State-of-the-art review of phase equilibria
Prausnitz, J.M.
1980-03-01
High-pressure phase-equilibrium calculations using an equation of state are more sensitive to the mixing rules than to details in the effect of density or temperature on pressure. Attention must be given to the problem of how to extend equations of state to mixtures. One possible technique is provided by perturbation theory; another by superposition of chemical equilibria. At low or moderate pressures, vapor-phase corrections are often important. When specific intermolecular forces produce formation of molecular aggregates, strong deviations from ideal-gas behavior can be significant even at pressures well below 1 bar. When vapor-liquid equilibrium data are reduced using conventional expressions for the excess Gibbs energy, the resulting binary parameters tend to be partially correlated, it difficult, but no impossible, to calculate ternary liquid-liquid equilibria using binary parameters only. New models for calculating properties of liquid-phase mixtures mist allow for changes in free volume to give consideration to the effect of mixing on changes in rotational and vibrational degrees of freedom. Liquid-phase volumetric effects are also important in describing the solubilities of gases in solvent mixtures. Therefore, future liquid-phase models should incorporate a liquid-phase equation of state, either of the van der Waals type or, perhaps, as given by the direct-correlation function theory of liquids.
Phase Equilibria Diagrams Database
National Institute of Standards and Technology Data Gateway
SRD 31 NIST/ACerS Phase Equilibria Diagrams Database (PC database for purchase) The Phase Equilibria Diagrams Database contains commentaries and more than 21,000 diagrams for non-organic systems, including those published in all 21 hard-copy volumes produced as part of the ACerS-NIST Phase Equilibria Diagrams Program (formerly titled Phase Diagrams for Ceramists): Volumes I through XIV (blue books); Annuals 91, 92, 93; High Tc Superconductors I & II; Zirconium & Zirconia Systems; and Electronic Ceramics I. Materials covered include oxides as well as non-oxide systems such as chalcogenides and pnictides, phosphates, salt systems, and mixed systems of these classes.
Solid state phase equilibria and intermetallic compounds of the Al-Cr-Ho system
Pang, Mingjun; Zhan, Yongzhong; Du, Yong
2013-02-15
The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C were experimentally investigated. The phase relations at 500 Degree-Sign C are governed by 14 three-phase regions, 29 two-phase regions and 15 single-phase regions. The existences of 10 binary compounds and 2 ternary phases have been confirmed. Al{sub 11}Cr{sub 2}, Al{sub 11}Cr{sub 4} and Al{sub 17}Ho{sub 2} were not found at 500 Degree-Sign C. Crystal structures of Al{sub 9}Cr{sub 4} and Al{sub 8}Cr{sub 4}Ho were determined by the Rietveld X-ray powder data refinement. Al{sub 9}Cr{sub 4} was found to exhibit cubic structure with space group I4-bar 3m (no. 217) and lattice parameters a=0.9107(5) nm. Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} structure type with space group I4/mmm (no. 139) and lattice parameters a=0.8909(4) nm, c=0.5120(5) nm. It is concluded that the obtained Al{sub 4}Cr phase in this work should be {mu}-Al{sub 4}Cr by comparing with XRD pattern of the hexagonal {mu}-Al{sub 4}Mn compound. - Graphical abstract: The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Al-Cr-Ho system has been investigated. Black-Right-Pointing-Pointer Al{sub 9}Cr{sub 4} has cubic structure with space group I4-bar 3m. Black-Right-Pointing-Pointer Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} type with space group I4/mmm. Black-Right-Pointing-Pointer Al{sub 4}Cr phase is {mu}-type at 500 Degree-Sign C.
Phase equilibria and volumetric properties of aqueous CaCl{sub 2} by an equation of state
Jiang, S.; Pitzer, K.S. |
1996-02-01
A comprehensive equation of state was developed to represent the phase equilibria and volumetric properties of aqueous calcium chloride solutions at temperatures above 523 K. The equation consists of a reference part and a perturbation contribution. The reference function is developed from the statistical mechanical theory for mixtures of dipolar and quadrupolar hard spheres, which agrees well with the Monte carlo simulation results. In this treatment, calcium chloride is described by the completely undissociated model. The empirical perturbation function is a truncated series of virial expansion terms. Thus, mixing rules are guided by those of virial coefficients, which are derived rigorously from statistical mechanics. The equation reproduces experimental saturated vapor pressures and volumetric data within experimental uncertainty for temperatures to 623 K. At higher temperatures, few and less accurate experimental data are available, but values of the saturated vapor pressures of the liquid have been reported and are represented satisfactorily.
Phase equilibria for complex fluid mixtures
Prausnitz, J.M.
1983-04-01
After defining complex mixtures, attention is given to the canonical procedure used for the thermodynamics of fluid mixtures: first, we establish a suitable, idealized reference system and then we establish a perturbation (or excess function) which corrects the idealized system for real behavior. For complex mixtures containing identified components (e.g. alcohols, ketones, water) discussion is directed at possible techniques for extending to complex mixtures our conventional experience with reference systems and perturbations for simple mixtures. Possible extensions include generalization of the quasi-chemical approximation (local compositions) and superposition of chemical equilibria (association and solvation) on a physical equation of state. For complex mixtures containing unidentified components (e.g. coal-derived fluids), a possible experimental method is suggested for characterization; conventional procedures can then be used to calculate phase equilibria using the concept of pseudocomponents whose properties are given by the characterization data. Finally, as an alternative to the pseudocomponent method, a brief introduction is given to phase-equilibrium calculations using continuous thermodynamics.
Steady State Tokamak Equilibria without Current Drive
Shaing, K.C.; Aydemir, A.Y.; Lin-Liu, Y.R.; Miller, R.L.
1997-11-01
Steady state tokamak equilibria without current drive are found. This is made possible by including the potato bootstrap current close to the magnetic axis. Tokamaks with this class of equilibria do not need seed current or current drive, and are intrinsically steady state. {copyright} {ital 1997} {ital The American Physical Society}
Phase Equilibria and Crystallography of Ceramic Oxides
Wong-Ng, W.; Roth, R. S.; Vanderah, T. A.; McMurdie, H. F.
2001-01-01
Research in phase equilibria and crystallography has been a tradition in the Ceramics Division at National Bureau of Standards/National Institute of Standatrds and Technology (NBS/NIST) since the early thirties. In the early years, effort was concentrated in areas of Portland cement, ceramic glazes and glasses, instrument bearings, and battery materials. In the past 40 years, a large portion of the work was related to electronic materials, including ferroelectrics, piezoelectrics, ionic conductors, dielectrics, microwave dielectrics, and high-temperature superconductors. As a result of the phase equilibria studies, many new compounds have been discovered. Some of these discoveries have had a significant impact on US industry. Structure determinations of these new phases have often been carried out as a joint effort among NBS/NIST colleagues and also with outside collaborators using both single crystal and neutron and x-ray powder diffraction techniques. All phase equilibria diagrams were included in Phase Diagrams for Ceramists, which are collaborative publications between The American Ceramic Society (ACerS) and NBS/NIST. All x-ray powder diffraction patterns have been included in the Powder Diffraction File (PDF). This article gives a brief account of the history of the development of the phase equilibria and crystallographic research on ceramic oxides in the Ceramics Division. Represented systems, particularly electronic materials, are highlighted. PMID:27500068
Phase Equilibria, Phase Diagrams and Phase Transformations - 2nd Edition
NASA Astrophysics Data System (ADS)
Hillert, Mats
2006-03-01
Computational tools allow material scientists to model and analyze increasingly complicated systems to appreciate material behavior. Accurate use and interpretation however, requires a strong understanding of the thermodynamic principles that underpin phase equilibrium, transformation and state. This fully revised and updated edition covers the fundamentals of thermodynamics, with a view to modern computer applications. The theoretical basis of chemical equilibria and chemical changes is covered with an emphasis on the properties of phase diagrams. Starting with the basic principles, discussion moves to systems involving multiple phases. New chapters cover irreversible thermodynamics, extremum principles, and the thermodynamics of surfaces and interfaces. Theoretical descriptions of equilibrium conditions, the state of systems at equilibrium and the changes as equilibrium is reached, are all demonstrated graphically. With illustrative examples - many computer calculated - and worked examples, this textbook is an valuable resource for advanced undergraduates and graduate students in materials science and engineering. Fully revised and updated edition covering the fundamentals of thermodynamics with a view to modern computer applications such as Thermo-Calc Emphasis is placed on phase diagrams, the key application of thermodynamics Contains numerous illustrative examples, many computer-calculated and some for real systems, and worked examples to help demonstrate the principles
Multicomponent three-phase equilibria
Ho, C.K.
1995-06-01
This paper presents the relations that describe thermodynamic equilibrium in a three-phase system. Multiple components, including air, water, and oil components, are considered in three phases: (1) aqueous, (2) oil, and (3) gas. Primary variables are specified for each of seven possible phase combinations. These primary variables are then used to determine the necessary secondary variables to completely describe the system. Criteria are also developed to check the stability of each phase configuration and determine possible transitions from one phase configuration to another phase configuration via phase appearances and disappearances.
Thermodynamics of mantle minerals - II. Phase equilibria
NASA Astrophysics Data System (ADS)
Stixrude, Lars; Lithgow-Bertelloni, Carolina
2011-03-01
We complete the development and description of a thermodynamic method for the computation of phase equilibria and physical properties of multiphase mantle assemblages. Our previous paper focused on the computation of physical properties. In this paper, our focus shifts to the phase equilibria. We further develop our theory to specify the ideal and excess contributions to solution properties and derive properties of multiphase assemblages. We discuss our global inversion strategy for determining the values of the free parameters in our theory and compare inverted parameter values with expectations based on scaling arguments. Comparisons between our method and experimental phase equilibria data encompass the pressure-temperature regime of Earth's mantle. Finally, we present applications of our method that illustrate how it may be used to explore the origins of mantle structure and mantle dynamics. Continuing rapid advances in experimental and theoretical petrology and mineral physics have motivated an expansion of the scope of our model via the addition of several new phases, and of the soda component: an appendix lists all parameters in our model and references to the experimental and theoretical studies that constrain them. Our algorithm for global minimization of the Gibbs free energy is embodied in a code called HeFESTo, and is detailed in a second appendix.
NASA Astrophysics Data System (ADS)
Zuend, A.; Marcolli, C.; Peter, T.
2009-04-01
The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part
NASA Astrophysics Data System (ADS)
van Westen, Thijs; Oyarzún, Bernardo; Vlugt, Thijs J. H.; Gross, Joachim
2015-06-01
We develop an equation of state (EoS) for describing isotropic-nematic (IN) phase equilibria of Lennard-Jones (LJ) chain fluids. The EoS is developed by applying a second order Barker-Henderson perturbation theory to a reference fluid of hard chain molecules. The chain molecules consist of tangentially bonded spherical segments and are allowed to be fully flexible, partially flexible (rod-coil), or rigid linear. The hard-chain reference contribution to the EoS is obtained from a Vega-Lago rescaled Onsager theory. For the description of the (attractive) dispersion interactions between molecules, we adopt a segment-segment approach. We show that the perturbation contribution for describing these interactions can be divided into an "isotropic" part, which depends only implicitly on orientational ordering of molecules (through density), and an "anisotropic" part, for which an explicit dependence on orientational ordering is included (through an expansion in the nematic order parameter). The perturbation theory is used to study the effect of chain length, molecular flexibility, and attractive interactions on IN phase equilibria of pure LJ chain fluids. Theoretical results for the IN phase equilibrium of rigid linear LJ 10-mers are compared to results obtained from Monte Carlo simulations in the isobaric-isothermal (NPT) ensemble, and an expanded formulation of the Gibbs-ensemble. Our results show that the anisotropic contribution to the dispersion attractions is irrelevant for LJ chain fluids. Using the isotropic (density-dependent) contribution only (i.e., using a zeroth order expansion of the attractive Helmholtz energy contribution in the nematic order parameter), excellent agreement between theory and simulations is observed. These results suggest that an EoS contribution for describing the attractive part of the dispersion interactions in real LCs can be obtained from conventional theoretical approaches designed for isotropic fluids, such as a Perturbed
Electronic structure and phase equilibria in ternary substitutional alloys
Traiber, A.J.S.; Allen, S.M.; Turchi, P.E.A.; Waterstrat, R.M.
1996-04-26
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 {ital ab}{ital initio} 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{sub 0.5}(Ru, Pd){sub 0.5}.
Modeling phase equilibria in mixtures containing hydrogen fluoride and halocarbons
Lencka, M. ); Anderko, A. Polish Academy of Sciences, Warszawa )
1993-03-01
Recently, much attention has been focused on the production of environmentally acceptable refrigerants, which not only offer desirable physico-chemical properties, but do not deplete the ozone layer and do not cause the greenhouse effect. The production of such refrigerants involves the separation of multicomponent mixtures containing hydrogen fluoride, hydrogen chloride, and various chlorinated and fluorinated hydrocarbons. Therefore, it is indispensable to know the phase behavior of these mixtures. While the phase behavior of refrigerant mixtures can be adequately modeled in the absence of HF using standard thermodynamic techniques, drastically increases the complexity of the mixture because of its unusually strong association. The association of HF manifests itself in its significantly reduced gas-phase compressibility factor and the strong nonideality of mixtures containing HF and hydrocarbons or halocarbons. In this work, the authors develop an accurate, yet simple, association model for HF and compare it with simulation data. The model is combined with a simple equation of state to yield a closed-form expression that is applicable to both pure fluids and mixtures. In addition to representing the pure-component data for HF, the theory accurately predicts phase equilibria in HF + halocarbon systems.
Experimental methods for phase equilibria at high pressures.
Dohrn, Ralf; Fonseca, José M S; Peper, Stephanie
2012-01-01
Knowledge of high-pressure phase equilibria is crucial in many fields, e.g., for the design and optimization of high-pressure chemical and separation processes, carbon capture and storage, hydrate formation, applications of ionic liquids, and geological processes. This review presents the variety of methods to measure phase equilibria at high pressures and, following a classification, discusses the measurement principles, advantages, challenges, and error sources. Examples of application areas are given. A detailed knowledge and understanding of the different methods is fundamental not only for choosing the most suitable method for a certain task but also for the evaluation of experimental data. The discrepancy between the (sometimes low) true accuracy of published experimental data and the (high) accuracy claimed by authors is addressed. Some essential requirements for the generation of valuable experimental results are summarized.
Phase equilibria of chlorofluorocarbon alternative refrigerant mixtures
Lee, B.G.; Park, J.Y.; Lim, J.S.; Cho, S.Y.; Park, K.Y.
1999-03-01
Isothermal vapor-liquid equilibrium data were determined for binary systems of difluoromethane/1,1,1,2-tetrafluoroethane (HFC-32/HFC-134a), difluoromethane/pentafluoroethane (HFC-32/HFC-125), difluoromethane/1,1,1-trifluoroethane (HFC-32/HFC-143A), and difluoromethane/1,1-difluoroethane (HFC-32/HFC-152a). The vapor and liquid compositions and pressures were measured in a circulation-type apparatus at 303.15 K and 323.15 K. The experimental data were compared with literature results and correlated with the Canahan-Starling-De Santis equation of state within the uncertainty of {+-}1.0%.
Phosphorus Equilibria Among Mafic Silicate Phases
NASA Technical Reports Server (NTRS)
Berlin, Jana; Xirouchakis, Dimitris
2002-01-01
Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The
Phase Equilibria and Compressibility of bastnaesite-(La)
NASA Astrophysics Data System (ADS)
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
Furnace refractory corrosion and phase equilibria in electric smelting
Kaibicheva, M.N.
1985-07-01
By calculating the melting curves in smelting, in accordance with the phase equilibria in the FeO-Fe/sub 2/O/sub 3/-SiO/sub 2/ system, it is shown that at the approach to the ternary points (1140, 1150 and 1456/sup 0/C), the amount of liquid phase in the samples of smelting dust reaches 47%. The dust from all the compositions is wholly transferred into the melt at 1560/sup 0/C. The components of the smelting dust interact with the phases of the refractory where there is a temperature gradient and cause the formation of zones in the components and wear in the lining of the electric furnaces by chipping. The smelting dust causes a change in the chemical composition of the refractory which leads to a reduction in the refractoriness of the working layer and to wear on this layer by flashing off.
Fu, Dong; Li, Xiao-Sen
2006-08-28
The excess Helmholtz free energy functional for associating hard sphere fluid is formulated by using a modified fundamental measure theory [Y. X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)]. Within the framework of density functional theory, the thermodynamic properties including phase equilibria for both molecules and monomers, equilibrium plate-fluid interfacial tensions and isotherms of excess adsorption, average molecule density, average monomer density, and plate-fluid interfacial tension for four-site associating hard sphere fluids confined in slit pores are investigated. The phase equilibria inside the hard slit pores and attractive slit pores are determined according to the requirement that temperature, chemical potential, and grand potential in coexistence phases should be equal and the plate-fluid interfacial tensions at equilibrium states are predicted consequently. The influences of association energy, fluid-solid interaction, and pore width on phase equilibria and equilibrium plate-fluid interfacial tensions are discussed.
NASA Astrophysics Data System (ADS)
Budkov, Yu. A.; Kolesnikov, A. L.; Georgi, N.; Nogovitsyn, E. A.; Kiselev, M. G.
2015-05-01
We develop a first-principle equation of state of salt-free polyelectrolyte solution in the limit of infinitely long flexible polymer chains in the framework of a field-theoretical formalism beyond the linear Debye-Hueckel theory and predict a liquid-liquid phase separation induced by a strong correlation attraction. As a reference system, we choose a set of two subsystems—charged macromolecules immersed in a structureless oppositely charged background created by counterions (polymer one component plasma) and counterions immersed in oppositely charged background created by polymer chains (hard-core one component plasma). We calculate the excess free energy of polymer one component plasma in the framework of modified random phase approximation, whereas a contribution of charge densities' fluctuations of neutralizing backgrounds we evaluate at the level of Gaussian approximation. We show that our theory is in a very good agreement with the results of Monte Carlo and MD simulations for critical parameters of liquid-liquid phase separation and osmotic pressure in a wide range of monomer concentration above the critical point, respectively.
Metamorphism and partial melting of ordinary chondrites: Calculated phase equilibria
NASA Astrophysics Data System (ADS)
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 (<1 kbar) that typify thermal metamorphism, several compositional variables are good thermometers. Although those based on Fe-Mg exchange are likely to have been reset during slow cooling, those based on coupled substitution, in particular Ca and Al in orthopyroxene and Na in clinopyroxene, are less susceptible to retrograde diffusion and are potentially more faithful 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
Correlation of three-liquid-phase equilibria involving ionic liquids.
Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A
2016-08-01
The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results.
Correlation of three-liquid-phase equilibria involving ionic liquids.
Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A
2016-08-01
The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results. PMID:27427420
Phase equilibria of carbon dioxide hydrate system in the presence of sucrose, glucose, and fructose
Chun, M.K.; Lee, H.
1999-09-01
The three-phase (H-L{sub w}-V) equilibria of the carbon dioxide hydrate formation system in aqueous solutions containing sucrose, glucose, and fructose were experimentally determined at pressures ranging from 1.580 to 4.355 MPa and at temperatures between 273.6 and 281.7 K. The upper quadruple points (H-L{sub w}-L{sub CO{sub 2}}-V) were also measured at concentrations of 10, 20, and 30 mass % sucrose, glucose, and fructose. The addition of carbohydrates exhibited a similar inhibition effect as that observed for electrolytes and alcohols. A thermodynamic model predicting the three- and four-phase hydrate equilibria while accounting for the inhibition effect of carbohydrates was developed on the basis of the van der Waals-Platteeuw model and the Redlich-Kwong-Soave equation of state with a modified version of the Huron-Vidal mixing rule. The calculated results were found to be in good agreement with the experimental data.
Schaefer, B.; Lambert, S.M.; Song, Y.; Prausnitz, J.M.
1994-10-01
Goal of this work is the extension of a Perturbed-Hard-Sphere-Chain equation of state (PHSC EOS) to systems containing strong polar components. Three different types of association models (ten Brinke/Karasz, SAFI, modified Veytsman) were used to calculate the contribution of specific interactions like hydrogen bonding to thermodynamic quantities. Pure component parameters obtained from regression of temperature dependent density and vapor pressure data allow the prediction of VLE and LLE data. The results of simple fluids and polymer solutions were compared with experimental data. The SAFT and the modified Veytsman extension give similar results for pure fluids and mixtures with components of similar segment size. Differences increase with increasing difference of segment size.
Phase equilibria in the Ni-Al-Ti system at 1173 k
NASA Astrophysics Data System (ADS)
Nash, P.; Liang, W. W.
1985-03-01
The phase equilibria at 1173 K have been determined in the Ni-AI-Ti system for Al contents less than 50 at. pct. The extent of the H (Ni2AlTi) phase field has been established as well as the extent of solubility in the binary compounds γ (Ni3Al), ν(Ni3Ti), β2(NiTi), NiTi2, and ζ(AlTi3). Substantial differences were found between the phase equilibria determined in this study and previous studies, in part due to the large solubility of Al in NiTi2.
Phase Equilibria Impetus For Large-Volume Explosive Volcanic Eruptions
NASA Astrophysics Data System (ADS)
Fowler, S. J.; Spera, F. J.; Bohrson, W. A.; Ghiorso, M. S.
