three vertical sections with molar ratio Cu:Pb = 1, Cu:Pb = 1:3 and Bi:Cu = 1. Alloys, with compositions along three predicted vertical sections, were measured using differential scanning calorimetry (DSC). The experimentally determined phase transition temperatures were compared with calculated results and good mutual agreement was noticed.

The study of long-term stability in liquid-solid phases for HLW disposal

International Nuclear Information System (INIS)

Wei, Y.Y.; Tseng, C.L.; Yang, J.Y.; Ke, C.H.; Wang, T.H.; Jan, Y.L.; Lee, C.B.; Lan, P.L.; Hsu, C.N.; Tsai, S.C.; Li, M.H.; Teng, S.P.

2005-01-01

Full text of publication follows: This study is conducted to observe changes in both chemical properties of buffer materials and liquid phases over an experimental period of 2 years. In our experiments, bentonite powder and crushed granite are separately mixed with synthetic groundwater, synthetic seawater and de-ionised water at a fixed liquid-solid ratio of 30. A mixed set with both bentonite and granite together as solid phase is also investigated. During this study, aliquots of the liquid phases are sampled every two months and pH and Eh values are measured immediately. Concentrations of Na, Mg, K, Al, Ca, Ti, Mn, Ba, Fe, Sr, Li and Th are analyzed in the liquid phase directly by ICP-AES. After separation by centrifugation followed by freeze drying and digestion, the solid phases are analyzed as well for elemental composition. Alteration of solid phases during the experimental period is discussed. The preliminary results show that the pH values of the three solutions vary considerably in the individual experimental systems containing bentonite, granite or the mixed system. In general, higher pH values are found in DI-water for all solid phases. Eh values fluctuate a lot in the range 100 to 300 mV in all experiment sets. Different to the experiments with granite for which similar Eh values are found in all solutions, a significantly different Eh-value is found in the experiment with bentonite in DI-water as compared to the other solutions. The results from element analysis indicate that equilibrium is achieved after only two months and element concentrations change only slightly thereafter. We conclude from our experiments that both bentonite and granite keep their characteristics as radionuclide sorbents in the vicinity of a nuclear waste repository. Reaction equilibria appear to be attained rapidly. Because there are just a few alterations in this study, it would be a huge error source in analyzing from the inhomogeneous solid phase such as granite and losses

High-Pressure Phase Equilibria in Systems Containing CO2 and Ionic Liquid of the [Cnmim][Tf2N] Type

OpenAIRE

Sedláková, Z. (Zuzana); Wagner, Z. (Zdeněk)

2012-01-01

In this review, we present a comparison of the high-pressure phase behaviour of binary systems constituted of CO2 and ionic liquids of the [Cn(m)mim][Tf2N] type. The comparative study shows that the solubility of CO2 in ionic liquids of the [Cnmim][Tf2N] type generally increases with increasing pressure and decreasing temperature, but some peculiarities have been observed. The solubility of CO2 in ionic liquid solvents was correlated using the Soave–Redlich–Kwong equation of state. The result...

Phase equilibria of the Al-Pr-Zr ternary system at 773 K

Energy Technology Data Exchange (ETDEWEB)

She, Jia [Laboratory of Nonferrous Metal Materials and New Processing Technology, Ministry of Education, Guangxi University, Nanning, Guangxi 530004 (China); Zhan, Yongzhong, E-mail: zyzmatres@yahoo.com.c [Laboratory of Nonferrous Metal Materials and New Processing Technology, Ministry of Education, Guangxi University, Nanning, Guangxi 530004 (China); Li, Chunliu [Laboratory of Nonferrous Metal Materials and New Processing Technology, Ministry of Education, Guangxi University, Nanning, Guangxi 530004 (China); Du, Yong; Xu, Honghui; He, Yuehui [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China)

2010-07-30

The phase equilibria of the Al-Pr-Zr ternary system at 773 K have been investigated mainly by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and differential thermal analysis (DTA). The 14 binary compounds, i.e. AlZr{sub 3}, AlZr{sub 2}, Al{sub 2}Zr{sub 3}, Al{sub 3}Zr{sub 4}, AlZr, Al{sub 3}Zr{sub 2}, Al{sub 2}Zr, Al{sub 3}Zr, {alpha}-Al{sub 11}Pr{sub 3}, Al{sub 3}Pr, Al{sub 2}Pr, {beta}-AlPr, AlPr{sub 2} and {beta}-AlPr{sub 3} were confirmed. No binary compound was found in the Pr-Zr binary system. The result shows that the isothermal section of the Al-Pr-Zr ternary system at 773 K consists of 17 single-phase regions, 31 two-phase regions and 15 three-phase regions. All the intermediate compounds phases in this system have not a remarkable solid solution at 773 K. No ternary compound is found in this work.

Liquid-liquid phase transition in Stillinger-Weber silicon

International Nuclear Information System (INIS)

Beaucage, Philippe; Mousseau, Normand

2005-01-01

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

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.

Phase Equilibria of the Sn-Ni-Si Ternary System and Interfacial Reactions in Sn-(Cu)/Ni-Si Couples

Science.gov (United States)

Fang, Gu; Chen, Chih-chi

2015-07-01

Interfacial reactions in Sn/Ni-4.5 wt.%Si and Sn-Cu/Ni-4.5 wt.%Si couples at 250°C, and Sn-Ni-Si ternary phase equilibria at 250°C were investigated in this study. Ni-Si alloys, which are nonmagnetic, can be regarded as a diffusion barrier layer material in flip chip packaging. Solder/Ni-4.5 wt.%Si interfacial reactions are crucial to the reliability of soldered joints. Phase equilibria information is essential for development of solder/Ni-Si materials. No ternary compound is present in the Sn-Ni-Si ternary system at 250°C. Extended solubility of Si in the phases Ni3Sn2 and Ni3Sn is 3.8 and 6.1 at.%, respectively. As more Si dissolves in these phases their lattice constants decrease. No noticeable ternary solubility is observed for the other intermetallics. Interfacial reactions in solder/Ni-4.5 wt.%Si are similar to those for solder/Ni. Si does not alter the reaction phases. No Si solubility in the reaction phases was detected, although rates of growth of the reaction phases were reduced. Because the alloy Ni-4.5 wt.%Si reacts more slowly with solders than pure Ni, the Ni-4.5 wt.%Si alloy could be a potential new diffusion barrier layer material for flip chip packaging.

Modeling phase equilibria of alkanols with the simplified PC-SAFT equation of state and generalized pure compound parameters

DEFF Research Database (Denmark)

Grenner, Andreas; Kontogeorgis, Georgios; von Solms, Nicolas

2007-01-01

The simplified PC-SAFT equation of state has been applied to liquid-liquid, vapor-liquid and solid-liquid equilibria for mixtures containing 1-or 2-alkanols with alkanes, aromatic hydrocarbons, CO2 and water. For the alkanols we use generalized pure compound parameters. This means that two...... of the physical pure compound parameters, in (segment number) and or (segment diameter), are obtained from linear extrapolations, since m and m sigma(3), increase linearly with respect to the molar mass, and moreover, the two association parameters (association energy and association volume) were assumed...... to be constant for all alkanols. Only the dispersion energy is fitted to experimental data. Thus it is possible to estimate parameters for several 1-and 2-alkanols. The final aim is to develop a group contribution approach for PC-SAFT which is suitable for complex compounds, considering that the motivation...

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.

Phase equilibria in the BaUO3-BaZrO3-BaMoO3 system

International Nuclear Information System (INIS)

Kurosaki, Ken; Yamanaka, Shinsuke; Matsuda, Tetsushi; Uno, Masayoshi; Yamamoto, Kazuya; Namekawa, Takashi

2002-01-01

The phase equilibria in the pseudo-ternary BaUO 3 -BaZrO 3 -BaMoO 3 system were studied to understand the thermochemical properties of the perovskite type gray oxide phase in high burnup MOX fuel. Thermodynamic equilibrium calculation for the system was performed by using a Chem Sage program under the various oxygen potentials. Solid solutions existing in the system were treated by an ideal solution model. The present calculation results well agreed with the previous reported post irradiation examination results, showing that BaMoO 3 was scarcely included in the gray oxide phase. (author)

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

DEFF Research Database (Denmark)

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

2004-01-01

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

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.

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

for a great diversity of mixtures. Nevertheless, the models for representing phase equilibria and physico-chemical properties of asymmetric systems may require more flexible mixing rules than the classical quadratic van der Waals (vdW) mixing rules or their equivalent (with regard to the number of available...... interaction parameters) in modern equations of state.In particular, the phase equilibria of binary mixtures containing CO2 and heavy n-alkanes have been studied by an important number of authors and using different types of models, achieving only partially accurate results and realizing the difficulties...

Effect of mono-, di- and tri-ethanolammonium tetrafluoroborate protonic ionic liquids on vapour liquid equilibria of ethanol aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Shen Chong [State Key Laboratory of Chemical Resource Engineering and College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Ma Xiaoyan [College of Science, Beijing University of Chemical Technology, Beijing 100029 (China); Lu Yingzhou [State Key Laboratory of Chemical Resource Engineering and College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Li Chunxi, E-mail: Licx@mail.buct.edu.c [State Key Laboratory of Chemical Resource Engineering and College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

2011-03-15

Vapour pressures were measured using a quasi-static ebulliometer for the binary mixture of (water + ethanol) containing one of three protonic ionic liquids (PIL), namely, mono-, di- or tri-ethanolammonium tetrafluoroborate, over the temperature range of (318.24 to 356.58) K at fixed PIL content of 0.30 in mass fraction. The vapour pressure data of the PIL-containing ternary systems were correlated using the NRTL equation with an overall root mean square deviation (RMSD) of 0.0092. The regressed NRTL parameters were used to predict the isobaric vapour liquid equilibria (VLE) for ternary systems (water + ethanol + PIL) at varying mass fraction of PIL and atmospheric pressure (101.3 kPa). It is shown that the effect of PILs on the VLE of the (water + ethanol) mixture follows the order: [HTEA][BF{sub 4}] > [HDEA][BF{sub 4}] > [HMEA][BF{sub 4}]. In addition, the relative volatilities of ethanol to water for pseudo-binary systems (water + ethanol + PIL) were calculated. The results indicate that the PILs studied can enhance the relative volatility of ethanol to water and even break the azeotropic behaviour of ethanol aqueous solution when PIL content is increased to a specified content.

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

International Nuclear Information System (INIS)

Pitsch, H.K.

1986-03-01

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

Computed phase equilibria for burnable neutron absorbing materials for advanced pressurized heavy water reactors

Energy Technology Data Exchange (ETDEWEB)

Corcoran, E.C. [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, P.O. Box 17000, St. Forces, Kingston, Ont., K7K 7B4 (Canada)], E-mail: emily.corcoran@rmc.ca; Lewis, B.J.; Thompson, W.T. [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, P.O. Box 17000, St. Forces, Kingston, Ont., K7K 7B4 (Canada); Hood, J. [Atomic Energy of Canada Ltd., Sheridan Park, 2251 Speakman Drive, Mississauga, Ont., L5K 1B2 (Canada); Akbari, F.; He, Z. [Atomic Energy of Canada Ltd., Chalk River Laboratories, Chalk River, Ont., K0J 1J0 (Canada); Reid, P. [Atomic Energy of Canada Ltd., Sheridan Park, 2251 Speakman Drive, Mississauga, Ont., L5K 1B2 (Canada)

2009-03-31

Burnable neutron absorbing materials are expected to be an integral part of the new fuel design for the Advanced CANDU [CANDU is as a registered trademark of Atomic Energy of Canada Limited.] Reactor. The neutron absorbing material is composed of gadolinia and dysprosia dissolved in an inert cubic-fluorite yttria-stabilized zirconia matrix. A thermodynamic model based on Gibbs energy minimization has been created to provide estimated phase equilibria as a function of composition and temperature. This work includes some supporting experimental studies involving X-ray diffraction.

Attractive evolutionary equilibria

NARCIS (Netherlands)

Joosten, Reinoud A.M.G.; Roorda, Berend

2011-01-01

We present attractiveness, a refinement criterion for evolutionary equilibria. Equilibria surviving this criterion are robust to small perturbations of the underlying payoff system or the dynamics at hand. Furthermore, certain attractive equilibria are equivalent to others for certain evolutionary

Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

Science.gov (United States)

Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

2016-09-14

Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined.

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.

Measurements of liquid-phase turbulence in gas–liquid two-phase flows using particle image velocimetry

International Nuclear Information System (INIS)

Zhou, Xinquan; Doup, Benjamin; Sun, Xiaodong

2013-01-01

Liquid-phase turbulence measurements were performed in an air–water two-phase flow loop with a circular test section of 50 mm inner diameter using a particle image velocimetry (PIV) system. An optical phase separation method-–planar laser-induced fluorescence (PLIF) technique—which uses fluorescent particles and an optical filtration technique, was employed to separate the signals of the fluorescent seeding particles from those due to bubbles and other noises. An image pre-processing scheme was applied to the raw PIV images to remove the noise residuals that are not removed by the PLIF technique. In addition, four-sensor conductivity probes were adopted to measure the radial distribution of the void fraction. Two benchmark tests were performed: the first was a comparison of the PIV measurement results with those of similar flow conditions using thermal anemometry from previous studies; the second quantitatively compared the superficial liquid velocities calculated from the local liquid velocity and void fraction measurements with the global liquid flow rate measurements. The differences of the superficial liquid velocity obtained from the two measurements were bounded within ±7% for single-phase flows and two-phase bubbly flows with the area-average void fraction up to 18%. Furthermore, a preliminary uncertainty analysis was conducted to investigate the accuracy of the two-phase PIV measurements. The systematic uncertainties due to the circular pipe curvature effects, bubble surface reflection effects and other potential uncertainty sources of the PIV measurements were discussed. The purpose of this work is to facilitate the development of a measurement technique (PIV-PLIF) combined with image pre-processing for the liquid-phase turbulence in gas–liquid two-phase flows of relatively high void fractions. The high-resolution data set can be used to more thoroughly understand two-phase flow behavior, develop liquid-phase turbulence models, and assess high

Phase Equilibria of Mixtures Containing Organic Sulfur Species (OSS) and Water/Hydrocarbons: VLE Measurements and Modeling Using the Cubic-Plus-Association Equation of State

DEFF Research Database (Denmark)

Awan, Javeed; Tsivintzelis, Ioannis; Breil, Martin

2010-01-01

with the cubic-plus-association (CPA) equation of state. Useful remarks are presented about the application of Henry’s constant values to estimate binary interaction parameters of the CPA EoS for the description of whole vapor−liquid equilibria. The results using CPA EoS show that the cross association...

Enthalpy of phase transition and prediction of phase Equilibria in systems of glycols and glycol ethers

OpenAIRE

Esina, Zoya; Miroshnikov, Aleksandr; Korchuganova, Margarita

2014-01-01

The PCEAS model was used to study the liquid-solid and liquid-vapor phase transitions at constant pressure in systems containing glycols and glycol ethers. This method is based on minimizing the excess Gibbs energy over the solvation parameter, which takes into account the processes of association of molecules in various phases. To compute the diagrams, the data on enthalpy and phase transition temperatures of pure components are required, while the information about the interactions in the b...

Density, refraction index and vapor–liquid equilibria of N-methyl-2-hydroxyethylammonium butyrate plus (methyl acetate or ethyl acetate or propyl acetate) at several temperatures

International Nuclear Information System (INIS)

Alvarez, V.H.; Mattedi, S.; Aznar, M.

2013-01-01

Highlights: ► Densities, refraction indices and VLE were measured for ester + m-2-HEAB mixtures. ► V E , apparent molar volumes and thermal expansion coefficients were calculated. ► Peng–Robinson EoS + Wong–Sandler mixing rule + COSMO-SAC predicted the data. -- Abstract: This paper reports the densities, refraction indices, and vapor liquid equilibria for binary systems ester + N-methyl-2-hydroxyethylammonium butyrate (m-2-HEAB): methyl acetate (1) + m-2-HEAB (2), ethyl acetate (1) + m-2-HEAB and propyl acetate (1) + m-2-HEAB (2). The excess molar volumes, deviations in the refraction index, apparent molar volumes, and thermal expansion coefficients for the binary systems were fitted to polynomial equations. The Peng–Robinson equation of state, coupled with the Wong–Sandler mixing rule, is used to describe the experimental data. Since the predictive 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 1.0% and 1.1%, respectively

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

International Nuclear Information System (INIS)

Byun, Hun-Soo

2016-01-01

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

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.

Modelling of phase equilibria for associating mixtures using an equation of state

International Nuclear Information System (INIS)

Ferreira, Olga; Brignole, Esteban A.; Macedo, Eugenia A.

2004-01-01

In the present work, the group contribution with association equation of state (GCA-EoS) is extended to represent phase equilibria in mixtures containing acids, esters, and ketones, with water, alcohols, and any number of inert components. Association effects are represented by a group-contribution approach. Self- and cross-association between the associating groups present in these mixtures are considered. The GCA-EoS model is compared to the group-contribution method MHV2, which does not take into account explicitly association effects. The results obtained with the GCA-EoS model are, in general, more accurate when compared to the ones achieved by the MHV2 equation with less number of parameters. Model predictions are presented for binary self- and cross-associating mixtures

Attractive evolutionary equilibria

OpenAIRE

Roorda, Berend; Joosten, Reinoud

2011-01-01

We present attractiveness, a refinement criterion for evolutionary equilibria. Equilibria surviving this criterion are robust to small perturbations of the underlying payoff system or the dynamics at hand. Furthermore, certain attractive equilibria are equivalent to others for certain evolutionary dynamics. For instance, each attractive evolutionarily stable strategy is an attractive evolutionarily stable equilibrium for certain barycentric ray-projection dynamics, and vice versa.

The Potential of Soave-Redlich-Kwong Equation of State in Describing Phase Equilibria Data at High Pressures for the CO2 + 1-Alcohol Systems

Czech Academy of Sciences Publication Activity Database

Teodorescu, M.; Barhala, A.; Wichterle, Ivan

2005-01-01

Roč. 49, č. 11 (2005), s. 927-934 ISSN 0035-3930 R&D Projects: GA ČR(CZ) GA104/03/1555; GA AV ČR(CZ) IAA4072102 Institutional research plan: CEZ:AV0Z40720504 Keywords : vapor liquid equilibria * description Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.226, year: 2005

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 InNi 6 Sn 5 was confirmed whereas the ternary compound In 2 NiSn, 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 Ni 3 Sn LT and InNi 3 as well as between Ni 3 Sn 2 HT and InNi 2 . 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.

A review of solid-fluid selection options for optical-based measurements in single-phase liquid, two-phase liquid-liquid and multiphase solid-liquid flows

Science.gov (United States)

Wright, Stuart F.; Zadrazil, Ivan; Markides, Christos N.

2017-09-01

Experimental techniques based on optical measurement principles have experienced significant growth in recent decades. They are able to provide detailed information with high-spatiotemporal resolution on important scalar (e.g., temperature, concentration, and phase) and vector (e.g., velocity) fields in single-phase or multiphase flows, as well as interfacial characteristics in the latter, which has been instrumental to step-changes in our fundamental understanding of these flows, and the development and validation of advanced models with ever-improving predictive accuracy and reliability. Relevant techniques rely upon well-established optical methods such as direct photography, laser-induced fluorescence, laser Doppler velocimetry/phase Doppler anemometry, particle image/tracking velocimetry, and variants thereof. The accuracy of the resulting data depends on numerous factors including, importantly, the refractive indices of the solids and liquids used. The best results are obtained when the observational materials have closely matched refractive indices, including test-section walls, liquid phases, and any suspended particles. This paper reviews solid-liquid and solid-liquid-liquid refractive-index-matched systems employed in different fields, e.g., multiphase flows, turbomachinery, bio-fluid flows, with an emphasis on liquid-liquid systems. The refractive indices of various aqueous and organic phases found in the literature span the range 1.330-1.620 and 1.251-1.637, respectively, allowing the identification of appropriate combinations to match selected transparent or translucent plastics/polymers, glasses, or custom materials in single-phase liquid or multiphase liquid-liquid flow systems. In addition, the refractive indices of fluids can be further tuned with the use of additives, which also allows for the matching of important flow similarity parameters such as density and viscosity.

Quantitative NMR spectroscopy of binary liquid mixtures (aldehyde + alcohol) Part I: Acetaldehyde + (methanol or ethanol or 1-propanol)

International Nuclear Information System (INIS)

Jaubert, Silke; Maurer, Gerd

2014-01-01

Highlights: • Formation of hemiacetal/poly(oxymethylene) hemiacetals in liquid binary mixtures. • Acetaldehyde and a low molecular alcohol (methanol or ethanol or 1-propanol). • Quantitative 13 C NMR spectroscopy at temperatures between (255 and 295) K. • Hemiacetals are the predominant species. • (Acetaldehyde + methanol (50 + 50)) at 255 K: hemiacetal (polymers) >80% (≈10%). -- Abstract: Aldehydes react with alcohols to hemiacetals and poly(oxymethylene) hemiacetals. The chemical reaction equilibria of such reactions, in particular in the liquid state, can have an essential influence on the thermodynamic properties and related phenomena like, for example, on the vapour + liquid phase equilibrium. Therefore, thermodynamic models that aim to describe quantitatively such phase equilibria have to consider the chemical reaction equilibrium in the coexisting phases. This is well known in the literature for systems such as, for example, formaldehyde and methanol. However, experimental information on the chemical reaction equilibria in mixtures with other aldehydes (than formaldehyde) and alcohols is extremely scarce. Therefore, quantitative NMR spectroscopy was used to investigate the chemical reaction equilibria in binary mixtures of acetaldehyde and a single alcohol (here either methanol, ethanol or 1-propanol) at temperatures between (255 and 295) K. The results reveal that the majority of the constituents of the mixture is present as hemiacetal and the first two poly(oxymethylene) hemiacetals: in an equimolar mixture of (acetaldehyde + methanol or ethanol or 1-propanol), between about 90% at T = 255 K and about 75% at 295 K. The mole-fraction based chemical reaction equilibrium constants for the formation of those species were determined and some derived properties are reported

Multiple critical points and liquid-liquid equilibria from the van der Waals like equations of state

International Nuclear Information System (INIS)

Artemenko, Sergey; Lozovsky, Taras; Mazur, Victor

2008-01-01

The principal aim of this work is a comprehensive analysis of the phase diagram of water via the van der Waals like equations of state (EoSs) which are considered as superpositions of repulsive and attractive forces. We test more extensively the modified van der Waals EoS (MVDW) proposed by Skibinski et al (2004 Phys. Rev. E 69 061206) and refine this model by introducing instead of the classical van der Waals repulsive term a very accurate hard sphere EoS over the entire stable and metastable regions (Liu 2006 Preprint cond-mat/0605392). It was detected that the simplest form of MVDW EoS displays a complex phase behavior, including three critical points, and identifies four fluid phases (gas, low density liquid (LDL), high density liquid (HDL), and very high density liquid (VHDL)). Moreover the experimentally observed (Mallamace et al 2007 Proc. Natl Acad. Sci. USA 104 18387) anomalous behavior of the density of water in the deeply supercooled region (a density minimum) is reproduced by the MWDW EoS. An improvement of the repulsive part does not change the topological picture of the phase behavior of water in the wide range of thermodynamic variables. The new parameters set for second and third critical points are recognized by thorough analysis of experimental data for the loci of thermodynamic response function extrema

Simulating Osmotic Equilibria: A New Tool for Calculating Activity Coefficients in Concentrated Aqueous Salt Solutions.

Science.gov (United States)

Bley, Michael; Duvail, Magali; Guilbaud, Philippe; Dufrêche, Jean-François

2017-10-19

Herein, a new theoretical method is presented for predicting osmotic equilibria and activities, where a bulk liquid and its corresponding vapor phase are simulated by means of molecular dynamics using explicit polarization. Calculated time-averaged number density profiles provide the amount of evaporated molecules present in the vapor phase and consequently the vapor-phase density. The activity of the solvent and the corresponding osmotic coefficient are determined by the vapor density at different solute concentrations with respect to the reference vapor density of the pure solvent. With the extended Debye-Hückel equation for the activity coefficient along with the corresponding Gibbs-Duhem relation, the activity coefficients of the solutes are calculated by fitting the osmotic coefficients. A simple model based on the combination of Poisson processes and Maxwell-Boltzmann velocity distributions is introduced to interpret statistical phenomena observed during the simulations, which are related to evaporation and recondensation. This method is applied to aqueous dysprosium nitrate [Dy(NO 3 ) 3 ] solutions at different concentrations. The obtained densities of the liquid bulk and the osmotic and activity coefficients are in good agreement with the experimental results for concentrated and saturated solutions. Density profiles of the liquid-vapor interface at different concentrations provide detailed insight into the spatial distributions of all compounds.

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 (K_j for the reactions involved in the metal extraction which minimizes the differences between experimental distribution coefficient (D_exp and theoretical distribution coefficients according to the mechanism proposed (D_theor- 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 (K_j 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

Isobaric vapour-liquid-liquid equilibrium and vapour-liquid equilibrium for the system water + ethanol + iso-octane at 101.3 kPa

OpenAIRE

Ruiz Beviá, Francisco; Gomis Yagües, Vicente; Asensi Steegmann, Juan Carlos; Font Escamilla, Alicia

2002-01-01

Poster enviado a Equifase 2002, VI Iberoamerican Conference on Phase Equilibria for Process Design, Foz de Iguazú (Brazil), October 12th to 16th, 2002. Many studies have been carried out in the heterogeneous azeotropic distillation field either by experiment or by simulation. The development of all these studies requires the use of sets of isobaric vapour–liquid–liquid equilibrium (VLLE) data. However, the number of ternary systems with experimental VLLE data is very limited, since it is d...