2006-12-01
We have investigated the phase equilibria and associated variations in melt and magma thermodynamic and transport properties of seven large-volume silicic explosive volcanic systems through application of the MELTS (Ghiorso &Sack, 1995) algorithm. Each calculation is based on fractional crystallization along an oxygen buffer at low-pressure (0.1 - 0.3 GPa), starting from a mafic parental liquid. Site-specific geological constraints provide starting conditions for each system. We have performed calculations for seven tuffs; the Otowi (~400 km3) and Tshirege (~200 km3) members of the Bandelier Tuff, the ~600 km3 Bishop Tuff, and the 2500, 300, and 1000 km3 Yellowstone high-silica rhyolite tuffs. These represent the six largest eruptions within North America over the past ~2 million years. The seventh tuff, the 39.3 ka Campanian Ignimbrite, a 200 km3 trachytic to phonolitic ignimbrite located near Naples, Italy, is the largest explosive eruption in the Mediterranean area in the last 200 kyr. In all cases, MELTS faithfully tracks the liquid line of descent as well as the identity and composition of phenocrysts. The largest discrepancy between predicted and observed melt compositions is for CaO in all calculations. A key characteristic for each system is a pseudoinvariant temperature, Tinv, where abrupt shifts in crystallinity (1-fm, where fm is the fraction of melt), volume fraction of supercritical fluid (θ), magma compressibility, melt and magma density, and viscosity occur over a small temperature interval of order 1 - 10 K. In particular, the volume fraction of vapor increases from θ ~0.1 just below Tinv to θ >0.7 just above Tinv for each case. The rheological transition between melt-dominated (high viscosity) and bubble-dominated (low viscosity) magma occurs at θ ~0.6. We emphasize that this effect is observed under isobaric conditions and is distinct from the oft-studied phenomenon of volatile exsolution accompanying magma decompression and subsequent
New investigation of phase equilibria in the system Al–Cu–Si
Ponweiser, Norbert; Richter, Klaus W.
2012-01-01
The phase equilibria and invariant reactions in the system Al–Cu–Si were investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and electron probe micro analysis (EPMA). Isothermal phase equilibria were investigated within two isothermal sections. The isothermal section at 500 °C covers the whole ternary composition range and largely confirms the findings of previous phase diagram investigations. The isothermal section at 700 °C describes phase equilibria only in the complex Cu-rich part of the phase diagram. A new ternary compound τ was found in the region between (Al,Cu)-γ1 and (Cu,Si)-γ and its solubility range was determined. The solubility of Al in κ-CuSi was found to be extremely high at 700 °C. In contrast, no ternary solubility in the β-phase of Cu–Al was found, although this phase is supposed to form a complete solid solution according to previous phase diagram assessments. Two isopleths, at 10 and 40 at.% Si, were investigated by means of DTA and a partial ternary reaction scheme (Scheil diagram) was constructed, based on the current work and the latest findings in the binary systems Al–Cu and Cu–Si. The current study shows that the high temperature equilibria in the Cu-rich corner are still poorly understood and additional studies in this area would be favorable. PMID:22287828
The Representation of Highly Non-Ideal Phase Equilibria Using Computer Graphics.
ERIC Educational Resources Information Center
Charos, Georgios N.; And Others
1986-01-01
Previous work focused on use of computer graphics in teaching thermodynamic phase equilibria for classes I and II. Extends this work to include the considerably more non-ideal phase behavior shown by classes III, IV, and V. Student and instructor response has been overwhelmingly positive about the approach. (JN)
Study of Phase Equilibria of Petrochemical Fluids using Gibbs Ensemble Monte Carlo Methods
NASA Astrophysics Data System (ADS)
Nath, Shyamal
2001-03-01
Knowledge of phase behavior of hydrocarbons and related compounds are highly of interest to chemical and petrochemical industries. For example, design of processes such as supercritical fluid extraction, petroleum refining, enhanced oil recovery, gas treatment, and fractionation of wax products. A precise knowledge of the phase equilibria of alkanes, alkenes and related compounds and their mixtures are required for efficient design of these processes. Experimental studies to understand the related phase equilibria often become unsuitable for various reasons. With the advancement of simulation technology, molecular simulations could provide a useful complement and alternative in the study and description of phase behavior of these systems. In this work we study vapor-liquid phase equilibria of pure hydrocarbons and their mixtures using Gibbs ensemble simulation. Insertion of long and articulated chain molecules are facilitated in our simulations by means of configurational bias and expanded ensemble methods. We use the newly developed NERD force field in our simulation. In this work NERD force field is extended to provide coverage for hydrocarbons with any arbitrary architecture. Our simulation results provide excellent quantitative agreement with available experimental phase equilibria data for both the pure components and mixtures.
Direct calculation of solid-liquid equilibria from density-of-states Monte Carlo simulations.
Mastny, Ethan A; de Pablo, Juan J
2005-03-22
A density-of-states Monte Carlo method is proposed for simulations of solid-liquid phase equilibria. A modified Wang-Landau density-of-states sampling approach is used to perform a random walk in regions of potential energy and volume relevant to solid-liquid equilibrium. The method provides a direct estimate of the relative density of states [Omega(U,V)] and thus the relative free energy within these regions, which is subsequently used to determine portions of the melting curve over wide ranges of pressure and temperature. The validity and usefulness of the method are demonstrated by performing crystallization simulations for the Lennard-Jones fluid and for NaCl.
NASA Astrophysics Data System (ADS)
Anikeev, V. I.; Stepanov, D. A.; Ermakova, A.
2011-08-01
Calculations of thermodynamic data are performed for fatty acid triglycerides, free fatty acids, and fatty acid methyl esters, participants of the transesterification reaction of vegetable oils that occurs in methanol. Using the obtained thermodynamic parameters, the phase diagrams for the reaction mixture are constructed, and the chemical equilibria of the esterification reaction of free fatty acids and the transesterification reaction of fatty acid triglycerides attained upon treatment with supercritical methanol are determined. Relying on our analysis of the obtained equilibria for the esterification reaction of fatty acids and the transesterification reaction of triglycerides attained upon treatment with lower alcohols, we select the optimum conditions for performing the reaction in practice.
Transport and Phase Equilibria Properties for Steam Flooding of Heavy Oils
Gabitto, Jorge; Barrufet, Maria
2001-12-18
The objectives of this research included experimental determination and rigorous modeling and computation of phase equilibria, volumetric, and transport properties of hydrocarbon/CO2/water mixtures at pressures and temperatures typical of steam injection processes for thermal recovery of heavy oils.
Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations.
Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas; Wierzchowski, Scott; Walsh, Matthew R; Koh, Carolyn A; Sloan, E Dendy; Wu, David T; Sum, Amadeu K
2010-05-01
Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential, respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials, (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems.
Electronic Structure and Phase Equilibria in Ternary Substitutional Alloys: a Tight-Binding Approach
NASA Astrophysics Data System (ADS)
Traiber, Ariel Javier Sebastian
1995-01-01
The goal of this thesis is to develop and apply alloy theory methods to transition metals and alloys (particularly ternary systems) based on the tight-binding (TB) model of atomic cohesion in studies of stability and phase equilibria. At least two factors make this kind of formalism desirable: it can bring a clear understanding of the underlying physical mechanisms that many times get obscured in first-principles calculations, and it is easily adapted to complex problems and multicomponent solutions, at low computational cost. The original physical insight given by the TB method is demonstrated by the study of the relation between the atomic local environment and the relative stability of simple phases, through the calculation of the moments of the electronic density of states. We show that the relative stability of phases related to the Bain transformation is mainly controlled by the moment of order five, and we have identified the main contributions to this moment. We present a model for cohesive energy based on the assumption that it can be written as the sum of a band -structure contribution and a repulsive short-range contribution. We have calculated the band contribution using a TB Hamiltonian with d states and applied the linearized Green's function method based on the recursion technique. For the repulsive part of the energy we employ a Born-Mayer potential. The model was used to study total energies for Mo. We show that a six-moment approximation to the band energy is sufficient to reproduce more accurate results, using the standard recursion method, for the energetics of this transition metal. We describe a reliable and consistent scheme to study phase equilibria in ternary substitutional alloys based on the TB approximation. The TB electronic parameters are obtained from linear muffin-tin orbital calculations. The transfer integrals are scaled in distance with an orbital -dependent exponential decay parametrization, while the on-site energies are scaled
Determination of phase equilibria in confined systems by open pore cell Monte Carlo method.
Miyahara, Minoru T; Tanaka, Hideki
2013-02-28
We present a modification of the molecular dynamics simulation method with a unit pore cell with imaginary gas phase [M. Miyahara, T. Yoshioka, and M. Okazaki, J. Chem. Phys. 106, 8124 (1997)] designed for determination of phase equilibria in nanopores. This new method is based on a Monte Carlo technique and it combines the pore cell, opened to the imaginary gas phase (open pore cell), with a gas cell to measure the equilibrium chemical potential of the confined system. The most striking feature of our new method is that the confined system is steadily led to a thermodynamically stable state by forming concave menisci in the open pore cell. This feature of the open pore cell makes it possible to obtain the equilibrium chemical potential with only a single simulation run, unlike existing simulation methods, which need a number of additional runs. We apply the method to evaluate the equilibrium chemical potentials of confined nitrogen in carbon slit pores and silica cylindrical pores at 77 K, and show that the results are in good agreement with those obtained by two conventional thermodynamic integration methods. Moreover, we also show that the proposed method can be particularly useful for determining vapor-liquid and vapor-solid coexistence curves and the triple point of the confined system.
Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria
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.
Development of the Transferable Potentials for Phase Equilibria Model for Hydrogen Sulfide.
Shah, Mansi S; Tsapatsis, Michael; Siepmann, J Ilja
2015-06-11
The transferable potentials for phase equilibria force field is extended to hydrogen sulfide. The pure-component and binary vapor-liquid equilibria with methane and carbon dioxide and the liquid-phase relative permittivity are used for the parametrization of the Lennard-Jones (LJ) and Coulomb interactions, and models with three and four interaction sites are considered. For the three-site models, partial point charges are placed on the sites representing the three atoms, while the negative partial charge is moved to an off-atom site for the four-site models. The effect of molecular shape is probed using either only a single LJ interaction site on the sulfur atom or adding sites also on the hydrogen atoms. This procedure results in four distinct models, but only those with three LJ sites can accurately reproduce all properties considered for the parametrization. These two are further assessed for predictions of the liquid-phase structure, the lattice parameters and relative permittivity for the face-centered-cubic solid, and the triple point. An effective balance between LJ interactions and the dipolar and quadrupolar terms of the first-order electrostatic interactions is struck in order to obtain a four-site model that describes the condensed-phase properties and the phase equilibria with high accuracy. PMID:25981731
Development of the Transferable Potentials for Phase Equilibria Model for Hydrogen Sulfide.
Shah, Mansi S; Tsapatsis, Michael; Siepmann, J Ilja
2015-06-11
The transferable potentials for phase equilibria force field is extended to hydrogen sulfide. The pure-component and binary vapor-liquid equilibria with methane and carbon dioxide and the liquid-phase relative permittivity are used for the parametrization of the Lennard-Jones (LJ) and Coulomb interactions, and models with three and four interaction sites are considered. For the three-site models, partial point charges are placed on the sites representing the three atoms, while the negative partial charge is moved to an off-atom site for the four-site models. The effect of molecular shape is probed using either only a single LJ interaction site on the sulfur atom or adding sites also on the hydrogen atoms. This procedure results in four distinct models, but only those with three LJ sites can accurately reproduce all properties considered for the parametrization. These two are further assessed for predictions of the liquid-phase structure, the lattice parameters and relative permittivity for the face-centered-cubic solid, and the triple point. An effective balance between LJ interactions and the dipolar and quadrupolar terms of the first-order electrostatic interactions is struck in order to obtain a four-site model that describes the condensed-phase properties and the phase equilibria with high accuracy.
Effects of gravity reduction on phase equilibria. Part 1: Unary and binary isostructural solids
NASA Technical Reports Server (NTRS)
Larson, D. J., Jr.
1975-01-01
Analysis of the Skylab II M553 Experiment samples resulted in the hypothesis that the reduced gravity environment was altering the melting and solidification reactions. A theoretical study was conducted to define the conditions under which such alteration of phase relations is feasible, determine whether it is restricted to space processing, and, if so, ascertain which alloy systems or phase reactions are most likely to demonstrate such effects. Phase equilibria of unary and binary systems with a single solid phase (unary and isomorphous) were considered.
Phase and chemical equilibria in multicomponent fluid systems with a chemical reaction
NASA Astrophysics Data System (ADS)
Toikka, A. M.; Samarov, A. A.; Toikka, M. A.
2015-04-01
Studies of the phase and chemical equilibria in the systems with chemical reaction cover a wide range of problems related to both experimental determination of physicochemical characteristics of these systems and various aspects of thermodynamic analysis of the phase and chemical processes occurring there. The main goal of this review consists in systematization and analysis of available experimental data concerning the vapour-liquid and liquid-liquid equilibria in multicomponent systems where chemical reactions occur. The studies considered here have been mainly published in recent years, and they include rather detailed data on physicochemical properties, phase transitions and chemical processes in fluid systems, i.e., the data which are essential for thermodynamic analysis. Available approaches to the thermodynamic analysis of heterogeneous systems with chemical reactions are also discussed. Particular attention is paid to the studies of the simultaneous phase and chemical equilibria. We hope that this review could be useful both for fundamental studies of heterogeneous reactive systems and for solving applied problems on the design of combined reactive and mass-transfer processes. The bibliography includes 79 references.
Phase transitions and connectivity in three-dimensional vortex equilibria
Akao, J.H.
1994-05-01
The statistical mechanics of collections of closed self avoiding vortex loops on a lattice are studied. The system is related to the vortex form of the three dimensional XY model and to lattice vortex equilibrium models of turbulence. The system exhibits vortex connectivity and screening effects, and models in vorticity variables the superfluid transition. The equilibrium states of the system are simulated by a grand canonical Monte Carlo method. A set of geometric transformations for self-avoiding loops is developed. The numerical method employs histogram sampling techniques and utilizes a modification to the Metropolis flow which enhances efficiency. Results are given for a region in the temperature-chemical potential plane, where the chemical potential is related to the vortex fugacity. A line of second order transitions is identified at low temperature. The transition is shown to be a percolation threshold at which connected vortex loops of infinite size appear in the system. The nature of the transition supports the assumption that the lambda transition in bulk superfluid helium is driven by vortices. An asymptotic analysis is performed for the energy and entropy scaling of the system as functions of the system size and the lattice spacing. These estimates indicate that the infinite temperature line is a phase boundary between small scale fractal vortices and large scale smooth vortices. A suggestion is made that quantum vortices have uniform structure on the scale of the lattice spacing and lie in the positive temperature regime, while classical vortices have uniform structure on the scale of the domain and lie in the negative temperature regime.
Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite
Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.
2007-01-01
The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent
Phase equilibria in a system of 'breathing' molecules
Wu, Jianzhong; Prausnitz, John
2001-09-30
It is now well known that details in the intermolecular potential can significantly affect the qualitative features of a phase diagram where temperature is plotted against density for the coexistence curves among fluid and solid phases. While previous calculations of phase diagrams have assumed a time-invariant potential function, this report concerns the phase diagram for ''breathing'' molecules, i.e., molecules whose strength of intermolecular attraction fluctuates in time. Such fluctuations can occur in biomacromolecules where an active site can switch between ''on'' and ''off'' positions. Phase-equilibrium calculations were performed for molecules that have a periodic (breathing) attractive force in addition to the conventional intermolecular forces. The phase diagram for such molecules is as expected when the ''breathing'' properties are independent of density. However, when (more realistically), the ''breathing'' properties are density dependent, the phase diagram exhibits dramatic changes. These calculations may be useful for interpreting experimental data for protein precipitation, for plaque formation in blood vessels and for scaffold-supported tissue formation.
Partitioning and phase equilibria of PEGylated excipients in fluorinated liquids.
Paul, Alison; Talbot, Gemma L; Bowles, James W; James, Jennifer; Griffiths, Peter C; Rogueda, Philippe G
2010-03-15
Mixtures of common polymeric excipients and hydrofluoroalkane (HFA) liquids show rich and complex phase behaviour. Phase diagrams and phase compositions are reported for poly(ethylene glycol)s with varying levels of end-group methylation in mixed solvent systems consisting of the model propellant 2H,3H-perfluoropentane (HPFP) and the fully fluorinated analogue perfluoropentane (PFP). Studies have been performed as a function of molecular weight as well as end group chemistry (monomethyl, MM; dimethyl, DM; and dihydroxyl, DH), and for binary polymer mixtures in HPFP/PFP solvent systems. The solvent composition required to induce phase separation by addition of the non-hydrogen bonding PFP is strongly dependent on end-group concentrations. It shows a linear increase with increasing methylation, whilst remaining insensitive to OH group concentration in dihydroxylated PEG systems. For single polymer systems it is observed that strong partitioning of the polymer is observed, and changes in polymer concentration occurring across the phase diagram are a result of changing solvent partitioning between upper and lower phases. These solvent effects are dependent on the composition (wt% PFP) in the solvent mixture. The linear dependence of solvent composition required to induce phase separation at fixed polymer concentration on end group concentrations can be used to predict the phase behaviour for mixtures of monomethylated PEG with either dimethyl or dihydroxyl PEGs, whereas mixtures of dihydroxyl with dimethyl end-capped PEGs show a deviation from linear behaviour with dominance of the dihydroxyl end groups, which is reflected in the obtained phase diagrams. This study hence progresses understanding of factors that influence solubility of PEG-type polymers in HFAs and will facilitate the identification of predictive methodologies for formulation.
Phase equilibria and crystal chemistry of rubidium niobates and rubidium tantalates
NASA Technical Reports Server (NTRS)
Minor, D. B.; Roth, R. S.; Parker, H. S.; Brower, W. S.
1977-01-01
The phase equilibria relations and crystal chemistry of portions of the Rb2O-Nb2O5 and Rb2O-Ta2O5 systems were investigated for structures potentially useful as ionic conductors. A hexagonal tungsten bronze-type (HTB) structure was found in both systems as well as three hexagonal phases with mixed HTB-pyrochlore type structures. Ion exchange experiments between various alkali ions are described for several phases. Unit cell dimensions and X-ray diffraction powder patterns are reported.
NASA Astrophysics Data System (ADS)
Mullen, E. K.; McCallum, I. S.
2010-12-01
Primitive arc basalts provide information on sub-arc mantle compositions and processes. The relative abundance of basalts in the Cascade arc decreases northward, and basalts are rare in the most northerly segment of the arc (Garibaldi belt) where the Mt. Baker volcanic field (MBVF) is located. Following reconstruction of the compositions of the primary basalts at MBVF (olivine addition ± plag subtraction), we have applied phase equilibria and forward-modeled trace element abundances and isotope ratios to obtain petrogenetic constraints. The most primitive lavas are the Sulphur Cr, Lk Shannon, and Park Butte basalts and the Hogback, Tarn Plateau, and Cathedral Crag basaltic andesites, ranging from 716 to 10 ka. Most erupted peripheral to the major centers. Spinel/olivine and Fe-Ti oxide oxybarometry indicate redox states of ~QFM + 1 corresponding to Fe3+/ΣFe = 0.20. Mg# ranges from 51 to 71. The lavas are medium-K and similar to calc-alkaline basalts and high-Mg basaltic andesites from the High Cascades. MBVF basalts have higher MgO and lower CaO and Al2O3 than typical CAB and HAOT, grading to alkalic compositions with TiO2 and Na2O of up to 1.65 and 5.4 wt%, respectively (Sulphur Cr). Phenocryst contents are 5 to 33% (plag + olivine ± cpx) and the lavas are holo- or hypocrystalline with glass contents of up to 15%. The whole rocks are close to equilibrium with olivine cores (range Fo 87-68). Plagioclase cores range from An 88-68. Reconstructed primary basalt compositions give liquidus T and P values (from olivine-liquid equilibria and silica activities) ranging from 1280°C and 1 GPa (Tarn Plateau) to 1350°C and 1.4 GPa (Sulphur Cr), corresponding to the upper mantle above the core of the mantle wedge. These estimates take into account the 1 to 3 wt% initial H2O contents of the basalts calculated using plagioclase cores. Phase equilibria of the primary basalts indicate a similar pressure range of 1-2 GPa and indicate a residual mantle assemblage of harzburgite
Integral equation theory description of phase equilibria in classical fluids
NASA Astrophysics Data System (ADS)
Caccamo, C.
1996-09-01
We review the present status of applications of integral equation theories (IETs) for the radial distribution function g( r), to the determination of phase diagrams and stability conditions of simple and charged classical fluids. After having recalled some basic concepts and definitions in the structural description of fluid systems, a number of IETs are examined by reporting the constituting equations and solution procedures; these last are discussed also in relationship with the actual calculation of coexistence lines and description of the critical behavior of each envisaged theory. In this context, the crucial role played by the fulfilment of thermodynamic consistency in the improvement of the performances of the various approximations, is highlighted. Then, a number of results of phase diagram determinations, phase stability investigations, and estimates of critical exponents, are reported for several neutral and charged model fluids (and their mixtures) such as the hard sphere fluid, the square-well fluid, the hard-core Yukawa fluid, the Lennard-Jones fluid, and charged hard spheres in different regimes of density, sizes and charges. Calculations of the phase diagram of a rigid molecule model of C 60 are also reported. Besides their theoretical interest, these models are investigated by many authors also because they can reasonably mimic real systems like rare gas liquids, electrolyte solutions, molten salts, neutral and charged micellar systems, and colloidal solutions. The related experimental evidence is therefore frequently referred, and comparison with experimental results is also performed in some case. Theoretical results are usually presented in parallel with the available computer simulation data, which are extensively quoted both with the aim of a systematic assessment of the theories, and in order to offer a more complete scenario of phase behavior calculations in classical fluids. Perspectives and advantages of future extensions and applications
Phase equilibria in water-(1-, 2-, iso-)butanol-18-crown-6 systems
NASA Astrophysics Data System (ADS)
Kovalenko, N. A.; Golovina, N. B.; Bogachev, A. G.; Uspenskaya, I. A.