Modification of Peng Robinson EOS for modelling (vapour + liquid) equilibria with electrolyte solutions

International Nuclear Information System (INIS)

Baseri, Hadi; Lotfollahi, Mohammad Nader

2011-01-01

Highlights: → Extended PR-EOS was presented for VLE of H 2 O/Salt/CO 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.

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 the solution state the 2-bond and 3-bond J(1H–13C) coupling constants have been used to confirm the equilibrium positions. The isotope effects due to deuteriation at the OH position are shown to be superior to chemical shift in determination of equilibrium positions of these almost symmetrical -pyridoyl......-benzoyl methanes. The assignments of the NMR spectra are supported by calculations of the chemical shifts at the DFT level. The equilibrium positions are shown to be different in the liquid and the solid state. In the liquid state the 4-pyridoyl derivative is at the B-form (C-1 is OH), whereas the 2-and 3-pyridoyl...

Phase equilibria of toluene/heptane with deep eutectic solvents based on ethyltriphenylphosphonium iodide for the potential use in the separation of aromatics from naphtha

International Nuclear Information System (INIS)

Kareem, Mukhtar A.; Mjalli, Farouq S.; Hashim, Mohd Ali; Hadj-Kali, Mohamed K.O.; Ghareh Bagh, Fatemeh Saadat; Alnashef, Inas M.

2013-01-01

Highlights: • Ionic liquid analogues are introduced as potential replacements for ionic liquids. • Deep eutectic solvents presented in this work were successful for extracting aromatics. • Hand correlation was applied to ascertain the experimental measurements. • The NRTL thermodynamic model was capable for correlating the LLE experimental data. -- Abstract: In this work, the liquid–liquid extraction of toluene from hydrocarbons mixtures (toluene/heptane) was investigated using deep eutectic solvents as solvents. Ethyltriphenylphosphonium iodide as a salt with either ethylene glycol or sulfolane as hydrogen-bond donors (HBDs) were utilized for synthesizing six DESs. (Liquid + liquid) equilibria data were determined experimentally for the ternary system (toluene + heptane + DES) at (30, 40, 50, and 60) °C and atmospheric pressure. Hand correlation was applied to establish the reliability of the experimental data. In many cases the correlation factor is found close to unity which indicates high reliability of the data. The selectivities and distribution coefficients were used to determine the suitability of these DESs as solvents for this extraction process. Higher selectivities than those published for sulfolane as a commercial solvent were observed. The DES made from ethyltriphenylphosphonium iodide and sulfolane at salt:HBD of 1:4 showed the best separation capability at 30 °C. Thus, it was further characterized by measuring its viscosity and refractive index at a range of temperatures to help understand its physical behaviour needed for process design. The non-random two-liquid (NRTL) model was applied successfully to correlate the experimental tie-lines and to calculate the phase compositions of the ternary systems. It has been found that the third non-randomness parameter varies linearly with the HBD number of moles

Recent development of ionic liquid stationary phases for liquid chromatography.

Science.gov (United States)

Shi, Xianzhe; Qiao, Lizhen; Xu, Guowang

2015-11-13

Based on their particular physicochemical characteristics, ionic liquids have been widely applied in many fields of analytical chemistry. Many types of ionic liquids were immobilized on a support like silica or monolith as stationary phases for liquid chromatography. Moreover, different approaches were developed to bond covalently ionic liquids onto the supporting materials. The obtained ionic liquid stationary phases show multi-mode mechanism including hydrophobic, hydrophilic, hydrogen bond, anion exchange, π-π, and dipole-dipole interactions. Therefore, they could be used in different chromatographic modes including ion-exchange, RPLC, NPLC and HILIC to separate various classes of compounds. This review mainly summarizes the immobilized patterns and types of ionic liquid stationary phases, their retention mechanisms and applications in the recent five years. Copyright © 2015 Elsevier B.V. All rights reserved.

Evaluating the Liquid Liquid Phase Transition Hypothesis of Supercoooled Water

Science.gov (United States)

Limmer, David; Chandler, David

2011-03-01

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

Correlation and prediction of ion exchange equilibria on weak-acid resins by means of the surface complex formation model

International Nuclear Information System (INIS)

Horst, J.

1988-11-01

The present work summarizes investigations of the equilibrium of the exchange of protons, copper, zinc, calcium, magnesium and sodium ions on two weak-acid exchange resins in hydrochloric and carbonic acid bearing solutions at 25 0 C. The description of the state of equilibrium between resin and solution is based on the individual chemical equilibria which have to be adjusted simultaneously. The equilibrium in the liquid phase is described by the mass action law and the condition of electroneutrality using activity coefficients calculated according to the theory of Debye and Hueckel. The exchange equilibria are described by means of a surface complex formation model, which was developed by Davis, James and Leckie for activated aluminia and which has been applied to weak-acid resins. The model concept assumes the resin as a plane surface in which the functional groups are distributed uniformly. (orig./RB) [de

Correlation of phase equilibria for water + hydrocarbon systems at high temperatures and pressures by cubic equation of state

Energy Technology Data Exchange (ETDEWEB)

Haruki, Masashi; Yahiro, Yukihito; Higashi, Hidenori; Iwai, Yoshio; Arai, Yasuhiko [Kyushu University, FUkuoka (Japan). Graduate School of Engineering

1999-08-01

A modified-Soave-Redlich-Kwong (MSRK) equation of state with an exponent-type mixing rule for the energy parameter and a conventional rule for the size parameter is applied to correlate the phase equilibria for four binary mixtures of water + hydrocarbon (benzene, hexane, decane, and dodecane) systems at high temperatures and pressures. It is noted that good correlation results are obtained by using the mixing rules with interaction parameters between unlike molecules. (author)

Solid-state phase equilibria in the Fe-Pt-Pr ternary system at 1173 K

International Nuclear Information System (INIS)

Ren Jing; Gu Zhengfei; Cheng Gang; Zhou Huaiying

2005-01-01

The solid-state phase equilibria in the Fe-Pt-Pr ternary system at 1173 K (Pr ≤ 70%) were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS) techniques. The 1173 K isothermal section consists of 13 single-phase regions, 22 two-phase regions and 10 three-phase regions. At 1173 K, we have observed that the maximum solid solubility of Pt in α-Fe is below 1.5 at.% and the solid solution region of Pt in γ-Fe is from 2 to 35 at.%; the maximum solid solubility of Fe in Pt is 18 at.%. The maximum solubility of Fe in PrPt 5 , PrPt 3 , PrPt 2 , Pr 3 Pt 4 , PrPt, Pr 3 Pt 2 and Pr 7 Pt 3 is below 1 at.%. The maximum solubility of Pr in α-(Fe, Pt), γ-(Fe, Pt), FePt, FePt 3 and (Pt, Fe) (the solid solution of Fe in Pt) is 6, 2, 4, 4.5 and 1.5 at.%, respectively. In this work, it is found that the phase Pr 3 Pt 4 does not exist in the ternary system. The binary compounds Fe 7 Pr and Fe 2 Pr and any new ternary compounds were not observed

(Solid + liquid) phase equilibria of (Ca(H2PO2)2 + CaCl2 + H2O) and (Ca(H2PO2)2 + NaH2PO2 + H2O) ternary systems at T = 323.15 K

International Nuclear Information System (INIS)

Cao, Hong-yu; Zhou, Huan; Bai, Xiao-qin; Ma, Ruo-xin; Tan, Li-na; Wang, Jun-min

2016-01-01

Graphical abstract: Solubility diagram of the (Ca(H 2 PO 2 ) 2 + NaH 2 PO 2 + H 2 O) system at T = (323.15 and 298.15) K. - Highlights: • Phase diagrams of Ca 2+ -H 2 PO 2 − -Cl − -H 2 O, Ca 2+ -Na + -H 2 PO 2 − -H 2 O at 323.15 K were obtained. • Incompatible double salt of NaCa(H 2 PO 2 ) 3 in Ca 2+ -Na + -H 2 PO 2 − -H 2 O system was determined. • Density diagram of the corresponding liquid were simultaneously measured. - Abstract: Calcium hypophosphite has been widely used as an anti-corrosive agent, flame retardant, fertilizer, assistant for Ni electroless plating, and animal nutritional supplement. High purity calcium hypophosphite can be synthesized via the replacement reaction of sodium hypophosphite and calcium chloride. In this work, the (solid + liquid) phase equilibria of (Ca(H 2 PO 2 ) 2 + CaCl 2 + H 2 O) and (Ca(H 2 PO 2 ) 2 + NaH 2 PO 2 + H 2 O) ternary systems at T = 323.15 K were studied experimentally via the classical isothermal solubility equilibrium method, and the phase diagrams for these two systems were obtained. It was found that two solid salts of CaCl 2 ·2H 2 O and Ca(H 2 PO 2 ) 2 exist in the (Ca(H 2 PO 2 ) 2 + CaCl 2 + H 2 O) system, and three salts of Ca(H 2 PO 2 ) 2 , NaH 2 PO 2 ·H 2 O and one incompatible double salt, NaCa(H 2 PO 2 ) 3 occur in the (Ca(H 2 PO 2 ) 2 + NaH 2 PO 2 + H 2 O) system.

Determination of species activities in organic phase. Modelling of liquid-liquid extraction system using uniquac and unifac models; Determination des activites des especes en phase organique. Application d`uniquac et unifac a la modelisation des systemes d`extraction liquide-liquide

Energy Technology Data Exchange (ETDEWEB)

Rat, B. [CEA Saclay, 91 - Gif-sur-Yvette (France). Dept. de Recherche en Retraitement et en Vitrification]|[Paris-6 Univ., 75 (France)

1998-12-31

The aim of nuclear fuel reprocessing is to separate reusable elements, uranium and plutonium from the other elements, fission products and minor actinides. PUREX process uses liquid-liquid extraction as separation method. Numerical codes for modelling the extraction operations of PUREX process use a semi-empirical model to represent the partition of species. To improve the precision and precision and predictive nature of the models, we looked for a theoretical tool which permits to quantify medium effects, especially in the organic phase, for which few models are available. The Sergeivskii-Dannus model permits to quantify deviations from ideality in organic phase equilibrated with aqueous phase, but with parameters depending on extractant/diluent ratio. We decided to investigate UNIQUAC and UNIFAC models which permit to estimate activity coefficients in non-electrolytic phases taking account of the mutual interactions of molecules and their morphology. UNIFAC is based on UNIQUAC but molecules are considered as structural groups assemblies. Before applying these model to extraction systems, we investigate their abilities to describe simple systems, binary and ternary systems. UNIQUAC has been applied to TBP/diluent mixtures and permits to estimate activity coefficients for diluents whose interactions with TPB are very different in nature and strength. Group contribution (UNIFAC) applied to TBP/alkane mixtures permits to represent the effect of lengthening alkane chain but not the effect of branching. UNIQUAC fails to describe the TBP/diluent/water/non-extractable-salt systems in case of strong TBP diluent interactions. In order to obtain a correct description of these systems, we used the Chem-UNIFAC model, where the INIFAC equation is supplemented with chemical equilibria allowing explicitly for complexes formation and where group contribution is used to describes complexes. We have with Chem-UNIFAC a model available which can take the effect of the diluent into

High-pressure anatectic paragneisses from the Namche Barwa, Eastern Himalayan Syntaxis: Textural evidence for partial melting, phase equilibria modeling and tectonic implications

Science.gov (United States)

Guilmette, C.; Indares, A.; Hébert, R.

2011-05-01

Rare kyanite-bearing anatectic paragneisses are found as boudins within sillimanite-bearing paragneisses of the core of the Namche Barwa Antiform, Tibet. In the present study, we document an occurrence from the NW side of the Yarlung Zangbo River. These rocks mainly consist of the assemblage garnet + K-feldspar + kyanite ± biotite + quartz + rutile ± plagioclase with kyanite locally pseudomorphed by sillimanite. The documented textures are consistent with the rocks having undergone biotite-dehydration melting in the kyanite stability field, under high-P granulite facies conditions, and having experienced melt extraction. However textures related to melt crystallization are ubiquitous both in polymineralic inclusions in garnet and in the matrix, suggesting that a melt fraction had remained in these rocks. Phase equilibria modelling was undertaken in the NCKFMASTHO system with THERMOCALC. P-T pseudosections built with the bulk compositions of one aluminous and one sub-aluminous paragneiss samples predict a biotite-kyanite-garnet-quartz-plagioclase-K-feldspar-liquid-rutile ± ilmenite field, in which biotite-dehydration melting occurs, located in the P-T range of ~ 800-875 °C and ~ 10-17 kbar. In addition, the topologies of these pseudosections are consistent with substantial melt loss during prograde metamorphism. A second set of P-T pseudosections with melt-reintegrated model bulk compositions were thus constructed to evaluate the effect of melt loss. The integration of textural information, precise mineral modes, mineral chemistry, and phase equilibria modelling allowed to constrain a P-T path where the rocks are buried to lower crustal depths at peak P-T conditions higher than 14 kbar and 825 °C, possibly in the order of 15-16 kbar and 850 °C, followed by decompression and cooling to P-T conditions of around 9 kbar and 810 °C, under which the remaining melt was solidified. The implications for granite production at the NBA and for Himalayan tectonic models

Crystal-liquid-gas phase transitions and thermodynamic similarity

CERN Document Server

Skripov, Vladimir P; Schmelzer, Jurn W P

2006-01-01

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

Design and test of a new high pressure phase equlibrium apparatus for highly corrosive mixtures of importance for natural gas

NARCIS (Netherlands)

Mota Martinez, M.; Samdani, S.; Berrouk, A.S.; Alves da Rocha, M.A.; Elhseinat, E.Y.; Banat, F.; Kroon, M.C.; Peters, C.J.

2015-01-01

A new static analytical apparatus for high-pressure phase equilibrium measurements has been designed and built. The new apparatus enables the measurement of vapor–liquid and liquid–liquid equilibria, which can operate at temperatures ranging from 225 K to 475 K and pressures up to 20 MPa. It is

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

International Nuclear Information System (INIS)

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

2002-01-01

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

Phase coexistence in thin liquid films stabilized by colloidal particles: equilibrium and non-equilibrium properties

International Nuclear Information System (INIS)

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-sphere suspension using a Monte-Carlo method to evaluate thermodynamic equations of state. Coexisting phases are determined for systems in constrained- and full-equilibrium states that correspond to different stages of film relaxation. We also evaluated the effective viscosity coefficients for two-dimensional compressional and shear flows of a film and the self and collective mobility coefficients of the stabilizing particles. The hydrodynamic calculations were performed using a multiple-reflection representation of Stokes flow between two free surfaces. In this approach, the particle-laden film is equivalent to a periodic system of spheres with a unit cell that is much smaller in the transverse direction than in the lateral direction. (author)

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.

Phase Equilibria and Compressibility of bastnaesite-(La)

Science.gov (United States)

Rowland, R. L., II; Burnley, P. C.

2015-12-01

Bastnaesite (Ce,La,Y)CO3(F,OH) is a rare earth element (REE) bearing ore mineral. REEs are more common in the Earth's crust than precious metals like gold or platinum, but are not commonly concentrated in economically viable ore deposits. For over a decade, China has been the world's leading supplier of REEs. Recent export restrictions from China have necessitated the search for new deposits. Determining basic material properties such as phase equilibria and the equation of state for bastnaesite helps in understanding the processes that form REE ore deposits and thereby assist in locating new deposits. For this study we focus on the lanthanum-fluoride variant of bastnaesite (LaCO3F) since it can be easily synthesized in the laboratory. Previous work by others determined that in both open and closed systems at atmospheric pressure bastnaesite decomposes to lanthanum oxyfluoride and carbon dioxide (LaOF + CO2) above 325°C; at 100 MPa bastnaesite decomposes above 860°C (Hsu, 1992). Using a Griggs-type modified piston cylinder apparatus, we pressurized samples of synthetic bastnaesite-(La) to conditions ranging from 250 MPa to 1.2 GPa, and then subjected each sample to constant temperatures ranging from 700°C to 1050°C for a minimum of five hours. We then analyzed the samples with X-ray powder diffraction to identify phases present and determined that bastnaesite-(La) is stable at 250 MPa up to approximately 800°C and at 1.0 GPa up to approximately 900°C. Reversal experiments are underway. In order to develop an equation of state for bastnaesite-(La), we studied single crystals via monochromatic synchrotron X-ray diffraction in the diamond anvil cell at HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. Measurements were made at pressures ranging from ambient to nearly 4 GPa. From these diffraction patterns, we determine the structure of bastnaesite-(La), and the change in unit cell volume as a function of pressure can be fit to a Birch

The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O

Science.gov (United States)

Anovitz, Lawrence M.; Treiman, A.H.; Essene, E.J.; Hemingway, B.S.; Westrum, E.F.; Wall, V.J.; Burriel, R.; Bohlen, S.R.

1985-01-01

Low temperature adiabatic calorimetry and high temperature differential scanning calorimetry have been used to measure the heat-capacity of ilmenite (FeTiO3) from 5 to 1000 K. These measurements yield S2980 = 108.9 J/(mol ?? K). Calculations from published experimental data on the reduction of ilmenite yield ??2980(I1) = -1153.9 kJ/(mol ?? K). These new data, combined with available experimental and thermodynamic data for other phases, have been used to calculate phase equilibria in the system Fe-Ti-O. Calculations for the subsystem Ti-O show that extremely low values of f{hook}O2 are necessary to stabilize TiO, the mineral hongquiite reported from the Tao district in China. This mineral may not be TiO, and it should be re-examined for substitution of other elements such as N or C. Consideration of solid-solution models for phases in the system Fe-Ti-O allows derivation of a new thermometer/oxybarometer for assemblages of ferropseudobrookite-pseudobrookitess and hematite-ilmenitess. Preliminary application of this new thermometer/oxybarometer to lunar and terrestrial lavas gives reasonable estimates of oxygen fugacities, but generally yields subsolidus temperatures, suggesting re-equilibration of one or more phases during cooling. ?? 1985.

Prediction of the vapor–liquid equilibria and speed of sound in binary systems of 1-alkanols and n-alkanes with the simplified PC-SAFT equation of state

DEFF Research Database (Denmark)

Liang, Xiaodong; Thomsen, Kaj; Yan, Wei

2013-01-01

(or other derivative properties) with satisfactory accuracy over wide temperature, pressure and composition conditions. This work presents the prediction of the vapor–liquid equilibria and speed of sound in binary mixtures of 1-alkanols and n-alkanes using the simplified PC-SAFT equation of state...... of sound with a satisfactory accuracy for 1-alkanols and n-alkanes binary systems within the PC-SAFT framework....

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

International Nuclear Information System (INIS)

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

2006-01-01

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

Thermodynamic calculation of Al-Gd and Al-Gd-Mg phase equilibria checked by key experiments

International Nuclear Information System (INIS)

Groebner, J.; Kevorkov, D.; Schmid-Fetzer, R.

2001-01-01

The binary Al-Gd and the ternary Al-Gd-Mg systems were calculated using the Calphad method. It is demonstrated that previous interpretation of ternary liquidus temperatures below 700 C must be related to other phase equilibria. The actual ternary liquidus temperatures are much higher, up to some 600 C above the previous interpretation in literature. They are widely governed by the high-melting compounds Al 2 Gd and Al 3 Gd with liquidus surfaces stretching far into the ternary system. A small number of key experiments in this work confirmed the calculated liquidus temperature and the phase relations. The available experimental data in literature fit excellently with the calculation in the binary Al-Gd system. In the ternary Al-Gd-Mg system, which is shown in several sections of the phase diagram, a good agreement can be observed too, considering the necessary reinterpretation of the liquidus temperatures suggested by Rokhlin et al. Ternary solubilities were not found experimentally. The ternary compound Al 4 GdMg (τ) forms in a ternary peritectic reaction at 761 C. (orig.)

Use of isoconcentrational phase diagrams for prediction of amorphization of binary systems

International Nuclear Information System (INIS)

Lazarev, A.I.; Belashchenko, D.K.

1992-01-01

Based on the application of isoconcentrational diagrams of phase equilibria of liquid with solid solutions of various crystal structures the thermodynamic method was considered for prediction of concentration ranges of amorphization in binary systems.To confirm the applicability of the thermodynamic criterion in practice caclulations of phase diagrams were accomplished for complex binary eutectic systems (Hf-Be, Zr-Be) with the known concentration ranges of amorphization

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....

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

Directory of Open Access Journals (Sweden)

G. Malmary

2001-12-01

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

Experimental study on the phase equilibria of the Ag-Ti system

International Nuclear Information System (INIS)

Fu Xiaoliang; Li Changrong; Wang Fuming; Li Mei; Zhang Weijing

2005-01-01

The Ag-Ti diffusion couples were prepared by small pure silver plates closely packed in pure titanium powder, sealed in quartz tube, and annealed at 750 deg. C, 980 deg. C, 1100 deg. C and 1200 deg. C, respectively. The phase equilibrium relationship and the conjugate phase compositions in the Ag-Ti system were determined by means of the metallographic microscope and the electron probe microanalysis. Partial liquidus and solidus for the two-phase equilibrium, liquid + (βTi), were obtained. The narrow solution range for the intermediate phase (TiAg) was determined

Vapor-liquid equilibria of a minute amount of furfural in water-methanol-ethanol system; Mizu-methanol-ethanol keichu no biryo no furfural no kieki heiko

Energy Technology Data Exchange (ETDEWEB)

Ikari, A.; Hatate, Y.; Uemura, Y. [Kagoshima University, Kagoshima (Japan). Faculty of Engineering

1997-01-10

Vapor-liquid equilibria of a water-methanol-ethanol system containing a minute amount of furfural were measured at atmospheric pressure by use of an Othmer-type still. The experimental results are represented by four triangular diagrams against the liquid compositions of the major components (water, methanol and ethanol), in which three diagrams show the vapor composition of the major components, respectively, and one diagram shows the equilibrium ratio of the trace component (furfural). The curved surface of the equilibrium ratio of the trace component exhibits a gentle downward slope in most areas, but shows a half-saddle face in the neighborhood of the water-ethanol side. 4 refs., 10 figs., 3 tabs.

Supported ionic liquid-phase (SILP) catalysis

DEFF Research Database (Denmark)

Riisager, Anders; Fehrmann, Rasmus; Wasserscheid, P.

2005-01-01

The concept of supported ionic liquid-phase (SILP) catalysis has been demonstrated for gas- and liquid-phase continuous fixed-bed reactions using rhodium phosphine catalyzed hydroformylation of propene and 1-octene as examples. The nature of the support had important influence on both the catalytic...

Thermodynamic model for the phase equilibria of gases and brines. Example in the H{sub 2}S-H{sub 2}O-NaCl system

Energy Technology Data Exchange (ETDEWEB)

Martinez Reyes, Jose; Gonzalez Partida, Eduardo; Tinoco-Michel, Jorge A [Centro de Geociencias, Universidad Nacional Autonoma de Mexico Campo de Juriquilla, Qro., Mexico, apartado postal 76230 (Mexico); Perez, Renee J; Heidemann, Robert A [Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive, Calgary Alberta, T2N 1N4 (Canada)

2008-10-01

We present a thermodynamic model for the phase equilibria of gases and brines, which couples Henry's Law with the Soave-Redlich-Kwong equation of state to reproduce experimental data. In this communication we focus on the H{sub 2}S H{sub 2}O NaCl system.

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.

Learning efficient correlated equilibria

KAUST Repository

Borowski, Holly P.; Marden, Jason R.; Shamma, Jeff S.

2014-01-01

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.

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

KAUST Repository

Dudebout, Nicolas; Shamma, Jeff S.

2014-01-01

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.

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.

Evolution of the Campanian Ignimbrite Magmatic System I: Constraints on Compositional Zonation and Eruption Probability Imposed By Phase Equilibria

Science.gov (United States)

Fowler, S.; Spera, F.; Bohrson, W.; Belkin, H.; Devivo, B.

2005-12-01

The eruption and deposition of the ~39.3 ka Campanian Ignimbrite (CI), a large volume (~200 km3 DRE) trachytic to phonolitic ignimbrite, is the dominant event in the history of the Campi Flegrei volcanic field near Naples, Italy. In an effort to comprehend its petrological evolution, we have conducted ~~110 MELTS (Ghiorso, 1997) phase equilibria simulations of the major element evolution of parental CI magma. The goals of this work are to approximate oxygen fugacity (fO2), initial dissolved water content and pressure at which isobaric closed system fractional crystallization of parental melt most accurately captures the observed liquid line of descent and to study the implications of heat extraction from parental CI magma with respect to the origin of compositional zonation and the probability of explosive eruption. Although the CI magma body did not evolve as a perfectly closed system, this assumption allows quantitative insight into magma-host rock mass exchange using trace element and isotopic data (see companion contribution by Bohrson et al.). The parental melt composition was reconstructed using data for melt inclusions trapped within CI clinopyroxene phenocrysts reported by Webster et al. (2003), while allowing for reaction between parental melt and clinopyroxene host. The inferred parental melt is a basaltic trachyandesite. The search space for pressure, (fO2) and initial dissolved H2O was 0.1-0.5 in 0.05 GPa increments, QFM-1 to QFM+3 and 1, 2 and 3 wt. % H2O, respectively. The criteria used to judge the quality of a simulation include correspondence of the MELTS prediction with CI liquid and phenocryst compositions. Results indicate that a good first-order model involves evolution from a basaltic trachyandesite parent by isobaric (~0.15 GPa) crystal fractionation initially containing ~3 wt% dissolved H2O along the QFM+1 buffer. H2O first saturates at 1127°C at 0.15 GPa when the dissolved water content is ~4 wt %. A striking result is the

Crystalline liquids: the blue phases

Science.gov (United States)

Wright, David C.; Mermin, N. David

1989-04-01

The blue phases of cholesteric liquid crystals are liquids that exhibit orientational order characterized by crystallographic space-group symmetries. We present here a pedagogical introduction to the current understanding of the equilibrium structure of these phases accompanied by a general overview of major experimental results. Using the Ginzburg-Landau free energy appropriate to the system, we first discuss in detail the character and stability of the usual helical phase of cholesterics, showing that for certain parameter ranges the helical phase is unstable to the appearance of one or more blue phases. The two principal models for the blue phases are two limiting cases of the Ginzburg-Landau theory. We explore each limit and conclude with some general considerations of defects in both models and an exact minimization of the free energy in a curved three-dimensional space.

Isothermal phase equilibria for the (HFC-32 + HFC-134a) mixed-gas hydrate system

International Nuclear Information System (INIS)

Miyauchi, Hiroshi; Yasuda, Kenjiro; Matsumoto, Yuuki; Hashimoto, Shunsuke; Sugahara, Takeshi; Ohgaki, Kazunari

2012-01-01

Highlights: ► Structural phase transition results in the heterogeneous azeotropic-like behaviour. ► HFC-134a molecules, in spite of an s-II former, occupy the large cages of s-I. ► Negative azeotropic-like behaviour becomes more remarkable at higher temperatures. - Abstract: Isothermal phase equilibria (pressure-composition relations in hydrate, gas, and aqueous phases) in the {difluoromethane (HFC-32) + 1,1,1,2-tetrafluoroethane (HFC-134a)} mixed-gas hydrate system were measured at the temperatures 274.15 K, 279.15 K, and 283.15 K. The heterogeneous azeotropic-like behaviour derived from the structural phase transition of (HFC-32 + HFC-134a) mixed-gas hydrates appears over the whole temperature range of the present study. In addition to the heterogeneous azeotropic-like behaviour, the isothermal phase equilibrium curves of the (HFC-32 + HFC-134a) mixed-gas hydrate system exhibit the negative homogeneous azeotropic-like behaviour at temperatures 279.15 K and 283.15 K. The negative azeotropic-like behaviour, which becomes more remarkable at higher temperatures, results in the lower equilibrium pressure of (HFC-32 + HFC-134a) mixed-gas hydrates than those of both simple HFC-32 and HFC-134a hydrates. Although the HFC-134a molecule forms the simple structure-II hydrate at the temperatures, the present findings reveal that HFC-134a molecules occupy a part of the large cages of the structure-I mixed-gas hydrate.

Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile-ketenimine equilibria.

Science.gov (United States)

Giussi, Juan M; Gastaca, Belen; Albesa, Alberto; Cortizo, M Susana; Allegretti, Patricia E

2011-02-01

The study of tautomerics equilibria is really important because the reactivity of each compound with tautomeric capacity can be determined from the proportion of each tautomer. In the present work the tautomeric equilibria in some γ,δ-unsaturated β-hydroxynitriles and γ,δ-unsaturated β-ketonitriles were studied. The first family of compounds presents two possible theoretical tautomers, nitrile and ketenimine, while the second one presents four possible theoretical tautomers, keto-nitrile, enol (E and Z)-nitrile and keto-ketenimine. The equilibrium in gas phase was studied by gas chromatography-mass spectrometry (GC-MS). Tautomerization enthalpies were calculated by this methodology, and results were compared with those obtained by density functional theory (DFT) calculations, observing a good agreement between them. Nitrile tautomers were favored within the first family of compounds, while keto-nitrile tautomers were favored in the second family. Copyright © 2010 Elsevier B.V. All rights reserved.

Vapor-liquid equilibria for nitric acid-water and plutonium nitrate-nitric acid-water solutions

International Nuclear Information System (INIS)

Maimoni, A.

1980-01-01

The liquid-vapor equilibrium data for nitric acid and nitric acid-plutnonium nitrate-water solutions were examined to develop correlations covering the range of conditions encountered in nuclear fuel reprocessing. The scanty available data for plutonium nitrate solutions are of poor quality but allow an order of magnitude estimate to be made. A formal thermodynamic analysis was attempted initially but was not successful due to the poor quality of the data as well as the complex chemical equilibria involved in the nitric acid and in the plutonium nitrate solutions. Thus, while there was no difficulty in correlating activity coefficients for nitric acid solutions over relatively narrow temperature ranges, attempts to extend the correlations over the range 25 0 C to the boiling point were not successful. The available data were then analyzed using empirical correlations from which normal boiling points and relative volatilities can be obtained over the concentration ranges 0 to 700 g/l Pu, 0 to 13 M nitric acid. Activity coefficients are required, however, if estimates of individual component vapor pressures are needed. The required ternary activity coefficients can be approximated from the correlations

Partial Cooperative Equilibria: Existence and Characterization

Directory of Open Access Journals (Sweden)

Amandine Ghintran

2010-09-01

Full Text Available We study the solution concepts of partial cooperative Cournot-Nash equilibria and partial cooperative Stackelberg equilibria. The partial cooperative Cournot-Nash equilibrium is axiomatically characterized by using notions of rationality, consistency and converse consistency with regard to reduced games. We also establish sufficient conditions for which partial cooperative Cournot-Nash equilibria and partial cooperative Stackelberg equilibria exist in supermodular games. Finally, we provide an application to strategic network formation where such solution concepts may be useful.

α-NiPt(Al) and phase equilibria in the Ni-Al-Pt system at 1150 deg C

International Nuclear Information System (INIS)

Hayashi, S.; Ford, S.I.; Young, D.J.; Sordelet, D.J.; Besser, M.F.; Gleeson, B.

2005-01-01

The α-NiPt(Al) phase and its associated equilibria in the Ni-Al-Pt system at 1150 deg C were investigated by analyzing equilibrated bulk alloys and the interdiffusion zones of diffusion couples. Phase constitutions, tie-lines and microstructures were determined using a combination of techniques, including high-energy synchrotron X-ray diffraction, scanning electron microscopy and electron probe microanalysis. A large Pt solubility limit was found to exist in the β-NiAl, ∼42 at.%, and in γ'-Ni 3 Al, ∼32 at.%. The α-NiPt(Al) phase was found to have wide Pt solubility range of about 33-60 at.% and to skew along an almost constant Pt/Al ratio of 1.5. The α-NiPt(Al) has an ordered face-centered tetragonal L1 0 crystal structure, with the Al and Pt atoms found to be preferentially located in the corners and prismatic faces, respectively. The temperature dependence of the lattice parameters and unit cell volume of the α phase were also determined

Phase transitions in liquids with directed intermolecular bonding

OpenAIRE

Son, L.; Ryltcev, R.

2005-01-01

Liquids with quasi - chemical bonding between molecules are described in terms of vertex model. It is shown that this bonding results in liquid - liquid phase transition, which occurs between phases with different mean density of intermolecular bonds. The transition may be suggested to be a universal phenomena for those liquids.

Phase stability analysis of liquid-liquid equilibrium with stochastic methods

Directory of Open Access Journals (Sweden)

G. Nagatani

2008-09-01

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

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

Science.gov (United States)

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

2010-01-01

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

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

Directory of Open Access Journals (Sweden)

Nicolas Giovambattista

2010-12-01

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

Hydrostatic Equilibria of Rotating Stars with Realistic Equation of State

Science.gov (United States)

Yasutake, Nobutoshi; Fujisawa, Kotaro; Okawa, Hirotada; Yamada, Shoichi

Stars rotate generally, but it is a non-trivial issue to obtain hydrostatic equilibria for rapidly rotating stars theoretically, especially for baroclinic cases, in which the pressure depends not only on the density, but also on the temperature and compositions. It is clear that the stellar structures with realistic equation of state are the baroclinic cases, but there are not so many studies for such equilibria. In this study, we propose two methods to obtain hydrostatic equilibria considering rotation and baroclinicity, namely the weak-solution method and the strong-solution method. The former method is based on the variational principle, which is also applied to the calculation of the inhomogeneous phases, known as the pasta structures, in crust of neutron stars. We found this method might break the balance equation locally, then introduce the strong-solution method. Note that our method is formulated in the mass coordinate, and it is hence appropriated for the stellar evolution calculations.

Lyotropic liquid crystalline phase behaviour in amphiphile-protic ionic liquid systems.

Science.gov (United States)

Chen, Zhengfei; Greaves, Tamar L; Fong, Celesta; Caruso, Rachel A; Drummond, Calum J

2012-03-21

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.

Description of gas hydrates equilibria in sediments using experimental data of soil water potential

Energy Technology Data Exchange (ETDEWEB)

Istomin, V. [NOVATEK, Moscow (Russian Federation); Chuvilin, E. [Moscow State Univ., Moscow (Russian Federation). Dept. of Geology; Makhonina, N.; Kvon, V. [VNIIGAZ, Moscow (Russian Federation); Safonov, S. [Schlumberger Moscow Research, Moscow (Russian Federation)

2008-07-01

Analytical relationships have been developed between hydrate dissociation pressure and vapor pressure above the pore water surface. In addition, experiments have been discussed in numerous publications on the effect of narrow interconnected throats between pores on clathrate dissociation conditions in porous media. This paper presented an approach that improved upon the available thermodynamic methods for calculation of hydrate phase equilibria. The approach took into account the properties of pore water in natural sediments including three-phase equilibrium of gas-pore water-gas hydrate in a similar way as for unfrozen water in geocryology science. The purpose of the paper was to apply and adapt geocryology and soil physics method to the thermodynamic calculation of non-clathrated water content in sediments. It answered the question of how to estimate the non-clathrated water content if pore water potential was known. The paper explained the thermodynamics of water phase in porous media including the thermodynamic properties of supercooled water, the thermodynamic properties of pore water and pore ice in sediments, and the phase equilibria of pore water. The paper also discussed the quantitative techniques that were utilized for determination of unfrozen water content in sediments and its dependence on temperature variation. These included contact-saturation, calorimetric, dielectric, nuclear magnetic resonance, and others. The thermodynamic calculations of pore water phase equilibria were also presented. 30 refs., 5 tabs., 8 figs.

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...

Isobaric (vapour + liquid + liquid) equilibrium data for (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) systems at 100 kPa

International Nuclear Information System (INIS)

Lladosa, Estela; Monton, Juan B.; Burguet, MaCruz; Torre, Javier de la

2008-01-01

Isobaric (vapour + liquid + liquid) equilibria were measured for the (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) system at 100 kPa. The apparatus used for the determination of (vapour + liquid + liquid) equilibrium data was an all-glass dynamic recirculating still with an ultrasonic homogenizer couple to the boiling flask. The experimental data demonstrated the existence of a heterogeneous ternary azeotrope for both ternary systems. The (vapour + liquid + liquid) equilibria data were found to be thermodynamically consistent for both systems. The experimental data were compared with the estimation using UNIQUAC and NRTL models and the prediction of UNIFAC model

Phase equilibrium at high pressure of heavy oil fraction in propane and n-butane; Equilibrio de fases em alta pressao de fracoes pesadas do petroleo em propano e n-butano

Energy Technology Data Exchange (ETDEWEB)

Canziani, Daniel B.; Ndiaye, Papa M. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil); Oliveira, Jose V. de; Corazza, Marcos L. [Universidade Regional Integrada, Erechim, RS (Brazil)

2008-07-01

One of the biggest challenge of the oil industry is the preparation and adequacy of existing refineries for processing of heavy oil in large quantities. Specifically aims of this work is to measure phase equilibria date at high-pressure with systems involving GOP (Heavy Gasoil), RAT (Atmospheric Residue) and Marlim (crude oil) in n-butane and propane, using the static-synthetic method. The influence of the addition of methanol on the transition pressure is also investigated. With regard to tests made with the use of methanol as a co-solvent, those with higher levels of methanol (5% in mass fraction) had presented transition pressures a little higher than systems with 1% of methanol and systems without methanol. The systems without methanol showed similar pressures. All systems are PT diagrams of the type Lower Critical Solution Temperature (LCST). Among the solvents used the n-butane shown to be the most soluble for all solutes, in particular for the RAT. With the n-butane were observed only liquid-vapour equilibria, and with propane the liquid-liquid, liquid-liquid-vapour and liquid-liquid-fluid equilibria could be observed. The system Propane-5%Methanol-GOP presented liquid-liquid-vapour transitions, indicates be a diagram of the type V (according to the classification of van Konynenburg and Scott). (author)

Phase equilibrium engineering

CERN Document Server

Brignole, Esteban Alberto

2013-01-01

Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and

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

Directory of Open Access Journals (Sweden)

M. Perumalsamy

2009-03-01

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

Solubility data and modeling for sugar alcohols in ionic liquids

International Nuclear Information System (INIS)

Okuniewski, Marcin; Ramjugernath, Deresh; Naidoo, Paramespri; Domańska, Urszula

2014-01-01

Highlights: • Solubility of D-sorbitol and xylitol in six ILs. • The (liquid + liquid) phase equilibrium of (SA + IL) with UCST. • Interesting properties of [BMIM][TDI] IL. • The correlation with NRTL model. - Abstract: Ionic liquids (ILs) are novel media characterized by strong interactions with different organic substances which leads to a wide spectrum of applications involving extraction. Ionic liquids have been used as a solvent for sugar alcohols, sugars and hydrates. This work demonstrates the experimental and theoretical study of (liquid + liquid) phase equilibria for two sugar alcohols, D-sorbitol and xylitol in a few ILs based on different cations and anions (namely, 1-ethyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide [EMPIP][NTf 2 ], 1-hexyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide [HMPIP][NTf 2 ], N-hexylquinolinium bis(trifluoromethylsulfonyl)imide [HQuin][NTf 2 ], N-hexylisoquinolinium bis(trifluoromethylsulfonyl)imide [HiQuin][NTf 2 ], 1-butyl-1-methylimidazolium 4,5-dicyano-2-(trifluoromethyl)-imidazolide [BMIM][TDI] and 1-(cyanomethyl)-3-methylimidazolium 4,5-dicyano-2-(trifluoromethyl)-imidazolide [CCNMIM][TDI]). This study was conducted to assess the applicability of the studied ILs for dissolution of these biomass-related materials. (Liquid + liquid) phase equilibrium diagrams (LLE) in binary systems (sugar alcohol + ionic liquid) were measured using the dynamic technique. The influence of the chemical structure of both the ionic liquids and sugar alcohols were established and is discussed

Physical property, phase equilibrium, distillation. Measurement and prediction of vapor-liquid and liquid-liquid equilibria; Bussei / heiko / joryu. Kieki, ekieki heiko no sokutei to suisan

Energy Technology Data Exchange (ETDEWEB)

Tochigi, K. [Nihon Univ., Tokyo (Japan)

1998-08-05

The data on vapor-liquid equilibrium are basic data indispensable to the designing of a distillation process. The stage required for separation depends greatly upon the x-y curve, and the existence/nonexistence of an azeotropic point is also an important item to be checked. This paper describes the measurement of vapor-liquid equilibrium and liquid-liquid equilibrium, and then introduces reliable data on vapor-liquid equilibrium and parameters of an activity coefficient formula. For the prediction of vapor-liquid equilibrium, the ASOG, UNIFAC, and modified NIFAC, all being group contributive methods are utilized. The differences between these group contributive methods are based on the differences between the contributive items based on the differences in size of molecules influencing the activity coefficients and the expression of the group activity coefficient formula. The applicable number of groups of the ASOG is 43, while that of groups of the UNIFAC is 50. The modified UNIFAC covers 43 groups. The prediction of liquid-liquid equilibrium by using a group contributive method has little progressed since the of the results of the study of Magnussen et al. using the UNIFAC. 12 refs., 8 figs., 1 tab.

Insight into the Am-O Phase Equilibria: A Thermodynamic Study Coupling High-Temperature XRD and CALPHAD Modeling.

Science.gov (United States)

Epifano, Enrica; Guéneau, Christine; Belin, Renaud C; Vauchy, Romain; Lebreton, Florent; Richaud, Jean-Christophe; Joly, Alexis; Valot, Christophe; Martin, Philippe M

2017-07-03

In the frame of minor actinide transmutation, americium can be diluted in UO 2 and (U, Pu)O 2 fuels burned in fast neutron reactors. The first mandatory step to foresee the influence of Am on the in-reactor behavior of transmutation targets or fuel is to have fundamental knowledge of the Am-O binary system and, in particular, of the AmO 2-x phase. In this study, we coupled HT-XRD (high-temperature X-ray diffraction) experiments with CALPHAD thermodynamic modeling to provide new insights into the structural properties and phase equilibria in the AmO 2-x -AmO 1.61+x -Am 2 O 3 domain. Because of this approach, we were able for the first time to assess the relationships between temperature, lattice parameter, and hypostoichiometry for fcc AmO 2-x . We showed the presence of a hyperstoichiometric existence domain for the bcc AmO 1.61+x phase and the absence of a miscibility gap in the fcc AmO 2-x phase, contrary to previous representations of the phase diagram. Finally, with the new experimental data, a new CALPHAD thermodynamic model of the Am-O system was developed, and an improved version of the phase diagram is presented.

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

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

Phase equilibria of Al3(Ti,V,Zr) intermetallic system

International Nuclear Information System (INIS)

Park, S.I.; Han, S.Z.; Choi, S.K.; Lee, H.M.

1996-01-01

Trialuminides such as DO 22 -structured Al 3 Ti are promising candidates as potential materials for elevated temperature applications because of their attractive high temperature strength and excellent oxidation resistance along with their low density. However, in the tetragonal structure, slip systems are restricted due to low symmetry and the primary deformation mode is twinning. And, therefore, monolithic trialuminide compounds have been very impractical to be used as structural materials. When transition elements such as Ti, V and Zr which constitute trialuminides are alloyed in aluminum, they have low solubilities and low diffusion coefficients in the Al matrix. If precipitated as trialuminide intermetallics, they maintain a small lattice mismatch with the Al matrix, which reduces the interfacial energy between matrix and precipitates. As a result, these precipitates would have a large coarsening resistance in the matrix. As most of the previous works have been concentrated on the microstructural stability and mechanical properties, thermochemical properties will be treated in this work. In this study, phase equilibria and diagrams of Al 3 (Ti,V,Zr) systems will be experimentally determined and then thermodynamically analyzed with a hope to extend to the Al-Al 3 (Ti,V,Zr) composite system. This approach will then be used as a guide for alloy design of Al-Al 3 (Ti,V,Zr) composite system

Purification of flavonoids from licorice using an off-line preparative two-dimensional normal-phase liquid chromatography/reversed-phase liquid chromatography method.

Science.gov (United States)

Fan, Yunpeng; Fu, Yanhui; Fu, Qing; Cai, Jianfeng; Xin, Huaxia; Dai, Mei; Jin, Yu

2016-07-01

An orthogonal (71.9%) off-line preparative two-dimensional normal-phase liquid chromatography/reversed-phase liquid chromatography method coupled with effective sample pretreatment was developed for separation and purification of flavonoids from licorice. Most of the nonflavonoids were firstly removed using a self-made Click TE-Cys (60 μm) solid-phase extraction. In the first dimension, an industrial grade preparative chromatography was employed to purify the crude flavonoids. Click TE-Cys (10 μm) was selected as the stationary phase that provided an excellent separation with high reproducibility. Ethyl acetate/ethanol was selected as the mobile phase owing to their excellent solubility for flavonoids. Flavonoids co-eluted in the first dimension were selected for further purification using reversed-phase liquid chromatography. Multiple compounds could be isolated from one normal-phase fraction and some compounds with bad resolution in one-dimensional liquid chromatography could be prepared in this two-dimensional system owing to the orthogonal separation. Moreover, this two-dimensional liquid chromatography method was beneficial for the preparation of relatively trace flavonoid compounds, which were enriched in the first dimension and further purified in the second dimension. Totally, 24 flavonoid compounds with high purity were obtained. The results demonstrated that the off-line two-dimensional liquid chromatography method was effective for the preparative separation and purification of flavonoids from licorice. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase equilibria of binary, ternary and quaternary systems for polymerization/depolymerization of polycarbonate

NARCIS (Netherlands)

Margon, V.; Agarwal, U.S.; Peters, C.J.; Wit, de G.; Bailly, C.M.E.; Kasteren, van J.M.N.; Lemstra, P.J.

2005-01-01

Vapor–liquid phase equilibrium is studied for the systems composed of phenol, diphenyl carbonate (DPC), bisphenol A (BPA) and CO2. Bubble point pressures and vapor-phase compositions are measured at various temperatures (343.15–473.15 K) for several compositions of the following systems: two binary

The Al-rich region of the Al-Mn-Ni alloy system. Part II. Phase equilibria at 620-1000 oC

International Nuclear Information System (INIS)

Balanetskyy, S.; Meisterernst, G.; Grushko, B.; Feuerbacher, M.

2011-01-01

Research highlights: → Phase equilibria in the Al-rich region of the Al-Mn-Ni alloy system were studied at 1000, 950, 850, 750, 700, 645 and 620 deg. C by means of SEM, TEM, powder XRD and DTA. → Three ternary thermodynamically stable intermetallics, the φ-phase (Al 5 Co 2 -type, hP26, P63/mmc; a = 0.76632(16), c = 0.78296(15) nm), the κ-phase (κ-Al 14.4 Cr 3.4 Ni l.1 -type, hP227, P63/m; a = 1.7625(10), c = 1.2516(10) nm), and the O-phase (O-Al 77 Cr 14 Pd 9 -type, Pmmn, oP650,: a = 2.3316(16), b = 1.2424(15), c = 3.2648(14) nm), as well as three ternary metastable phases, the decagonal D 3 -phase with periodicity about 1.25 nm, the Al 9 (Mn,Ni) 2 -phase (Al 9 Co 2 -type, P1121/a, mP22; a = 0.8585(16), b = 0.6269(9), c = 0.6205(11) nm, β = 95.34(10) o ) and the O 1 -phase (basecentered orthorhombic, a ∼ 23.8, b ∼ 12.4, c ∼ 32.2 nm) were revealed. → The existence of a thermodynamically stable R-phase of stoichiometry Al 60 Mn 11 Ni 4 , reported earlier in literature, was not confirmed in the present study. - Abstract: Phase equilibria in the Al-rich region of the Al-Mn-Ni alloy system were studied at 1000, 950, 850, 750, 700, 645 and 620 o C. Three ternary thermodynamically stable intermetallics, the φ-phase (Al 5 Co 2 -type, hP26, P6 3 /mmc; a = 0.76632(16), c = 0.78296(15) nm), the κ-phase (κ-Al 14.4 Cr 3.4 Ni l.1 -type, hP227, P6 3 /m; a = 1.7625(10), c = 1.2516(10) nm), and the O-phase (O-Al 77 Cr 14 Pd 9 -type, Pmmn, oP650,: a = 2.3316(16), b = 1.2424(15), c = 3.2648(14) nm), as well as three ternary metastable phases, the decagonal D 3 -phase with periodicity about 1.25 nm, the Al 9 (Mn,Ni) 2 -phase (Al 9 Co 2 -type, P112 1 /a, mP22; a = 0.8585(16), b = 0.6269(9), c = 0.6205(11) nm, β = 95.34(10) o ) and the O 1 -phase (base-centered orthorhombic, a ∼ 23.8, b ∼ 12.4, c ∼ 32.2 nm) were revealed. Their physicochemical behaviour in the Al-Mn-Ni alloy system was studied.

Study of phase equilibria in function of temperature in UO2-PuO2-Pu2O3 system for nuclear ceramics with high plutonium contents

International Nuclear Information System (INIS)

Truphemus, Thibaut

2013-01-01

In the UO 2 -PuO 2 -Pu 2 O 3 section, a monophasic (U 1-y ,Pu y )O 2-x domain is stable for y≤0,20 at 25 C and up to solid-liquid equilibrium. At higher Pu content, phase equilibria are more unclear with a phase separation process. The main objective of this work consisted in upgrading the representation of this system for 0,15≤y≤0,65 and 25≤T(C)≤1500. At 25 C, a miscibility gap composed by two different (U 1-y ,Pu y )O 2-x phases has been observed for y≤0,45, with one very closed to stoichiometric state (Oxygen/Metal=2) and one other very reduced. For the first time, a triphasic domain has been characterized at higher Pu contents, with two (U 1-y ,Pu y )O 2-x phases near y=0,45 and one (U 1-y ,Pu y ) 2 O 3 phase with a low U content inside. Concerning the study in function of temperature, we have demonstrated that phase separation temperature increase when Pu content grows. Several representations have been established. At 200 C, the representation is closed to that at 25 C. At 400 C, the phase separation have been specified at a lower Pu content than that of literature: y=0,35. At 600 C, our results have clarified the section, until then very unclear, with a phase separation appearing at y=0,60.The microstructural analysis has clearly demonstrated the significant impact of the phase separation on the material. Indeed many cracks have been observed in our samples, and quantity of these defects increases when Pu content grows. (author) [fr

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

Quantum equilibria for macroscopic systems

International Nuclear Information System (INIS)

Grib, A; Khrennikov, A; Parfionov, G; Starkov, K

2006-01-01

Nash equilibria are found for some quantum games with particles with spin-1/2 for which two spin projections on different directions in space are measured. Examples of macroscopic games with the same equilibria are given. Mixed strategies for participants of these games are calculated using probability amplitudes according to the rules of quantum mechanics in spite of the macroscopic nature of the game and absence of Planck's constant. A possible role of quantum logical lattices for the existence of macroscopic quantum equilibria is discussed. Some examples for spin-1 cases are also considered

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-07-01

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

Surface-bonded ionic liquid stationary phases in high-performance liquid chromatography--a review.