2011-09-01
We present the results from measuring the solubility of 18-crown-6 in isobutanol in the temperature interval of 280-308 K and information about liquid-liquid equilibria in water-(1-, 2-, iso-)butanol-18-crown-6 systems at 298 K. The parameter values of the extended UNIQUAC model were determined on the basis of information about the thermodynamic properties and phase equilibria in the binary systems. It is shown that we must use parameters of ternary interaction in addition to binary parameters to adequately describe the miscibility gap on the basis of the results of turbidimetric titration in ternary water-(1-,2-, iso)butanol-18-crown-6 systems.
Phase equilibria in an athermal solution of platelike particles
Sokolowska; Moscicki
2000-10-01
A molecular frame lattice theory of athermal solutions of platelike particles is presented. Steric repulsion between the particles is assumed to be the sole interaction present in the system (the athermal limit). The theory is developed for flat rectangular parallelepipeds, and examined in detail for two opposite shape anisotropy limits: rods and square boards. Numerical calculations show that in a pure system of either long rods or square boards, a nematic phase is formed once the shape anisotropy exceeds some critical value: for rods the critical aspect ratio x(crit)(r) is 8. 019, and for boards x(crit)(d) is 3.742. For higher values of the ratio, a narrow concentration region of coexistence for the nematic and isotropic phases, which separates the isotropic (low concentration) from the nematic (high concentration) solution, is found on dilution of each system. PMID:11089050
Phase equilibria and thermodynamics of p-hydroxybenzoic acid.
Nordström, Fredrik L; Rasmuson, Ake C
2006-04-01
The prevalence of phases and associated solubilities of p-hydroxybenzoic acid have been investigated in methanol, acetonitrile, acetic acid, acetone, water, and ethyl acetate at temperatures from 10 to 50 degrees C. Thermodynamic data was acquired through determination of van't Hoff enthalpy of solution, enthalpy of fusion, and melting temperature. Indications of polymorphic enantiotropy were found primarily through solubility analysis and FTIR-ATR. A comprehensive thermodynamic investigation disclosed correlation between the van't Hoff enthalpy of solution and the solubility in different solvents. A higher solubility is linked to a lower van't Hoff enthalpy of solution. A thermodynamic analysis to discriminate between different solid phases is presented.
Floating zone crystal growth and phase equilibria - A review
NASA Astrophysics Data System (ADS)
Kimura, Shigeyuki; Kitamura, Kenji
1992-06-01
The thermal-imaging floating zone technique can be used to grow crystals of yttrium iron garnet aluminum-doped yttrium orthoferrite and magnetite, which represent peritectic compounds, solid-solution crytals, and atmosphere-sensitive materials, respectively. The reactions involved in floating zone crystal growth are explained on the basis of phase diagrams. A review of crystal growth reports, including unpublished findings by the present authors, demonstrates how the crystallization processes, the reaction with the ambient atmosphere, and the composition variation in the obtained crystals can be explained or controlled on the basis of phase equilibrium. The floating zone technique is applicable to a variety of materials and remains a handy tool for materials research; however, its industrial application may be limited.
Phase equilibria of size-asymmetric primitive model electrolytes.
Yan, Q; de Pablo, J J
2001-03-01
The low-temperature phase coexistence of size-asymmetric primitive model electrolyte solutions has been investigated by means of Monte Carlo simulations. Binodal curves and critical parameters are reported as a function of size ratio lambda = sigma(+)/sigma(-) in the range 0.05 to 1. Both the critical temperature and the critical density are found to decrease as lambda decreases. These trends are in conflict with available theoretical predictions. For highly asymmetric systems, the depression of the critical parameters is accompanied by the formation of large chainlike and ringlike structures, thereby giving rise to considerable finite-size effects.
Phase equilibria in the neodymium–cadmium binary system
Skołyszewska-Kühberger, Barbara; Reichmann, Thomas L.; Ipser, Herbert
2014-01-01
The equilibrium phase diagram of the neodymium–cadmium system has been established by thermal, metallographic and X-ray analysis based on a study of 70 alloys. The system contains three congruently melting intermetallic compounds, i.e. NdCd (1040 °C), NdCd2 (995 °C), Nd11Cd45 (855 °C), and four incongruently melting compounds NdCd3 (860 °C), Nd13Cd58 (740 °C), NdCd6 (655 °C) and NdCd11 (520 °C). Four eutectic reactions are found in this binary system, i.e. at ∼25 at.% Cd and 770 °C, at 58 at.% Cd and 955 °C, at 79 at.% Cd and 850 °C, and very close to pure Cd at 318 °C, as well as one eutectoid reaction at ∼15 at.% Cd and 500 °C. The solid solubility of Nd in Cd is negligible. Dilatometric curves were recorded for three Nd–Cd compositions up to 4 at.% Cd, to accurately determine phase transitions between the solid solutions of Cd in the low- and high-temperature modification of Nd. PMID:25197164
Thermodynamic properties and phase equilibria of selected Heusler compounds
NASA Astrophysics Data System (ADS)
Yin, Ming
Heusler compounds are ternary intermetallics with many promising properties such as spin polarization and magnetic shape memory effect. A better understanding of their thermodynamic properties facilitates future design and development. Therefore, standard enthalpies of formation and heat capacities from room temperature to 1500 K of selected Heusler compounds X2YZ (X = Co, Fe, Ni, Pd, Rh, Ru; Y = Co, Cu, Fe, Hf, Mn, Ni, Ti, V, Zr; Z = Al, Ga, In, Si, Ge, Sn) and half-Heusler compounds XYSn (X = Au, Co, Fe, Ir, Ni, Pd, Pt, Rh; Y = Hf, Mn, Ti, Zr) were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation were compared with those predicted from ab initio calculations and the extended semi-empirical Miedema's model. Trends in standard enthalpy of formation with respect to the periodic classification of elements were discussed. The effect of a fourth element (Co, Cu, Fe, Pd; Ti, V; Al, Ga, In, Si, Ge) on the standard enthalpy of formation of Ni2MnSn was also investigated. Lattice parameters of the compounds with an L21 structure were determined using X-ray powder diffraction analysis. Differential scanning calorimetry was used to determine melting points and phase transformation temperatures. Phase relationships were investigated using scanning electron microscopy with an energy dispersive spectrometer. The isothermal section of the Fe-Sn-Ti ternary system at 873 K was established using equilibrated alloys. Three ternary compounds including the Heusler compound Fe2SnTi were observed. A new ternary compound Fe5Sn9Ti 6 was reported and the crystal structure of FeSnTi2 was determined for the first time.
Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds
NASA Technical Reports Server (NTRS)
Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.
1995-01-01
Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.
Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds
NASA Technical Reports Server (NTRS)
Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.
1995-01-01
Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.
Thermodynamic properties and phase equilibria for Pt-Rh alloys
Jacob, K.T.; Priya, S.; Waseda, Yoshio
1998-06-01
The activity of rhodium in solid Pt-Rh alloys is measured in the temperature range from 900 to 1,300 K using the solid-state cell Pt-Rh, Rh + Rh{sub 2}O{sub 3}/(Y{sub 2}O{sub 3})ZrO{sub 2}/Pt{sub 1{minus}x}Rh{sub x} + Rh{sub 2}O{sub 3}, Pt-Rh. The activity of platinum and the free energy, enthalpy, and entropy of mixing are derived. Activities exhibit moderate negative deviation from Raoult`s law. The mixing properties can be represented by a pseudosubregular solution model in which excess entropy has the same type of functional dependence on composition as the enthalpy of mixing, {Delta}H = X{sub Rh} (1 {minus} X{sub Rh})[{minus}10,970 + 45X{sub Rh}] J/mol, {Delta}S{sup E} = X{sub Rh} (1 {minus} X{sub Rh})[{minus}3.80 + 1.55 {times} 10{sup {minus}2} X{sub Rh}] J/mol{center_dot}K. The negative enthalpy of mixing obtained in this study is in qualitative agreement with predictions of semiempirical models of Miedema and co-workers and Colinet et al. The results of this study do not support the solid-state miscibility gap suggested in the literature, but are consistent with liquidus data within experimental uncertainty limits.
Monte carlo simulation of carboxylic acid phase equilibria.
Clifford, Scott; Bolton, Kim; Ramjugernath, Deresh
2006-11-01
Configurational-bias Monte Carlo simulations were carried out in the Gibbs ensemble to generate phase equilibrium data for several carboxylic acids. Pure component coexistence densities and saturated vapor pressures were determined for acetic acid, propanoic acid, 2-methylpropanoic acid, and pentanoic acid, and binary vapor-liquid equilibrium (VLE) data for the propanoic acid + pentanoic acid and 2-methylpropanoic acid + pentanoic acid systems. The TraPPE-UA force field was used, as it has recently been extended to include parameters for carboxylic acids. To simulate the branched compound 2-methylpropanoic acid, certain minor assumptions were necessary regarding angle and torsion terms involving the -CH- pseudo-atom, since parameters for these terms do not exist in the TraPPE-UA force field. The pure component data showed good agreement with the available experimental data, particularly with regard to the saturated liquid densities (mean absolute errors were less than 1.1%). On average, the predicted critical temperature and density were within 1% of the experimental values. All of the binary simulations showed good agreement with the experimental x-y data. However, the TraPPE-UA force field predicts saturated vapor pressures of pure components that are larger than the experimental values, and consequently the P-x-y and T-x-y data of the binary systems also deviate from the measured data.
10 kbar phase equilibria in the Y-Ba-Cu oxide system at 950 C
Lawanier, J.P.; Meen, J.K.; Elthon, D.
1996-02-01
Phase equilibria in the YO{sub 1.5}BaO-CuO system have been determined at 950 C at 10 kbar using a piston-cylinder apparatus. The oxide phases stable under these conditions are Y{sub 2}O{sub 3}, Y{sub 2}Cu{sub 2}O{sub 5}, CuO, Y{sub 2}BaCuO{sub 5}, YBa{sub 2}Cu{sub 3}O{sub 6.5}, BaCuO{sub 2}, Y{sub 2}BaO{sub 4}, Y{sub 2}Ba{sub 3}O{sub 6}, and YBa{sub 4}Cu{sub 2}O{sub 7.5}. The phase stabilities observed at 950 C at 10 kbar are identical to those observed at 950 C in air or oxygen at 1 atm for compositions with < 40% Ba of the cations. In more Ba-rich portions of the phase diagram, carbonates and oxycarbonates are stabilized and a systematic determination of the phase equilibria has not been successful.
Artificial multiple criticality and phase equilibria: an investigation of the PC-SAFT approach.
Yelash, Leonid; Müller, Marcus; Paul, Wolfgang; Binder, Kurt
2005-11-01
The perturbed-chain statistical associating fluid theory (PC-SAFT) is studied for a wide range of temperature, T, pressure, p, and (effective) chain length, m, to establish the generic phase diagram of polymers according to this theory. In addition to the expected gas-liquid coexistence, two additional phase separations are found, termed "gas-gas" equilibrium (at very low densities) and "liquid-liquid" equilibrium (at densities where the system is expected to be solid already). These phase separations imply that in one-component polymer systems three critical points occur, as well as equilibria of three fluid phases at triple points. However, Monte Carlo simulations of the corresponding system yield no trace of the gas-gas and liquid-liquid equilibria, and we conclude that the latter are just artefacts of the PC-SAFT approach. Using PC-SAFT to correlate data for polybutadiene melts, we suggest that discrepancies in modelling the polymer density at ambient temperature and high pressure can be related to the presumably artificial liquid-liquid phase separation at lower temperatures. Thus, particular care is needed in engineering applications of the PC-SAFT theory that aims at predicting properties of macromolecular materials.
Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system
NASA Technical Reports Server (NTRS)
Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.
1989-01-01
Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.
Phases, phase equilibria, and phase rules in low-dimensional systems
Frolov, T.; Mishin, Y.
2015-07-28
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.
Phase equilibria in the condensed system n-docosane-cyclododecane- n-decane
NASA Astrophysics Data System (ADS)
Shamitov, A. A.; Garkushin, I. K.; Kolyado, A. V.
2016-07-01
Phase equilibria in the system n-docosane-cyclododecane-n-decane are studied by means of differential thermal analysis. It is found that the system is of the eutectic type. The temperature of eutectic melting is found to be-34.9°C, the n-docosane content is 3.5 wt %, the n-decane content is 86.5 wt %, and the cyclododecane content is 10.0 wt %. It is concluded that the results can be used to create new optimal heatstorage materials.
Phase equilibria in a three-component water-soap-alcohol system. A thermodynamic model
Joensson, B.; Wennerstroem, H.
1987-01-15
A thermodynamic model is presented for ternary systems consisting of ionic surfactant-long-chain alcohol-water. The important contributions to the model free energy are (i) an electrostatic term; (ii) a free energy term; (iii) four entropy terms; (iv) constraints imposed by molecular packing restrictions; and (v) a hydration force. The free energy expressions are developed for (spherical) micellar solutions, normal hexagonal liquid crystals, lamellar liquid crystals, reversed hexagonal liquid crystals, and inverted (spherical) micellar solutions. For all these types of phases the aggregate geometries are optimized and the relative stabilities are determined. The phase equilibria are determined by deriving explicit expressions for the chemical potentials of the three components and using the criterion that they should be equal for phases in equilibrium. The model gives a nearly quantitative description of the equilibria in the test system potassium decanoate-octanol-water. The general conclusions are (i) at high ratios of ionic surfactant to alcohol the dominating factor is the electrostatics, with an additional effect from the fact that the alcohol decreases the free energy of the polar-apolar interface; (ii) the stability of the inverted micellar system is greatly influenced by the entropy of mixing between the palisade layer and the bulk alcohol medium; (iii) at low water contents one has to invoke the occurrence of a hydration force.
Solid-liquid phase equilibria from free-energy perturbation calculations
NASA Astrophysics Data System (ADS)
Angioletti-Uberti, Stefano; Asta, Mark; Finnis, Mike W.; Lee, P. D.
2008-10-01
A method for calculating free-energy differences based on a free-energy perturbation (FEP) formalism in an alloy system described by two different Hamiltonians is reported. The intended application is the calculation of solid-liquid phase equilibria in alloys with the accuracy of first-principles electronic density-functional theory (DFT). For this purpose free energies are derived with a classical interatomic potential, and FEP calculations are used to compute corrections to these reference values. For practical applications of this approach, due to the relatively high computational cost of DFT calculations, it is critical that the FEP calculations converge rapidly in terms of the number of samples used to estimate relevant ensemble averages. This issue is investigated in the current study employing two classical interatomic-potential models for Ni-Cu. These models yield differences in predicted phase-boundary temperatures of approximately 100 K, comparable to those that might be expected between a DFT Hamiltonian and a well-fit classical potential. We show that for pure elements the FEP calculations converge rapidly with the number of samples, yielding free-energy differences converged to within a fraction of a meV/atom in a few dozen energy calculations. For a concentrated equiatomic alloy similar precision requires roughly a hundred samples. The results suggest that the proposed methodology could provide a computationally tractable framework for calculating solid-liquid phase equilibria in concentrated alloys with DFT accuracy.
On the question of phase equilibria in the succinonitrile-(D)camphor system
NASA Astrophysics Data System (ADS)
Witusiewicz, V. T.; Hecht, U.; Rex, S.
2013-07-01
Alloys from the succinonitrile-(D)camphor (SCN-DC) system are widely used as model alloys for the in situ investigation of solidification using light optical microscopy, but literature on the binary phase diagram is contradictory with respect to the solubility limit of DC in (SCN). Phase equilibria of the system were therefore revisited experimentally and critically assessed in the present work. The results prove that the maximum solubility of DC in the succinonitrile solid solution (SCN) is far less 1 wt% and the volume fraction of the (DC) phase in the eutectic solid is 23.3%. On this basis and on recently reported experimental data the CALPHAD description of the SCN-DC system was re-optimized.
Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.
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.
NASA Astrophysics Data System (ADS)
Rivera-Rojas, Jose Luis
Molecular simulation is a very powerful technique that allows us to predict thermodynamic and transport properties of bulk and confined phases, as well as phase equilibria and interfacial properties. These properties are often crucial to the design of chemical and related industrial processes. Molecular simulation can predict these properties over a wide range of conditions, in contrast with experiments, which at extreme conditions (e.g., high temperature and/or high pressure) are often very difficult and in some cases dangerous. Furthermore, semi-empirical and empirical engineering models can frequently only be used for the specific systems to which they are fitted---that is, they are interpolative rather than predictive. Therefore molecular modeling methods, including simulation, can play a very useful role in the design of new processes, as well as the prediction of new phenomena. In this thesis, we applied molecular simulation methods to four separate problems: vapor-liquid equilibrium for a polarizable model of water, liquid-liquid interfacial properties, phase equilibrium in confined systems, and mechanical properties of nano scale systems. The first three problems imply the study of phases in equilibrium under different conditions. The most simple is the vapor-liquid equilibrium of a single component. Thermophysical properties such as coexistence densities, vapor pressure, surface tension, and interfacial thickness were obtained for a polarizable model of water and compared with other simpler potential models and experimental results. Using the same methodology, the interfacial properties of binary and ternary mixtures with polar and non-polar fluids exhibiting liquid-liquid equilibrium were studied. The dependence of the interfacial properties with increasing molecular size of one compound was studied. For ternary mixtures, the presence of a surfactant molecule was studied at different concentrations of the surfactant. Phase equilibria inside single carbon
NASA Astrophysics Data System (ADS)
Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.; Meshcheryakov, A. V.
2016-08-01
The boiling points of solutions of five binary systems are measured via ebulliometry in the pressure range of 2.05-103.3 kPa. Equilibrium vapor phase compositions, the values of the excess Gibbs energies, enthalpies, and entropies of solution of these systems are calculated. Patterns in the changes of phase equilibria and thermodynamic properties of solutions are established, depending on the compositions and temperatures of the systems. Liquid-vapor equilibria in the systems are described using the equations of Wilson and the NRTL (Non-Random Two-Liquid Model).
Phase equilibria of the magnesium sulfate-water system to 4 kbars
NASA Technical Reports Server (NTRS)
Hogenboom, D. L.; Kargel, J. S.; Ganasan, J. P.; Lee, L.
1993-01-01
Magnesium sulfate is the most abundant salt in carbonaceous chondrites, and it may be important in the low-temperature igneous evolution and aqueous differentiation of icy satellites and large chondritic asteroids. Accordingly, we are investigating high-pressure phase equilibria in MgSO4-H2O solutions under pressures up to four kbars. An initial report was presented two years ago. This abstract summarizes our results to date including studies of solutions containing 15.3 percent, 17 percent, and 22 percent MgSO4. Briefly, these results demonstrate that increasing pressure causes the eutectic and peritectic compositions to shift to much lower concentrations of magnesium sulfate, and the existence of a new low-density phase of magnesium sulfate hydrate.
MTDATA and the Prediction of Phase Equilibria in Oxide Systems: 30 Years of Industrial Collaboration
NASA Astrophysics Data System (ADS)
Gisby, John; Taskinen, Pekka; Pihlasalo, Jouni; Li, Zushu; Tyrer, Mark; Pearce, Jonathan; Avarmaa, Katri; Björklund, Peter; Davies, Hugh; Korpi, Mikko; Martin, Susan; Pesonen, Lauri; Robinson, Jim
2016-09-01
This paper gives an introduction to MTDATA, Phase Equilibrium Software from the National Physical Laboratory (NPL), and describes the latest advances in the development of a comprehensive database of thermodynamic parameters to underpin calculations of phase equilibria in large oxide, sulfide, and fluoride systems of industrial interest. The database, MTOX, has been developed over a period of thirty years based upon modeling work at NPL and funded by industrial partners in a project co-ordinated by Mineral Industry Research Organisation. Applications drawn from the fields of modern copper scrap smelting, high-temperature behavior of basic oxygen steelmaking slags, flash smelting of nickel, electric furnace smelting of ilmenite, and production of pure TiO2 via a low-temperature molten salt route are discussed along with calculations to assess the impact of impurities on the uncertainty of fixed points used to realize the SI unit of temperature, the kelvin.
NASA Astrophysics Data System (ADS)
Suntsov, Yu. K.; Vlasov, M. V.; Chuikov, A. M.
2015-06-01
The boiling points of solutions of five binary systems are measured using the ebulliometric method in the pressure range of 4.4-101.3 kPa. Compositions of the equilibrium vapor phases of systems are calculated, based on the constructed pressure isotherms of saturated vapor. The values of excess Gibbs energy and the enthalpy and entropy of solutions are calculated from the data on the liquid-vapor equilibrium. The patterns of change in the phase equilibria and thermodynamic properties of the solutions are established, based on the composition and temperature of the systems. The liquid-vapor equilibrium of systems is described using the equations of Wilson and the NRTL (Non-Random Two-Liquid model).
Critical comparison of classical and quantum mechanical treatments of the phase equilibria of water
Wick, Collin D.; Schenter, Gregory K.
2006-03-17
The Gibbs ensemble Monte Carlo simulation technique was used to compare the phase equilibria of the rigid TIP4P water model [J.\\ Chem.\\ Phys.\\ {\\bf 79}, 926, (1983)] utilizing classical and quantum statistical mechanical treatments. The quantum statistical mechanical treatment generally resulted in lower liquid densities and higher vapor densities, showing a narrowing in the phase envelope. As a result, the calculated critical temperature and normal boiling point were higher from the quantum simulations than the classical by 20~and 17~K, respectively, but the critical densities were very close. A semiclassical treatment, involving a low order expansion in Plank's constant, resulted in densities and vapor pressures that fluctuated between the values for the classical and quantum statistical mechanics values, with no definite agreement with either.
NASA Astrophysics Data System (ADS)
Budkov, Yu. A.; Kolesnikov, A. L.; Georgi, N.; Nogovitsyn, E. A.; Kiselev, M. G.
2015-11-01
We develop a first-principle equation of state of salt-free polyelectrolyte solution in the limit of infinitely long flexible polymer chains in the framework of a field-theoretical formalism beyond the linear Debye-Hueckel theory and predict a liquid-liquid phase separation induced by a strong correlation attraction. As a reference system we choose a set of two subsystems - charged macromolecules immersed in a structureless oppositely charged background created by counterions (polymer one component plasma) and counterions immersed in oppositely charged background created by polymer chains (hard-core one component plasma). We calculate the excess free energy of polymer one component plasma in the framework of Modified Random Phase Approximation, whereas a contribution of charge densities fluctuations of neutralizing backgrounds we evaluate at the level of Gaussian approximation. We show that our theory is in a very good agreement with the results of Monte-Carlo and MD simulations for critical parameters of liquid-liquid phase separation and osmotic pressure in a wide range of monomer concentration above the critical point, respectively.
Bayesian Nash equilibria using extended Werner-like states
NASA Astrophysics Data System (ADS)
Alid-Vaccarezza, M.; Soto, M. E.
2016-10-01
We study quantum strategies in games of incomplete information using a formalism of game theory based on multi-sector probability matrix. We analyze an extension of the well-known game of Battle of Sexes using an extended Werner-like state focusing in how its mixedness and entanglement affect the Bayesian Nash payoffs of the player. It is shown that entanglement is needed to outperform classical payoffs but not all entangled states are useful due to the presence of mixedness. A threshold for the mixedness parameter and the minimum entanglement value were found.
Bayesian Nash equilibria using extended Werner-like states
NASA Astrophysics Data System (ADS)
Alid-Vaccarezza, M.; Soto, M. E.
2016-07-01
We study quantum strategies in games of incomplete information using a formalism of game theory based on multi-sector probability matrix. We analyze an extension of the well-known game of Battle of Sexes using an extended Werner-like state focusing in how its mixedness and entanglement affect the Bayesian Nash payoffs of the player. It is shown that entanglement is needed to outperform classical payoffs but not all entangled states are useful due to the presence of mixedness. A threshold for the mixedness parameter and the minimum entanglement value were found.
The systems Sr-Zn-{l_brace}Si,Ge{r_brace}: Phase equilibria and crystal structure of ternary phases
Romaka, V.V.; Falmbigl, M.; Grytsiv, A.; Rogl, P.
2012-02-15
Phase relations have been established by electron probe microanalysis (EPMA) and X-ray powder diffraction (XPD) for the Sr-poor part of the ternary systems Sr-Zn-Si at 800 Degree-Sign C and Sr-Zn-Ge at 700 Degree-Sign C. In the Sr-Zn-Si system one new ternary compound SrZn{sub 2+x}Si{sub 2-x} (0{<=}x{<=}0.45) with CeAl{sub 2}Ga{sub 2} structure and a statistical mixture of Zn/Si in the 4e site was found. Neither a type-I nor a type-IX clathrate phase was encountered. This system is characterized by formation of two further phases, i.e. SrZn{sub 1-x}Si{sub 1+x} with ZrBeSi-type (0.16{<=}x{<=}0.22) and SrZn{sub 1-x}Si{sub 1+x} with AlB{sub 2}-type (0.35{<=}x{<=}0.65) with a random distribution of Zn/Si atoms in the 2c site. For the Sr-Zn-Ge system, the homogeneity regions of the isotypic phases SrZn{sub 1-x}Ge{sub 1+x} with ZrBeSi-type (0{<=}x{<=}0.17) and AlB{sub 2}-type (0.32{<=}x{<=}0.56), respectively, have been determined. Whereas the germanide SrZn{sub 2+x}Ge{sub 2-x} (CeAl{sub 2}Ga{sub 2}-type) is characterized by a homogeneity region (0{<=}x{<=}0.5), the clathrate type-I phase Sr{sub 8}Zn{sub 8}Ge{sub 38} shows a point composition. - Graphical abstract: Phase equilibria of ternary compounds in the Sr-Zn-Si-system at 800 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Phase equilibria in the Sr-Zn-Si-system are established at 800 Degree-Sign C. Black-Right-Pointing-Pointer Phase equilibria in the Sr-Zn-Ge-system are established at 700 Degree-Sign C. Black-Right-Pointing-Pointer Crystal structures of the ternary compounds were confirmed by X-ray powder diffraction. Black-Right-Pointing-Pointer All ternary compounds except the clathrate-I in the Ge-system are characterized by a homogeneity region.
NASA Astrophysics Data System (ADS)
Lesnov, A. E.; Golovkina, A. V.; Kudryashova, O. S.; Denisova, S. A.
2016-08-01
Phase equilibria in layering systems of water, polyethyleneglycol ethers of monoethanolamides of synthetic fatty acids (SFAs) (synthamide-5), and ammonium chloride are studied. The possibility of using such systems for the liquid extraction of metal ions is evaluated. The effect the nature of salting-out agents has on the processes of segregation of the systems has been considered.
Planet Alsioff - A problem set for students of phase equilibria or metamorphic petrology
NASA Technical Reports Server (NTRS)
Burt, Donald M.
1988-01-01
This paper presents a problem set that contains questions for students of phase equilibria or metamorphic petrology concerning a hypothetical planet Alsioff, for which incomplete data are given. On this panet, the SiF4 is the major volatile and Al, Si, O, and F are the only elements present. Progressive metamorphism on Alsioff mainly involves devolatilization of fluid SiF4. The problem set includes ten questions. Some of these are concerned with possible chemical reactions that should affect water, wollastonite, or Ca-SiO3 exposed to the atmosphere of Alsioff; the mechanism of controls of the O2 and F2 contents of the Alsioffian atmosphere; and the devolatilization reactions involving SiF4 with progressive thermal metamorphism.
Sokkalingam, Nandhini; Kamath, Ganesh; Coscione, Maria; Potoff, Jeffrey J
2009-07-30
The transferable potentials for phase equilibria force field is extended to dimethylmethylphosphonate (DMMP), sarin, and soman by introducing a new interaction site representing the phosphorus atom. Parameters for the phosphorus atom are optimized to reproduce the liquid densities at 303 and 373 K and the normal boiling point of DMMP. Calculations for sarin and soman are performed in predictive mode, without further parameter optimization. Vapor-liquid coexistence curves, critical properties, vapor pressures and heats of vaporization are predicted over a wide range of temperatures with histogram reweighting Monte Carlo simulations in the grand canonical ensemble. Excellent agreement with experiment is achieved for all compounds, with unsigned errors of less than 1% for vapor pressures and normal boiling points and under 5% for heats of vaporization and liquid densities at ambient conditions.
Bhatnagar, Navendu; Kamath, Ganesh; Potoff, Jeffrey J
2013-08-29
The Transferable Potentials for Phase Equilibria (TraPPE) is extended to zwitterionic and charged lipids including phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylserine (PS), and phosphatidylglycerol (PG). The performance of the force field is validated through isothermal-isobaric ensemble (NPT) molecular dynamics simulations of hydrated lipid bilayers performed with the aforementioned head groups combined with saturated and unsaturated alkyl tails containing 12-18 carbon atoms. The effects of water model and sodium ion parameters on the performance of the lipid force field are determined. The predictions of the TraPPE force field for the area per lipid, bilayer thickness, and volume per lipid are within 1-5% of experimental values. Key structural properties of the bilayer, such as order parameter splitting in the sn-2 chain and X-ray form factors, are found to be in close agreement with experimental data.
Phase equilibria constraints on the chemistry of hot spring fluids at mid-ocean ridges
Seyfried, W.E. Jr.; Ding, K.; Berndt, M.E. )
1991-12-01
Recent advances in experimental and theoretical geochemistry have made it possible to assess both homogeneous and heterogeneous equilibria involving a wide range of aqueous species at temperatures and pressures appropriate to model hydrothermal alteration processes at mid-ocean ridges. The authors have combined selected aspects of the chemistry of hot spring fluids with constraints imposed by a geologically reasonable assemblage of minerals in the system Na{sub 2}O-K{sub 2}O-CaO-MgO-FeO-Fe{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-SiO{sub 2}-H{sub 2}O-HCl-H{sub 2}S to assess the effect of temperature on the composition of the aqueous phase and the activities of mineral components in plagioclase and epidote solid solutions. Assuming fO{sub 2(g)} and fS{sub 2(g)} controlled by pyrite-pyrrhotite-magnetite equilibria, a constant dissolved Ca concentration, and a dissolved Cl concentration equivalent to that of seawater, increasing temperature from 250 to 400C at 500 bars results in systematic changes in the composition of mineral phases, which in turn constrain pH and the distribution of aqueous species. The model predicts that dissolved concentrations of Fe, SiO{sub 2}, K, H{sub 2}S, and H{sub 2} increase, while Na and pH{sub (25C)} decrease with increasing temperature. That many hot springs vent fluids are characterized by variable degrees of conductive heat loss renders measured temperatures unreliable as indicators of the maximum temperature of subseafloor hydrothermal alteration processes. The implications of this are significant for hot spring fluids which reveal large Cl variations relative to seawater, since likely mechanisms to account for such variability typically require temperatures in excess of those inferred for subseafloor reaction zones by simply correcting measured temperatures for the effects of adiabatic cooling.
Phase Equilibria Experiments on Nisyros, Greece:``the Right Stuff" in -``the Right Stuff" out
NASA Astrophysics Data System (ADS)
Pyle, D. M.; Hunt, C. A.; Barclay, J.; Charlier, B. L.
2005-12-01
To extract meaningful information from phase equilibrium experiments the starting composition must be made of ``the right stuff'' and the results compared with the ``real phenocrysts''. Nisyros island is one of the most active volcanic centres on the South Aegean Volcanic Arc. Pleistocene to recent volcanism has evolved from submarine to sub-aerial in style, culminating in the large caldera-forming eruptions at ca. 33 ka. Post caldera activity has been confined to the extrusion of viscous domes, which fill almost half of the caldera, and hydrothermal eruptions. Studies on the sub-volcanic plumbing dynamics of Nisyros have shown that it is a complex and poorly constrained system, and the need to constrain these parameters is gaining impetus given that Nisyros is showing signs of unrest. The domes are dacitic (SiO2 68 wt. %). Phenocryst phases in decreasing order of abundance are plagioclase, clinopyroxene, orthopyroxene and Fe-Ti oxides. Amphibole is present only as a xenocryst phase, derived from the disaggregation of andesitic magmatic inclusions which are prominent in the dome rocks. There are no eruption dates for the post-caldera activity, but the domes are probably Holocene in age. Age differentiation between the domes is based solely on the extent of weathering and position relative to adjacent domes. Preliminary U/Th investigations of zircons from the ca. 33 ka caldera phase by ion probe have shown that these are inherited, with ages of 92, +35/-27 ka. Low zircon saturation temperatures (731-769 °C) for the post-caldera domes suggest similarly that any zircons present will have been inherited. Extensive geochemical evidence for magma mixing indicates the need for caution in choosing an appropriate starting composition for the phase equilibria experiments. Simple major element modelling suggests limited bulk mixing between silicic and andesitic end-members. There is also little evidence to suggest that the dacite has been hybridised by the andesitic
Phase equilibria in the iron oxide-cobalt oxide-phosphorus oxide system
NASA Technical Reports Server (NTRS)
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.
Phase equilibria and transformations in the Ti-Al-Nb system
NASA Astrophysics Data System (ADS)
Mishurda, Joseph Constantine
The phase equilibria and transformations in the Nb-Ti-Al system in the vicinity of the Sigma phase field have been examined with respect to the Liquidus Surface (Phase 1), the Phase Equilibria and Equilibrium Transformations (Phase II), and the Phase Transformations, Mechanisms and Kinetics (Phase III). Eight alloy compositions were produced by arc melting. The alloys were characterized by differential thermal analysis, metallography, X-ray diffraction, scanning electron microscopy (BSEI), electron probe microanalysis and transmission electron microscopy. The liquidus examination shed new light on previous microstructural interpretations, opening up new possibilities for microstructural development and control of multiphase alloys. Differential thermal analysis has identified the existence of a beta to sigma + gamma transformation in an alloy where it was not previously thought to exist. The results differed from the calculated diagram by higher titanium solubility in the sigma and delta phases than predicted at lower temperatures and a lower solubility of alpha2 and gamma. The high temperature betao transforms to gamma + sigma in a eutectoid fashion resulting in a desirable lamellar structure of sigma and gamma. The existence of a new body centered tetragonal crystal structure ao = 5.11A and co 28.12A with a point group symmetry of P4/mmm, at 700°C was discovered. A plethel section was found for the sigma + beta two phase alloys. A betao + O + sigma three phase field passes through the alloys between 981 and 1000°C. The plethel section at the transformation has an eutectoid characteristic, however, the nature of the transformation changes to a peritectoid. At temperatures below 970°C, the first transformation to occur is the decomposition of the metastable betao phase to an intermediate metastable phase O'. Reasonable values for Q were obtained, applicable to the diffusion limited region of the TTT-curve. The microstructure evolution of the sigma + beta
The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O
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.
Phase Equilibria of the Fe-Ni-Sn Ternary System at 270°C
NASA Astrophysics Data System (ADS)
Huang, Tzu-Ting; Lin, Shih-Wei; Chen, Chih-Ming; Chen, Pei Yu; Yen, Yee-Wen
2016-07-01
The Fe-42 wt.% Ni alloy, also known as a 42 invar alloy (Alloy 42), is used as a lead-frame material because its thermal expansion coefficient is much closer to Si substrate than Cu or Ni substrates. In order to enhance the wettability between the substrate and solder, the Sn layer was commonly electroplated onto the Alloy 42 surface. A clear understanding of the phase equilibria of the Fe-Ni-Sn ternary system is necessary to ensure solder-joint reliability between Sn and Fe-Ni alloys. To determine the isothermal section of the Fe-Ni-Sn ternary system at 270°C, 26 Fe-Ni-Sn alloys with different compositions were prepared. The experimental results confirmed the presence of the Fe3Ni and FeNi phases at 270°C. Meanwhile, it observed that the isothermal section of the Fe-Ni-Sn ternary system was composed of 11 single-phase regions, 19 two-phase regions and nine tie-triangles. Moreover, no ternary compounds were found in the Fe-Ni-Sn system at 270°C.
NASA Astrophysics Data System (ADS)
Mullen, E.; McCallum, I. S.
2009-12-01
Basalts in continental arcs are volumetrically subordinate to andesites and this is the case for Mt. Baker in the northern Cascade magmatic arc. However, basalts provide indirect evidence on mantle compositions and processes that produce magmas parental to the abundant andesites and dacites of the stratocones. Basalts at Mt. Baker erupted from monogenetic vents peripheral to the andesitic stratocone. Flows are variable in composition; some samples would more appropriately be classified as basaltic andesites. The “basalts” have relatively low Mg/(Mg+Fe) indicating that they have evolved from their original compositions. Samples studied are Park Butte, Tarn Plateau, Lk. Shannon, Sulphur Cr. basalts, and Cathedral Crag, Hogback, and Rankin Ridge basaltic andesites. Mt. Baker lavas belong to the calc-alkaline basalt suite (CAB) defined by Bacon et al. (1997) and preserve arc geochemical features. High alumina olivine tholeiite (HAOT) are absent. Equilibrium mineral pairs and whole rock compositions were used to calculate pre-eruptive temperatures, water contents, and redox states of the “basalts.” All samples have zoned olivine phenocrysts with Fo68 to Fo87 cores and chromite inclusions. Cpx and zoned plagioclase occur in all flows, but opx occurs only in Cathedral Crag, Rankin Ridge, and Tarn Plateau. Ti-magnetite and ilmenite coexist in all flows except for Sulphur Cr., Lk. Shannon and Hogback, which contain a single Fe-Ti oxide. Liquidus temperatures range from 1080 to 1232°C and are negatively correlated with water contents. Water contents estimated using liquidus depression due to H2O (0.8 to 5.4 wt.%) agree well with plag core-whole rock equilibria estimates (1.2 to 3.9 wt.%). Park Butte, Sulphur Cr. and Lk. Shannon had <1.5 wt.% H2O, and Cathedral Crag is most hydrous. Redox states from ol-chr pairs (QFM +0.1 to +2.8) and Fe-Ti oxide pairs (QFM -0.6 to +1.8) indicate that Park Butte and Sulphur Cr. are most oxidized and Cathedral Crag most reduced
Direct molecular dynamics simulation of liquid-solid phase equilibria for a three-component plasma.
Hughto, J; Horowitz, C J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K
2012-12-01
The neutron-rich isotope ²²Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of ²²Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semianalytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two-component carbon and oxygen systems. This suggests that small amounts of ²²Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Γ) in our MD simulations compared to the semianalytic model. This difference seems to grow with impurity parameter Q_{imp} and suggests a problem with simple corrections to the linear mixing rule for the free energy of multicomponent solid mixtures that is used in the semianalytic model. PMID:23368065
Direct molecular dynamics simulation of liquid-solid phase equilibria for a three-component plasma.
Hughto, J; Horowitz, C J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K
2012-12-01
The neutron-rich isotope ²²Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of ²²Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semianalytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two-component carbon and oxygen systems. This suggests that small amounts of ²²Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Γ) in our MD simulations compared to the semianalytic model. This difference seems to grow with impurity parameter Q_{imp} and suggests a problem with simple corrections to the linear mixing rule for the free energy of multicomponent solid mixtures that is used in the semianalytic model.
Postperovskite phase equilibria in the MgSiO3-Al2O3 system.
Tsuchiya, Jun; Tsuchiya, Taku
2008-12-01
We investigate high-P,T phase equilibria of the MgSiO(3)-Al(2)O(3) system by means of the density functional ab initio computation methods with multiconfiguration sampling. Being different from earlier studies based on the static substitution properties with no consideration of Rh(2)O(3)(II) phase, present calculations demonstrate that (i) dissolving Al(2)O(3) tends to decrease the postperovskite transition pressure of MgSiO(3) but the effect is not significant ( approximately -0.2 GPa/mol% Al(2)O(3)); (ii) Al(2)O(3) produces the narrow perovskite+postperovskite coexisting P,T area (approximately 1 GPa) for the pyrolitic concentration (x(Al2O3) approximately 6 mol%), which is sufficiently responsible to the deep-mantle D'' seismic discontinuity; (iii) the transition would be smeared (approximately 4 GPa) for the basaltic Al-rich composition (x(Al2O3) approximately 20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh(2)O(3)(II) with increasing the Al concentration involving small displacements of the Mg-site cations.
NASA Astrophysics Data System (ADS)
Semenov, K. N.; Charykov, N. A.; Postnov, V. N.; Sharoyko, V. V.; Murin, I. V.
2016-01-01
This review is the first attempt to integrate the available data on all types of phase equilibria (solubility, extraction and sorption) in systems containing light fullerenes (C60 and C70). In the case of solubility diagrams, the following types of phase equilibria are considered: individual fullerene (C60 or C70)–solvent under polythermal and polybaric conditions; C60–C70–solvent, individual fullerene–solvent(1)–solvent(2), as well as multicomponent systems comprising a single fullerene or an industrial mixture of fullerenes and vegetable oils, animal fats or essential oils under polythermal conditions. All published experimental data on the extraction equilibria in C60–C70–liquid phase(1)–liquid phase(2) systems are described systematically and the sorption characteristics of various materials towards light fullerenes are estimated. The possibility of application of these experimental data for development of pre-chromatographic and chromatographic methods for separation of fullerene mixtures and application of fullerenes as nanomodifiers are described. The bibliography includes 87 references.
NASA Astrophysics Data System (ADS)
Semenov, K. N.; Charykov, N. A.; Postnov, V. N.; Sharoyko, V. V.; Murin, I. V.
2016-01-01
This review is the first attempt to integrate the available data on all types of phase equilibria (solubility, extraction and sorption) in systems containing light fullerenes (C60 and C70). In the case of solubility diagrams, the following types of phase equilibria are considered: individual fullerene (C60 or C70)-solvent under polythermal and polybaric conditions; C60-C70-solvent, individual fullerene-solvent(1)-solvent(2), as well as multicomponent systems comprising a single fullerene or an industrial mixture of fullerenes and vegetable oils, animal fats or essential oils under polythermal conditions. All published experimental data on the extraction equilibria in C60-C70-liquid phase(1)-liquid phase(2) systems are described systematically and the sorption characteristics of various materials towards light fullerenes are estimated. The possibility of application of these experimental data for development of pre-chromatographic and chromatographic methods for separation of fullerene mixtures and application of fullerenes as nanomodifiers are described. The bibliography includes 87 references.
Proteolytic Equilibria of Vanillic Acid in the Ground and Excited States
NASA Astrophysics Data System (ADS)
Vusovich, O. V.; Tchaikovskaya, O. N.; Sokolova, I. V.; Vasil‧eva, N. Yu.
2016-03-01
Proteolytic equilibria of vanillic acid in aqueous solutions were studied using electronic spectroscopy. The pH ranges for anionic, dianionic, cationic, and neutral forms of vanillic acid in the ground and excited states were determined. The electron density distribution on atoms in the proteolytic forms was determined using quantum-chemistry methods. The anion formed as a result of dissociation of the carboxylic acid. The dianion formed in the presence of two and more equivalents of alkali as a result of proton loss from the phenol and carboxylic acid. The vanillic acid cation formed via protonation of the carbonyl oxygen. Differences in spectral features of the proteolytic forms in the ground and excited states were observed.