Science.gov (United States)

Pino, Verónica; Afonso, Ana M

2012-02-10

Ionic liquids (ILs) are a class of ionic, nonmolecular solvents which remain in liquid state at temperatures below 100°C. ILs possess a variety of properties including low to negligible vapor pressure, high thermal stability, miscibility with water or a variety of organic solvents, and variable viscosity. IL-modified silica as novel high-performance liquid chromatography (HPLC) stationary phases have attracted considerable attention for their differential behavior and low free-silanol activity. Indeed, around 21 surface-confined ionic liquids (SCIL) stationary phases have been developed in the last six years. Their chromatographic behavior has been studied, and, despite the presence of a positive charge on the stationary phase, they showed considerable promise for the separation of neutral solutes (not only basic analytes), when operated in reversed phase mode. This aspect points to the potential for truly multimodal stationary phases. This review attempts to summarize the state-of-the-art about SCIL phases including their preparation, chromatographic behavior, and analytical performance. Copyright © 2011 Elsevier B.V. All rights reserved.

Preliminary investigation of liquid phase sintering in ferrous systems

International Nuclear Information System (INIS)

Klein, J.

1975-04-01

Liquid phase sintering was utilized to achieve, by a simple compaction and sintering procedure involving short times and moderate temperatures, a virtually full dense high carbon Fe:C alloy and high boron Fe:B alloy. Parameters such as powder characteristics and mixing, compacting pressure, heating program and the liquid phase fraction were found to influence the sintered density. The response of the Fe:C alloy to a heat treatment is reported along with preliminary experiments in the iron base ternary system Fe:W:C. Residual porosities observed in microstructures of certain liquid phase sintered compacts were accounted for by a proposed capillary flow of the liquid phase and a local densification competing against an overall densification. Some general recommendations are made for liquid phase sintering of powder aggregates. 15 fig., 7 tables

Data Requirements and Modeling for Gas Hydrate-Related Mixtures and a Comparison of Two Association Models

DEFF Research Database (Denmark)

Liang, Xiaodong; Aloupis, Georgios; Kontogeorgis, Georgios M.

2017-01-01

the performance of the CPA and sPC-SAFT EOS for modeling the fluid-phase equilibria of gas hydrate-related systems and will try to explore how the models can help in suggesting experimental measurements. These systems contain water, hydrocarbon (alkane or aromatic), and either methanol or monoethylene glycol...... parameter sets have been chosen for the sPC-SAFT EOS for a fair comparison. The comparisons are made for pure fluid properties, vapor liquid-equilibria, and liquid liquid equilibria of binary and ternary mixtures as well as vapor liquid liquid equilibria of quaternary mixtures. The results show, from...

Some stable hydromagnetic equilibria

Energy Technology Data Exchange (ETDEWEB)

Johnson, J L; Oberman, C R; Kulsrud, R M; Frieman, E A [Project Matterhorn, Princeton University, Princeton, NJ (United States)

1958-07-01

We have been able to find and investigate the properties of equilibria which are hydromagnetically stable. These equilibria can be obtained, for example, by wrapping conductors helically around the stellarator tube. Systems with I = 3 or 4 are indicated to be optimum for stability purposes. In some cases an admixture of I = 2 fields can be advantageous for achieving equilibrium. (author)

First principles calculation of L21+A2 coherent equilibria in the Fe-Al-Ti system

International Nuclear Information System (INIS)

Alonso, Paula R.; Gargano, Pablo H.; Ramirez-Caballero, Gustavo E.; Balbuena, Perla B.; Rubiolo, Gerardo H.

2009-01-01

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 1 and B2+L2 1 .

Magnetoacoustic heating and FCT-equilibria in the belt pinch

International Nuclear Information System (INIS)

Erckmann, V.

1983-02-01

In the HECTOR belt pinch of high β plasma is produced by magnetic compression in a Tokamak geometry. After compresseion the initial β value can be varied between 0.2 and 0.8. During 5 μs the plasma is further heated by a fast magnetoacoustic wave with a frequency near the first harmonic of the ion cyclotronfrequency. For the first time the β-value of a pinch plasma could be increased further from 0.34 after compression to 0.46 at the end of the rf-heating cycle. By proper selection of the final β-value the region for resonance absorption of the heating wave can be shifted. Strong heating (200 MW) has been observed in the cases, where the resonance region has been located in the center of the plasma. In deuterium discharges an increase in ion temperature is observed during the heating process, whereas the electrons are energetically decoupled, showing no temperature increase. Strong plasma losses are found in the 200 MW range after the rf-heating process. The dominant mechanisms are charge exchange collisions with neutral gas atoms. During rf-heating and the subsequent cooling phase the magnetic flux is frozen due to the high conductivity of the plasma. The observed equilibria could be identified as flux conserving Tokamak (FCT) equilibria. Based on a two-dimensional code the time-evolution of the equilibria has been calculated. The q-profiles are time-independent, with increasing β the magnetic axis of the plasma is shifted towards the outer boundary of the torus, and finally the linear relation between β and βsub(pol), which is characteristic for low-β-equilibria, is no longer valid. Thus for the first time the existence of FCT-equilibria at high β has been demonstrated experimentally together with a qualitative agreement with FCT-theory. (orig./AH) [de

Jump conditions in transonic equilibria

International Nuclear Information System (INIS)

Guazzotto, L.; Betti, R.; Jardin, S. C.

2013-01-01

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-β, 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-β, 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 β, while they agree with the results obtained with the old implementation of FLOW in lower-β equilibria.

MINTEQ, Geochemical Equilibria in Ground Water

International Nuclear Information System (INIS)

Krupka, K.M.

1990-01-01

1 - Description of program or function: MINTEQ is a geochemical program to model aqueous solutions and the interactions of aqueous solutions with hypothesized assemblages of solid phases. It was developed for the Environmental Protection Agency to perform the calculations necessary to simulate the contact of waste solutions with heterogeneous sediments or the interaction of ground water with solidified wastes. MINTEQ can calculate ion speciation/solubility, adsorption, oxidation-reduction, gas phase equilibria, and precipitation/dissolution of solid phases. MINTEQ can accept a finite mass for any solid considered for dissolution and will dissolve the specified solid phase only until its initial mass is exhausted. This ability enables MINTEQ to model flow-through systems. In these systems the masses of solid phases that precipitate at earlier pore volumes can be dissolved at later pore volumes according to thermodynamic constraints imposed by the solution composition and solid phases present. The ability to model these systems permits evaluation of the geochemistry of dissolved traced metals, such as low-level waste in shallow land burial sites. MINTEQ was designed to solve geochemical equilibria for systems composed of one kilogram of water, various amounts of material dissolved in solution, and any solid materials that are present. Systems modeled using MINTEQ can exchange energy and material (open systems) or just energy (closed systems) with the surrounding environment. Each system is composed of a number of phases. Every phase is a region with distinct composition and physically definable boundaries. All of the material in the aqueous solution forms one phase. The gas phase is composed of any gaseous material present, and structurally distinct solid forms a separate phase. 2 - Method of solution: MINTEQ applies the fundamental principles of thermodynamics to solve geochemical equilibria from a set of mass balance equations, one for each component. Because the

Liquid-liquid extraction and separation of VIII group elements, especially ruthenium, by synergic combinations or aromatic polyimines and micellar cationic exchangers

International Nuclear Information System (INIS)

Vitart, X.

1991-01-01

This thesis aims to characterize and to quantify the chemical equilibria involved in d-elements liquid-liquid extraction systems, especially elements belonging to the VIII group (Fe, Ni, Co, Ru, Rh, Pd, Pt). These systems are composed of synergic combination of aromatic polyimines and micellar cationic exchangers. Substitutions are first performed in aqueous acidic media by aromatic polyimines; then extractions are operated using micellic canionic exchangers. Chemical equilibria, selectivity effects, especially those due to ion-pair formations, kinetics, extractant behaviour are analysed and quantified [fr

Monosilicide-disilicide-silicon phase equilibria in the nickel-platinum-silicon and nickel-palladium-silicon systems

Science.gov (United States)

Loomans, M. E.; Chi, D. Z.; Chua, S. J.

2004-10-01

Bulk-phase equilibria in Ni-rich/Si-rich alloys of the Ni-Pt-Si and Ni-Pd-Si systems were investigated. Results suggest that a bulk monosilicide solid solution, containing up to at least 11 at. pct Pt, exists in the Ni-Pt-Si system. Monosilicides containing more than 11 at. pct Pt were not examined. Results from both ternary systems point convincingly to the existence of a NiSi+Si↔NiSi2 eutectoid reaction near 700 °C in the Ni-Si binary system; data from the Ni-Pt-Si system, which yield the more accurate determination of the eutectoid temperature, place it at roughly 710 °C. The Pt and Pd concentrations of monosilicide in equilibrium with disilicide and Si were measured using energy-dispersive spectrometry (EDS) and were found to increase with temperature.

Quantum equilibria for macroscopic systems

Energy Technology Data Exchange (ETDEWEB)

Grib, A [Department of Theoretical Physics and Astronomy, Russian State Pedagogical University, St. Petersburg (Russian Federation); Khrennikov, A [Centre for Mathematical Modelling in Physics and Cognitive Sciences Vaexjoe University (Sweden); Parfionov, G [Department of Mathematics, St. Petersburg State University of Economics and Finances (Russian Federation); Starkov, K [Department of Mathematics, St. Petersburg State University of Economics and Finances (Russian Federation)

2006-06-30

Nash equilibria are found for some quantum games with particles with spin-1/2 for which two spin projections on different directions in space are measured. Examples of macroscopic games with the same equilibria are given. Mixed strategies for participants of these games are calculated using probability amplitudes according to the rules of quantum mechanics in spite of the macroscopic nature of the game and absence of Planck's constant. A possible role of quantum logical lattices for the existence of macroscopic quantum equilibria is discussed. Some examples for spin-1 cases are also considered.

Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

Science.gov (United States)

Tournier, Robert F.

2018-01-01

Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

Application of Ionic Liquids in High Performance Reversed-Phase Chromatography

Directory of Open Access Journals (Sweden)

Wentao Bi

2009-06-01

Full Text Available Ionic liquids, considered “green” chemicals, are widely used in many areas of analytical chemistry due to their unique properties. Recently, ionic liquids have been used as a kind of novel additive in separation and combined with silica to synthesize new stationary phase as separation media. This review will focus on the properties and mechanisms of ionic liquids and their potential applications as mobile phase modifier and surface-bonded stationary phase in reversed-phase high performance liquid chromatography (RP-HPLC. Ionic liquids demonstrate advantages and potential in chromatographic field.

Supported Ionic Liquid Phase (SILP) catalysis

DEFF Research Database (Denmark)

Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco

2006-01-01

Applications of ionic liquids to replace conventional solvents in homogeneous transition-metal catalysis have increased significantly during the last decade. Biphasic ionic liquid/organic liquid systems offer advantages with regard to product separation, catalyst stability, and recycling...... but utilise in the case of fast chemical reactions only a small amount of expensive ionic liquid and catalyst. The novel Supported Ionic Liquid Phase (SILP) catalysis concept overcomes these drawbacks and allows the use of fixed-bed reactors for continuous reactions. In this Microreview the SILP catalysis...

Pierce instability and bifurcating equilibria

International Nuclear Information System (INIS)

Godfrey, B.B.

1981-01-01

The report investigates the connection between equilibrium bifurcations and occurrence of the Pierce instability. Electrons flowing from one ground plane to a second through an ion background possess a countable infinity of static equilibria, of which only one is uniform and force-free. Degeneracy of the uniform and simplest non-uniform equilibria at a certain ground plan separation marks the onset of the Pierce instability, based on a newly derived dispersion relation appropriate to all the equilibria. For large ground plane separations the uniform equilibrium is unstable and the non-uniform equilibrium is stable, the reverse of their stability properties at small separations. Onset of the Pierce instability at the first bifurcation of equilibria persists in more complicated geometries, providing a general criterion for marginal stability. It seems probable that bifurcation analysis can be a useful tool in the overall study of stable beam generation in diodes and transport in finite cavities

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 combinat...... CPA yields the best results of all the models for the prediction of dew point pressures....

Phase equilibria in the Ni–Al–Ga system at 700 °C

International Nuclear Information System (INIS)

Belyavina, N.; Markiv, V.; Nakonechna, O.; Lozovyi, F.

2014-01-01

Graphical abstract: - Highlights: • We study phase equilibria in ternary Ni–Al–Ga in the whole concentration range. • Ni(Al,Ga), Ni 2 (Al,Ga) 3 , Ni 5 (Al,Ga) 3 extended solid solutions exist in this system. • Isothermal section (700 °C) of the Ni–Al–Ga system has been constructed. • Small additions of Ga increase compressive strength of Ni 3 (Al,Ga) solid solution. - Abstract: Phase relations in the ternary Ni–Al–Ga system at 700 °C have been established by the X-ray powder diffraction methods. In addition to already known Ni 3 (Al,Ga) continuous solid solution, Ni(Al,Ga) continuous solid solution as well as Ni 2 (Al,Ga) 3 and Ni 5 (Al,Ga) 3 extended solid solutions were found to exist in this system. It was shown that the ternary Ni 2 (Al,Ga) 3 and Ni 5 (Al,Ga) 3 compounds do not belong to the continuous solid solutions because of two-phase gaps on the Ni 2 Al 3 –Ni 2 Ga 3 (∼30–50 at.% Ga) and Ni 5 Al 3 –Ni 5 Ga 3 (∼12–25 at.% Ga) isolines at 700 °C. Some crystal structure peculiarities such as atomic ordering–disordering and presence of structural vacancies have been revealed for all solid solutions existing in the Ni–Al–Ga system. It was found that the compressive strength of the Ni 3 (Al,Ga) solid solution increases with small additions of gallium (about 2.5 at.%). The isothermal section (700 °C) of the ternary Ni–Al–Ga system including four extended solid solutions (Ni 3 (Al,Ga), Ni 5 (Al,Ga) 3 , Ni(Al,Ga) and Ni 2 (Al,Ga) 3 ) has been constructed and plotted

Axisymmetric ideal magnetohydrodynamic equilibria with incompressible flows

International Nuclear Information System (INIS)

Tasso, H.; Throumoulopoulos, G.N.

1997-12-01

It is shown that the ideal MHD equilibrium states of an axisymmetric plasma with incompressible flows are governed by an elliptic partial differential equation for the poloidal magnetic flux function ψ containing five surface quantities along with a relation for the pressure. Exact equilibria are constructed including those with non vanishing poloidal and toroidal flows and differentially varying radial electric fields. Unlike the case in cylindrical incompressible equilibria with isothermal magnetic surfaces which should have necessarily circular cross sections [G. N. Throumoulopoulos and H. Tasso, Phys. Plasmas 4, 1492 (1997)], no restriction appears on the shapes of the magnetic surfaces in the corresponding axisymmetric equilibria. The latter equilibria satisfy a set of six ordinary differential equations which for flows parallel to the magnetic field B can be solved semianalytically. In addition, it is proved the non existence of incompressible axisymmetric equilibria with (a) purely poloidal flows and (b) non-parallel flows with isothermal magnetic surfaces and vertical stroke B vertical stroke = vertical stroke B vertical stroke (ψ) (omnigenous equilibria). (orig.)

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.

Isothermal sections of phase equilibria diagrams for systems (terbium, dysprosium, holmium)-molybdenum-boron at 1273 K

International Nuclear Information System (INIS)

Kuz'ma, Yu.B.; Zakharchuk, N.P.; Maksimova, L.T.

1988-01-01

The methods of X-ray analysis are used to study the R-Mo-B (R-Tb, Dy, Ho) systems and isothermal sections of phase equilibria diagrams at 1273 K are plotted. A formation of RMoB 4 (structure of the YCrB 4 type) is confirmed and borides R 3 MoB 7 (structure of the Er 3 CrB 7 type) and ∼ RMo 4 B 8 (of the unknown structure) are obtained for the first time. Borides DyMoB 3 and HoMoB 3 are of the ErMoB 3 structure. Lattice periods of new compounds are indicated. Diffractogrammes of borides Dy 3 MoB 7 and DyMoB 3 are calculated. A peculiarity of components interaction in the systems rare-earth metal-molybdenum-boron is considered

Critical point analysis of phase envelope diagram

International Nuclear Information System (INIS)

Soetikno, Darmadi; Siagian, Ucok W. R.; Kusdiantara, Rudy; Puspita, Dila; Sidarto, Kuntjoro A.; Soewono, Edy; Gunawan, Agus Y.

2014-01-01

Phase diagram or phase envelope is a relation between temperature and pressure that shows the condition of equilibria between the different phases of chemical compounds, mixture of compounds, and solutions. Phase diagram is an important issue in chemical thermodynamics and hydrocarbon reservoir. It is very useful for process simulation, hydrocarbon reactor design, and petroleum engineering studies. It is constructed from the bubble line, dew line, and critical point. Bubble line and dew line are composed of bubble points and dew points, respectively. Bubble point is the first point at which the gas is formed when a liquid is heated. Meanwhile, dew point is the first point where the liquid is formed when the gas is cooled. Critical point is the point where all of the properties of gases and liquids are equal, such as temperature, pressure, amount of substance, and others. Critical point is very useful in fuel processing and dissolution of certain chemicals. Here in this paper, we will show the critical point analytically. Then, it will be compared with numerical calculations of Peng-Robinson equation by using Newton-Raphson method. As case studies, several hydrocarbon mixtures are simulated using by Matlab

Critical point analysis of phase envelope diagram

Energy Technology Data Exchange (ETDEWEB)

Soetikno, Darmadi; Siagian, Ucok W. R. [Department of Petroleum Engineering, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia); Kusdiantara, Rudy, E-mail: rkusdiantara@s.itb.ac.id; Puspita, Dila, E-mail: rkusdiantara@s.itb.ac.id; Sidarto, Kuntjoro A., E-mail: rkusdiantara@s.itb.ac.id; Soewono, Edy; Gunawan, Agus Y. [Department of Mathematics, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

2014-03-24

Phase diagram or phase envelope is a relation between temperature and pressure that shows the condition of equilibria between the different phases of chemical compounds, mixture of compounds, and solutions. Phase diagram is an important issue in chemical thermodynamics and hydrocarbon reservoir. It is very useful for process simulation, hydrocarbon reactor design, and petroleum engineering studies. It is constructed from the bubble line, dew line, and critical point. Bubble line and dew line are composed of bubble points and dew points, respectively. Bubble point is the first point at which the gas is formed when a liquid is heated. Meanwhile, dew point is the first point where the liquid is formed when the gas is cooled. Critical point is the point where all of the properties of gases and liquids are equal, such as temperature, pressure, amount of substance, and others. Critical point is very useful in fuel processing and dissolution of certain chemicals. Here in this paper, we will show the critical point analytically. Then, it will be compared with numerical calculations of Peng-Robinson equation by using Newton-Raphson method. As case studies, several hydrocarbon mixtures are simulated using by Matlab.

Rollover risk, liquidity and macroprudential regulation

OpenAIRE

Ahnert, Toni

2014-01-01

I study rollover risk in the wholesale funding market when intermediaries can hold liquidity ex ante and are subject to fire sales ex post. Precautionary liquidity restores multiple equilibria in a global rollover game. An intermediate liquidity level supports both the usual run equilibrium and an efficient equilibrium. I provide a uniqueness refinement to characterize the privately optimal liquidity choice. Because of fire sales, liquidity holdings are strategic substitutes. Intermediaries f...

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

Science.gov (United States)

Raut, Ashlesha S; Kalonia, Devendra S

2016-05-02

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

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

2017-04-01

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.

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

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...

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

Science.gov (United States)

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

2018-04-01

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

Multiple equilibria of divertor plasmas

International Nuclear Information System (INIS)

Vu, H.X.; Prinja, A.K.

1993-01-01

A one-dimensional, two-fluid transport model with a temperature-dependent neutral recycling coefficient is shown to give rise to multiple equilibria of divertor plasmas (bifurcation). Numerical techniques for obtaining these multiple equilibria and for examining their stability are presented. Although these numerical techniques have been well known to the scientific community, this is the first time they have been applied to divertor plasma modeling to show the existence of multiple equilibria as well as the stability of these solutions. Numerical and approximate analytical solutions of the present one-dimensional transport model both indicate that there exists three steady-state solutions corresponding to (1) a high-temperature, low-density equilibrium, (2) a low-temperature, high-density equilibrium, and (3) an intermediate-temperature equilibrium. While both the low-temperature and the high-temperature equilibria are stable, with respect to small perturbations in the plasma conditions, the intermediate-temperature equilibrium is physically unstable, i.e., any small perturbation about this equilibrium will cause a transition toward either the high-temperature or low-temperature equilibrium

Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles

Energy Technology Data Exchange (ETDEWEB)

McGrath, M; Siepmann, J I; Kuo, I W; Mundy, C J; Vandevondele, J; Sprik, M; Hutter, J; Mohamed, F; Krack, M; Parrinello, M

2004-10-20

Efficient Monte Carlo algorithms are combined with the Quickstep energy routines of CP2K to develop a program that allows for Monte Carlo simulations in the canonical, isobaric-isothermal, and Gibbs ensembles using a first principles description of the physical system. Configurational-bias Monte Carlo techniques and pre-biasing using an inexpensive approximate potential are employed to increase the sampling efficiency and to reduce the frequency of expensive ab initio energy evaluations. The new Monte Carlo program has been validated through extensive comparison with molecular dynamics simulations using the programs CPMD and CP2K. Preliminary results for the vapor-liquid coexistence properties (T = 473 K) of water using the Becke-Lee-Yang-Parr exchange and correlation energy functionals, a triple-zeta valence basis set augmented with two sets of d-type or p-type polarization functions, and Goedecker-Teter-Hutter pseudopotentials are presented. The preliminary results indicate that this description of water leads to an underestimation of the saturated liquid density and heat of vaporization and, correspondingly, an overestimation of the saturated vapor pressure.

Industrial aspects of gas-liquid two-phase flow

International Nuclear Information System (INIS)

Hewitt, G.F.

1977-01-01

The lecture begins by reviewing the various types of plant in which two phase flow occurs. Specifically, boiling plant, condensing plant and pipelines are reviewed, and the various two phase flow problems occurring in them are described. Of course, many other kinds of chemical engineering plant involve two phase flow, but are somewhat outside the scope of this lecture. This would include distillation columns, vapor-liquid separators, absorption towers etc. Other areas of industrial two phase flow which have been omitted for space reasons from this lecture are those concerned with gas/solids, liquid/solid and liquid/liquid flows. There then follows a description of some of the two phase flow processes which are relevant in industrial equipment and where special problems occur. The topics chosen are as follows: (1) pressure drop; (2) horizontal tubes - separation effects non-uniformites in heat transfer coefficient, effect of bends on dryout; (3) multicomponent mixtures - effects in pool boiling, mass transfer effects in condensation and Marangoni effects; (4) flow distribution - manifold problems in single phase flow, separation effects at a single T-junction in two phase flow and distribution in manifolds in two phase flow; (5) instability - oscillatory instability, special forms of instability in cryogenic systems; (6) nucleate boiling - effect of variability of surface, unresolved problems in forced convective nucleate boiling; and (7) shell side flows - flow patterns, cross flow boiling, condensation in cross flow

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

Science.gov (United States)

Limmer, David T; Chandler, David

2015-01-01

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

Non-conventional solvents in liquid phase microextraction and aqueous biphasic systems.

Science.gov (United States)

An, Jiwoo; Trujillo-Rodríguez, María J; Pino, Verónica; Anderson, Jared L

2017-06-02

The development of rapid, convenient, and high throughput sample preparation approaches such as liquid phase microextraction techniques have been continuously developed over the last decade. More recently, significant attention has been given to the replacement of conventional organic solvents used in liquid phase microextraction techniques in order to reduce toxic waste and to improve selectivity and/or extraction efficiency. With these objectives, non-conventional solvents have been explored in liquid phase microextraction and aqueous biphasic systems. The utilized non-conventional solvents include ionic liquids, magnetic ionic liquids, and deep eutectic solvents. They have been widely used as extraction solvents or additives in various liquid phase microextraction modes including dispersive liquid-liquid microextraction, single-drop microextraction, hollow fiber-liquid phase microextraction, as well as in aqueous biphasic systems. This review provides an overview into the use of non-conventional solvents in these microextraction techniques in the past 5 years (2012-2016). Analytical applications of the techniques are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Corium phase equilibria based on MASCA, METCOR and CORPHAD results

Energy Technology Data Exchange (ETDEWEB)

Bechta, S.V.; Granovsky, V.S.; Khabensky, V.B. [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Gusarov, V.V.; Almiashev, V.I.; Mezentseva, L.P. [Grebenshikov Institute of Silicate Chemistry, Russian Academy of Sciences (ISCh RAS), St. Petersburg (Russian Federation); Krushinov, E.V.; Kotova, S.Yu.; Kosarevsky, R.A. [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Barrachin, M. [Institut de Radioprotection et Surete Nucleaire IRSN/DPAM, St Paul lez Durance (France); Bottomley, D. [EUROPAISCHE KOMMISSION, Joint Research Centre Institut fuer Transurane (ITU), Karlsruhe (Germany); Fichot, F. [Institut de Radioprotection et Surete Nucleaire IRSN/DPAM, St Paul lez Durance (France); Fischer, M. [AREVA NP GmbH, Erlangen (Germany)], E-mail: Manfred.Fischer@areva.com

2008-10-15

Experimental data on component partitioning between suboxidized corium melt and steel in the in-vessel melt retention (IVR) conditions are compared. The data are produced within the OECD MASCA program and the ISTC CORPHAD project under close-to-isothermal conditions and in the ISTC METCOR project under thermal gradient conditions. Chemical equilibrium in the U-Zr-Fe(Cr,Ni,...)-O system is reached in all experiments. In MASCA tests the molten pool formed under inert atmosphere has two immiscible liquids, oxygen-enriched (oxidic) and oxygen-depleted (metallic), resulting of the miscibility gap of the mentioned system. Sub-system data of the U-Zr-Fe(Cr,Ni,...)-O phase diagram investigated within the ISTC CORPHAD project are interpreted in relation with the MASCA results. In METCOR tests the equilibrium is established between oxidic liquid and mushy metallic part of the system. Results of comparison are discussed and the implications for IVR noted.

High-pressure (vapor + liquid) equilibria in the (nitrogen + n-heptane) system

Energy Technology Data Exchange (ETDEWEB)

Garcia-Sanchez, Fernando [Laboratorio de Termodinamica, Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico, D.F. (Mexico)]. E-mail: fgarcias@imp.mx; Eliosa-Jimenez, Gaudencio [Laboratorio de Termodinamica, Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico, D.F. (Mexico); Silva-Oliver, Guadalupe [Laboratorio de Termodinamica, Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico, D.F. (Mexico); Godinez-Silva, Armando [Laboratorio de Termodinamica, Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico, D.F. (Mexico)

2007-06-15

In this work, new (vapor + liquid) equilibrium data for the (N{sub 2} + n-heptane) system were experimentally measured over a wide temperature range from (313.6 to 523.7) K and pressures up to 50 MPa. A static-analytic apparatus with visual sapphire windows and pneumatic capillary samplers was used in the experimental measurements. Equilibrium phase compositions and (vapor + liquid) equilibrium ratios are reported. The new results were compared with those reported by other authors. The comparison showed that the pressure-composition data reported in this work are less scattered than those determined by others. Hence, the results demonstrate the reliability of the experimental apparatus at high temperatures and pressures. The experimental data were represented with the PR and PC-SAFT equations of state by using one-fluid mixing rules and a single temperature independent interaction parameter. Results of the representation showed that the PC-SAFT equation was superior to the PR equation in correlating the experimental data of the (N{sub 2} + n-heptane) system.

High-pressure (vapor + liquid) equilibria in the (nitrogen + n-heptane) system

International Nuclear Information System (INIS)

Garcia-Sanchez, Fernando; Eliosa-Jimenez, Gaudencio; Silva-Oliver, Guadalupe; Godinez-Silva, Armando

2007-01-01

In this work, new (vapor + liquid) equilibrium data for the (N 2 + n-heptane) system were experimentally measured over a wide temperature range from (313.6 to 523.7) K and pressures up to 50 MPa. A static-analytic apparatus with visual sapphire windows and pneumatic capillary samplers was used in the experimental measurements. Equilibrium phase compositions and (vapor + liquid) equilibrium ratios are reported. The new results were compared with those reported by other authors. The comparison showed that the pressure-composition data reported in this work are less scattered than those determined by others. Hence, the results demonstrate the reliability of the experimental apparatus at high temperatures and pressures. The experimental data were represented with the PR and PC-SAFT equations of state by using one-fluid mixing rules and a single temperature independent interaction parameter. Results of the representation showed that the PC-SAFT equation was superior to the PR equation in correlating the experimental data of the (N 2 + n-heptane) system

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

KAUST Repository

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

2014-01-01

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

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

KAUST Repository

Hellmann, Christoph

2014-12-17

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

Oxygen potentials and phase equilibria of the quaternary Y-Ba-Cu-O system in the region involving the YBa2Cu3O7-x phase

International Nuclear Information System (INIS)

Fitzner, K.; Musbah, O.; Hsieh Kerchang; Zhang Minxian; Chang, Y.A.

1993-01-01

The equilibrium oxygen potentials of four-phase equilibria (counting only the condensed phases) in the CuO-Cu 2 O-BaCuO 2 -Y 2 BaCuO 5 (211)-YBa 2 Cu 3 O 7-x (123) phase region were determined using the following solid-oxide electrolyte e.m.f. cell: Pt10Rh, air (psub(O 2 )=0.21 atm) vertical stroke ZrO 2 +Y 2 O 3 vertical stroke mixtures of oxides, Pt. The oxide mixtures whose oxygen potentials were measured were CuO-Cu 2 O-211-123, CuO-Cu 2 O-BaCuO 2 -123, Cu 2 O-BaCuO 2 -211-123 and CuO-BaCuO 2 -211-123. The phase in some of the mixtures were identified by X-ray diffraction. These data were analyzed and are presented using stability diagrams, i.e., oxygen potential as a function of the reciprocal of the temperature. Extrapolation of these data for the four four-phase equilibra to high temperatures yields a metastable five-phase equilibrium, i.e., 123=CuO+Cu 2 O+BaCuO 2 +211, at ∼1243 K (970 ) and log psub(O 2 ) ∼ -1.21 (psub(O 2 )∼0.062 atm). (orig.)

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

DEFF Research Database (Denmark)

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

2013-01-01

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

Vapor phase versus liquid phase grafting of meso-porous alumina

NARCIS (Netherlands)

Sripathi, V.G.P.; Mojet, Barbara; Nijmeijer, Arian; Benes, Nieck Edwin

2013-01-01

Functionalization of meso-porous c-alumina has been performed by grafting of 3-Aminopropyltrimethoxysilane (3APTMS) simultaneously from either the liquid phase or from the vapor phase. In both cases, after grafting nitrogen physisorption indicates that the materials remain meso-porous with

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.

Modeling vapor liquid equilibrium of ionic liquids + gas binary systems at high pressure with cubic equations of state

Directory of Open Access Journals (Sweden)

A. C. D. Freitas

2013-03-01

Full Text Available Ionic liquids (IL have been described as novel environmentally benign solvents because of their remarkable characteristics. Numerous applications of these solvents continue to grow at an exponential rate. In this work, high pressure vapor liquid equilibria for 17 different IL + gas binary systems were modeled at different temperatures with Peng-Robinson (PR and Soave-Redlich-Kwong (SRK equations of state, combined with the van der Waals mixing rule with two binary interaction parameters (vdW-2. The experimental data were taken from the literature. The optimum binary interaction parameters were estimated by minimization of an objective function based on the average absolute relative deviation of liquid and vapor phases, using the modified Simplex algorithm. The solubilities of all gases studied in this work decrease as the temperature increases and increase with increasing pressure. The correlated results were highly satisfactory, with average absolute relative deviations of 2.10% and 2.25% for PR-vdW-2 and SRK-vdW-2, respectively.

Ionic liquid stationary phases for gas chromatography.

Science.gov (United States)

Poole, Colin F; Poole, Salwa K

2011-04-01

This article provides a summary of the development of ionic liquids as stationary phases for gas chromatography beginning with early work on packed columns that established details of the retention mechanism and established working methods to characterize selectivity differences compared with molecular stationary phases through the modern development of multi-centered cation and cross-linked ionic liquids for high-temperature applications in capillary gas chromatography. Since there are many reviews on ionic liquids dealing with all aspects of their chemical and physical properties, the emphasis in this article is placed on the role of gas chromatography played in the design of ionic liquids of low melting point, high thermal stability, high viscosity, and variable selectivity for separations. Ionic liquids provide unprecedented opportunities for extending the selectivity range and temperature-operating range of columns for gas chromatography, an area of separation science that has otherwise been almost stagnant for over a decade. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CFD analysis of laboratory scale phase equilibrium cell operation

Science.gov (United States)

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process.: Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

CFD analysis of laboratory scale phase equilibrium cell operation.

Science.gov (United States)

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

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

Science.gov (United States)

Limmer, David T.; Chandler, David

2015-01-01

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

FORTRAN program for calculating liquid-phase and gas-phase thermal diffusion column coefficients

International Nuclear Information System (INIS)

Rutherford, W.M.

1980-01-01

A computer program (COLCO) was developed for calculating thermal diffusion column coefficients from theory. The program, which is written in FORTRAN IV, can be used for both liquid-phase and gas-phase thermal diffusion columns. Column coefficients for the gas phase can be based on gas properties calculated from kinetic theory using tables of omega integrals or on tables of compiled physical properties as functions of temperature. Column coefficients for the liquid phase can be based on compiled physical property tables. Program listings, test data, sample output, and users manual are supplied for appendices

Neoclassical MHD equilibria with ohmic current

International Nuclear Information System (INIS)

Tokuda, Shinji; Takeda, Tatsuoki; Okamoto, Masao.

1989-01-01

MHD equilibria of tokamak plasmas with neoclassical current effects (neoclassical conductivity and bootstrap current) were calculated self-consistently. Neoclassical effects on JFT-2M tokamak plasmas, sustained by ohmic currents, were studied. Bootstrap currents flow little for L-mode type equilibria because of low attainable values of poloidal beta, β J . H-mode type equilibria give bootstrap currents of 30% ohmic currents for β J attained by JFT-2M and 100% for β J ≥ 1.5, both of which are sufficient to change the current profiles and the resultant MHD equilibria. Neoclassical conductivity which has roughly half value of the classical Spitzer conductivity brings peaked ohmic current profiles to yield low safety factor at the magnetic axis. Neoclassical conductivity reduces the value of effective Z(Z eff ) which is necessary to give the observed one-turn voltage but it needs impurities accumulating at the center when such peaked current profiles are not observed. (author)

Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase (SILP) Rh catalysts

DEFF Research Database (Denmark)

Riisager, Anders; Wasserscheid, Peter; Van Hal, R.

2003-01-01

Continuous flow gas-phase hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1-n-butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1-n-butyl...

Structure analysis of turbulent liquid phase by POD and LSE techniques

International Nuclear Information System (INIS)

Munir, S.; Muthuvalu, M. S.; Siddiqui, M. I.; Heikal, M. R.; Aziz, A. Rashid A.

2014-01-01

In this paper, vortical structures and turbulence characteristics of liquid phase in both single liquid phase and two-phase slug flow in pipes were studied. Two dimensional velocity vector fields of liquid phase were obtained by Particle image velocimetry (PIV). Two cases were considered one single phase liquid flow at 80 l/m and second slug flow by introducing gas at 60 l/m while keeping liquid flow rate same. Proper orthogonal decomposition (POD) and Linear stochastic estimation techniques were used for the extraction of coherent structures and analysis of turbulence in liquid phase for both cases. POD has successfully revealed large energy containing structures. The time dependent POD spatial mode coefficients oscillate with high frequency for high mode numbers. The energy distribution of spatial modes was also achieved. LSE has pointed out the coherent structured for both cases and the reconstructed velocity fields are in well agreement with the instantaneous velocity fields

Structure analysis of turbulent liquid phase by POD and LSE techniques

Energy Technology Data Exchange (ETDEWEB)

Munir, S., E-mail: shahzad-munir@comsats.edu.pk; Muthuvalu, M. S.; Siddiqui, M. I. [Department of Fundamental and Applied Science, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak Darul Ridzuan (Malaysia); Heikal, M. R., E-mail: morgan.heikal@petronas.com.my; Aziz, A. Rashid A., E-mail: morgan.heikal@petronas.com.my [Department of Mechanical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak Darul Ridzuan (Malaysia)

2014-10-24

In this paper, vortical structures and turbulence characteristics of liquid phase in both single liquid phase and two-phase slug flow in pipes were studied. Two dimensional velocity vector fields of liquid phase were obtained by Particle image velocimetry (PIV). Two cases were considered one single phase liquid flow at 80 l/m and second slug flow by introducing gas at 60 l/m while keeping liquid flow rate same. Proper orthogonal decomposition (POD) and Linear stochastic estimation techniques were used for the extraction of coherent structures and analysis of turbulence in liquid phase for both cases. POD has successfully revealed large energy containing structures. The time dependent POD spatial mode coefficients oscillate with high frequency for high mode numbers. The energy distribution of spatial modes was also achieved. LSE has pointed out the coherent structured for both cases and the reconstructed velocity fields are in well agreement with the instantaneous velocity fields.

Rollover risk, liquidity, and macro-prudential regulation

OpenAIRE

Ahnert, Toni

2014-01-01

I study rollover risk in the wholesale funding market when intermediaries can hold liquidity ex-ante and are subject to fire sales ex-post. I demonstrate that precautionary liquidity restores multiple equilibria in a global rollover game. An intermediate liquidity level supports both the usual run equilibrium and an efficient equilibrium. I provide a uniqueness refinement to characterize the privately optimal liquidity choice. Because of fire sales, liquidity holdings are strategic substitute...

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.

Learning to Play Efficient Coarse Correlated Equilibria

KAUST Repository

Borowski, Holly P.; Marden, Jason R.; Shamma, Jeff S.

2018-01-01

The majority of the distributed learning literature focuses on convergence to Nash equilibria. Coarse correlated equilibria, on the other hand, can often characterize more efficient collective behavior than even the best Nash equilibrium. However

The nuclear liquid gas phase transition and phase coexistence

International Nuclear Information System (INIS)

Chomaz, Ph.

2001-01-01

In this talk we will review the different signals of liquid gas phase transition in nuclei. From the theoretical side we will first discuss the foundations of the concept of equilibrium, phase transition and critical behaviors in infinite and finite systems. From the experimental point of view we will first recall the evidences for some strong modification of the behavior of hot nuclei. Then we will review quantitative detailed analysis aiming to evidence phase transition, to define its order and phase diagram. Finally, we will present a critical discussion of the present status of phase transitions in nuclei and we will draw some lines for future development of this field. (author)

The nuclear liquid gas phase transition and phase coexistence

Energy Technology Data Exchange (ETDEWEB)

Chomaz, Ph

2001-07-01

In this talk we will review the different signals of liquid gas phase transition in nuclei. From the theoretical side we will first discuss the foundations of the concept of equilibrium, phase transition and critical behaviors in infinite and finite systems. From the experimental point of view we will first recall the evidences for some strong modification of the behavior of hot nuclei. Then we will review quantitative detailed analysis aiming to evidence phase transition, to define its order and phase diagram. Finally, we will present a critical discussion of the present status of phase transitions in nuclei and we will draw some lines for future development of this field. (author)

Manipulating Liquids With Acoustic Radiation Pressure Phased Arrays

Science.gov (United States)

Oeftering, Richard C.

1999-01-01

High-intensity ultrasound waves can produce the effects of "Acoustic Radiation Pressure" (ARP) and "acoustic streaming." These effects can be used to propel liquid flows and to apply forces that can be used to move or manipulate floating objects or liquid surfaces. NASA's interest in ARP includes the remote-control agitation of liquids and the manipulation of bubbles and drops in liquid experiments and propellant systems. A high level of flexibility is attained by using a high-power acoustic phased array to generate, steer, and focus a beam of acoustic waves. This is called an Acoustic Radiation Pressure Phased Array, or ARPPA. In this approach, many acoustic transducer elements emit wavelets that converge into a single beam of sound waves. Electronically coordinating the timing, or "phase shift," of the acoustic waves makes it possible to form a beam with a predefined direction and focus. Therefore, a user can direct the ARP force at almost any desired point within a liquid volume. ARPPA lets experimenters manipulate objects anywhere in a test volume. This flexibility allow it to be used for multiple purposes, such as to agitate liquids, deploy and manipulate drops or bubbles, and even suppress sloshing in spacecraft propellant tanks.

Phase equilibria and homogeneity range of the high temperature superconducting compound (Bi,Pb)2+xSr2Ca2Cu3O10+δ

International Nuclear Information System (INIS)

Kaesche, S.

1995-01-01

For the superconducting cuprates (Bi,Pb) 2+x Sr 2 Ca 2 Cu 3 O 10+y phase equilibria, the homogeneity region, and the phase formation has been studied in the temperture range 800 to 890 C. Sintered samples were prepared by a solid state reaction starting from Bi 2 O 3 , PbO, CuO and carbonates CaCO 3 and SrCO 3 in a three-stage calcination process. For the phase identification polarization microscopy, X-ray diffraction and susceptibility measurements have been applied. Multi-phase regions were determined in the cross section of the quasi-ternary system (Bi,Pb) 2 O 3 -SrO-CaO-CuO with constant Bi/(Bi+Pb) ratio 0.84 taking into account the 2223-phase. The homogeneity region was determined as function of Sr, Ca, Bi and Pb concentration. Its maximum size was found at 850 C

Phase equilibria in M-X-X' and M-Al-X ternary systems (M-transition metal, X,X'-B,C,N,Si) and crystal chemistry of ternary compounds

International Nuclear Information System (INIS)

Gusev, A.I.

1996-01-01

The data on phase equilibria in the M-X-X' and M-Al-X ternary systems (M-transition metal of 3 to 8 groups, X-B,C, N, Si) have been considered and summarized. modern oxygen-free advanced ceramics is based on these ternary systems. Phase diagrams of the 130 ternary systems have been discussed, more than two hundred ternary phases forming in these systems have been systematized and described. The typical crystal structures of ternary compounds and phase have been considered, the common and distinctive features of these structures have been analysed. It has been shown that the ternary compounds with octahedral atomic groups XM 6 have a regions of homogeneity. Refs. 240

Phases, phase equilibria, and phase rules in low-dimensional systems

International Nuclear Information System (INIS)

Frolov, T.; Mishin, Y.

2015-01-01

We present a unified approach to thermodynamic description of one, two, and three dimensional phases and phase transformations among them. The approach is based on a rigorous definition of a phase applicable to thermodynamic systems of any dimensionality. Within this approach, the same thermodynamic formalism can be applied for the description of phase transformations in bulk systems, interfaces, and line defects separating interface phases. For both lines and interfaces, we rigorously derive an adsorption equation, the phase coexistence equations, and other thermodynamic relations expressed in terms of generalized line and interface excess quantities. As a generalization of the Gibbs phase rule for bulk phases, we derive phase rules for lines and interfaces and predict the maximum number of phases than may coexist in systems of the respective dimensionality

Visualization and measurement of liquid velocity field of gas-liquid metal two-phase flow using neutron radiography

International Nuclear Information System (INIS)

Saito, Yasushi; Suzuki, Tohru; Matsubayashi, Masahito

2000-01-01

In a core melt accident of a fast breeder reactor, a possibility of re-criticality is anticipated in the molten fuel-steel mixture pool. One of the mechanisms to suppress the re-criticality is the boiling of steel in the molten fuel-steel mixture pool because of the negative void reactivity effect. To evaluate the reactivity change due to boiling, it is necessary to know the characteristics of gas-liquid two-phase flow in the molten fuel-steel mixture pool. For this purpose, boiling bubbles in a molten fuel-steel mixture pool were simulated by adiabatic gas bubbles in a liquid metal pool to study the basic characteristics of gas-liquid metal two-phase mixture. Visualization of the two-phase mixture and measurements of liquid phase velocity and void fraction were conducted by using neutron radiography and image processing techniques. From these measurements, the basic characteristics of gas-liquid metal two-phase mixture were clarified. (author)

How ionic species structure influences phase structure and transitions from protic ionic liquids to liquid crystals to crystals.

Science.gov (United States)

Greaves, Tamar L; Broomhall, Hayden; Weerawardena, Asoka; Osborne, Dale A; Canonge, Bastien A; Drummond, Calum J

2017-12-14

The phase behaviour of n-alkylammonium (C6 to C16) nitrates and formates has been characterised using synchrotron small angle and wide angle X-ray scattering (SAXS/WAXS), differential scanning calorimetry (DSC), cross polarised optical microscopy (CPOM) and Fourier transform infrared spectroscopy (FTIR). The protic salts may exist as crystalline, liquid crystalline or ionic liquid materials depending on the alkyl chain length and temperature. n-Alkylammonium nitrates with n ≥ 6 form thermotropic liquid crystalline (LC) lamellar phases, whereas n ≥ 8 was required for the formate series to form this LC phase. The protic ionic liquid phase showed an intermediate length scale nanostructure resulting from the segregation of the polar and nonpolar components of the ionic liquid. This segregation was enhanced for longer n-alkyl chains, with a corresponding increase in the correlation length scale. The crystalline and liquid crystalline phases were both lamellar. Phase transition temperatures, lamellar d-spacings, and liquid correlation lengths for the n-alkylammonium nitrates and formates were compared with those for n-alkylammonium chlorides and n-alkylamines. Plateau regions in the liquid crystalline to liquid phase transition temperatures as a function of n for the n-alkylammonium nitrates and formates are consistent with hydrogen-bonding and cation-anion interactions between the ionic species dominating alkyl chain-chain van der Waals interactions, with the exception of the mid chained hexyl- and heptylammonium formates. The d-spacings of the lamellar phases for both the n-alkylammonium nitrates and formates were consistent with an increase in chain-chain layer interdigitation within the bilayer-based lamellae with increasing alkyl chain length, and they were comparable to the n-alkylammonium chlorides.

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....

Ternary systems Sr-{Ni,Cu}-Si: Phase equilibria and crystal structure of ternary phases

International Nuclear Information System (INIS)

Nasir, Navida; Melnychenko-Koblyuk, Nataliya; Grytsiv, Andriy; Rogl, Peter; Giester, Gerald; Wosik, Jaroslaw; Nauer, Gerhard E.

2010-01-01

Phase relations were established in the Sr-poor part of the ternary systems Sr-Ni-Si (900 deg. C) and Sr-Cu-Si (800 deg. C) by light optical microscopy, electron probe microanalysis and X-ray diffraction on as cast and annealed alloys. Two new ternary compounds SrNiSi 3 (BaNiSn 3 -type) and SrNi 9-x Si 4+x (own-type) were found in the Sr-Ni-Si system along with previously reported Sr(Ni x Si 1-x ) 2 (AlB 2 -type). The crystal structure of SrNi 9-x Si 4+x (own-type, x=2.7, a=0.78998(3), c=1.1337(2) nm; space group P4/nbm) was determined from X-ray single crystal counter to be a low symmetry derivative of the cubic, parent NaZn 13 -type. At higher Si-content X-ray Rietveld refinements reveal the formation of a vacant site (□) corresponding to a formula SrNi 5.5 Si 6.5 □ 1.0 . Phase equilibria in the Sr-Cu-Si system are characterized by the compounds SrCu 2-x Si 2+x (ThCr 2 Si 2 -type), Sr(Cu x Si 1-x ) 2 (AlB 2 -type), SrCu 9-x Si 4+x (0≤x≤1.0; CeNi 8.5 Si 4.5 -type) and SrCu 13-x Si x (4≤x≤1.8; NaZn 13 -type). The latter two structure types appear within a continuous solid solution. Neither a type-I nor a type-IX clathrate compound was encountered in the Sr-{Cu,Ni}-Si systems. Structural details are furthermore given for about 14 new ternary compounds from related alloy systems with Ba. - Graphical abstract: The crystal structure of SrNi 9-x Si 4+x (own-type, x=2.7, a=0.78998(3), c=1.1337(2) nm; space group P4/nbm) was determined from X-ray single crystal counter to be a low symmetry derivative of the cubic, parent NaZn 13 -type and is related to CeNi 8.5 Si 4.5 -type.

Learning to Play Efficient Coarse Correlated Equilibria

KAUST Repository

Borowski, Holly P.

2018-03-10

The majority of the distributed learning literature focuses on convergence to Nash equilibria. Coarse 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 coarse correlated equilibria. In this paper, we provide one such algorithm, which guarantees that the agents’ collective joint strategy will constitute an efficient coarse 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.

Multiple Equilibria in Noisy Rational Expectations Economies

DEFF Research Database (Denmark)

Pálvölgyi, Dömötör; Venter, Gyuri

with a continuous price function. However, we also construct a tractable class of equilibria with discontinuous prices that have very different economic implications, including (i) jumps and crashes, (ii) significant revisions in uninformed belief due to small changes in the market price, (iii) “upward......-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)....

Phase Equilibria Study in the TeO2-Na2O-SiO2 System in Air Between 723 K (500 °C) and 1473 K (1200 °C)

Science.gov (United States)

Santoso, Imam; Taskinen, Pekka

2016-08-01

Knowledge of phase equilibria in the TeO2-Na2O-SiO2 system at elevated temperatures is important for ceramic and glass industries and for improving the operation of the smelting process of tellurium-containing materials. A review of previous investigations has indicated, however, that there are omissions in the available datasets on the liquidus temperatures of the molten TeO2-Na2O-SiO2 mixtures. The employed experimental method included equilibration of mixtures made from high purity oxides, rapid quenching of the equilibrated samples in water and followed by compositional analysis of the phases using an electron probe X-ray microanalyzer. The liquidus and phase equilibria in the TeO2-SiO2, TeO2-Na2O, and SiO2-TeO2-Na2O systems have been studied for a wide range of compositions between 723 K (500 °C) and 1473 K (1200 °C) at TeO2, SiO2, and Na2SiO3 saturations. New data have been generated in the SiO2-TeO2-Na2O system at SiO2 saturation. The liquidus compositions in the TeO2-Na2O system at TeO2 saturation have been compared with the previous data and an assessed phase diagram.

Calculation of phase equilibria in the Na2SO4-K2SO4-Cs2SO4-H2O system at 25 deg C

International Nuclear Information System (INIS)

Filippov, V.K.; Kalinkin, A.M.; Vasin, S.K.