Visual investigation of solid-liquid phase equilibria for nonflammable mixed refrigerant
NASA Astrophysics Data System (ADS)
Lee, C.; Yoo, J.; Park, I.; Park, J.; Cha, J.; Jeong, S.
2015-12-01
Non-flammable mixed refrigerant (NF-MR) Joule Thomson (J-T) refrigerators have desirable characteristics and wide cooling temperature range compared to those of pure J-T refrigerators. However, the operating challenge due to freezing is a critical issue to construct this refrigerator. In this paper, the solid-liquid phase equilibria (i.e. freezing point) of the NF-MR which is composed of Argon, R14 (CF4), and R218 (C3F8), has been experimentally investigated by a visualized apparatus. Argon, R14 and R218 mixtures are selected to be effectively capable of reaching 100 K in the MR J-T refrigerator system. Freezing points of the mixtures have been measured with the molar compositions from 0.1 to 0.8 for each component. Each test result is simultaneously acquired by a camcorder for visual inspection and temperature measurement during a warming process. Experimental results show that the certain mole fraction of Argon, R14, and R218 mixture can achieve remarkably low freezing temperature even below 77 K. This unusual freezing point depression characteristic of the MR can be a useful information for designing a cryogenic MR J-T refrigerator to reach further down to 77 K.
NASA Astrophysics Data System (ADS)
Afonso, Juan Carlos; Zlotnik, Sergio; Díez, Pedro
2015-10-01
We present a flexible, general, and efficient approach for implementing thermodynamic phase equilibria information (in the form of sets of physical parameters) into geophysical and geodynamic studies. The approach is based on Tensor Rank Decomposition methods, which transform the original multidimensional discrete information into a separated representation that contains significantly fewer terms, thus drastically reducing the amount of information to be stored in memory during a numerical simulation or geophysical inversion. Accordingly, the amount and resolution of the thermodynamic information that can be used in a simulation or inversion increases substantially. In addition, the method is independent of the actual software used to obtain the primary thermodynamic information, and therefore, it can be used in conjunction with any thermodynamic modeling program and/or database. Also, the errors associated with the decomposition procedure are readily controlled by the user, depending on her/his actual needs (e.g., preliminary runs versus full resolution runs). We illustrate the benefits, generality, and applicability of our approach with several examples of practical interest for both geodynamic modeling and geophysical inversion/modeling. Our results demonstrate that the proposed method is a competitive and attractive candidate for implementing thermodynamic constraints into a broad range of geophysical and geodynamic studies. MATLAB implementations of the method and examples are provided as supporting information and can be downloaded from the journal's website.
NASA Astrophysics Data System (ADS)
Afonso, J. C.; Zlotnik, S.; Diez, P.
2015-12-01
We present a flexible, general and efficient approach for implementing thermodynamic phase equilibria information (in the form of sets of physical parameters) into geophysical and geodynamic studies. The approach is based on multi-dimensional decomposition methods, which transform the original multi-dimensional discrete information into a dimensional-separated representation. This representation has the property of increasing the number of coefficients to be stored linearly with the number of dimensions (opposite to a full multi-dimensional cube requiring exponential storage depending on the number of dimensions). Thus, the amount of information to be stored in memory during a numerical simulation or geophysical inversion is drastically reduced. Accordingly, the amount and resolution of the thermodynamic information that can be used in a simulation or inversion increases substantially. In addition, the method is independent of the actual software used to obtain the primary thermodynamic information, and therefore it can be used in conjunction with any thermodynamic modeling program and/or database. Also, the errors associated with the decomposition procedure are readily controlled by the user, depending on her/his actual needs (e.g. preliminary runs vs full resolution runs). We illustrate the benefits, generality and applicability of our approach with several examples of practical interest for both geodynamic modeling and geophysical inversion/modeling. Our results demonstrate that the proposed method is a competitive and attractive candidate for implementing thermodynamic constraints into a broad range of geophysical and geodynamic studies.
High temperature phase equilibria studies in the Bi-Sr-Ca-Cu-O-Ag system
Margulies, Lawrence
1999-11-08
A variety of experimental techniques were utilized to examine the high temperature phase equilibria in the Bi-Sr-Ca-Cu-O-Ag system. Quenching studies were used to determine the liquid solubility of Ag in the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO{sub 2}). A liquid immiscibility region between oxide and Ag liquids in the 8--98 at% range was found above 900 C. Two eutectics were found in the Bi2212-Ag pseudobinary. On the oxide rich side, a eutectic exists at approximately 4 at% Ag. On the Ag rich side, a eutectic exists at approximately 98 at% Ag at a temperature of 15 C below the melting point of pure Ag. Six distinct solid phases were found to be in equilibrium with the partial melt within the Ag content and PO{sub 2} range studied. The stability of these solid phases were found to be highly sensitive to PO{sub 2}, and to a much lesser extent Ag content. High temperature x-ray diffraction (HTXRD) studies of this system are in conflict with these results. It is suggested that these discrepancies are due to experimental artifacts caused by the significant thermal gradients and lack of full bulk sampling which is inherent in conventional HTXRD designs. In part 2, a new furnace design compatible with synchrotron radiation sources is introduced to address these problems. This design allows for full bulk sampling in a low thermal gradient environment using Debye-Scherrer transmission geometry. Sample spinning is also introduced in the design to eliminate preferred orientation and incomplete powder averaging and allow for quantitative phase analysis and structural refinement. Studies on model systems are presented to demonstrate the capabilities for high resolution structural studies (Al{sub 2}O{sub 3}) and time resolved phase transformation studies (SrCO{sub 3}). Finally, the Bi2212 system is examined to confirm the quenching results
Phase equilibria of binary liquid crystal mixtures involving induced ordered phases
NASA Astrophysics Data System (ADS)
Huang, Tsang-Min
A phenomenological model for elucidating phase diagrams of hexagonal columnar/nematic liquid crystal mixtures has been developed on the basis of the combination of the Flory-Huggins (FH) free energy of isotropic mixing, Maier-Saupe (MS) free energy for nematic ordering, and Chandrasekhar-Clark free energy for hexagonal ordering. Self-consistent calculations show the theory is capable of predicting the various phase diagrams, covering nematic, hexagonal columnar, and isotropic phases. The model has been tested with the eutectic phase diagram of hexagonal columnar liquid crystal, 2, 3, 6, 7, 10, 11-hexapentyloxy triphenylene (HPTP)/reactive nematic mesogens, 4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1, 4-phenylene ester (RM257) mixtures determined by using DSC, polarized optical microscope (POM), and wide-angle X-ray diffraction (WAXD). The self-consistent calculation displays isotropic (I), nematic (N), hexagonal columnar (Colh), N + I, and Colh + I, and Colh + N coexistence regions. These phase regions has been confirmed by thermal quenching various compositions from the isotropic melt to different phase regions. Guided by the established phase diagram of HPTP/RM257 mixtures, photo-polymerization of the mixture has been carried out in different phase regions. The as-cured HPTP/p-(RM257) composites fabricated at isotropic phase (130 °C) remains single isotropic phase under optical microscope, whereas the SEM and TEM results show the bead-like microstructure with sub-micrometer scale. Polymerization-induced mesophase transition experiments have been carried out at isotropic temperatures slightly above the clearing point of the mixtures. Of particular interest is the development of liquid crystalline spherulites. Moreover, the fixation of the morphology is observed when the photopolymerization is carried out in the N, N + I, and N + Colh region. A generalized thermodynamic model for describing smectic A and smectic B ordering has been developed based on
Phase Equilibria of the Sn-Ni-Si Ternary System and Interfacial Reactions in Sn-(Cu)/Ni-Si Couples
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Zhang, Fan; Hu, Biao; Xu, Honghui; Liu, Shuhong; Zhou, Tao; Jin, Zhanpeng
2015-10-01
The phase equilibria of the Mg-Gd-Mn system at 773 K (500 °C) were investigated with sixteen alloys, by means of X-ray diffraction technique and electron probe microanalyses. Eight three-phase equilibria were accurately determined. No ternary compound was observed at 773 K (500 °C). The solubility of the third elements in the binary phases was measured. The isothermal section of the Mg-Gd-Mn system at 773 K (500 °C) was firstly established. It is worth mentioning that the three-phase field GdMg3-GdMg5-( αMn) was experimentally observed and is different from the three-phase field GdMg3-GdMg5-GdMn12 predicted using only the binary interaction parameters. Using the CALPHAD method, a thermodynamic modeling of the Mg-Gd-Mn system has been carried out in order to reasonably describe the experimental observations. The substitutional solution and sublattice models were used to describe the solution phases and intermediate phases. Comprehensive comparison between the calculated and measured isothermal sections shows that the experimental information is satisfactorily accounted for by the present thermodynamic modeling.
NASA Astrophysics Data System (ADS)
Tan, S. P.; Kargel, J. S.; Adidharma, H.; Marion, G. M.
2014-12-01
Until in-situ measurements can be made regularly on extraterrestrial bodies, thermodynamic models are the only tools to investigate the properties and behavior of chemical systems on those bodies. The resulting findings are often critical in describing physicochemical processes in the atmosphere, surface, and subsurface in planetary geochemistry and climate studies. The extremely cold conditions on Triton, Pluto and other Kuiper Belt Objects, and Titan introduce huge non-ideality that prevents conventional models from performing adequately. At such conditions, atmospheres as a whole—not components individually—are subject to phase equilibria with their equilibrium solid phases or liquid phases or both. A molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, the development of which is still in progress, was shown to reproduce the vertical composition profile of Titan's atmospheric methane measured by the Huygens probe (Tan et al., Icarus 2013, 222, 53). Recently, the model was also used to describe Titan's global circulation where the calculated composition of liquid in Ligeia Mare is consistent with the bathymetry and microwave absorption analysis of T91 Cassini fly-by data (Tan et al., 2014, submitted). Its capability to deal with equilibria involving solid phases has also been demonstrated (Tan et al., Fluid Phase Equilib. 2013, 360, 320). With all those previous works done, our attention is now shifting to the lower temperatures in Titan's tropopause and on Pluto's surface, where much technical development remains for CRYOCHEM to assure adequate performance at low temperatures. In these conditions, solid-vapor equilibrium (SVE) is the dominant phase behavior that determines the composition of the atmosphere and the existing ices. Another potential application is for the subsurface phase equilibrium, which also involves liquid, thus three-phase equilibrium: solid-liquid-vapor (SLV). This presentation will discuss the
NASA Astrophysics Data System (ADS)
Creamer, J. B.; Spera, F. J.; Bohrson, W. A.; Ghiorso, M. S.
2009-12-01
Mafic magmas generated by partial melting of mantle peridotites, eclogites or clinopyroxenites are hotter than, compositionally distinct from and have higher liquidus temperatures than the crustal rocks through which they ascend or are emplaced. The low thermal conductivity of crystalline and molten silicates implies that steep thermal gradients along the margins of propagating melt-filled fractures and stagnant magma bodies can develop and lead to crustal anatexis especially at depths >~10 km. Small differences in ambient deviatoric stresses within the crust can lead to the percolation of anatectic melts into adjacent magma. The magnitude of contamination is strongly dependant upon permeability which in turn depends upon the square of the volume fraction of anatectic melt, itself controlled by local phase equilibria. From the thermochemical vantage, AFC processes may be quantified using the Magma Chamber Simulator (MCS) by studying the variables that define the extent of AFC: thermal interaction mass ratio (ratio of pristine magma mass to mass of wallrock), bulk composition (including volatiles) of pristine magma and wallrock, the mean pressure and prevailing oxygen fugacity at which AFC occurs. Here we present MCS phase equilibria and major element solutions for a number of scenarios in which the sensible variables defining the extent of assimilation have been systematically varied. In particular, initial magma and wallrock temperatures, relative masses of wallrock and magma, oxygen fugacity and the mean pressure of AFC interaction are defined. The sub-systems are then allowed to proceed towards thermodynamic (thermal and chemical potential) equilibrium. Incremental enthalpy changes associated with magma cooling and crystallization are transferred to wallrock where heating and possible partial melting can occur. Fractional crystallization occurs in the magma and once the wallrock temperature exceeds its solidus, equilibrium melting in wallrock is enabled. When
Lubna, Nusrat; Kamath, Ganesh; Potoff, Jeffrey J; Rai, Neeraj; Siepmann, J Ilja
2005-12-22
An extension of the transferable potentials for phase equilibria united-atom (TraPPE-UA) force field to thiol, sulfide, and disulfide functionalities and thiophene is presented. In the TraPPE-UA force field, nonbonded interactions are governed by a Lennard-Jones plus fixed point charge functional form. Partial charges are determined through a CHELPG analysis of electrostatic potential energy surfaces derived from ab initio calculations at the HF/6-31g+(d,p) level. The Lennard-Jones well depth and size parameters for four new interaction sites, S (thiols), S(sulfides), S(disulfides), and S(thiophene), were determined by fitting simulation data to pure-component vapor-equilibrium data for methanethiol, dimethyl sulfide, dimethyl disulfide, and thiophene, respectively. Configurational-bias Monte Carlo simulations in the grand canonical ensemble combined with histogram-reweighting methods were used to calculate the vapor-liquid coexistence curves for methanethiol, ethanethiol, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol, 2-butanethiol, pentanethiol, octanethiol, dimethyl sulfide, diethyl sulfide, ethylmethyl sulfide, dimethyl disulfide, diethyl disulfide, and thiophene. Excellent agreement with experiment is achieved, with unsigned errors of less than 1% for saturated liquid densities and less than 3% for critical temperatures. The normal boiling points were predicted to within 1% of experiment in most cases, although for certain molecules (pentanethiol) deviations as large as 5% were found. Additional calculations were performed to determine the pressure-composition behavior of ethanethiol+n-butane at 373.15 K and the temperature-composition behavior of 1-propanethiol+n-hexane at 1.01 bar. In each case, a good reproduction of experimental vapor-liquid equilibrium separation factors is achieved; both of the coexistence curves are somewhat shifted because of overprediction of the pure-component vapor pressures.
Phase equilibria in the lysozyme-ammonium sulfate-water system.
Moretti, J J; Sandler, S I; Lenhoff, A M
2000-12-01
Ternary phase diagrams were measured for lysozyme in ammonium sulfate solutions at pH values of 4 and 8. Lysozyme, ammonium sulfate, and water mass fractions were assayed independently by UV spectroscopy, barium chloride titration, and lyophilization respectively, with mass balances satisfied to within 1%. Protein crystals, flocs, and gels were obtained in different regions of the phase diagrams, and in some cases growth of crystals from the gel phase or from the supernatant after floc removal was observed. These observations, as well as a discontinuity in protein solubility between amorphous floc precipitate and crystal phases, indicate that the crystal phase is the true equilibrium state. The ammonium sulfate was generally found to partition unequally between the supernatant and the dense phase, in disagreement with an assumption often made in protein phase equilibrium studies. The results demonstrate the potential richness of protein phase diagrams as well as the uncertainties resulting from slow equilibration.
Phase Equilibria of the Ternary Sn-Zn-Co System at 250°C and 500°C
NASA Astrophysics Data System (ADS)
Wang, Chao-hong; Huang, Sheng-en; Huang, Po-yen
2015-12-01
The isothermal sections of the ternary Sn-Zn-Co system (<60 at.% Co) at 250°C and 500°C have been experimentally determined. A series of Sn-Zn-Co alloys of various compositions were prepared and annealed at the respective temperatures to reach phase equilibrium. The equilibrium phases in these alloys were examined metallographically and characterized by electron probe microanalysis and x-ray diffraction. In this system, the ternary solubilities of all the binary Sn-Co and Co-Zn intermetallic compounds (IMCs) are very limited. For the phase equilibria at 250°C, two ternary IMCs, T1 and T2, were found, whose compositions were Sn-25 at.%Zn-25 at.%Co and Sn-15 at.%Zn-41 at.%Co, respectively. For the phase equilibria at 500°C, in addition to the T2 phase, another ternary IMC, namely T3 (Sn-18 at.%Zn-37 at.%Co), was also found. Moreover, the phase stability of the T1 and T3 phases was investigated at temperatures of 260°C to 400°C in detail. The equilibrium phase was the T1 phase below 300°C, and changed to the T3 phase at 400°C. The crystal structures of these three ternary IMCs were also studied. The T1 phase has a cubic structure ( Pm3m), and the T2 and T3 phases are orthorhombic in space group Cmcm and Pnma, respectively.
Heat capacity and phase equilibria of almandine, Fe 3Al 2Si 3O 12
NASA Astrophysics Data System (ADS)
Anovitz, L. M.; Essene, E. J.; Metz, G. W.; Bohlen, S. R.; Westrum, E. F., Jr.; Hemingway, B. S.
1993-09-01
The heat capacity of a synthetic almandine, Fe 3Al 2Si 3O 12, was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp298 = 342.80 ± 1.4 J/mol · K and S298o = 342.60 J/mol · K. Mössbauer characterizations show the almandine to contain less than 2 ± 1% of the total iron as Fe 3+. X-ray diffraction studies of this synthetic almandine yield a = 11.521 ± 0.001 Å and V298o = 115.11 +- 0.01 cm 3/mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with TN = 7.5 K. Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ΔGf,298 o = -4938.3 kJ/mol and ΔHf,298 o= - 5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T/P for almandine and is metastably located at ca. 570°C at P = 1 bar, with a dP/dT of +17 bars/°C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In ‖ O2- T space, almandine oxidizes near QFM by the reactions almandine + O2 = magnetite + sillimanite + quartzandalmandine + 02 = hercynite + magnetite + quartz. With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks.
Heat capacity and phase equilibria of almandine, Fe3Al2Si3O12
Anovitz, Lawrence M.; Essene, E.J.; Metz, G.W.; Bohlen, S.R.; Westrum, E.F.; Hemingway, B.S.
1993-01-01
The heat capacity of a synthetic almandine, Fe3Al2Si3O12, was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp298 = 342.80 ?? 1.4 J/mol ?? K and S298o = 342.60 J/mol ?? K. Mo??ssbauer characterizations show the almandine to contain less than 2 ?? 1% of the total iron as Fe3+. X-ray diffraction studies of this synthetic almandine yield a = 11.521 ?? 0.001 A?? and V298o = 115.11 +- 0.01 cm3/mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with TN = 7.5 K. Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ??Gf,298o = -4938.3 kJ/mol and ??Hf,298o= -5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T P for almandine and is metastably located at ca. 570??C at P = 1 bar, with a dP dT of +17 bars/??C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In {norm of matrix}O2-T space, almandine oxidizes near QFM by the reactions almandine + O2 = magnetite + sillimanite + quartz and almandine + 02 = hercynite + magnetite + quartz. With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks. ?? 1993.
Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts
NASA Technical Reports Server (NTRS)
Filiberto, Justin; Wood, Justin; Loan, Le; Dasgupta, Rajdeep; Shimizu, Nobumichi; Treiman, Allan H.
2010-01-01
Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future
Michalis, Vasileios K.; Costandy, Joseph; Economou, Ioannis G.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.
2015-01-28
The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal–isobaric ensemble in order to determine the coexistence temperature (T{sub 3}) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T{sub 3}, is treated with long simulations in the range of 1000–4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T{sub 3} predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T{sub 3} of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.
NASA Astrophysics Data System (ADS)
Michalis, Vasileios K.; Costandy, Joseph; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.; Economou, Ioannis G.
2015-01-01
The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.
Michalis, Vasileios K; Costandy, Joseph; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G
2015-01-28
The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models. PMID:25637989
Michalis, Vasileios K; Costandy, Joseph; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G
2015-01-28
The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.
NASA Astrophysics Data System (ADS)
Urusova, A. S.; Cherepanov, V. A.; Aksenova, T. V.; Gavrilova, L. Ya.; Kiselev, E. A.
2013-06-01
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, YBaCo4O7 and BaCo1-yYyO3-δ (0.09≤y≤0.42). It was shown that YBaCo2O5+δ possesses tetragonal structure with the 3ap×3ap×2ap superstructure (sp. gr. P4/mmm). High-temperature X-ray diffraction analysis of the YBaCo2O5+δ in the temperature range from 298 K up to 1073 K under Po2=0.21 аtm has not shown any phase transformations. The value of oxygen content for the YBaCo2O5+δ at room temperature was estimated as 5.40 and at 1323 K it was equal to 5.04. Thermal expansion of sample shows a linear characteristics and the average thermal expansion coefficient (TEC) is about 13.8×10-6, K-1 in the temperature range 298-1273 K. The homogeneity range and crystal structure of the BaCo1-yYyO3-δ (0.09≤y≤0.42) solid solutions were determined by X-ray diffraction of quenched samples. All BaCo1-yYyO3-δ solid solutions were found to have cubic structure (sp. gr. Pm3m). The unit cell parameters were refined using Rietveld full-profile analysis. Oxygen nonstoichiometry of BaCo1-yYyO3-δ solid solutions with 0.1≤y≤0.4 was measured by means of thermogravimetric technique within the temperature range 298-1373 K in air. Thermal expansion of BaCo1-yYyO3-δ (у=0.0; 0.1; 0.2; 0.3) samples was studied within the temperature range 298-1200 K in air. The projection of isothermal-isobaric phase diagram for the Y-Ba-Co-O system to the compositional triangle of metallic components was presented.
Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System
NASA Technical Reports Server (NTRS)
Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan
2001-01-01
Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.