1990-01-01

Calculation results of solubility diagram and water activity in saturated solutions of Na 2 SO 4 -K 2 SO 4 -Cs 2 SO 4 -H 2 O system at 25 deg C are presented. It is shown that for the calculation of quaternary systems one can use the Pitzer equations. Solubility diagram for the system studied is plotted and data on composition and water activity of solutions saturated by two or three solid phases are given. Classification of nonvariant equilibria from the viewpoint of isomorphism of solubility and fusibility diagrams permits to depict the direction of phase processes during isothermal evaporation of water

Stability of relative equilibria of three vortices

DEFF Research Database (Denmark)

Aref, Hassan

2009-01-01

Three point vortices on the unbounded plane have relative equilibria wherein the vortices either form an equilateral triangle or are collinear. While the stability analysis of the equilateral triangle configurations is straightforward, that of the collinear relative equilibria is considerably mor...

Tube Radial Distribution Flow Separation in a Microchannel Using an Ionic Liquid Aqueous Two-Phase System Based on Phase Separation Multi-Phase Flow.

Science.gov (United States)

Nagatani, Kosuke; Shihata, Yoshinori; Matsushita, Takahiro; Tsukagoshi, Kazuhiko

2016-01-01

Ionic liquid aqueous two-phase systems were delivered into a capillary tube to achieve tube radial distribution flow (TRDF) or annular flow in a microspace. The phase diagram, viscosity of the phases, and TRDF image of the 1-butyl-3-methylimidazolium chloride and NaOH system were examined. The TRDF was formed with inner ionic liquid-rich and outer ionic liquid-poor phases in the capillary tube. The phase configuration was explained using the viscous dissipation principle. We also examined the distribution of rhodamine B in a three-branched microchannel on a microchip with ionic liquid aqueous two-phase systems for the first time.

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

DEFF Research Database (Denmark)

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

2017-01-01

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

Liquid phase chromatography on microchips

DEFF Research Database (Denmark)

Kutter, Jörg Peter

2012-01-01

explosive development of, in particular, chromatographic separation systems on microchips, has, however, slowed down in recent years. This review takes a closer, critical look at how liquid phase chromatography has been implemented in miniaturized formats over the past several years, what is important...

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

International Nuclear Information System (INIS)

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

2012-01-01

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

Existence of pareto equilibria for multiobjective games without compactness

OpenAIRE

Shiraishi, Yuya; Kuroiwa, Daishi

2013-01-01

In this paper, we investigate the existence of Pareto and weak Pareto equilibria for multiobjective games without compactness. By employing an existence theorem of Pareto equilibria due to Yu and Yuan([10]), several existence theorems of Pareto and weak Pareto equilibria for the multiobjective games are established in a similar way to Flores-B´azan.

Balance of liquid-phase turbulence kinetic energy equation for bubble-train flow

International Nuclear Information System (INIS)

Ilic, Milica; Woerner, Martin; Cacuci, Dan Gabriel

2004-01-01

In this paper the investigation of bubble-induced turbulence using direct numerical simulation (DNS) of bubbly two-phase flow is reported. DNS computations are performed for a bubble-driven liquid motion induced by a regular train of ellipsoidal bubbles rising through an initially stagnant liquid within a plane vertical channel. DNS data are used to evaluate balance terms in the balance equation for the liquid phase turbulence kinetic energy. The evaluation comprises single-phase-like terms (diffusion, dissipation and production) as well as the interfacial term. Special emphasis is placed on the procedure for evaluation of interfacial quantities. Quantitative analysis of the balance equation for the liquid phase turbulence kinetic energy shows the importance of the interfacial term which is the only source term. The DNS results are further used to validate closure assumptions employed in modelling of the liquid phase turbulence kinetic energy transport in gas-liquid bubbly flows. In this context, the performance of respective closure relations in the transport equation for liquid turbulence kinetic energy within the two-phase k-ε and the two-phase k-l model is evaluated. (author)

Highly Selective Continuous Gas-Phase Methoxycarbonylation of Ethylene with Supported Ionic Liquid Phase (SILP) Catalysts

DEFF Research Database (Denmark)

Khokarale, Santosh Govind; Garcia Suárez, Eduardo José; Fehrmann, Rasmus

2017-01-01

Supported ionic liquid phase (SILP) technology was applied for the first time to the Pd-catalyzed continuous, gas-phase methoxycarbonylation of ethylene to selectively produce methyl propanoate (MP) in high yields. The influence of catalyst and reaction parameters such as, for example, ionic liquid...

Comparison of cryopreserved human sperm in vapor and liquid phases of liquid nitrogen: effect on motility parameters, morphology, and sperm function.

Science.gov (United States)

Punyatanasakchai, Piyaphan; Sophonsritsuk, Areephan; Weerakiet, Sawaek; Wansumrit, Surapee; Chompurat, Deonthip

2008-11-01

To compare the effects of cryopreserved sperm in vapor and liquid phases of liquid nitrogen on sperm motility, morphology, and sperm function. Experimental study. Andrology laboratory at Ramathibodi Hospital, Thailand. Thirty-eight semen samples with normal motility and sperm count were collected from 38 men who were either patients of an infertility clinic or had donated sperm for research. Each semen sample was divided into two aliquots. Samples were frozen with static-phase vapor cooling. One aliquot was plunged into liquid nitrogen (-196 degrees C), and the other was stored in vapor-phase nitrogen (-179 degrees C) for 3 days. Thawing was performed at room temperature. Motility was determined by using computer-assisted semen analysis, sperm morphology was determined by using eosin-methylene blue staining, and sperm function was determined by using a hemizona binding test. Most of the motility parameters of sperm stored in the vapor phase were not significantly different from those stored in the liquid phase of liquid nitrogen, except in amplitude of lateral head displacement. The percentages of normal sperm morphology in both vapor and liquid phases also were not significantly different. There was no significant difference in the number of bound sperm in hemizona between sperm cryopreserved in both vapor and liquid phases of liquid nitrogen. Cryopreservation of human sperm in a vapor phase of liquid nitrogen was comparable to cryopreservation in a liquid phase of liquid nitrogen.

Computing Nash equilibria through computational intelligence methods

Science.gov (United States)

Pavlidis, N. G.; Parsopoulos, K. E.; Vrahatis, M. N.

2005-03-01

Nash equilibrium constitutes a central solution concept in game theory. The task of detecting the Nash equilibria of a finite strategic game remains a challenging problem up-to-date. This paper investigates the effectiveness of three computational intelligence techniques, namely, covariance matrix adaptation evolution strategies, particle swarm optimization, as well as, differential evolution, to compute Nash equilibria of finite strategic games, as global minima of a real-valued, nonnegative function. An issue of particular interest is to detect more than one Nash equilibria of a game. The performance of the considered computational intelligence methods on this problem is investigated using multistart and deflection.

Stochastic Equilibria under Imprecise Deviations in Terminal-Reward Concurrent Games

Directory of Open Access Journals (Sweden)

Patricia Bouyer

2016-09-01

Full Text Available We study the existence of mixed-strategy equilibria in concurrent games played on graphs. While existence is guaranteed with safety objectives for each player, Nash equilibria need not exist when players are given arbitrary terminal-reward objectives, and their existence is undecidable with qualitative reachability objectives (and only three players. However, these results rely on the fact that the players can enforce infinite plays while trying to improve their payoffs. In this paper, we introduce a relaxed notion of equilibria, where deviations are imprecise. We prove that contrary to Nash equilibria, such (stationary equilibria always exist, and we develop a PSPACE algorithm to compute one.

Thermal analysis and prediction of phase equilibria in the TiO2-Bi2O3 system

International Nuclear Information System (INIS)

Lopez-Martinez, Jaqueline; Romero-Serrano, Antonio; Hernandez-Ramirez, Aurelio; Zeifert, Beatriz; Gomez-Yanez, Carlos; Martinez-Sanchez, Roberto

2011-01-01

A thermodynamic study on the TiO 2 -Bi 2 O 3 system was carried out using differential thermal analysis (DTA) and X-Ray diffraction (XRD) techniques covering the composition range from 65 to 90 mol% Bi 2 O 3 . From the XRD results the only two intermediate compounds in the Bi 2 O 3 rich region were Bi 4 Ti 3 O 12 and Bi 12 TiO 20 . The Bi 4 Ti 3 O 12 phase presents the well known plate-like morphology. The experimentally determined phase transition temperatures with DTA technique were compared with thermodynamic calculated results and good agreement was obtained. The DTA results also showed that the limit of the peritectic reaction between liquid and Bi 4 Ti 3 O 12 occurs approximately at 90 mol% Bi 2 O 3 . The phase diagram of the TiO 2 -Bi 2 O 3 system was calculated using a quasichemical model for the liquid phase. The thermodynamic properties of the intermediate compounds were estimated from the data of TiO 2 and Bi 2 O 3 pure solids. In this manner, data for this binary system have been analysed and represented with a small adjustable parameter for the liquid phase.

Discontinuous structural phase transition of liquid metal and alloys (2)

International Nuclear Information System (INIS)

Wang, Li; Liu, Jiantong

2004-01-01

The diameter (d f ) of diffusion fluid cluster before and after phase transition has been calculated in terms of the paper ''Discontinuous structural phase transition of liquid metal and alloy (1)'' Physics Letters. A 326 (2004) 429-435, to verify quantitatively the discontinuity of structural phase transition; the phenomena of thermal contraction and thermal expansion during the phase transition, together with the evolution model of discontinuous structural phase transition are also discussed in this Letter to explore further the nature of structural transition; In addition, based on the viscosity experimental result mentioned in paper [Y. Waseda, The Structure of Non-Crystalline Materials--Liquids and Amorphous Solids, McGraw-Hill, New York, 1980], we present an approach to draw an embryo of the liquid-liquid (L-L) phase diagram for binary alloys above liquidus in the paper, expecting to guide metallurgy process so as to improve the properties of alloys. The idea that controls amorphous structure and its properties by means of the L-L phase diagram for alloys and by the rapid cooling technique to form the amorphous alloy has been brought forward in the end

Laser-induced partial oxidation of cyclohexane in liquid phase

International Nuclear Information System (INIS)

Oshima, Y.; Wu, X.W.; Koda, S.

1995-01-01

A laser-induced partial oxidation of cyclohexane was studied in the liquid phase. With KrF excimer laser (248 nm) irradiation to neat liquid cyclohexane in which O 2 was dissolved, cyclohexanol and cyclohexanone were obtained with very high selectivities, together with cyclohexane as a minor product. Radical recombination reactions to produce dicyclohexyl ether and bicyclohexyl also took place, while these products were not observed in the gas phase reaction. These experimental results were considered to be due not only to higher concentration of cyclohexane but to the cage effect in the liquid phase oxidation. To clarify the reaction progress including the photoabsorption process, the effects of laser intensity and O 2 pressure on product distribution were studied. (author)

Elastic energy and metastable phase equilibria for coherent mixtures in cubic systems

International Nuclear Information System (INIS)

Williams, R.O.

1979-02-01

Expressions were derived for the elastic energy due to coherency for cubic systems for an isotropic structure and for (100) or (111) habit planes for a lamellar structure. For the metastable equilibria the usual tangent compositions are replaced by compositions that are tangent to the elastic energy curve. For a loss of coherency there is an energy decrease due to the elastic effects and a further decrease associated with compositional changes. Information contained within this treatment permits calculation of the x-ray diffraction effects for such structures

Fluid phase equilibria during propylene carbonate synthesis from propylene oxide in carbon dioxide medium

DEFF Research Database (Denmark)

Gharnati, Loubna; Musko, Nikolai; Jensen, Anker Degn

2013-01-01

-cyclic guanidinium bromide on SBA-15 (HEPCGBr/SBA-15) as catalyst in the absence of any co-catalyst. It was found that the yield was strongly dependent on the amount of CO2 added to the system and that the phase behavior strongly changes along the reaction pathway. The Cubic-Plus-Association (CPA) equation of state...... was used to predict the phase behavior during the reaction and the number and composition of coexisting phases in the multicomponent reaction system were determined. In accordance with the experimental data, the maximum conversion was achieved in the transition region between the two- and the one-phase...... region where a CO2-expanded reactant/product phase (larger volume due to the dissolution of carbon dioxide in the liquid phase) is present. Optimal conditions for performing the reaction have been derived which requires consideration not only of the phase behavior of the starting phase but also...

Preparation and evaluation of surface-bonded tricationic ionic liquid silica as stationary phases for high-performance liquid chromatography.

Science.gov (United States)

Qiao, Lizhen; Shi, Xianzhe; Lu, Xin; Xu, Guowang

2015-05-29

Two tricationic ionic liquids were prepared and then bonded onto the surface of supporting silica materials through "thiol-ene" click chemistry as new stationary phases for high-performance liquid chromatography. The obtained columns of tricationic ionic liquids were evaluated respectively in the reversed-phase liquid chromatography (RPLC) mode and hydrophilic interaction liquid chromatography (HILIC) mode, and possess ideal column efficiency of 80,000 plates/m in the RPLC mode with naphthalene as the test solute. The tricationic ionic liquid stationary phases exhibit good hydrophobic and shape selectivity to hydrophobic compounds, and RPLC retention behavior with multiple interactions. In the HILIC mode, the retention and selectivity were evaluated through the efficient separation of nucleosides and bases as well as flavonoids, and the typical HILIC retention behavior was demonstrated by investigating retention changes of hydrophilic solutes with water volume fraction in mobile phase. The results show that the tricationic ionic liquid columns possess great prospect for applications in analysis of hydrophobic and hydrophilic samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Liquid phase sintered superconducting cermet

International Nuclear Information System (INIS)

Ray, S.P.

1990-01-01

This patent describes a method of making a superconducting cermet having superconducting properties with improved bulk density, low porosity and in situ stabilization. It comprises: forming a structure of a superconducting ceramic material having the formula RM 2 Cu 3 O (6.5 + x) wherein R is one or more rare earth elements capable of reacting to form a superconducting ceramic, M is one or more alkaline earth metal elements selected from barium and strontium capable of reacting to form a superconducting ceramic, x is greater than 0 and less than 0.5; and a precious metal compound in solid form selected from the class consisting of oxides, sulfides and halides of silver; and liquid phase sintering the mixture at a temperature wherein the precious metal of the precious metal compound is molten and below the melting point of the ceramic material. The liquid phase sintering is carried out for a time less than 36 hours but sufficient to improve the bulk density of the cermet

Highly tilted liquid crystalline materials possessing a direct phase transition from antiferroelectric to isotropic phase

Energy Technology Data Exchange (ETDEWEB)

Milewska, K.; Drzewiński, W. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Czerwiński, M., E-mail: mczerwinski@wat.edu.pl [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Dąbrowski, R. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Piecek, W. [Institute of Applied Physics, Military University of Technology, 00-908 Warsaw (Poland)

2016-03-01

Pure compounds and multicomponent mixtures with a broad temperature range of high tilted liquid crystalline antiferroelectric phase and a direct phase transition from antiferroelectric to isotropic phase, were obtained. X-ray diffraction analysis confirms these kinds of materials form a high tilted anticlinic phase, with a fixed layer spacing and very weak dependency upon temperature, after the transition from the isotropic phase. Due to this, not only pure orthoconic antiferroelectric liquid crystals but also those with a moderate tilt should generate a good dark state. Furthermore, due to the increased potential for forming anticlinic forces, such materials could minimize a commonly observed asymmetry of a rise and fall switching times at a surface stabilized geometry. - Highlights: • The new class of liquid crystalline materials with the direct SmC{sub A}*. • Iso phase transition were obtained. • Materials possess the layer spacing fixed and very weak dependent upon temperature. • Smectic layers without shrinkage are observed. • A good dark state can be generate in SSAFLC.

The liquid to vapor phase transition in excited nuclei

Energy Technology Data Exchange (ETDEWEB)

Elliott, J.B.; Moretto, L.G.; Phair, L.; Wozniak, G.J.; Beaulieu, L.; Breuer, H.; Korteling, R.G.; Kwiatkowski, K.; Lefort, T.; Pienkowski, L.; Ruangma, A.; Viola, V.E.; Yennello, S.J.

2001-05-08

For many years it has been speculated that excited nuclei would undergo a liquid to vapor phase transition. For even longer, it has been known that clusterization in a vapor carries direct information on the liquid-vapor equilibrium according to Fisher's droplet model. Now the thermal component of the 8 GeV/c pion + 197 Au multifragmentation data of the ISiS Collaboration is shown to follow the scaling predicted by Fisher's model, thus providing the strongest evidence yet of the liquid to vapor phase transition.

Using the minimum principle for the Helmholtz free energy in the analysis of the equilibria of a van der Waals fluid

International Nuclear Information System (INIS)

Ascoli, Sergio; Malvestuto, Vincenzo

2004-01-01

For a fluid system, obeying a state equation of the van der Waals type, the gas and the liquid phases can coexist in equilibrium, at a given temperature, only if the volume of the system is kept fixed. Thus, in order to study the two-phase equilibria of a fluid system, it seemed quite natural to choose the molar volume as the independent variable, and, consequently, the Helmholtz free energy as the proper thermodynamic potential for the application of the minimum principle. Specific computations are here carried out for a single van der Waals fluid, namely, pure water at 300 0 C. As a result, the present treatment indicates a simple and effective way to identify the whole range of molar volumes where the equilibrium preferred by the system is a two-phase equilibrium. This range results to be wider than the interval of strict instability of the van der Waals isotherm. Finally, it is pointed out that all the results, obtained here for the van der Waals state equation, can be extended to all the state equations of the same type

Strong Nash Equilibria and the Potential Maimizer

NARCIS (Netherlands)

van Megen, F.J.C.; Facchini, G.; Borm, P.E.M.; Tijs, S.H.

1996-01-01

A class of non cooperative games characterized by a `congestion e ect' is studied, in which there exists a strong Nash equilibrium, and the set of Nash equilibria, the set of strong Nash equilibria and the set of strategy pro les maximizing the potential function coincide.The structure of the class

Liquid Crystals - The 'Fourth' Phase of Matter

Indian Academy of Sciences (India)

possibilities of novel technological applications. Liquid crystalline materials ... advanced instrumentation, including laptops and futuristic flat panel displays. .... The twist grain-boundary phase is formed when the layers of a smectic A phase are .... the optic axis) is uniformly oriented parallel to the glass plate. (see Figure IIa).

Plasmas in Multiphase Media: Bubble Enhanced Discharges in Liquids and Plasma/Liquid Phase Boundaries

Energy Technology Data Exchange (ETDEWEB)

Kushner, Mark Jay [University of Michigan

2014-07-10

In this research project, the interaction of atmospheric pressure plasmas with multi-phase media was computationally investigated. Multi-phase media includes liquids, particles, complex materials and porous surfaces. Although this investigation addressed fundamental plasma transport and chemical processes, the outcomes directly and beneficially affected applications including biotechnology, medicine and environmental remediation (e.g., water purification). During this project, we made advances in our understanding of the interaction of atmospheric pressure plasmas in the form of dielectric barrier discharges and plasma jets with organic materials and liquids. We also made advances in our ability to use computer modeling to represent these complex processes. We determined the method that atmospheric pressure plasmas flow along solid and liquid surfaces, and through endoscopic like tubes, deliver optical and high energy ion activation energy to organic and liquid surfaces, and produce reactivity in thin liquid layers, as might cover a wound. We determined the mechanisms whereby plasmas can deliver activation energy to the inside of liquids by sustaining plasmas in bubbles. These findings are important to the advancement of new technology areas such as plasma medicine

Reliable Correlation for Liquid-Liquid Equilibria Outside the Critical Region

DEFF Research Database (Denmark)

Ruszczynski, Lukasz; Zubov, Alexandr; O’Connell, John P.

2017-01-01

, uncertainty analysis of regression results, obtained parameters, and predicted mole fractions has been formulated. The procedure is applied to three cases: hydrocarbons + water, ionic liquids + water, and nitroethane + hydrocarbons. The model has four parameters in the most basic formulation. Depending upon...

Free-boundary perturbed MHD equilibria

International Nuclear Information System (INIS)

Nührenberg, C

2012-01-01

The concept of perturbed ideal MHD equilibria [Boozer A H and Nuhrenberg C 2006 Phys. Plasmas 13 102501] is employed to study the influence of external error-fields and of small plasma-pressure changes on toroidal plasma equilibria. In tokamak and stellarator free-boundary calculations, benchmarks were successful of the perturbed-equilibrium version of the CAS3D stability code [Nührenberg C et al. 2009 Phys. Rev. Lett. 102 235001] with the ideal MHD equilibrium code NEMEC [Hirshman S P et al. 1986 Comput. Phys. Commun. 43 143].

Coal ash fusion temperatures -- New characterization techniques, and associations with phase equilibria

Energy Technology Data Exchange (ETDEWEB)

Wall, T.F.; Gupta, R.P.; Gupta, S. [Univ. of Newcastle, New South Wales (Australia). Dept. of Chemical Engineering; Creelman, R.A. [R.A. Creelman and Associates, Epping, New South Wales (Australia); Coin, C. [ACIRL Ipswich, Booval, Queensland (Australia); Lowe, A. [Pacific Power, Sydney, New South Wales (Australia)

1996-12-31

The well-documented shortcomings of the standard technique for estimating the fusion temperature of coal ash are its subjective nature and poor accuracy. Alternative measurements based on the shrinkage and electrical conductivity of heating samples are therefore examined with laboratory ash prepared at about 800 C in crucibles, as well as combustion ash sampled from power stations. Sensitive shrinkage measurements indicate temperatures of rapid change which correspond to the formation of liquid phases that can be identified on ternary phase diagrams. The existence and extent of formation of these phases, as quantified by the magnitude of peaks in the test, provide alternative ash fusion temperatures. The peaks from laboratory ashes and corresponding combustion ashes derived from the same coals show clear differences which may be related to the evaporation of potassium during combustion and the reactions of the mineral residues to form combustion ash.

Characterisation of GERDA Phase-I detectors in liquid argon

Energy Technology Data Exchange (ETDEWEB)

Barnabe Heider, Marik; Schoenert, Stefan [Max-Planck-Institut fuer Kernphysik (Germany); Gusev, Konstantin [Russian Research Center, Kurchatov Institute (Russian Federation); Joint Institute for Nuclear Research (Russian Federation)

2009-07-01

GERDA will search for neutrinoless double beta decay in {sup 76}Ge by submerging bare enriched HPGe detectors in liquid argon. In GERDA Phase-I, reprocessed enriched-Ge detectors, which were previously operated by the Heidelberg-Moscow and IGEX collaborations, and reprocessed natural-Ge detectors from Genius-TF, will be redeployed. We have tested the operation and performance of bare HPGe detectors in liquid nitrogen and in liquid argon over more than three years with three non-enriched p-type prototype detectors. The detector handling and mounting procedures have been defined and the Phase-I detector technology, the low-mass assembly and the long-term stability in liquid argon have been tested successfully. The Phase-I detectors were reprocessed by Canberra Semiconductor NV, Olen, according to their standard technology but without the evaporation of a passivation layer. After their reprocessing, the detectors have been mounted in their low-mass holders and their characterisation in liquid argon performed. The leakage current, the counting characteristics and the efficiency of the detectors have been measured. The testing of the detectors was carried out in the liquid argon test stand of the GERDA underground Detector Laboratory (GDL) at LNGS. The detectors are now stored underground under vacuum until their operation in GERDA.

Origins of phase contrast in the atomic force microscope in liquids

OpenAIRE

Melcher, John; Carrasco, Carolina; Xu, Xianfan; Carrascosa, Jose L; Gomez-Herrero, Julio; Jose de Pablo, Pedro; Raman, Arvind

2009-01-01

We study the physical origins of phase contrast in dynamic atomic force microscopy (dAFM) in liquids where low-stiffness microcantilever probes are often used for nanoscale imaging of soft biological samples with gentle forces. Under these conditions, we show that the phase contrast derives primarily from a unique energy flow channel that opens up in liquids due to the momentary excitation of higher eigenmodes. Contrary to the common assumption, phase-contrast images in liquids using soft mic...

Separation of thiophene from heptane with ionic liquids

International Nuclear Information System (INIS)

Domańska, Urszula; Lukoshko, Elena Vadimovna; Królikowski, Marek

2013-01-01

Highlights: ► The ternary (liquid + liquid) equilibria in 1-butyl-1-methylpyrrolidinium-based ILs was measured. ► High selectivity and distribution ratio for the extraction of thiophene was found. ► [BMPYR][TCM] was proposed as entrainer for the separation process. ► Extraction of sulphur-compounds from alkanes was proposed. -- Abstract: Ionic liquids (ILs) are well known novel green solvents, which can be used for removing sulfur compounds from gasoline and diesel oils. Ternary (liquid + liquid) equilibrium data are presented for mixtures of {ionic liquid (1) + thiophene (2) + heptane (3)} at T = 298.15 K and ambient pressure to analyze the performance of the ionic liquid (IL) in the extraction of thiophene from the alkanes. Three pyrrolidinium-based ionic liquids have been studied: 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, ([BMPYR][FAP]), 1-butyl-1-methylpyrrolidinium tetracyanoborate, [BMPYR][TCB] and 1-butyl-1-methylpyrrolidinium tricyanomethanide, [BMPYR][TCM]. The results are discussed in terms of the selectivity and distribution ratio of separation of related systems. The immiscibility in the binary liquid systems of (thiophene + heptane) with all used ILs was observed. The [TCM] − anion in comparison with [TCB] − and [FAP] − anions shows much higher selectivity and slightly lower distribution ratio for extraction of thiophene. The non-random two liquid NRTL model was used successfully to correlate the experimental tie-lines and to calculate the phase composition error in mole fraction in the ternary systems. The average root mean square deviation (RMSD) of the phase composition was 0.047. The densities of [BMPYR][TCM] in temperature range from (298.15 to 348.15) K were measured. The data presented here show that the [BMPYR][TCM] ionic liquid can be used as an alternative solvent for the separation of thiophene from the hydrocarbon stream using solvent liquid–liquid extraction at ambient conditions

Surface current equilibria from a geometric point of view

International Nuclear Information System (INIS)

Kaiser, R.; Salat, A.

1993-04-01

This paper addresses the inverse problem of the existence of surface current MHD equilibria in toroidal geometry with vanishing magnetic field inside. Inverse means that the plasma-vacuum interface rather than the external wall or conductors are given and the latter remain to be determined. This makes a reformulation of the problem possible in geometric terms: What toroidal surfaces with analytic parameterization allow a simple analytic covering by geodesics? If such a covering by geodesics (field lines) exists, their orthogonal trajectories (current lines) also form a simple covering and are described by a function satisfying a nonlinear partial differential equation of the Hamilton-Jacobi type whose coefficients are combinations of the metric elements of the surface. All known equilibria - equilibria with zero and infinite rotational transform and the symmetric ones in the case of finite rotational transform - turn out to be solutions of separable cases of that equation and allow a unified description if the toroidal surface is parametrized in the moving trihedral associated with a closed curve. Analogously to volume current equilibria, the only continuous symmetries compatible with separability are plane, helical and axial symmetry. In the nonseparable case numerical evidence is presented for cases with chaotic behaviour of geodesics, thus restricting possible equilibria for these surfaces. For weak deviation from axisymmetry KAM-type behaviour is observed, i.e. destruction of geodesic coverings with a low rational rotational transform and preservation of those with irrational rotational transform. A previous attempt to establish three-dimensional surface current equilibria on the basis of the KAM theorem is rejected as incomplete, and a complete proof of the existence of equilibria in the weakly nonaxisymmetric case, based on the twist theorem for mappings, is given. Finally, for a certain class of strong deviations from axisymmetry an analytic criterion is

Spatial heterogeneity in liquid–liquid phase transition

International Nuclear Information System (INIS)

Duan Yun-Rui; Li Tao; Wu Wei-Kang; Li Jie; Zhou Xu-Yan; Liu Si-Da; Li Hui

2017-01-01

Molecular dynamics simulations are performed to investigate the liquid–liquid phase transition (LLPT) and the spatial heterogeneity in Al–Pb monotectic alloys. The results reveal that homogeneous liquid Al–Pb alloy undergoes an LLPT, separating into Al-rich and Pb-rich domains, which is quite different from the isocompositional liquid water with a transition between low-density liquid (LDL) and high-density liquid (HDL). With spatial heterogeneity becoming large, LLPT takes place correspondingly. The relationship between the cooling rate, relaxation temperature and percentage of Al and the spatial heterogeneity is also reported. This study may throw light on the relationship between the structure heterogeneity and LLPT, which provides novel strategies to control the microstructures in the fabrication of the material with high performance. (paper)

Laser-induced microscopic phase-transition on an ionic liquid

International Nuclear Information System (INIS)

Iguchi, Natsuki; Datta, Alokmay; Yoshikawa, Kenichi; Ma Yue

2009-01-01

Nematic-isotropic transition is induced in a 5 μm 'droplet' within an oriented bulk of a mixture of a liquid crystalline material with a room-temperature ionic liquid, by a laser working at 532 nm with an output power of 200 mW and a beam diameter of 1 μm. No microscopic phase transition is observed either in absence of the ionic liquid or at the other wavelength of 1064 nm, available to the Nd-YAG laser. This indicates the essential role on a resonant transfer of energy to the ionic liquid from the laser radiation, which is subsequently transferred to the liquid crystal. Spectroscopy of the pure liquid crystal and ionic liquid samples confirms this concept. Spatio-temporal image of the droplet growth shows, however, that the phase transition remains confined within the microscopic domain for the first 50 s, and then spreads out rapidly. Since resonant, quantum transitions between molecular levels takes place in less than microseconds, the about seven orders of magnitude slowing down of energy transfer observed here suggests unique hierarchical dynamics including the coupling between the intra-molecular motions in the ionic liquid and the inter-molecular forces between ionic liquid and liquid crystal.

The liquid protein phase in crystallization: a case study—intact immunoglobulins

Science.gov (United States)

Kuznetsov, Yurii G.; Malkin, Alexander J.; McPherson, Alexander

2001-11-01

A common observation by protein chemists has been the appearance, for many proteins in aqueous solutions, of oil like droplets, or in more extreme cases the formation of a second oil like phase. These may accompany the formation of precipitate in "salting out" or "salting in' procedures, but more commonly appear in place of any precipitate. Such phase separations also occur, with even greater frequency, in the presence of polymeric precipitants such as polyethyleneglycol (PEG). In general the appearance of a second liquid phase has been taken as indicative of protein aggregation, though an aggregate state distinctly different from that characteristic of amorphous precipitate. While the latter is thought to be composed of linear and branched assemblies, polymers of a sort, the oil phase suggests a more compact, three-dimensional, but fluid state. An important property of an alternate, fluid phase is that it can mediate transitions between other states, for example, between protein molecules free in solution and protein molecules immobilized in amorphous precipitate or crystals. The "liquid protein" phase can be readily observed in many crystallization experiments either prior to the appearance of visible crystals, or directly participating in the crystal growth process. In some cases the relationship between the liquid phase and developing crystals is intimate. Crystals grow directly from the liquid phase, or appear only after the visible formation of the liquid phase. We describe here our experience with a class of macromolecules, immunoglobulins, and particularly IDEC-151, an IgG specific for CD4 on human lymphocytes. This protein has been crystallized from a Jeffamine-LiSO 4 mother liquor and, its crystallization illustrates many of the features associated with the liquid protein, or protein rich phase.

Cone-shaped membrane liquid phase micro extraction

International Nuclear Information System (INIS)

Hong, Heng See; Sanagi, M.M.; Ibrahim, W.A.W.; Naim, A.A.

2008-01-01

A novel sample pre-treatment technique termed cone-shaped membrane liquid phase micro extraction (CSM-LPME) was developed and combined with micro-liquid chromatography (micro-LC) for the determination of selected pesticides in water samples. Several important extraction parameters such as types of extraction solvent, agitation rate, pH value, total exposure time and effect of salt and humic acids were investigated and optimized. Enrichment factors of >50 folds were easily achieved within 20 min of extraction. The new developed method demonstrated an excellent performance in terms of speed, cost effectiveness, reproducibility, as well as exceptional low detection limits. Current work provides a great interest to further investigate on the applicability of the CSM-LPME technique in analytical chemistry and explores the possibility of replacing conventional extraction techniques such as soxhlet, solid phase extraction (SPE) and solid phase micro extraction (SPME). (author)

Glass phase expelling during liquid phase sintering of YSZ

International Nuclear Information System (INIS)

Souza, Milton Ferreira de; Souza, Dulcina Pinatti Ferreira de

1998-01-01

Expelling of the liquid phase during sintering of Zr O 2 -6.5 mol % Y 2 O 3 - 0.5 mol % Pr 2 O 3 ceramic was observed as a result of grain coarsening. ZrO 2 - 7.0 mol % Y 2 O 3 samples, without Pr 2 O 3 addition, do not show this effect under the same sintering conditions. The expelling process is caused by surface tension forces and attracting van der Waals forces between the grains, coupled with the existence of two glass phases on the grain boundaries. The amount of expelled glass phase increases with grain growth, but saturates above 16 μm average grain size. (author)

Local gas- and liquid-phase measurements for air-water two-phase flows in a rectangular channel

International Nuclear Information System (INIS)

Zhou, X.; Sun, X.; Williams, M.; Fu, Y.; Liu, Y.

2014-01-01

Local gas- and liquid-phase measurements of various gas-liquid two-phase flows, including bubbly, cap-bubbly, slug, and churn-turbulent flows, were performed in an acrylic vertical channel with a rectangular cross section of 30 mm x 10 mm and height of 3.0 m. All the measurements were carried out at three measurement elevations along the flow channel, with z/D h = 9, 72, and 136, respectively, to study the flow development. The gas-phase velocity, void fraction, and bubble number frequency were measured using a double-sensor conductivity probe. A high-speed imaging system was utilized to perform the flow regime visualization and to provide additional quantitative information of the two-phase flow structure. An image processing scheme was developed to obtain the gas-phase velocity, void fraction, Sauter mean diameter, bubble number density, and interfacial area concentration. The liquid-phase velocity and turbulence measurements were conducted using a particle image velocimetry-planar laser-induced fluorescence (PIV-PLIF) system, which enables whole-field and high-resolution data acquisition. An optical phase separation method, which uses fluorescent particles and optical filtration technique, is adopted to extract the velocity information of the liquid phase. An image pre-processing scheme is imposed on the raw PIV images acquired to remove noises due to the presence of bubble residuals and optically distorted particles in the images captured by the PIV-PLIF system. Due to the better light access and less bubble distortion in the narrow rectangular channel, the PIV-PLIF system were able to perform reasonably well in flows of even higher void fractions as compared to the situations with circular pipe test sections. The flow conditions being studied covered various flow regime transitions, void fractions, and liquid-phase flow Reynolds numbers. The obtained experimental data can also be used to validate two-phase CFD results. (author)

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

Directory of Open Access Journals (Sweden)

A. Zuend

2012-05-01

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

Nash Equilibria in Fisher Market

Science.gov (United States)

Adsul, Bharat; Babu, Ch. Sobhan; Garg, Jugal; Mehta, Ruta; Sohoni, Milind

Much work has been done on the computation of market equilibria. However due to strategic play by buyers, it is not clear whether these are actually observed in the market. Motivated by the observation that a buyer may derive a better payoff by feigning a different utility function and thereby manipulating the Fisher market equilibrium, we formulate the Fisher market game in which buyers strategize by posing different utility functions. We show that existence of a conflict-free allocation is a necessary condition for the Nash equilibria (NE) and also sufficient for the symmetric NE in this game. There are many NE with very different payoffs, and the Fisher equilibrium payoff is captured at a symmetric NE. We provide a complete polyhedral characterization of all the NE for the two-buyer market game. Surprisingly, all the NE of this game turn out to be symmetric and the corresponding payoffs constitute a piecewise linear concave curve. We also study the correlated equilibria of this game and show that third-party mediation does not help to achieve a better payoff than NE payoffs.

Liquid formation in the Y-Si-Al-O-N system

Energy Technology Data Exchange (ETDEWEB)

Redington Keely, W.; Redington, M.; Hampshire, S. [Limerick Univ. (Ireland). Materials Research Centre

2000-07-01

Some silicon nitride ceramics are sintered using a combination of Y{sub 2}O{sub 3} and Al{sub 2}O{sub 3} additives to form a Y-Si-Al-O-N liquid that promotes densification and allows the {alpha}{yields}{beta} transformation to take place by solution/precipitation through the liquid which cools as an intergranular phase. The type and amount of additive determines the nature and quantity of the resulting grain boundary phase as indicated and this can affect high temperature strength, creep resistance and oxidation resistance. Thus it is important to understand the phase equilibria in these complex systems and then apply this knowledge to processing, the development of beneficial microstructures and the relationship between these and properties. One difficulty is that, for any particular composition, the quantity and composition of the liquid at the sintering temperature is not known accurately and a full compositional representation has not been achieved. This paper attempts to represent the liquid region at various temperatures in the Jaenecke prism of the Y-Si-Al-O-N system. Published information on liquid compositions, standardised into eq.% format, was combined with experimental data interpolated from the less well defined regions to build a composite picture of liquid in this system. Representation was achieved using a customised graphical environment, AutoCAD trademark. AutoLISP trademark routines combined with this drafting package allow data from multiple sources to be integrated. This results in a series of overlays which indicate the liquid region from its initial formation at 1335 C and its subsequent development at different ''milestone'' temperatures. At 1700 C the orthographic projections of the liquid region are combined to give a volume bounded by nurbs surfaces, using ALIAS trademark software, to enable visualisation of the proposed liquid region. (orig.)

Structural crossover in a supercooled metallic liquid and the link to a liquid-to-liquid phase transition

Energy Technology Data Exchange (ETDEWEB)

Lan, S.; Ma, J. L.; Fan, J. [Department of Physics and Material Science, City University of Hong Kong 83 Tat Chee Ave., Kowloon (Hong Kong); Blodgett, M.; Kelton, K. F. [Department of Physics and Institute of Materials Science and Engineering, Washington University One Brookings Drive, St. Louis, Missouri 63130-4899 (United States); Wang, X.-L., E-mail: xlwang@cityu.edu.hk [Department of Physics and Material Science, City University of Hong Kong 83 Tat Chee Ave., Kowloon (Hong Kong); City University of Hong Kong Shenzhen Research Institute, Shenzhen 518057 (China)

2016-05-23

Time-resolved synchrotron measurements were carried out to capture the structure evolution of an electrostatically levitated metallic-glass-forming liquid during free cooling. The experimental data shows a crossover in the liquid structure at ∼1000 K, about 115 K below the melting temperature and 150 K above the crystallization temperature. The structure change is characterized by a dramatic growth in the extended-range order below the crossover temperature. Molecular dynamics simulations have identified that the growth of the extended-range order was due to an increased correlation between solute atoms. These results provide structural evidence for a liquid-to-liquid-phase-transition in the supercooled metallic liquid.

Isotope effects in ion-exchange equilibria in aqueous and mixed solvent systems

International Nuclear Information System (INIS)

Gupta, A.R.

1979-01-01

Isotope effects in ion-exchange equilibria in aqueous and mixed solvents are analyzed in terms of the general features of ion-exchange equilibria and of isotope effects in chemical equilibria. The special role of solvent fractionation effects in ion-exchange equilibria in mixed solvents is pointed out. The various situations arising in isotope fractionation in ion exchange in mixed solvents due to solvent fractionation effects are theoretically discussed. The experimental data on lithium isotope effects in ion-exchange equilibria in mixed solvents are shown to conform to the above situations. The limitations of ion-exchange equilibria in mixed solvents for isotope fractionation are pointed out. 3 tables

(Vapour + liquid) equilibria of ternary systems with ionic liquids using headspace gas chromatography

International Nuclear Information System (INIS)

Mokhtarani, Babak; Gmehling, Juergen

2010-01-01

(Vapour + liquid) equilibrium (VLE) data for the ternary systems (hexane + benzene), (hexane + cyclohexane), (benzene + cyclohexane), and (ethanol + water) with an ionic liquid as entrainer for extractive distillation were measured by headspace gas chromatography. As ionic liquids, 1-hexyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [HMIM][BTI], 1-octyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [OMIM][BTI], 1-octyl-3-methyl-imidazolium trifluoro-methanesulfonate [OMIM][OTF], and 1-butyl-3-methyl-imidazolium trifluoro-methanesulfonate [BMIM][OTF] were used. The experimental data show that the ionic liquids investigated have a great influence on the separation factors of the systems (hexane + benzene), (hexane + cyclohexane), and (benzene + cyclohexane). The experimental data were compared with the predicted results using mod. UNIFAC (Do). The predicted results are in good agreement with the experimental data.

(Vapour + liquid) equilibria of ternary systems with ionic liquids using headspace gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Mokhtarani, Babak [Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran (Iran, Islamic Republic of); Gmehling, Juergen, E-mail: gmehling@tech.chem.uni-oldenburg.d [Carl von Ossietzky Universitaet Oldenburg, Technische Chemie, D-26111 Oldenburg (Germany)

2010-08-15

(Vapour + liquid) equilibrium (VLE) data for the ternary systems (hexane + benzene), (hexane + cyclohexane), (benzene + cyclohexane), and (ethanol + water) with an ionic liquid as entrainer for extractive distillation were measured by headspace gas chromatography. As ionic liquids, 1-hexyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [HMIM][BTI], 1-octyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [OMIM][BTI], 1-octyl-3-methyl-imidazolium trifluoro-methanesulfonate [OMIM][OTF], and 1-butyl-3-methyl-imidazolium trifluoro-methanesulfonate [BMIM][OTF] were used. The experimental data show that the ionic liquids investigated have a great influence on the separation factors of the systems (hexane + benzene), (hexane + cyclohexane), and (benzene + cyclohexane). The experimental data were compared with the predicted results using mod. UNIFAC (Do). The predicted results are in good agreement with the experimental data.

Multiphase, multicomponent phase behavior prediction

Science.gov (United States)

Dadmohammadi, Younas

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

Experimental study on liquid velocity in upward and downward two-phase flows

International Nuclear Information System (INIS)

Sun, X.; Paranjape, S.; Kim, S.; Ozar, B.; Ishii, M.

2003-01-01

Local characteristics of the liquid phase in upward and downward air-water two-phase flows were experimentally investigated in a 50.8-mm inner-diameter round pipe. An integral Laser Doppler Anemometry (LDA) system was used to measure the axial liquid velocity and its fluctuations. No effect of the flow direction on the liquid velocity radial profile was observed in single-phase liquid benchmark experiments. Local multi-sensor conductivity probes were used to measure the radial profiles of the bubble velocity and the void fraction. The measurement results in the upward and downward two-phase flows are compared and discussed. The results in the downward flow demonstrated that the presence of the bubbles tended to flatten the liquid velocity radial profile, and the maximum liquid velocity could occur off the pipe centerline, in particular at relatively low flow rates. However, the maximum liquid velocity always occurred at the pipe center in the upward flow. Also, noticeable turbulence enhancement due to the bubbles in the two-phase flows was observed in the current experimental flow conditions. Furthermore, the distribution parameter and the void weighted area-averaged drift velocity were obtained based on the definitions

On Nash-Equilibria of Approximation-Stable Games

Science.gov (United States)

Awasthi, Pranjal; Balcan, Maria-Florina; Blum, Avrim; Sheffet, Or; Vempala, Santosh

One reason for wanting to compute an (approximate) Nash equilibrium of a game is to predict how players will play. However, if the game has multiple equilibria that are far apart, or ɛ-equilibria that are far in variation distance from the true Nash equilibrium strategies, then this prediction may not be possible even in principle. Motivated by this consideration, in this paper we define the notion of games that are approximation stable, meaning that all ɛ-approximate equilibria are contained inside a small ball of radius Δ around a true equilibrium, and investigate a number of their properties. Many natural small games such as matching pennies and rock-paper-scissors are indeed approximation stable. We show furthermore there exist 2-player n-by-n approximation-stable games in which the Nash equilibrium and all approximate equilibria have support Ω(log n). On the other hand, we show all (ɛ,Δ) approximation-stable games must have an ɛ-equilibrium of support O(Δ^{2-o(1)}/ɛ2{log n}), yielding an immediate n^{O(Δ^{2-o(1)}/ɛ^2log n)}-time algorithm, improving over the bound of [11] for games satisfying this condition. We in addition give a polynomial-time algorithm for the case that Δ and ɛ are sufficiently close together. We also consider an inverse property, namely that all non-approximate equilibria are far from some true equilibrium, and give an efficient algorithm for games satisfying that condition.

Symmetry protected topological Luttinger liquids and the phase transition between them

Energy Technology Data Exchange (ETDEWEB)

None

2018-01-01

We show that a doped spin-1/2 ladder with antiferromagnetic intra-chain and ferromagnetic inter-chain coupling is a symmetry protected topologically non-trivial Luttinger liquid. Turning on a large easy-plane spin anisotropy drives the system to a topologically-trivial Luttinger liquid. Both phases have full spin gaps and exhibit power-law superconducting pair correlation. The Cooper pair symmetry is singlet $d_{xy}$ in the non-trivial phase and triplet $S_z=0$ in the trivial phase. The topologically non-trivial Luttinger liquid exhibits gapless spin excitations in the presence of a boundary, and it has no non-interacting or mean-field theory analog even when the fluctuating phase in the charge sector is pinned. As a function of the strength of spin anisotropy there is a topological phase transition upon which the spin gap closes. We speculate these Luttinger liquids are relevant to the superconductivity in metalized integer spin ladders or chains.

Visualization of velocity field and phase distribution in gas-liquid two-phase flow by NMR imaging

International Nuclear Information System (INIS)

Matsui, G.; Monji, H.; Obata, J.

2004-01-01

NMR imaging has been applied in the field of fluid mechanics, mainly single phase flow, to visualize the instantaneous flow velocity field. In the present study, NMR imaging was used to visualize simultaneously both the instantaneous phase structure and velocity field of gas-liquid two-phase flow. Two methods of NMR imaging were applied. One is useful to visualize both the one component of liquid velocity and the phase distribution. This method was applied to horizontal two-phase flow and a bubble rising in stagnant oil. It was successful in obtaining some pictures of velocity field and phase distribution on the cross section of the pipe. The other is used to visualize a two-dimensional velocity field. This method was applied to a bubble rising in a stagnant water. The velocity field was visualized after and before the passage of a bubble at the measuring cross section. Furthermore, the distribution of liquid velocity was obtained. (author)

Extraction Equilibrium of Acrylic Acid by Aqueous Two-Phase Systems Using Hydrophilic Ionic Liquids

International Nuclear Information System (INIS)

Lee, Yong Hwa; Lee, Woo Youn; Kim, Ki-Sub; Hong, Yeon Ki

2014-01-01

As an effective method for extraction of acrylic acid, aqueous two-phase systems based on morpholinium ionic liquids were used in this study. Effects of the alkyl chain length of cation in morpholinium ionic liquids on phase diagram and extraction efficiencies were investigated. Experimental results show that aqueous two phase systems can be formed by adding appropriate amount of morpholinium ionic liquids to aqueous K 2 HPO 4 solutions. It can be found that the ability of morpholinium ionic liquids for phase separation followed the order [HMMor][Br]>[OMMor][Br]>[BMMor][Br]>[EMMor][Br]. There was little difference between binodal curves of imidazolium ionic liquids and those of morpholinium ionic liquids. 50-90% of the extraction efficiency was observed for acrylic acid by aqueous two phase extraction of acrylic acid with morpholinium ionic liquids. It can be concluded that morpholinium ionic liquids/K 2 HPO 4 were effective for aqueous two phases extraction of acrylic acid comparing to imidazolium ionic liquids/K 2 HPO 4 systems because of their lower cost

The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2

Science.gov (United States)

Sharp, Z.D.; Essene, E.J.; Anovitz, Lawrence M.; Metz, G.W.; Westrum, E.F.; Hemingway, B.S.; Valley, J.W.

1986-01-01

The heat capacity of a natural monticellite (Ca1.00Mg.09Fe.91Mn.01Si0.99O3.99) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields Cp0(298) and S2980 of 123.64 ?? 0.18 and 109.44 ?? 0.16 J ?? mol-1 K-1 respectively. Extrapolation of this entropy value to end-member monticellite results in an S0298 = 108.1 ?? 0.2 J ?? mol-1 K-1. High-temperature heat-capacity data were measured between 340-1000 K with a differential scanning calorimeter. The high-temperature data were combined with the 290-350 K adiabatic values, extrapolated to 1700 K, and integrated to yield the following entropy equation for end-member monticellite (298-1700 K): ST0(J ?? mol-1 K-1) = S2980 + 164.79 In T + 15.337 ?? 10-3 T + 22.791 ?? 105 T-2 - 968.94. Phase equilibria in the CaO-MgO-SiO2 system were calculated from 973 to 1673 K and 0 to 12 kbar with these new data combined with existing data for akermanite (Ak), diopside (Di), forsterite (Fo), merwinite (Me) and wollastonite (Wo). The location of the calculated reactions involving the phases Mo and Fo is affected by their mutual solid solution. A best fit of the thermodynamically generated curves to all experiments is made when the S0298 of Me is 250.2 J ?? mol-1 K-1 less than the measured value of 253.2 J ?? mol-1 K-1. A best fit to the reversals for the solid-solid and decarbonation reactions in the CaO-MgO-SiO2-CO2 system was obtained with the ??G0298 (kJ ?? mole-1) for the phases Ak(-3667), Di(-3025), Fo(-2051), Me(-4317) and Mo(-2133). The two invariant points - Wo and -Fo for the solid-solid reactions are located at 1008 ?? 5 K and 6.3 ?? 0.1 kbar, and 1361 ?? 10 K and 10.2 ?? 0.2 kbar respectively. The location of the thermodynamically generated curves is in excellent agreement with most experimental data on decarbonation equilibria involving these phases. ?? 1986.

Phase equilibria in the system Nd(PO3)3 - KPO3

International Nuclear Information System (INIS)

Znamierowska, T.; Mizer, D.

2002-01-01

The system Nd(PO 3 ) 3 - KPO 3 has been investigated by differential thermal analysis (during heating), thermogravimetric analysis, mass spectrometry, Raman spectroscopy and X-ray powder diffraction and its phase diagram was proposed. It was discovered that initial metaphosphates react at a 1:1 molar ratio forming intermediate compound KNd(PO 3 ) 4 . It was found that it melts incongruently at 854 o C giving Nd(po)3) 3 and a liquid rich in KPO 3 . Phosphate KNd(PO 3 ) 4 is stable down to room temperature and does not show any polymorphic transitions. (author)

Lyotropic Liquid Crystal Phases from Anisotropic Nanomaterials

Directory of Open Access Journals (Sweden)

Ingo Dierking

2017-10-01

Full Text Available Liquid crystals are an integral part of a mature display technology, also establishing themselves in other applications, such as spatial light modulators, telecommunication technology, photonics, or sensors, just to name a few of the non-display applications. In recent years, there has been an increasing trend to add various nanomaterials to liquid crystals, which is motivated by several aspects of materials development. (i addition of nanomaterials can change and thus tune the properties of the liquid crystal; (ii novel functionalities can be added to the liquid crystal; and (iii the self-organization of the liquid crystalline state can be exploited to template ordered structures or to transfer order onto dispersed nanomaterials. Much of the research effort has been concentrated on thermotropic systems, which change order as a function of temperature. Here we review the other side of the medal, the formation and properties of ordered, anisotropic fluid phases, liquid crystals, by addition of shape-anisotropic nanomaterials to isotropic liquids. Several classes of materials will be discussed, inorganic and mineral liquid crystals, viruses, nanotubes and nanorods, as well as graphene oxide.