Weil, K. Scott; Darsell, Jens T.
2006-01-18
This paper describes the effects of small palladium additions on the phase equilibria in the Ag-CuOx system. Below a concentration of 5 mol%, palladium was found to increase the temperature of the eutectic reaction present in the pseudobinary system, but have little effect on a higher temperature monotectic reaction. However once enough palladium was added to increase the pseudoternary solidus temperature to that of the lower boundary for this three-phase field (~970°C), the lower boundary begins to increase in temperature as well. The addition of palladium also causes the original eutectic point to move to lower silver concentrations, which also causes a convergence of the two new three-phase fields, CuOx + L1 + L2 and CuOx + α + L1. This suggests that with higher palladium concentrations, a peritectic reaction, α + L1 + L2 → CuOx, may eventually be observed in the system.
NASA Astrophysics Data System (ADS)
Stepanov, D. A.; Ermakova, A.; Anikeev, V. I.
2011-01-01
The objects of study were mixtures containing triglycerides and lower alcohols and also the products of the transesterification of triglycerides, glycerol and fatty acid esters. The Redlich-Kwong-Soave equation of state was used as a thermodynamic model for the phase state of the selected mixtures over wide temperature, pressure, and composition ranges. Group methods were applied to determine the critical parameters of pure substances and their acentric factors. The parameters obtained were used to calculate the phase diagrams and critical parameters of mixtures containing triglycerides and lower alcohols and the products of the transesterification of triglycerides, glycerol and fatty acid esters, at various alcohol/oil ratios. The conditions of triglyceride transesterification in various lower alcohols providing the supercritical state of reaction mixtures were selected.
Applying Lu-Hf garnet geochronology and inverse phase equilibria modeling to migmatites
NASA Astrophysics Data System (ADS)
Yakymchuk, C.; Brown, M.; Vervoort, J. D.
2013-12-01
Garnet-bearing assemblages are common in HT metamorphic rocks and are widely used to determine P-T conditions. Garnet is also a host for accessory minerals that may be used to determine the timing of garnet growth or breakdown. However, using accessory minerals to date garnet in HT metamorphic rocks may produce ambiguous or erroneous age results if these minerals were grown or modified subsequently due to fluid or melt infiltration along microfractures. Direct dating of garnet using the Sm-Nd and/or Lu-Hf isotope systems potentially avoids these problems. However, at temperatures above the solidus, the Sm-Nd isotope composition of garnet may become homogenized during post-peak cooling and evidence of prograde growth may be removed. The Lu-Hf isotope system in garnet is more robust and less susceptible to diffusion-controlled re-equilibration. Therefore, Lu-Hf dating of garnet has the potential to constrain the period of prograde garnet growth in HT metamorphic rocks. In the Fosdick migmatite-granite complex of West Antarctica, two episodes of HT garnet growth have been proposed based on U-Pb monazite ages from garnet-bearing migmatitic paragneisses and orthogneisses and U-Pb zircon ages from spatially associated peraluminous granites. Cores of monazite inclusions in garnet yield Carboniferous ages whereas the rims yield Cretaceous ages, and the garnet itself records Cretaceous Sm-Nd ages. The Sm-Nd ages were interpreted to represent diffusional resetting during the Cretaceous of garnet that grew in the Carboniferous. In this study, Lu-Hf garnet geochronology is used to test the hypothesis that garnet in the migmatitic paragneisses and orthogneisses is Carboniferous in age. We also assess the utility of the Lu-Hf system for dating garnet growth in rocks that have experienced superimposed HT metamorphic events. In addition, inverse phase equilibria modeling of open system melting is used to constrain the P-T conditions of garnet growth in migmatitic paragneisses and
Urusova, A.S.; Cherepanov, V.A. Aksenova, T.V.; Gavrilova, L.Ya.; Kiselev, E.A.
2013-06-01
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: YBaCo₂O_{5+δ}, YBaCo₄O₇ and BaCo_{1–y}Y_{y}O_{3–δ} (0.09≤y≤0.42). It was shown that YBaCo₂O_{5+δ} possesses tetragonal structure with the 3aₚ×3aₚ×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 transformations. The value of oxygen content for the YBaCo₂O_{5+δ} at room temperature was estimated as 5.40 and at 1323 K it was equal to 5.04. Thermal expansion of sample shows a linear characteristics and the average thermal expansion coefficient (TEC) is about 13.8×10⁻⁶, K⁻¹ in the temperature range 298–1273 K. The homogeneity range and crystal structure of the BaCo_{1–y}Y_{y}O_{3–δ} (0.09≤y≤0.42) solid solutions were determined by X-ray diffraction of quenched samples. All BaCo_{1–y}Y_{y}O_{3–δ} solid solutions were found to have cubic structure (sp. gr. Pm3m). The unit cell parameters were refined using Rietveld full-profile analysis. Oxygen nonstoichiometry of BaCo_{1–y}Y_{y}O_{3–δ} solid solutions with 0.1≤y≤0.4 was measured by means of thermogravimetric technique within the temperature range 298–1373 K in air. Thermal expansion of BaCo_{1–y}Y_{y}O_{3–δ} (y=0.0; 0.1; 0.2; 0.3) samples was studied within the temperature range 298–1200 K in air. The projection of isothermal–isobaric phase diagram for the Y–Ba–Co–O system to the compositional triangle of metallic components was presented. - Graphical abstract: A projection of isobaric isothermal phase diagram of the Y–Ba–Co–O system to the metallic components
Predicting mixture phase equilibria and critical behavior using the SAFT-VRX approach.
Sun, Lixin; Zhao, Honggang; Kiselev, Sergei B; McCabe, Clare
2005-05-12
The SAFT-VRX equation of state combines the SAFT-VR equation with a crossover function that smoothly transforms the classical equation into a nonanalytical form close to the critical point. By a combinination of the accuracy of the SAFT-VR approach away from the critical region with the asymptotic scaling behavior seen at the critical point of real fluids, the SAFT-VRX equation can accurately describe the global fluid phase diagram. In previous work, we demonstrated that the SAFT-VRX equation very accurately describes the pvT and phase behavior of both nonassociating and associating pure fluids, with a minimum of fitting to experimental data. Here, we present a generalized SAFT-VRX equation of state for binary mixtures that is found to accurately predict the vapor-liquid equilibrium and pvT behavior of the systems studied. In particular, we examine binary mixtures of n-alkanes and carbon dioxide + n-alkanes. The SAFT-VRX equation accurately describes not only the gas-liquid critical locus for these systems but also the vapor-liquid equilibrium phase diagrams and thermal properties in single-phase regions.
A New Approach to Modeling Densities and Equilibria of Ice and Gas Hydrate Phases
NASA Astrophysics Data System (ADS)
Zyvoloski, G.; Lucia, A.; Lewis, K. C.
2011-12-01
The Gibbs-Helmholtz Constrained (GHC) equation is a new cubic equation of state that was recently derived by Lucia (2010) and Lucia et al. (2011) by constraining the energy parameter in the Soave form of the Redlich-Kwong equation to satisfy the Gibbs-Helmholtz equation. The key attributes of the GHC equation are: 1) It is a multi-scale equation because it uses the internal energy of departure, UD, as a natural bridge between the molecular and bulk phase length scales. 2) It does not require acentric factors, volume translation, regression of parameters to experimental data, binary (kij) interaction parameters, or other forms of empirical correlations. 3) It is a predictive equation of state because it uses a database of values of UD determined from NTP Monte Carlo simulations. 4) It can readily account for differences in molecular size and shape. 5) It has been successfully applied to non-electrolyte mixtures as well as weak and strong aqueous electrolyte mixtures over wide ranges of temperature, pressure and composition to predict liquid density and phase equilibrium with up to four phases. 6) It has been extensively validated with experimental data. 7) The AAD% error between predicted and experimental liquid density is 1% while the AAD% error in phase equilibrium predictions is 2.5%. 8) It has been used successfully within the subsurface flow simulation program FEHM. In this work we describe recent extensions of the multi-scale predictive GHC equation to modeling the phase densities and equilibrium behavior of hexagonal ice and gas hydrates. In particular, we show that radial distribution functions, which can be determined by NTP Monte Carlo simulations, can be used to establish correct standard state fugacities of 1h ice and gas hydrates. From this, it is straightforward to determine both the phase density of ice or gas hydrates as well as any equilibrium involving ice and/or hydrate phases. A number of numerical results for mixtures of N2, O2, CH4, CO2, water
Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O
Capobianco, Ryan; Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R; Bodnar, Robert
2013-01-01
The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densities were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.
Phase Equilibria of the Carbon Dioxide + 1-Decanol System at High Pressures.
Ioniţă, Simona; Feroiu, Viorel; Geană, Dan
2013-11-14
In this work experimental vapor-liquid equilibrium (VLE) data and three-phase vapor-liquid-liquid equilibrium (VLLE) data are presented for the carbon dioxide + 1-decanol system. The VLE data were measured at five temperatures, (303.2, 308.2, 323.2, 333.2, and 343.2) K, and pressures up to 16 MPa. The VLLE data cover pressure-temperature (P-T) values from 289 K and 5 MPa to the upper critical end point (UCEP). We have used two models to represent the complex fluid phase behavior (P-T critical curve, VLLE line, and VLE isotherms) of the carbon dioxide + 1-decanol system: the cubic general equation of state (GEOS) and Peng-Robinson (PR) equation in conjunction with van der Waals two parameters conventional mixing rules (2PCMR). A correlation method involving temperature-dependent interaction parameters and a semipredictive approach with independent temperature interaction parameters have been used. Comparisons with experimental data reported in this work and available in the literature indicate that the topology of fluid phase behavior is satisfactorily given by the semipredictive procedure both for the critical line and in subcritical region, considering the relative simple used cubic equations of state. PMID:24249919
Phase Equilibria of the Carbon Dioxide + 1-Decanol System at High Pressures.
Ioniţă, Simona; Feroiu, Viorel; Geană, Dan
2013-11-14
In this work experimental vapor-liquid equilibrium (VLE) data and three-phase vapor-liquid-liquid equilibrium (VLLE) data are presented for the carbon dioxide + 1-decanol system. The VLE data were measured at five temperatures, (303.2, 308.2, 323.2, 333.2, and 343.2) K, and pressures up to 16 MPa. The VLLE data cover pressure-temperature (P-T) values from 289 K and 5 MPa to the upper critical end point (UCEP). We have used two models to represent the complex fluid phase behavior (P-T critical curve, VLLE line, and VLE isotherms) of the carbon dioxide + 1-decanol system: the cubic general equation of state (GEOS) and Peng-Robinson (PR) equation in conjunction with van der Waals two parameters conventional mixing rules (2PCMR). A correlation method involving temperature-dependent interaction parameters and a semipredictive approach with independent temperature interaction parameters have been used. Comparisons with experimental data reported in this work and available in the literature indicate that the topology of fluid phase behavior is satisfactorily given by the semipredictive procedure both for the critical line and in subcritical region, considering the relative simple used cubic equations of state.
NASA Astrophysics Data System (ADS)
Golovkina, A. V.; Kudryashova, O. S.; Lesnov, A. E.; Denisova, S. A.
2013-09-01
Phase equilibria in ternary aqueous layering systems containing a commercial nonionogen surfactant (Surf.) syntamide-5 or syntamide-5k and an inorganic salting-out agent ammonium sulfate were studied. The potential application of the systems for liquid extraction of metal ions was assessed.
Mie potentials for phase equilibria calculations: application to alkanes and perfluoroalkanes.
Potoff, Jeffrey J; Bernard-Brunel, Damien A
2009-11-01
Transferable united-atom force fields, based on n - 6 Lennard-Jones potentials, are presented for normal alkanes and perfluorocarbons. It is shown that by varying the repulsive exponent the range of the potential can be altered, leading to improved predictions of vapor pressures while also reproducing saturated liquid densities to high accuracy. Histogram-reweighting Monte Carlo simulations in the grand canonical ensemble are used to determine the vapor liquid coexistence curves, vapor pressures, heats of vaporization, and critical points for normal alkanes methane through tetradecane, and perfluorocarbons perfluoromethane through perfluorooctane. For all molecules studied, saturated liquid densities are reproduced to within 1% of experiment. Vapor pressures for normal alkanes and perfluorocarbons were predicted to within 3% and 6% of experiment, respectively. Calculations performed for binary mixture vapor-liquid equilibria for propane + pentane show excellent agreement with experiment, while slight deviations are observed for the ethane + perfluoroethane mixture.
Phase equilibria and structural investigations in the Ni-poor part of the system Al–Ge–Ni
Reichmann, Thomas L.; Duarte, Liliana I.; Effenberger, Herta S.; Leinenbach, Christian; Richter, Klaus W.
2012-01-01
The ternary phase diagram Al–Ge–Ni was investigated between 0 and 50 at.% Ni by a combination of differential thermal analysis (DTA), powder- and single-crystal X-ray diffraction (XRD), metallography and electron probe microanalysis (EPMA). Ternary phase equilibria and accurate phase compositions of the equilibrium phases were determined within two partial isothermal sections at 400 and 700 °C, respectively. The two binary intermediate phases AlNi and Al3Ni2 were found to form extended solid solutions with Ge in the ternary. Three new ternary phases were found to exist in the Ni-poor part of the phase diagram which were designated as τ1 (oC24, CoGe2-type), τ2 (at approximately Al67.5Ge18.0Ni14.5) and τ3 (cF12, CaF2-type). The ternary phases show only small homogeneity ranges. While τ1 was investigated by single crystal X-ray diffraction, τ2 and τ3 were identified from their powder diffraction pattern. Ternary phase reactions and melting behaviour were studied by means of DTA. A total number of eleven invariant reactions could be derived from these data, which are one ternary eutectic reaction, six transition reactions, three ternary peritectic reactions and one maximum. Based on the measured DTA values three vertical sections at 10, 20 and 35 at.% Ni were constructed. Additionally, all experimental results were combined to a ternary reaction scheme (Scheil diagram) and a liquidus surface projection. PMID:27087753
Ceria in an oxygen environment: Surface phase equilibria and its descriptors
NASA Astrophysics Data System (ADS)
Botu, Venkatesh; Ramprasad, Rampi; Mhadeshwar, Ashish B.
2014-01-01
Ceria offers great promise in catalysis, due to its facile switchable oxidation state manifested from its oxygen buffering capability. This work presents the first equilibrium surface phase diagram of ceria exposed to various oxygen providing reservoirs (e.g., a pure O2 reservoir as well as NO/NO2, H2/H2O, or CO/CO2 redox environments) using first principles thermodynamics. For a pure O2 environment, the stoichiometric ceria (111) surface is favored at ambient conditions. Any appreciable surface reduction is observed only at ultra-low oxygen partial pressures (< 10- 30 atm) and room temperature or at temperatures > 2000 K and ambient pressures. On the other hand, a redox environment promotes surface reduction at temperatures as low as 300 K. Semi-local, Hubbard modified semi-local, and hybrid electronic exchange-correlation functionals are used to capture the energetics and phase transitions. We observe no difference between the three theories in the energetics governing ceria surface reduction in the dilute limit. The predicted phase transitions by all levels of theory are in agreement with each other and in excellent agreement with literature experimental data. Creation of oxygen vacancies in the sub-surface is energetically favored over surface vacancies, and is pivotal in determining the key features of the surface phase diagram. Consequently, we identify the oxygen vacancy formation energy as a descriptor for the surface reactivity of ceria in various oxygen environments. This single governing factor could be used in future studies to probe the surface reactivity of ceria and also to design improved ceria-based materials for redox reactions.
Bifurcations of relative equilibria
NASA Technical Reports Server (NTRS)
Krupa, Martin
1990-01-01
The characteristics of equivariant dynamical systems near relative equilibria (RE: group orbits which are invariant in the flow of an equivariant vector field) are investigated analytically, with a focus on the dynamics and bifurcation (B) behavior. The principles of Lie-group theory are reviewed; the decomposition of the vector field is explained; and particular attention is given to the Bs of RE occurring when an eigenvalue passes through zero, Hopf Bs of RE, the classification of generic secondary steady-state and Hopf Bs with symmetry group O(2), Bs of the zero solution of the Kuramoto-Shivashinsky equation, and possible generic steady-state Bs in the two-dimensional Benard problem. In the latter case, it is shown that the primary generic Bs are to two types of equilibria (hexagons and rolls), while the secondary Bs result in trajectories which are either equilibria or rotating waves.
Chimera states in two populations with heterogeneous phase-lag
NASA Astrophysics Data System (ADS)
Martens, Erik A.; Bick, Christian; Panaggio, Mark J.
2016-09-01
The simplest network of coupled phase-oscillators exhibiting chimera states is given by two populations with disparate intra- and inter-population coupling strengths. We explore the effects of heterogeneous coupling phase-lags between the two populations. Such heterogeneity arises naturally in various settings, for example, as an approximation to transmission delays, excitatory-inhibitory interactions, or as amplitude and phase responses of oscillators with electrical or mechanical coupling. We find that breaking the phase-lag symmetry results in a variety of states with uniform and non-uniform synchronization, including in-phase and anti-phase synchrony, full incoherence (splay state), chimera states with phase separation of 0 or π between populations, and states where both populations remain desynchronized. These desynchronized states exhibit stable, oscillatory, and even chaotic dynamics. Moreover, we identify the bifurcations through which chimeras emerge. Stable chimera states and desynchronized solutions, which do not arise for homogeneous phase-lag parameters, emerge as a result of competition between synchronized in-phase, anti-phase equilibria, and fully incoherent states when the phase-lags are near ± /π 2 (cosine coupling). These findings elucidate previous experimental results involving a network of mechanical oscillators and provide further insight into the breakdown of synchrony in biological systems.
Phase equilibria in the oxide system Nd 2O 3-K 2O-P 2O 5
NASA Astrophysics Data System (ADS)
Szczygieł, Irena; Znamierowska, Teresa; Mizer, Dagmara
2010-07-01
A phase equilibria diagram of the partial system NdPO 4-K 3PO 4-KPO 3 has been developed as part of the research aimed at determining the phase equilibrium relationships in the oxide system Nd 2O 3-K 2O-P 2O 5. The investigations were conducted using thermoanalytical techniques, X-ray powder diffraction analysis and reflected-light microscopy. Three isopleths existing between: K 3Nd(PO 4) 2-K 4P 2O 7, NdPO 4-K 5P 3O 10 and NdPO 4-K 4P 2O 7 have been identified in the partial NdPO 4-K 3PO 4-KPO 3 system. Previously unknown potassium-neodymium phosphate "K 4Nd 2P 4O 15" has been discovered in the latter isopleth section. This phosphate exists in the solid phase up to a temperature of 890 °C at which it decomposes into the parent phosphates NdPO 4 and K 4P 2O 7. Four invariant points: two quasi-ternary eutectics, E 1 (1057 °C) and E 2 (580 °C) and two quasi-ternary peritectics, P 1 (1078 °C) and P 2 (610 °C), occur in the NdPO 4-K 3PO 4-KPO 3 region.
Phase equilibria of Fe-C binary alloys in a magnetic field
NASA Astrophysics Data System (ADS)
England, Roger Dale
phase nucleation created by the addition of a high flux magnetic field. Additionally, a pure iron sample was analyzed and found to be unique, in that the transformation temperature decreased with the application of a static magnetic field, opposite to what occurs in the iron carbon alloys. While the presence of a two-phase field is a viable cause due to the chromium impurity content in the sample creating a dilute binary alloy versus a pure element, this effect could also be attributed to the high magnetic field increasing the number of state variables present.
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. PMID:27507133
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.
Ranjan, V.; Yu, L.; Nakhmanson, S.; Bernholc, J.; Nardelli, M. B.; Materials Science Division; North Carolina State Univ.; ORNL
2010-01-01
Using first-principles calculations, the phase diagrams of polyvinylidene fluoride (PVDF) and its copolymers under an applied electric field are studied and phase transitions between their nonpolar {alpha} and polar {beta} phases are discussed. The results show that the degree of copolymerization is a crucial parameter controlling the structural phase transition. In particular, for tetrafluoroethylene (TeFE) concentration above 12%, PVDF-TeFE is stabilized in the {beta} phase, whereas the {alpha} phase is stable for lower concentrations. As larger electric fields are applied, domains with smaller concentrations ({le} 12%) undergo a transition from the {alpha} to the {beta} phase until a breakdown field of {approx}600 MV m{sup -1} is reached. These structural phase transitions can be exploited for efficient storage of electrical energy.
NASA Astrophysics Data System (ADS)
Shcherbakov, Vasily D.; Neill, Owen K.; Izbekov, Pavel E.; Plechov, Pavel Yu.
2013-08-01
Phase equilibria experiments were performed on andesites from the catastrophic 1956 eruption of Bezymianny Volcano, Kamchatka, Russia, to determine pre-eruptive magma storage conditions. Fifteen experiments were conducted under water-saturated conditions, with oxygen fugacity equal to the Ni-NiO oxygen buffer, at temperatures between 775 and 1100 °C and pressures between 50 and 200 MPa. Simultaneous amphibole and plagioclase crystallization is reproduced at ≤ 850 °C and ≥ 200 MPa. The simultaneous crystallization temperature range of the plagioclase-clinopyroxene-orthopyroxene-Fe-Ti oxide assemblage increases with decreasing pressure, from 840 to 940 °C at 150 MPa to 940-1020 °C at 50 MPa. Melt inclusion compositions in plagioclase phenocrysts and matrix glass match experimental melt compositions reproduced at 50-100 MPa and ≤ 50 MPa, respectively. Presence of the silica phase in groundmass and mature amphibole breakdown rims suggests that magma has been stored at ca. 3 km depth prior to the final ascent for at least 40 days. Syn-eruptive ascent led to decompression-driven crystallization, which caused a temperature increase from 850-900 °C to 950-1000 °C.
Keasler, Samuel J; Charan, Sophia M; Wick, Collin D; Economou, Ioannis G; Siepmann, J Ilja
2012-09-13
While the transferable potentials for phase equilibria-united atom (TraPPE-UA) force field has generally been successful at providing parameters that are highly transferable between different molecules, the polarity and polarizability of a given functional group can be significantly perturbed in small cyclic structures, which limits the transferability of parameters obtained for linear molecules. This has motivated us to develop a version of the TraPPE-UA force field specifically for five- and six-membered cyclic alkanes and ethers. The Lennard-Jones parameters for the methylene group obtained from cyclic alkanes are transferred to the ethers for each ring size, and those for the oxygen atom are common to all compounds for a given ring size. However, the partial charges are molecule specific and parametrized using liquid-phase dielectric constants. This model yields accurate saturated liquid densities and vapor pressures, critical temperatures and densities, normal boiling points, heat capacities, and isothermal compressibilities for the following molecules: cyclopentane, tetrahydrofuran, 1,3-dioxolane, cyclohexane, oxane, 1,4-dioxane, 1,3-dioxane, and 1,3,5-trioxane. The azeotropic behavior and separation factor for the binary mixtures of 1,3-dioxolane/cyclohexane and ethanol/1,4-dioxane are qualitively reproduced. PMID:22900670
Phase equilibria in the U-Si system from first-principles calculations
NASA Astrophysics Data System (ADS)
Noordhoek, Mark J.; Besmann, Theodore M.; Andersson, David; Middleburgh, Simon C.; Chernatynskiy, Aleksandr
2016-10-01
Density functional theory calculations have been used with spin-orbit coupling and on-site Coulomb correction (GGA + U) methods to investigate the U-Si system. Structural prediction methods were employed to identify alternate stable structures. Convex hulls of the U-Si system were constructed for each of the methods to highlight the competing energetics of various phases. For GGA calculations, new structures are predicted to be dynamically stable, but these have not been experimentally observed. When the GGA + U (Ueff > 1.3 eV) method is considered, the experimentally observed structures are predicted to be energetically preferred. Phonon calculations were used to investigate the energy predictions and showed that the use of the GGA + U method removes the significant imaginary frequencies observed for U3Si2 when the correction is not considered. Total and partial electron density of states calculations were also performed to understand the role of GGA + U methods and orbitals on the bonding and stability of U-Si compounds.
Phase Equilibria of a S- and C-Poor Lunar Core
NASA Technical Reports Server (NTRS)
Righter, K.; Pando, K.; Go, B. M.; Danielson, L. R.; Habermann, M.
2016-01-01
The composition of the lunar core can have a large impact on its thermal evolution, possible early dynamo creation, and physical state. Geochemical measurements have placed better constraints on the S and C content of the lunar mantle. In this study we have carried out phase equilibrium studies of geochemically plausible S- and C-poor lunar core compositions in the Fe-Ni-S-C system, and apply them to the early history of the Moon. We chose two bulk core compositions, with differing S and C content based on geochemical analyses of S and C trapped melts in Apollo samples, and on the partitioning of S and C between metal and silicate. This approach allowed calculation of core S and C contents - 90% Fe, 9% Ni, 0.5% C, and 0.375% S by weight; a second composition contained 1% each of S and C. Experiments were carried out from 1473K to 1973K and 1 GPa to 5 GPa, in piston cylinder and multi- anvil apparatuses. Combination of the thermal model of with our results, shows that a solid inner core (and therefore initiation of a dynamo) may have been possible in the earliest history of the Moon (approximately 4.2 Ga ago), in agreement with. Thus a volatile poor lunar core may explain the thermal and magnetic history of the Moon.
Ternary clathrates Ba Cd Ge: phase equilibria, crystal chemistry and physical properties
NASA Astrophysics Data System (ADS)
Melnychenko-Koblyuk, N.; Grytsiv, A.; Berger, St.; Kaldarar, H.; Michor, H.; Röhrbacher, F.; Royanian, E.; Bauer, E.; Rogl, P.; Schmid, H.; Giester, G.
2007-01-01
The present paper describes the formation, phase relations at subsolidus temperatures and at 800 °C, crystal chemistry and physical properties of a series of ternary clathrates as part of the solid solution {\\mathrm {Ba_{8}Cd}}_{x}\\mathrm {Ge}_{43-5x/8}\\square _{3-3x/8} , derived from binary {\\mathrm {Ba_{8}Ge_{43}}}\\square_{3} with a solubility limit of 8 Cd per formula unit at 800 °C. Structural investigations in all cases confirm cubic primitive symmetry with a lattice parameter aap1.1 nm, consistent with the space group type Pm{\\bar {3}}n . Both the temperature dependent x-ray spectra and the heat capacity define a low-lying, almost localized, phonon branch. Studies of transport properties show electrons to be the majority charge carriers in the systems. As the Cd content increases, the system is driven towards a metal-to-insulator transition, causing \\mathrm {Ba_{8}Cd_{4.7}Ge_{40.3}}\\square_{1.0} , for example, to show metallic behaviour at low temperatures while at high temperatures semiconducting features become obvious. A model based on a gap of the electronic density of states slightly above the Fermi energy perfectly explains such a scenario. Thermal conductivity exhibits a pronounced low temperature maximum, dominated by the lattice contribution, while at higher temperatures the electronic part becomes more important.
NASA Astrophysics Data System (ADS)
Kleykamp, Heiko
2001-04-01
Enthalpies of the hcp-bcc transformation ΔtrH and melting ΔmH of Be were measured by anisothermal calorimetry which gave ΔtrH=6100 J/mol and ΔmH=7200 J/mol. The high value of ΔtrH is explained by the strongly reduced c/ a-axis ratio of the hcp modification. Maximum solubilities of the metallic impurities Al, Cr, Fe, Mg and Si in different Be qualities which annealed at about 800°C are 0.01 mol% or less in each case. In the Al-Be-Fe system, Be(Al, Fe) is in equilibrium with Al 5Fe 2 at 870°C. The phases AlFeBe 4 and Al 2FeBe 2.3 were not observed. The Be-C-Si system is marked by two two-phase equilibria Be 2C-Si and Be 2C-SiC at 900°C. The phase diagram of the pseudo-ternary BeO-Li 2O-SiO 2 system was established on the basis of in-pile Be-BeO-Li 4SiO 4-Li 2SiO 3 compatibility studies at about 450°C. The system is characterised by Li 2BeSiO 4 which is in equilibrium with BeO, Be 2SiO 4,SiO 2,Li 2Si 2O 5,Li 2SiO 3 and Li 4SiO 4. The latter phase is also in equilibrium with Li 2Be 2O 3.
Phase equilibria and trace element partitioning in a magma ocean to 260 kilobars
NASA Technical Reports Server (NTRS)
Herzberg, Claude
1992-01-01
A magma ocean can solidify in a way that is intermediate between perfect equilibrium and perfect fractional crystallization. In order to model quantitatively any fractional crystallization scenario, it is necessary to understand the geochemical characteristics of the phases that crystallize from a magma ocean, and how they vary with pressure. The crystallizing phase is called the liquidus phase, and their identities were determined by numerous experiments utilizing the multianvil apparatus. For chondritic compositions the liquidus phases are as follows: olivine at 1 atmosphere to 100 kilobars; garnet from 100 to about 260 kilobars; silicate perovskite from 260 kilobars to possibly the core-mantle boundary in the Earth.
Direct evaluation of multicomponent phase equilibria using flat-histogram methods.
Errington, Jeffrey R; Shen, Vincent K
2005-10-22
We present a method for directly locating density-driven phase transitions in multicomponent systems. Phase coexistence conditions are determined through manipulation of a total density probability distribution evaluated over a density range that includes both coexisting phases. Saturation quantities are determined through appropriate averaging of density-dependent mean values of a given property of interest. We discuss how to implement the method in both the grand-canonical and isothermal-isobaric semigrand ensembles. Calculations can be conducted using any of the recently introduced flat-histogram techniques. Here, we combine the general algorithm with a transition-matrix approach to produce an efficient self-adaptive technique for determining multicomponent phase equilibrium properties. To assess the performance of the new method, we generate phase diagrams for a number of binary and ternary Lennard-Jones mixtures.
Multiple critical points and liquid liquid equilibria from the van der Waals like equations of state
NASA Astrophysics Data System (ADS)
Artemenko, Sergey; Lozovsky, Taras; Mazur, Victor
2008-06-01
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.
NASA Astrophysics Data System (ADS)
Sengupta, Angan; Adhikari, Jhumpa
2016-05-01
The triangle-well (TW) potential is a simple model which is able to capture the essence of the intermolecular attraction in real molecules. Transition matrix Monte Carlo simulations in the grand canonical ensemble (GC-TMMC) are performed to investigate the role of the range of attraction on the features of fluid phase equilibria. As the TW potential range increases, the vapour-liquid coexistence curves shift towards a higher temperature range with the critical temperature and pressure increasing, and the critical density values decreasing. These GC-TMMC results are in excellent agreement with the predictions of Gibbs ensemble Monte Carlo and replica exchange Monte Carlo (REMC) simulations reported in literature. Using the GC-TMMC method, the vapour pressures are also computed directly from the particle number probability distributions (PNPDs). It has been noted in literature that the surface tension values are computationally more expensive and difficult to determine than other coexistence properties using molecular simulations. The PNPDs from GC-TMMC simulations along with Binder's formalism allow for the calculation of the interfacial tension with relative ease. Also, our simulation generated results for the interfacial tension are in good agreement with the literature data obtained using REMC (via the virial route) and the plots of our interfacial tension values as a function of temperature are smooth unlike the literature data.
Protein salting-out: phase equilibria in two-protein systems.
Coen, C J; Prausnitz, J M; Blanch, H W
1997-03-20
The phase behavior of two aqueous binary protein mixtures, lysozyme-chymotrypsin and lysozyme-ovalbumin, was determined in ammonium sulfate solutions. Protein concentrations were determined in both phases as a function of pH and ionic strength. For lysozyme-chymotrypsin mixtures, the observed phase behavior was similar to that for each individual protein; the presence of the second protein had little influence. The phase behavior of lysozyme-ovalbumin mixtures, however, was different from that of the respective single-protein systems. Lysozyme and ovalbumin are found together in egg whites; their association is both pH and ionic-strength dependent. The association of proteins is a key determinant of protein solubility in salt solutions.
Direct molecular dynamics simulation of liquid-solid phase equilibria for two-component plasmas.
Schneider, A S; Hughto, J; Horowitz, C J; Berry, D K
2012-06-01
We determine the liquid-solid phase diagram for carbon-oxygen and oxygen-selenium plasma mixtures using two-phase molecular dynamics simulations. We identify liquid, solid, and interface regions using a bond angle metric. To study finite-size effects, we perform 27,648- and 55,296-ion simulations. To help monitor nonequilibrium effects, we calculate diffusion constants D(i). For the carbon-oxygen system we find that D(O) for oxygen ions in the solid is much smaller than D(C) for carbon ions and that both diffusion constants are 80 or more times smaller than diffusion constants in the liquid phase. There is excellent agreement between our carbon-oxygen phase diagram and that predicted by Medin and Cumming. This suggests that errors from finite-size and nonequilibrium effects are small and that the carbon-oxygen phase diagram is now accurately known. The oxygen-selenium system is a simple two-component model for more complex rapid proton capture nucleosynthesis ash compositions for an accreting neutron star. Diffusion of oxygen, in a predominantly selenium crystal, is remarkably fast, comparable to diffusion in the liquid phase. We find a somewhat lower melting temperature for the oxygen-selenium system than that predicted by Medin and Cumming. This is probably because of electron screening effects. PMID:23005226
Equilibria in Chemical Systems
1992-01-01
SOLGASMIX-PV calculates equilibrium relationships in complex chemical systems. Chemical equilibrium calculations involve finding the system composition, within certain constraints, which contains the minimum free energy. The constraints are the preservation of the masses of each element present and either constant pressure or volume. SOLGASMIX-PV can calculate equilibria in systems containing a gaseous phase, condensed phase solutions, and condensed phases of invariant and variable stoichiometry. Either a constant total gas volume or a constant total pressuremore » can be assumed. Unit activities for condensed phases and ideality for solutions are assumed, although nonideal systems can be handled provided activity coefficient relationships are available.« less
Phase Equilibria of Ternary and Quaternary Systems Containing Diethyl Carbonate with Water.
Chen, Yao; Wen, Caiyu; Zhou, Xiaoming; Zeng, Jun
2014-01-01
In this study liquid phase equilibrium compositions were measured at 298.15 K under atmospheric pressure for (water + propan-1-ol + diethyl carbonate (DEC) + benzene or cyclohexane or heptane) quaternary systems and (water + DEC + propan-1-ol or benzene or cyclohexane) ternary systems. Good correlation of the experimental LLE data was seen for the measured systems by both modified and extended UNIQUAC models. The solubility of DEC in aqueous and organic phases is shown by equilibrium distribution coefficients calculated from the LLE data.
Marshall, Bennett D; Chapman, Walter G
2013-08-01
We develop a new theory for associating fluids with multiple association sites. The theory accounts for small bond angle effects such as steric hindrance, ring formation, and double bonding. The theory is validated against Monte Carlo simulations for the case of a fluid of patchy colloid particles with three patches and is found to be very accurate. Once validated, the theory is applied to study the phase diagram of a fluid composed of three patch colloids. It is found that bond angle has a significant effect on the phase diagram and the very existence of a liquid-vapor transition.
Rai, Neeraj; Siepmann, J Ilja
2013-01-10
The explicit-hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to various substituted benzenes through the parametrization of the exocyclic groups -F, -Cl, -Br, -C≡N, and -OH and to polycyclic aromatic hydrocarbons through the parametrization of the aromatic linker carbon atom for multiple rings. The linker carbon together with the TraPPE-EH parameters for aromatic heterocycles constitutes a force field for fused-ring heterocycles. Configurational-bias Monte Carlo simulations in the Gibbs ensemble were carried out to compute vapor-liquid coexistence curves for fluorobenzene; chlorobenzene; bromobenzene; di-, tri-, and hexachlorobenzene isomers; 2-chlorofuran; 2-chlorothiophene; benzonitrile; phenol; dihydroxybenzene isomers; 1,4-benzoquinone; naphthalene; naphthalene-2-carbonitrile; naphthalen-2-ol; quinoline; benzo[b]thiophene; benzo[c]thiophene; benzoxazole; benzisoxazole; benzimidazole; benzothiazole; indole; isoindole; indazole; purine; anthracene; and phenanthrene. The agreement with the limited experimental data is very satisfactory, with saturated liquid densities and vapor pressures reproduced to within 1.5% and 15%, respectively. The mean unsigned percentage errors in the normal boiling points, critical temperatures, and critical densities are 0.9%, 1.2%, and 1.4%, respectively. Additional simulations were carried out for binary systems of benzene/benzonitrile, benzene/phenol, and naphthalene/methanol to illustrate the transferability of the developed potentials to binary systems containing compounds of different polarity and hydrogen-bonding ability. A detailed analysis of the liquid-phase structures is provided for selected neat systems and binary mixtures. PMID:23205778
Thermodynamic analysis of phase equilibria in the iron-zirconium system
Pelton, A.D.; Leibowitz, L.; Blomquist, R.A.
1992-09-01
Continuing interest in development of metallic fuels for nuclear reactors has prompted an examination of the phase relations of many of the relevant binary and ternary systems of interest. We performed a thermodynamic analysis and optimization of the Fe-Zr system. Overall reasonably good agreement was found with published diagrams, but some significant changes were required to ensure thermodynamic consistency.
Thermodynamic analysis of phase equilibria in the iron-zirconium system
Pelton, A.D. ); Leibowitz, L.; Blomquist, R.A. )
1992-01-01
Continuing interest in development of metallic fuels for nuclear reactors has prompted an examination of the phase relations of many of the relevant binary and ternary systems of interest. We performed a thermodynamic analysis and optimization of the Fe-Zr system. Overall reasonably good agreement was found with published diagrams, but some significant changes were required to ensure thermodynamic consistency.
A Classroom Experiment on Phase Equilibria Involving Orientational Disordering in Crystals.
ERIC Educational Resources Information Center
Mjojo, C. C.
1985-01-01
Background information, procedures used, and results obtained are provided for an experiment in which a phase diagram is determined using a differential scanning calorimeter. Commercial samples of D-camphoric anhydride (Eastman Kodak) and D,L-camphoric anhydride (Aldrich) were used in the experiment. (JN)
Transport and Phase Equilibria Properties for Steam Flooding of Heavy Oils
Gabitto, Jorge; Barrufet, Maria
2002-11-20
The objectives of this research included experimental determination and rigorous modeling and computation of phase equilibrium diagrams, volumetric, and transport properties of hydrocarbon/CO2/water mixtures at pressures and temperatures typical of steam injection processes for thermal recovery of heavy oils.
The system Ta-V-Si: Crystal structure and phase equilibria
Khan, A.U.; Broz, P.; Bursik, J.; Grytsiv, A.; Chen, X.-Q.; Giester, G.; Rogl, P.
2012-03-15
Phase relations have been evaluated for the Ta-V-Si system at 1500 and 1200 Degree-Sign C. Three ternary phases were found: {tau}{sub 1}-(Ta,V){sub 5}Si{sub 3} (Mn{sub 5}Si{sub 3}-type), {tau}{sub 2}-Ta(Ta,V,Si){sub 2} (MgZn{sub 2}-type) and {tau}{sub 3}-Ta(Ta,V,Si){sub 2} (MgCu{sub 2}-type). The crystal structure of {tau}{sub 2}-Ta(Ta,V,Si){sub 2} was solved by X-ray single crystal diffraction (space group P6{sub 3}/mmc). Atom order in the crystal structures of {tau}{sub 1}-(Ta,V){sub 5}Si{sub 3} (Mn{sub 5}Si{sub 3} type) and {tau}{sub 3}-Ta(Ta,V,Si){sub 2} was derived from X-ray powder diffraction data. A large homogeneity range was found for {tau}{sub 1}-(Ta{sub x}V{sub 1-x}){sub 5}Si{sub 3} revealing random exchange of Ta and V at a constant Si content. At 1500 Degree-Sign C, the end points of the {tau}{sub 1}-phase solution (0.082{<=}x{<=}0.624) are in equilibrium with the solutions (Ta{sub 1-x}V{sub x}){sub 5}Si{sub 3} (Cr{sub 5}B{sub 3} type, 0{<=}x{<=}0.128) and (Ta{sub x}V{sub 1-x}){sub 5}Si{sub 3} (W{sub 5}Si{sub 3} type, 0{<=}x{<=}0.048). - Graphical abstract: Phase relations have been evaluated for the Ta-V-Si system at 1500 and 1200 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Phase relations have been evaluated for the Ta-V-Si system at 1500 and 1200 Degree-Sign C. Black-Right-Pointing-Pointer Three ternary phases were found at 1500 Degree-Sign C. Black-Right-Pointing-Pointer At 1500 Degree-Sign C, {tau}{sub 1}-phase has large homogeneity region (0.064{<=}x{<=}0.624).
Monte Carlo simulations of high-pressure phase equilibria of CO2-H2O mixtures.
Liu, Yang; Panagiotopoulos, Athanassios Z; Debenedetti, Pablo G
2011-05-26
Histogram-reweighting grand canonical Monte Carlo simulations were used to obtain the phase behavior of CO(2)-H(2)O mixtures over a broad temperature and pressure range (50 °C ≤ T ≤ 350 °C, 0 ≤ P ≤ 1000 bar). We performed a comprehensive test of several existing water (SPC, TIP4P, TIP4P2005, and exponential-6) and carbon dioxide (EPM2, TraPPE, and exponential-6) models using conventional Lorentz-Berthelot combining rules for the unlike-pair parameters. None of the models we studied reproduce adequately experimental data over the entire temperature and pressure range, but critical assessments were made on the range of T and P where particular model pairs perform better. Away from the critical region (T ≤ 250 °C), the exponential-6 model combination yields the best predictions for the CO(2)-rich phase, whereas the TraPPE/TIP4P2005 model combination provides the most accurate coexistence composition and pressure for the H(2)O-rich phase. Near the critical region (250 °C < T ≤ 350 °C), the critical points are not accurately estimated by any of the models studied, but the exponential-6 models are able to qualitatively capture the critical loci and the shape of the phase envelopes. Local improvements can be achieved at specific temperatures by introducing modification factors to the Lorentz-Berthelot combining rules, but the modified combining rule is still not able to achieve global improvements over the entire temperature and pressure range. Our work points to the challenge and importance of improving current atomistic models so as to accurately predict the phase behavior of this important binary mixture.