Void fraction fluctuations in two-phase gas-liquid flow

International Nuclear Information System (INIS)

Ulbrich, R.

1987-01-01

Designs of the apparatus in which two-phase gas-liquid flow occurs are usually based on the mean value of parameters such as pressure drop and void fraction. The flow of two-phase mixtures generally presents a very complicated flow structure, both in terms of the unsteady formation on the interfacial area and in terms of the fluctuations of the velocity, pressure and other variables within the flow. When the gas void fraction is near 0 or 1 / bubble or dispersed flow regimes / then oscillations of void fraction are very small. The intermittent flow such as plug and slug/ froth is characterized by alternately flow portions of liquid and gas. It influences the change of void fractions in time. The results of experimental research of gas void fraction fluctuations in two-phase adiabatic gas-liquid flow in a vertical pipe are presented

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...... where the spin degrees of freedom are slaved by the translational degrees of freedom and develop a first-order singularity in the order-disorder transition that accompanies the lattice-melting transition. The internal degeneracy of the spin states in model III implies that the spin order...

Ionic liquids as entrainers for water + ethanol, water + 2-propanol, and water + THF systems: A quantum chemical approach

Energy Technology Data Exchange (ETDEWEB)

Verma, Vijay Kumar [Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam (India); Banerjee, Tamal, E-mail: tamalb@iitg.ernet.i [Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam (India)

2010-07-15

Ionic liquids (ILs) are used as entrainers in azeotropic systems such as water + ethanol, water + 2-propanol, and water + tetrahydrofuran (THF). Ionic liquids consisting of a cation and an anion has limitless combinations, thereby making experimentation expensive and time taking. For the prediction of the liquid phase nonidealities resulting from molecular interactions, 'COnductor-like Screening MOdel for Real Solvents' (COSMO-RS) approach is used in this work for the screening of potential ionic liquids. Initially benchmarking has been done on 12 reported isobaric IL based ternary systems with an absolute average deviation of 4.63% in vapor phase mole fraction and 1.07% in temperature. After successful benchmarking, ternary vapor + liquid equilibria for the azeotropic mixture of (a) ethanol + water, (b) 2-propanol + water, and (c) THF + water with combinations involving 10 cations (imidazolium, pyridinium, quinolium) and 24 anions were predicted. The VLE prediction, which gave the relative volatility, showed that the imidazolium based ionic liquid were the best entrainer for the separation of the three systems at their azeotropic point. ILs with [MMIM] cation in combination with acetate [OAc], chloride [Cl], and bromide [Br] anion gave the highest relative volatility.

Liquid-gas phase transition and isospin fractionation in intermediate energy heavy ion collisions

International Nuclear Information System (INIS)

Xing Yongzhong; Liu Jianye; Guo Wenjun

2004-01-01

The liquid-gas phase transition in the heavy ion collisions and nuclear matter has been an important topic and got achievements, such as, based on the studies by H.Q. Song et al the critical temperature of liquid-gas phase transition enhances with increasing the mass of system and reduces as the increase of the neutron proton ratio of system. As authors know that both the liquid-gas phase transition and the isospin fractionation occur in the spinodal instability region at the nuclear density below the normal nuclear density. In particular, these two dynamical processes lead to the separation of nuclear matter into the liquid phase and gas phase. In this case to compare their dynamical behaviors is interested. The authors investigate the dependence of isospin fractionation degree on the mass and neutron proton ratio of system by using the isospin dependent quantum molecular dynamics model. The authors found that the degree of isospin fractionation (N/Z) n /(N/Z) imf decreases with increasing the mass of the system. This is just similar to the enhance of the critical temperature of liquid-gas phase transition T c as the increase of system mass. Because the enhance of T c is not favorable for the liquid-gas transition taking place, which reduces the isospin fractionation process and leads to decrease of (N/Z) n /(N/Z) imf . However the degree of isospin fractionation enhances with increasing the neutron proton ratio of the system. It is just corresponding to the reduce of T c of the liquid-gas phase transition as the increase of the isospin fractionation of the system. Because the reduce of T c enhances the liquid-gas phase transition process and also prompts the isospin fractionation process leading the increase of the isospin fractionation degree. To sum up, there are very similar dynamical behaviors for the degree of isospin fractionation and the critical temperature of the liquid-gas phase transition. So dynamical properties of the liquid-gas phase transition can

The shape of the melting curve and phase transitions in the liquid state

International Nuclear Information System (INIS)

Yahel, Eyal

2014-01-01

The phase diagram of elemental liquids has been found to be surprisingly rich, including variations in the melting curve and transitions in the liquid phase. The effect of these transitions on the shape of the melting curve is reviewed and analyzed. First-order phase transitions intersecting the melting curve imply piecewise continuous melting curves, with solid-solid transitions generating upward kinks or minima and liquid-liquid transitions generating downward kinks or maxima

Unconventional phase transitions in liquid crystals

Science.gov (United States)

Kats, E. I.

2017-12-01

According to classical textbooks on thermodynamics or statistical physics, there are only two types of phase transitions: continuous, or second-order, in which the latent heat L is zero, and first-order, in which L ≠ 0. Present-day textbooks and monographs also mention another, stand-alone type—the Berezinskii-Kosterlitz-Thouless transition, which exists only in two dimensions and shares some features with first- and second-order phase transitions. We discuss examples of non-conventional thermodynamic behavior (i.e., which is inconsistent with the theoretical phase transition paradigm now universally accepted). For phase transitions in smectic liquid crystals, mechanisms for nonconventional behavior are proposed and the predictions they imply are examined.

On Equilibria of the Two-fluid Model in Magnetohydrodynamics

International Nuclear Information System (INIS)

Frantzeskakis, Dimitri J.; Stratis, Ioannis G.; Yannacopoulos, Athanasios N.

2004-01-01

We show how the equilibria of the two-fluid model in magnetohydrodynamics can be described by the double curl equation and through the study of this equation we study some properties of these equilibria

Liquid-phase and solid-phase radioimmunoassay with herpes simplex virus type 1 nucleocapsids

International Nuclear Information System (INIS)

Bystricka, M.; Rajcani, J.; Libikova, H.; Sabo, A.; Foeldes, O.; Sadlon, J.

1985-01-01

Liquid-phase radioimmunoassay and solid-phase radioimmunoassay are described using 125 I-labelled or immobilized nucleocapsids (NC) of herpes simplex virus (HSV) type1. These techniques appeared sensitive and specific for quantitation of HSV-NC antigens and corresponding antibodies. (author)

Observation of diffusion phenomena of liquid phase with multiple components

International Nuclear Information System (INIS)

Eguchi, Wataru

1979-01-01

The diffusion phenomena of liquid phase with multiple components was directly observed, and the factors contributing to complex material transfer were investigated, comparing to the former experimental results. The most excellent method of observing the diffusion behavior of liquid phase used heretofore is to trace the time history of concentration distribution for each component in unsteady diffusion process. The method of directly observing the concentration distribution is usually classified into the analysis of diffused samples, the checking of radioactive isotope tracers, and the measurement of light refraction and transmission. The most suitable method among these is to trace this time history by utilizing the spectrophotometer of position scanning type. An improved spectrophotometer was manufactured for trial. The outline of the measuring system and the detail of the optical system of this new type spectrophotometer are explained. The resolving power for position measurement is described with the numerical calculation. As for the observation examples of the diffusion phenomena of liquid phase with multiple components, the diffusion of multiple electrolytes in aqueous solution, the observation of the material transfer phenomena accompanied by heterogeneous and single phase chemical reaction, and the observation of concentration distribution in the liquid diaphragm in a reaction absorption system are described. For each experimental item, the test apparatus, the sample material, the test process, the test results and the evaluation are explained in detail, and the diffusion phenomena of liquid phase with multiple components were pretty well elucidated. (Nakai, Y.)

A unifying approach to existence of Nash equilibria

NARCIS (Netherlands)

Balder, E.J.

1997-01-01

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

Phase-field model of vapor-liquid-solid nanowire growth

Science.gov (United States)

Wang, Nan; Upmanyu, Moneesh; Karma, Alain

2018-03-01

We present a multiphase-field model to describe quantitatively nanowire growth by the vapor-liquid-solid (VLS) process. The free-energy functional of this model depends on three nonconserved order parameters that distinguish the vapor, liquid, and solid phases and describe the energetic properties of various interfaces, including arbitrary forms of anisotropic γ plots for the solid-vapor and solid-liquid interfaces. The evolution equations for those order parameters describe basic kinetic processes including the rapid (quasi-instantaneous) equilibration of the liquid catalyst to a droplet shape with constant mean curvature, the slow incorporation of growth atoms at the droplet surface, and crystallization within the droplet. The standard constraint that the sum of the phase fields equals unity and the conservation of the number of catalyst atoms, which relates the catalyst volume to the concentration of growth atoms inside the droplet, are handled via separate Lagrange multipliers. An analysis of the model is presented that rigorously maps the phase-field equations to a desired set of sharp-interface equations for the evolution of the phase boundaries under the constraint of force balance at three-phase junctions (triple points) given by the Young-Herring relation that includes torque term related to the anisotropy of the solid-liquid and solid-vapor interface excess free energies. Numerical examples of growth in two dimensions are presented for the simplest case of vanishing crystalline anisotropy and the more realistic case of a solid-liquid γ plot with cusped minima corresponding to two sets of (10 ) and (11 ) facets. The simulations reproduce many of the salient features of nanowire growth observed experimentally, including growth normal to the substrate with tapering of the side walls, transitions between different growth orientations, and crawling growth along the substrate. They also reproduce different observed relationships between the nanowire growth

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Extended UNIQUAC Model for Correlation and Prediction of Vapor-Liquid-Liquid-Solid Equilibria in Aqueous Salt Systems Containing Non-Electrolytes. Part B. Alcohol (Ethanol, Propanols, Butanols) - Water-salt systems

DEFF Research Database (Denmark)

Thomsen, Kaj; Iliuta, Maria Cornelia; Rasmussen, Peter

2004-01-01

The Extended UNIQUAC model for electrolyte solutions is an excess Gibbs energy function consisting of a Debye-Huckel term and a term corresponding to the UNIQUAC equation. For vapor-liquid equilibrium calculations, the fugacities of gas-phase components are calculated with the Soave-Redlich-Kwong......The Extended UNIQUAC model for electrolyte solutions is an excess Gibbs energy function consisting of a Debye-Huckel term and a term corresponding to the UNIQUAC equation. For vapor-liquid equilibrium calculations, the fugacities of gas-phase components are calculated with the Soave...... solid-liquid-vapor equilibrium and thermal property data for strongly non-ideal systems. In this work, the model is extended to aqueous salt systems containing higher alcohols. The calculations are based on an extensive database consisting of salt solubility data, vapor liquid equilibrium data...

Two-fluid equilibria with flow

International Nuclear Information System (INIS)

Steinhauer, L.

1999-01-01

The formalism is developed for flowing two-fluid equilibria. The equilibrium system is governed by a pair of second order partial differential equations for the magnetic stream function and the ion stream function plus a Bernoulli-like equation for the density. There are six arbitrary surface function. There are separate characteristic surfaces for each species, which are the guiding-center surfaces. This system is a generalization of the familiar Grad-Shafranov system for a single-fluid equilibrium without flow, which has only one equation and two arbitrary surface functions. In the case of minimum energy equilibria, the six surface functions take on particular forms. (author)

The Pierce diode with an external circuit: II, Non-uniform equilibria

International Nuclear Information System (INIS)

Lawson, W.S.

1987-01-01

The non-uniform (non-linear) equilibria of the classical (short circuit) Pierce diode and the extended (series RLC external circuit) Pierce diode are described theoretically, and explored via computer simulation. It is found that most equilibria are correctly predicted by theory, but that the continuous set of equilibria of the classical Pierce diode at α = 2π are not observed. The stability characteristics of the non-uniform equilibria are also worked out, and are consistent with the simulations. 8 refs., 22 figs., 3 tabs

Ginzburg-Landau equation and vortex liquid phase of Fermi liquid superconductors

International Nuclear Information System (INIS)

Ng, T-K; Tse, W-T

2007-01-01

In this paper we study the Ginzburg-Landau (GL) equation for Fermi liquid superconductors with strong Landau interactions F 0s and F 1s . We show that Landau interactions renormalize two parameters entering the GL equation, leading to the renormalization of the compressibility and superfluid density. The renormalization of the superfluid density in turn leads to an unconventional (2D) Berezinskii-Kosterlitz-Thouless (BKT) transition and vortex liquid phase. Application of the GL equation to describe underdoped high-T c cuprates is discussed

Profile of MIBI liquid phase radiopharmaceutical for myocardial imaging

International Nuclear Information System (INIS)

I Daruwati; ME Sriyani; NK Oekar; N Zainuddin; KA Hanafiah

2016-01-01

The 99m Tc-MIBI radiopharmaceutical has been used in nuclear medicine in Indonesia for myocardial imaging. BATAN researchers have mastered the technology to manufacture MIBI as a lyophilized kit. A reformulation of MIBI radiopharmaceutical has been conducted to improve the stability of the kit especially in the liquid-phase kit. Basically, radiopharmaceuticals in liquid form are not different from the dry kit. However in the manufacturing of liquid-phase kit, lyophilization process was not done. To improve the stability of liquid kit, a reformulation of the components was conducted by using two separate vials (Formulation 2) and the characteristics were compared with the one-vial formulation (Formulation 1). The MIBI Formulation 2 consists of two vials, vial A containing 0.06 mg of SnCl 2 2H 2 O and 2.6 mg Sodium Citrate 2H 2 O and vial B containing 0.5 mg of [Cu(MIBI) 4 ]BF 4 , 1 mg of cysteine hydrochloride, and 20 mg of mannitol. The purposes of this study were to determine the stability of two different formulations of MIBI as a liquid-phase kit, to compare their stability in different storage condition such as in refrigerator and freezer, and to compare the ratio of activities attained between target and nontarget organs after injection to animal model. As a diagnostic agent, MIBI was reconstituted with Technetium-99m as radionuclide tracer to 99m Tc-MIBI labeled compound. The radiochemical purity of 99m Tc-MIBI was determined by chromatography method using alumina thin-layer chromatography paper as the stationary phase and ethanol 95% as the mobile phase. The results showed MIBI Formulation 2 has a higher stability than Formulation 1. Formulation 2 also maintained a 96.68% radiochemical purity under 52-day storage and attained a target-to-nontarget activity ratio of 8.22. (author)

Void fraction prediction in two-phase flows independent of the liquid phase density changes

International Nuclear Information System (INIS)

Nazemi, E.; Feghhi, S.A.H.; Roshani, G.H.

2014-01-01

Gamma-ray densitometry is a frequently used non-invasive method to determine void fraction in two-phase gas liquid pipe flows. Performance of flow meters using gamma-ray attenuation depends strongly on the fluid properties. Variations of the fluid properties such as density in situations where temperature and pressure fluctuate would cause significant errors in determination of the void fraction in two-phase flows. A conventional solution overcoming such an obstacle is periodical recalibration which is a difficult task. This paper presents a method based on dual modality densitometry using Artificial Neural Network (ANN), which offers the advantage of measuring the void fraction independent of the liquid phase changes. An experimental setup was implemented to generate the required input data for training the network. ANNs were trained on the registered counts of the transmission and scattering detectors in different liquid phase densities and void fractions. Void fractions were predicted by ANNs with mean relative error of less than 0.45% in density variations range of 0.735 up to 0.98 gcm −3 . Applying this method would improve the performance of two-phase flow meters and eliminates the necessity of periodical recalibration. - Highlights: • Void fraction was predicted independent of density changes. • Recorded counts of detectors/void fraction were used as inputs/output of ANN. • ANN eliminated necessity of recalibration in changeable density of two-phase flows

Gas-liquid phase coexistence in a tetrahedral patchy particle model

International Nuclear Information System (INIS)

Romano, Flavio; Tartaglia, Piero; Sciortino, Francesco

2007-01-01

We evaluate the location of the gas-liquid coexistence line and of the associated critical point for the primitive model for water (PMW), introduced by Kolafa and Nezbeda (1987 Mol. Phys. 61 161). Besides being a simple model for a molecular network forming liquid, the PMW is representative of patchy proteins and novel colloidal particles interacting with localized directional short-range attractions. We show that the gas-liquid phase separation is metastable, i.e. it takes place in the region of the phase diagram where the crystal phase is thermodynamically favoured, as in the case of particles interacting via short-range attractive spherical potentials. We do not observe crystallization close to the critical point. The region of gas-liquid instability of this patchy model is significantly reduced as compared to that from equivalent models of spherically interacting particles, confirming the possibility of observing kinetic arrest in a homogeneous sample driven by bonding as opposed to packing. (fast track communication)

Ideal MHD stability of high poloidal beta equilibria in TFTR

International Nuclear Information System (INIS)

Sabbagh, S.A.; Mauel, M.E.; Navratil, G.A.; Bell, M.G.; Budny, R.V.; Chance, M.S.; Fredrickson, E.D.; Jardin, S.C.; Manickam, J.; McCune, D.C.; McGuire, K.M.; Wieland, R.M.; Zarnstorff, M.C.; Phillips, M.W.; Hughes, M.H.; Kesner, J.

1991-01-01

Recent experiments in TFTR have expanded the operating space of the device to include plasmas with values of var-epsilon β p dia ≡ 2μ 0 var-epsilon perpendicular >/ p >> 2 as large as 1.6, and Troyon normalized diamagnetic beta β N dia ≡ β t perpendicular aB t /10 -8 I p as large as 4.7. At values of var-epsilon β p dia ≥ 1.3, a separatrix was observed to enter the vacuum vessel, producing a naturally diverted discharge. Plasmas with large values of var-epsilon β p dia were created with both the plasma current, I p , held constant and with I p decreased, or ramped down, before the start of neutral beam injection. A convenient characterization of the change in I p using experimental parameters can be defined by the ratio of I p before the ramp down, to I p during the neutral beam heating phase, F I p . The ideal MHD stability of these equilibria is investigated to determine their location in stability space, and to study the role of plasma current and pressure profile modification in the creation of these high var-epsilon β p and β N plasmas. The evolution of these plasmas is modelled from experimental data using the TRANSP code. Two-dimensional equilibria are computed from the TRANSP results and used as input to both high and low-n stability codes including PEST. The high var-epsilon β p equilibria, which generally have an oblate cross-sectional shape, are in the first stability region to high-n ballooning modes. At constant I p , these equilibria generally have maximum pressure gradients near the magnetic axis and are stable to n=1 modes without a stabilizing conducting wall. The effect of the current profile shape on the stability of low-n kink/ballooning modes and the requirements for these plasmas to access the second stability region are examined. 6 refs

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...... requires binary experimental data for determining the interaction parameters of the Wilson equation; thus a large number of experiments are needed. The multicomponent equilibria model which is investigated for single component systems in this work is based on pure component data only. This means...... that the requirement for experimental data is reduced significantly.The two adsorption models are compared, using experimental pure gas adsorption data found in literature. The results obtained by the models are in close agreement for pure component equilibria and they give a good description of the experimental data...

Origins of phase contrast in the atomic force microscope in liquids.

Science.gov (United States)

Melcher, John; Carrasco, Carolina; Xu, Xin; Carrascosa, José L; Gómez-Herrero, Julio; José de Pablo, Pedro; Raman, Arvind

2009-08-18

We study the physical origins of phase contrast in dynamic atomic force microscopy (dAFM) in liquids where low-stiffness microcantilever probes are often used for nanoscale imaging of soft biological samples with gentle forces. Under these conditions, we show that the phase contrast derives primarily from a unique energy flow channel that opens up in liquids due to the momentary excitation of higher eigenmodes. Contrary to the common assumption, phase-contrast images in liquids using soft microcantilevers are often maps of short-range conservative interactions, such as local elastic response, rather than tip-sample dissipation. The theory is used to demonstrate variations in local elasticity of purple membrane and bacteriophage 29 virions in buffer solutions using the phase-contrast images.

Phase Equilibria in the Bi-In-Sn-Zn System. Thermal Analysis vs. Calculations

Directory of Open Access Journals (Sweden)

Dębski A.

2017-12-01

Full Text Available With the use of the differential thermal analysis (DTA, studies of the phase transitions were conducted for 90 of alloys from the quaternary Bi-In-Sn-Zn system and for the constant ratio of Bi:In and Bi:Sn. The studies were conducted for the alloys prepared from the purity metals (Bi, In, Sn, Zn = 99.999 mas. % by way of melting in a graphite crucible in a glove-box filled with Ar, in which the impurities level was less than 0.1 ppm. After melting and thorough mixing, the liquid alloys were poured out into a graphite test mold. The phase transition temperature data obtained from the DTA investigations were next confronted with those determined from the calculations based on the binary and ternary optimized thermodynamic parameters available in the literature. It was found that the experimental and the calculated phase transition temperatures were in good agreement.

High-pressure phase diagrams of liquid CO2 and N2

Science.gov (United States)

Boates, Brian; Bonev, Stanimir

2011-06-01

The phase diagrams of liquid CO2 and N2 have been investigated using first-principles theory. Both materials exhibit transitions to conducting liquids at high temperatures (T) and relatively modest pressures (P). Furthermore, both liquids undergo polymerization phase transitions at pressures comparable to their solid counterparts. The liquid phase diagrams have been divided into several regimes through a detailed analysis of changes in bonding, as well as structural and electronic properties for pressures and temperatures up to 200 GPa and 10 000 K, respectively. Similarities and differences between the high- P and T behavior of these fluids will be discussed. Calculations of the Hugoniot are in excellent agreement with available experimental data. Work supported by NSERC, LLNL, and the Killam Trusts. Prepared by LLNL under Contract DE-AC52-07NA27344.

Behaviour of liquid films and flooding in counter-current two-phase flow, (1)

International Nuclear Information System (INIS)

Suzuki, Shin-ichi; Ueda, Tatsuhiro.

1978-01-01

This paper reports on the results of study of the behavior of liquid film and flooding in counter-current two phase flow, and the flow speed of gas phase was measured over the wide ranges of tube diameter, tube length, amount of liquid flow, viscosity and surface tension. Liquid samples used for this experiment were water, glycerol, and second octyl alcohol. The phenomena were observed with a high speed camera. The maximum thickness of liquid film was measured, and the effects of various factors on the flooding were investigated. The results of investigation were as follows. The big waves which cause the flooding were developed by the interaction of one of the waves on liquid film surface with gas phase flow. The flow speed of gas phase at the time of beginning of flooding increases with the reduction of amount of liquid flow and the increase of tube diameter. The flooding flow speed is reduced with the increase of tube length. The larger maximum film thickness at the time of no gas phase flow causes flooding at low gas phase flow speed. (Kato, T.)

Isotropic–Nematic Phase Transitions in Gravitational Systems

Energy Technology Data Exchange (ETDEWEB)

Roupas, Zacharias; Kocsis, Bence [Institute of Physics, Eötvös University, Pázmány P. s. 1/A, Budapest, 1117 (Hungary); Tremaine, Scott [Institute for Advanced Study, Princeton, NJ 08540 (United States)

2017-06-20

We examine dense self-gravitating stellar systems dominated by a central potential, such as nuclear star clusters hosting a central supermassive black hole. Different dynamical properties of these systems evolve on vastly different timescales. In particular, the orbital-plane orientations are typically driven into internal thermodynamic equilibrium by vector resonant relaxation before the orbital eccentricities or semimajor axes relax. We show that the statistical mechanics of such systems exhibit a striking resemblance to liquid crystals, with analogous ordered-nematic and disordered-isotropic phases. The ordered phase consists of bodies orbiting in a disk in both directions, with the disk thickness depending on temperature, while the disordered phase corresponds to a nearly isotropic distribution of the orbit normals. We show that below a critical value of the total angular momentum, the system undergoes a first-order phase transition between the ordered and disordered phases. At a critical point, the phase transition becomes second order, while for higher angular momenta there is a smooth crossover. We also find metastable equilibria containing two identical disks with mutual inclinations between 90° and 180°.

Versatile ligands for high-performance liquid chromatography: An overview of ionic liquid-functionalized stationary phases.

Science.gov (United States)

Zhang, Mingliang; Mallik, Abul K; Takafuji, Makoto; Ihara, Hirotaka; Qiu, Hongdeng

2015-08-05

Ionic liquids (ILs), a class of unique substances composed purely by cation and anions, are renowned for their fascinating physical and chemical properties, such as negligible volatility, high dissolution power, high thermal stability, tunable structure and miscibility. They are enjoying ever-growing applications in a great diversity of disciplines. IL-modified silica, transforming the merits of ILs into chromatographic advantages, has endowed the development of high-performance liquid chromatography (HPLC) stationary phase with considerable vitality. In the last decade, IL-functionalized silica stationary phases have evolved into a series of branches to accommodate to different HPLC modes. An up-to-date overview of IL-immobilized stationary phases is presented in this review, and divided into five parts according to application mode, i.e., ion-exchange, normal-phase, reversed-phase, hydrophilic interaction and chiral recognition. Specific attention is channeled to synthetic strategies, chromatographic behavior and separation performance of IL-functionalized silica stationary phases. Copyright © 2015 Elsevier B.V. All rights reserved.

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.