TRANSPORT AND PHASE EQUILIBRIA PROPERITIES FOR STEAM FLOODING OF HEAVY OILS
Jorge Gabitto; Maria Barrufet
2002-09-01
Hydrocarbon/water and CO{sub 2} systems are frequently found in petroleum recovery processes, petroleum refining, and gasification of coals, lignites and tar sands. Techniques to estimate the phase volume and phase composition are indispensable to design and improve oil recovery processes such as steam, hot water, or CO{sub 2}/steam combinations of flooding techniques typically used for heavy oils. An interdisciplinary research program to quantify transport, PVT, and equilibrium properties of selected oil/CO{sub 2}/water mixtures at pressures up to 10,000 psia and at temperatures up to 500 F has been put in place. The objectives of this research include experimental determination and rigorous modeling and computation of phase equilibrium diagrams, and volumetric properties of hydrocarbon/CO{sub 2}/water mixtures at pressures and temperatures typical of steam injection processes for thermal recovery of heavy oils. Highlighting the importance of phase behavior, researchers ([1], and [2]) insist on obtaining truly representative reservoir fluids samples for experimental analysis. The prevailing sampling techniques used for compositional analysis of the fluids have potential for a large source of error. These techniques bring the sample to atmospheric conditions and collect the liquid and vapor portion of the samples for further analysis. We developed a new experimental technique to determine phase volumes, compositions and equilibrium K-values at reservoir conditions. The new methodology is able to measure phase volume and composition at reservoir like temperatures and pressures. We use a mercury free PVT system in conjunction with a Hewlett Packard gas chromatograph capable of measuring compositions on line at high pressures and temperatures. This is made possible by an essentially negligible disturbance of the temperature and pressure equilibrium during phase volume and composition measurements. In addition, not many samples are withdrawn for compositional analysis
Costandy, Joseph; Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G
2015-09-01
The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice. PMID:26342376
Costandy, Joseph; Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G
2015-09-01
The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice.
NASA Astrophysics Data System (ADS)
Costandy, Joseph; Michalis, Vasileios K.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.; Economou, Ioannis G.
2015-09-01
The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice.
Luigjes, Bob; Thies-Weesie, Dominique M E; Erné, Ben H; Philipse, Albert P
2012-06-20
The first experimental osmotic equation of state is reported for well-defined magnetic colloids that interact via a dipolar hard-sphere potential. The osmotic pressures are determined from the sedimentation equilibrium concentration profiles in ultrathin capillaries using a low-velocity analytical centrifuge, which is the subject of the accompanying paper I. The pressures of the magnetic colloids, measured accurately to values as low as a few pascals, obey Van 't Hoff's law at low concentrations, whereas at increasing colloid densities non-ideality appears in the form of a negative second virial coefficient. This virial coefficient corresponds to a dipolar coupling constant that agrees with the coupling constant obtained via independent magnetization measurements. The coupling constant manifests an attractive potential of mean force that is significant but yet not quite strong enough to induce dipolar chain formation. Our results disprove van der Waals-like phase behavior of dipolar particles for reasons that are explained. PMID:22617544
Goodwin, A.R.; Mehl, J.B.; Moldover, M.R.
1996-12-01
A reentrant rf cavity resonator has been developed for automated detection of phase separation of fluid mixtures contained within the cavity. Successful operation was demonstrated by redetermining the phase boundaries of a CO{sub 2}+C{sub 2}H{sub 6} mixture in the vicinity of its critical point. We developed an accurate electrical model for the resonator and used helium to determine the deformation of the resonator under pressure. With the model and pressure compensation, the resonator was capable of very accurate dielectric measurements. We confirmed this by remeasuring the molar dielectric polarizability {ital A}{sub {epsilon}} of argon and obtained the result {ital A}{sub {epsilon}}=(4.140{plus_minus}0.006) cm{sup 3}/mol (standard uncertainty) in excellent agreement with published values. We exploited the capability for accurate dielectric measurements to determine the densities of the CO{sub 2}+C{sub 2}H{sub 6} mixture at the phase boundaries and to determine the dipole moment of 1,1,1,2,3,3-hexafluoropropane, a candidate replacement refrigerant. Near the operating frequency of 375 MHz the capacitor in the resonator has an impedance near 14 {Omega}. This low impedance is more tolerant of electrical conductivity within the test fluid and in parallel paths in the support structures than comparable capacitors operating at audio frequencies. This will be an advantage for operation at high temperatures where some conductivity must be expected in all fluids. Of further value for high-temperature applications, the present rf resonator has only two metal{endash}insulator joints. These joints seal coaxial cables; neither joint is subjected to large mechanical stresses and neither joint is required to maintain precise dimensional tolerances. The resonator is rugged and may be operated with inexpensive electronics.
Phase equilibria and stability characteristics of chlorpropamide-urea solid dispersions.
Ford, J L; Rubinstein, M H
1977-04-01
Physical mixtures and melts of various compositions of chlorpropamide and urea have been prepared. The phase diagrams and the effects of ageing of the systems have been measured by differential scanning calorimetry. The eutectic composition was found to contain 89% w/w chlorpropamide. Greater concentrations of chlorpropamide produced solid solutions of urea in chlorpropamide, whereas solid solution formation did not occur at compositions less than 89%. Melts in the range 50-100% chlorpropamide, which included the eutectic, existed as glass solids. The effect of ageing produced generally an increase in the liquidus peak temperature which was considered to be due to a gradual increase in crystal size. PMID:17669
Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid
NASA Astrophysics Data System (ADS)
Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.
2013-05-01
The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.
The high-temperature phase equilibria of the Ni–Sn–Zn system: Isothermal sections
Schmetterer, Clemens; Rajamohan, Divakar; Ipser, Herbert; Flandorfer, Hans
2011-01-01
In this work three complete isothermal sections of the Ni–Sn–Zn system at 700, 800 and 900 °C are presented. They were constructed based on experimental investigation of more than 60 alloy samples. Powder XRD, single crystal XRD, EPMA, and DTA measurements on selected samples were carried out. Two new ternary compounds, designated as τ2 (Ni5Sn4Zn) and τ3 (Ni7Sn9Zn5), were identified and their homogeneity ranges and crystal structures could be described. Whereas τ3 is only present at 700 °C, the τ2-phase was found at both 700 and 800 °C. No truly ternary compound could be found in the isothermal section at 900 °C. A seemingly ternary compound at 20 at% Sn in the Ni-rich part of Ni–Sn–Zn was found at 800 and 900 °C. Our XRD results, however, indicate that this phase is a ternary solid solution of Ni3Sn-HT from constituent binary Ni–Sn. It is stabilized to lower temperatures by additions of Zn. These new experimental results will provide valuable information to the thermodynamic description of alloy systems relevant for high-temperature lead-free soldering. PMID:27087750
Phase equilibria and thermal expansion of CaTiO 3 doped with neptunium
NASA Astrophysics Data System (ADS)
Sato, Tsuyoshi; Yamashita, Toshiyuki; Matsui, Tsuneo
2005-09-01
Phase relationships between NpO 2 and CaTiO 3 or Ca(Ti,Al)O 3 were investigated by X-ray diffraction (XRD) analysis at room temperature, using specimens prepared at 1773 K in Ar-8%H 2 atmosphere. Single phase solid solutions were formed for 0-7.5 mol% Np doped CaTiO 3 and 1-10 mol% Np doped Ca(Ti,Al)O 3. By substituting Al for Ti in CaTiO 3, Np solubility in Ca(Ti,Al)O 3 increased. Thermal expansions of (Ca 1- xNp x)TiO 3 ( x = 0.03, 0.05 and 0.075) were measured for temperatures between room temperature and 1273 K in Ar-8%H 2 atmosphere using high-temperature XRD technique. Volumetric thermal expansion coefficients of these three specimens were nearly the same value, suggesting that the incorporation of tetravalent Np into CaTiO 3 had practically no effect on stabilization of the crystal lattice.
NASA Astrophysics Data System (ADS)
Li, H.-C.; McCabe, C.; Cui, S. T.; Cummings, P. T.; Cochran, H. D.
A first step towards the development of a general, realistic potential model for perfluoroether compounds has been to parameterize a united atom model for a short chain perfluoroether perfluoromethylpropyl ether (CF 3 CF 2 CF 2 OCF 3 ). The potential model takes the usual form in which separate bond bending and torsional terms describe the intramolecular interactions with the addition of van der Waals and electrostatic terms to describe the non-bonded interactions. Ab initio quantum calculations have been carried out to obtain the partial charges and intramolecular torsional and bending potentials. Phase equilibrium data were then used to optimize the van der Waals interaction parameters through Gibbs ensemble Monte Carlo simulations. The resulting model reproduces vapour-liquid equilibrium densities, the critical temperature and the critical density of perfluoromethylpropyl ether, in good agreement with those from experiment.
Phase equilibria of charge-, size-, and shape-asymmetric model electrolytes.
Yan, Qiliang; de Pablo, Juan J
2002-03-01
The low-temperature phase behavior of two 2:1 hard-core electrolyte models has been investigated by Monte Carlo simulations. In the first model, both bivalent cations and monovalent anions are spherical, and the charges are located at the ion's centers; in the second model, bivalent cations are modeled as rigid dimers composed of two tangent hard spheres, each carrying a positive charge at the center. It is found that the critical temperature and the critical density are strongly affected by the size asymmetry and the shape of the ions. The results presented in this work provide insights into the behavior of charged colloidal suspensions and polyelectrolytes, where large, symmetric or asymmetric ionic species carrying like charges can attract each other and give rise to thermodynamically unstable conditions.
NASA Astrophysics Data System (ADS)
Bohnenstiehl, Scot David
In this work, the low temperature synthesis of MgB2 from Mg/B and MgH2/B powder mixtures was studied using Differential Scanning Calorimetry (DSC). For the Mg/B powder mixture, two exothermic reaction events were observed and the first reaction event was initiated by the decomposition of Mg(OH)2 on the surface of the magnesium powder. For the MgH 2/B powder mixture, there was an endothermic event at ˜375 °C (the decomposition of MgH2 into H2 and Mg) and an exothermic event ˜600 °C (the reaction of Mg and B). The Kissinger analysis method was used to estimate the apparent activation energy of the Mg and B reaction using DSC data with different furnace ramp rates. The limitations of MgB2 low temperature synthesis led to the development of a high pressure induction furnace that was constructed using a pressure vessel and an induction heating power supply. The purpose was to not only synthesize more homogeneous MgB2 samples, but also to determine whether MgB2 melts congruently or incongruently. A custom implementation of the Smith Thermal Analysis method was developed and tested on aluminum and AlB2, the closest analogue to MgB2. Measurements on MgB2 powder and a high purity Mg/B elemental mixture confirmed that MgB2 melts incongruently and decomposes into a liquid and MgB4 at ˜1445 °C at 10 MPa via peritectic decomposition. Another measurement using a Mg/B elemental mixture with impure boron suggested that ˜0.7 wt% carbon impurity in the boron raised the incongruent melting temperature to ˜1490-1500 °C. Lastly, the solubility limit for carbon in MgB2 was studied by making samples from B4C and Mg at 1530 °C, 1600 °C and 1700 °C in the high pressure furnace. All three samples had three phases: Mg, MgB2C2, and carbon doped MgB2. The MgB 2C2 and carbon doped MgB2 grain size increased with temperature and the 1700 °C sample had needle-like grains for both phases. The presence of the ternary phase, MgB2C2, suggested that the maximum doping limit for carbon in
Anderson, Brian J; Bazant, Martin Z; Tester, Jefferson W; Trout, Bernhardt L
2005-04-28
We present the application of a mathematical method reported earlier by which the van der Waals-Platteeuw statistical mechanical model with the Lennard-Jones and Devonshire approximation can be posed as an integral equation with the unknown function being the intermolecular potential between the guest molecules and the host molecules. This method allows us to solve for the potential directly for hydrates for which the Langmuir constants are computed, either from experimental data or from ab initio data. Given the assumptions made in the van der Waals-Platteeuw model with the spherical-cell approximation, there are an infinite number of solutions; however, the only solution without cusps is a unique central-well solution in which the potential is at a finite minimum at the center to the cage. From this central-well solution, we have found the potential well depths and volumes of negative energy for 16 single-component hydrate systems: ethane (C2H6), cyclopropane (C3H6), methane (CH4), argon (Ar), and chlorodifluoromethane (R-22) in structure I; and ethane (C2H6), cyclopropane (C3H6), propane (C3H8), isobutane (C4H10), methane (CH4), argon (Ar), trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12), bromotrifluoromethane (R-13B1), chloroform (CHCl3), and 1,1,1,2-tetrafluoroethane (R-134a) in structure II. This method and the calculated cell potentials were validated by predicting existing mixed hydrate phase equilibrium data without any fitting parameters and calculating mixture phase diagrams for methane, ethane, isobutane, and cyclopropane mixtures. Several structural transitions that have been determined experimentally as well as some structural transitions that have not been examined experimentally were also predicted. In the methane-cyclopropane hydrate system, a structural transition from structure I to structure II and back to structure I is predicted to occur outside of the known structure II range for the cyclopropane hydrate. Quintuple (L
NASA Astrophysics Data System (ADS)
Huang, Fangfang; Scaillet, Bruno; Wang, Rucheng; Erdmann, Saskia; Chen, Yan; Faure, Michel; Liu, Hongsheng; Xie, Lei; Wang, Bo; Zhu, Jinchu
2016-04-01
In South China, the huge distribution of the Mesozoic metallogenic province reflects the abundant magmatism and associated mineralizations which occurred during that period. Building up the phase equilibrium diagrams of representative Mesozoic granites allows us to better understand Mesozoic magmatic events, an approach so far little applied to granites of South China. The Qitianling ganite is a representative Jurassic A-type metaluminous pluton which is associated with tin mineralization in South China. The dominant rock-types are hornblende-biotite monzonitic granites, biotite±hornblende bearing granites and fine-grained biotite-bearing granites. Three metaluminous granite samples (QTL38C, QTL14A and QTL13), of varying mafic character but all bearing hornblende, were chosen for constraining crystallization and magma generation conditions of the Qitianling composite batholith. Crystallization experiments were performed in the 100-700 MPa range, albeit mainly at 200 MPa, at an fO2 at NNO-1 or NNO +2.5, in a temperature range 700°C to 900°C. At 200 MPa, the water content in melt varies between 3 wt% and 6.5 wt% (water-saturated). Experimental results show that under H2O-saturated conditions and at NNO-1, ilmenite, magnetite and pyroxene are the liquidus phases, followed by hornblende, biotite and plagioclase. Hornblende is present only in the most mafic sample (QTL38C), below 900°C and above 5 wt% H2O. In contrast, for H2O-saturated conditions and at NNO+2.5, magnetite, pyroxene crystallize first, followed by biotite while ilmenite is rarely observed. Petrographic observations of natural samples show that magnetite and ilmenite coexist, whereas pyroxene is never observed. The Fe# value (Fe/Mg+Fe) of natural amphibole goes up to 0.69, being on average at 0.67. Experiments indicate that the crystallization of pyroxene occurs at early magmatic stages, but it breaks down to hornblende and biotite at low temperatures, explaining its absence in natural assemblages
Spin Equilibria in Monomeric Manganocenes: Solid State Magnetic and EXAFS Studies
Walter, M. D.; Sofield, C. D.; Booth, C. H.; Andersen, R. A.
2009-02-09
Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me{sub 3}C){sub n}C{sub 5}H{sub 5?n}]{sub 2}Mn (n = 1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp{sub 2}Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe{sub 3} groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sub 2}Mn is due to the significant bulk of the [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sup -} ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}]{sub 2}Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis ({Delta}T{sub c} = 16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe{sub 3}-substituted manganocenes [(Me{sub 3}Si){sub n}C{sub 5}H{sub 5-n}]{sub 2}Mn (n = 1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarly to [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn on rapid cooling.
Phase equilibria of NdC1 3NaClKCl
NASA Astrophysics Data System (ADS)
Hosoya, Yuji; Terai, Takayuki; Tanaka, Satoru; Takahashi, Yoichi
1997-08-01
Molten chloride is considered to be applied to a fast-breeder-reactor fuel and a solvent in the pyrochemical reprocessing of spent nuclear fuel. In this work, phase diagrams for molten chloride systems were constructed, using NdCl 3 as an imitative substance in place of UCl 3 or PuCl 3. A compound of 3NdC1 3 · NaCl, which melts incongruently at 540°C to NdCl 3 and liquid and a eutectic at 437°C were found in the NdC1 3NaCl system. In the NdCl 3KCl system, many invariant reactions were observed: the decomposition of NdCl 3 · 2KCl and 2NdCl 3 · KCl at 444 and 474°C, respectively; a eutectic at 489°C; a peritectic at 506°C and a monotectic at 624°C. It is thought that there should be a peritectic compound of 6NdCl 3 · KCl above 474°C. A compound of 2NdC1 3 · NaCl · KCl was considered to exist in the ternary system of NdCl 3NaClKCl, to which attention should be paid in determining the composition of the fuel of the molten-salt fast breeder reactor.
Phase equilibria in the UO 2-austenitic steel system up to 3000°C
NASA Astrophysics Data System (ADS)
Kleykamp, Heiko
1997-08-01
The pseudobinary UO 2-austenitic steel system was investigated by DTA up to 1500°C, by isothermal annealing up to 2000°C, by induction heating up to 2850°C and by arc melting up to about 3000°C. The system is characterized by a degenerate eutectic at 1433°C on the steel side and a monotectic at 2830°C and about 1 mol% steel. The maximum solubility of steel in solid U0 2 is 0.6 mol%, that in liquid U0 2 at 3000°C is about 4 mol%. U0 2 and steel form (Fe, Mn, Cr) 2O 3 precipitates between 1300 and 2600°C as U02 becomes hypostoichiometric. Liquid steel is stabilized to higher temperatures above its boiling point at 2790°C by dissolution of uranium and decomposes peritectically to liquid UO 2-χ and gas at estimated 3200°C. The critical data of the single-phase U0 2-steel melt based on the application of the Redlich-Kister model are Tc = 4900°C, Pc = 300 bar and χ c, steel = 0.41.
Anovitz, L.M.; Labotka, T.C.; Blencoe, J.G.; Singh, J.; Horita, J.
1999-09-12
An understanding of activity-composition (a/X) relations and phase equilibria for halite-bearing, mixed-species supercritical fluids is critically important in many geological and industrial applications. The authors have performed experiments on the a/X relations and phase equilibria of H{sub 2}O-CO{sub 2}-NaCl fluids at 5OO C, 500 bars, to obtain highly accurate and precise data for this ternary system. H{sub 2}O-CO{sub 2}-NaCl samples were reacted at a (H{sub 2}O) = 0.350, 0.425, 0.437, 0.448, 0.560, 0.606, 0.678, 0.798, and 0.841. Results indicate that fluids with these activities lie in the vapor-NaCl two-phase region, and that a fluid with the last value has a composition close to the three-phase (vapor + brine + halite) field. Data from these experiments and NaCl solubility runs also suggest that the vapor comer of the three-phase field lies near X(H{sub 2}O) = 0.760, X(NaCl) = 0.065, which is a significantly more water-rich composition than suggested by the model of [1].
NASA Astrophysics Data System (ADS)
Koepke, J.; Berndt, J.; Feig, S. T.
2003-04-01
For the genesis of oceanic plagiogranites at mid-ocean spreading systems, two models are under discussion: (1) Late-stage differentiation of a MORB-type melt and (2) partial melting of pre-existing gabbros within high-temperature shear zones. In this study, we have applied recent experimental data of the experimental lab in Hannover to the plagiogranite petrogenesis in order to test both models. The role of water during the genesis of these rocks (presence of amphibole as mafic phase in natural plagiogranites) was assessed by including water to the systems. Crystallization experiments were performed in a MORB system doped with different water contents at different redox conditions at 200 MPa (Berndt, 2002), and hydrous partial melting experiments were performed at 200 MPa on typical oceanic gabbros (Feig et al., this volume). For the experiments we have used an internally heated pressure vessel for high temperatures (up to 1250°C) equipped with a rapid-quench system and a hydrogen membrane for controlling the oxygen fugacity. Liquid lines of descent obtained via crystallization experiments are mainly controlled by oxygen fugacity and only to a little extent by water activity. SiO2-rich residual melts can be obtained under both oxidizing and reducing redox condition at low temperatures, but at least one fractionation step is required to reach high-silicic plagiogranites (SiO2 > 70 wt%). The partial melting of typical oceanic gabbro leads at low temperatures also to plagiogranitic melts. At 940°C, the normalized SiO2 contents of the experimental melts of the three investigated systems range between 60 and 61 wt%, and at 900°C from 63 and 68 wt%. These melts coexist with orthopyroxene, amphibole, plagioclase and in one sample also with olivine. The experimental melt compositions are compared with those of natural plagiogranites of different tectonic settings and show in general a broad compositional overlap with those. Our experiments imply, in concordance with the
NASA Astrophysics Data System (ADS)
Ghiorso, M. S.; Kress, V. C.
2004-12-01
Software tools like MELTS (Ghiorso and Sack, 1995, CMP 119:197) and its derivatives (Ghiorso et al., 2002, G3 3:10.1029/2001GC000217) are sophisticated calculators used by geoscientists to quantify the chemistry of melt production, transport and storage. These tools utilize computational thermodynamics to evaluate the equilibrium state of the system under specified external conditions by minimizing a suitably constructed thermodynamic potential. Like any thermodynamically based tool, the principal advantage in employing these techniques to model igneous processes is the intrinsic ability to couple the chemistry and energetics of the evolution of the system in a self consistent and rigorous formalism. Access to MELTS is normally accomplished via a standalone X11-based executable or as a Java-based web applet. The latter is a dedicated client-server application rooted at the University of Chicago. Our on-going objective is the development of a distributed computing infrastructure to provide "MELTS-like" computations on demand to remote network users by utilizing a language independent client-server protocol based on CORBA. The advantages of this model are numerous. First, the burden of implementing and executing MELTS computations is centralized with a software implementation optimized to a compute cluster dedicated for that purpose. Improvements and updates to MELTS software are handled locally on the server side without intervention of the user and the server-model lessens the burden of supporting the computational code on a variety of hardware and OS platforms. Second, the client hardware platform does not incur the computational cost of performing a MELTS simulation and the remote user can focus on the task of incorporating results into their model. Third, the client user can write software in a computer language of their choosing and procedural calls to the MELTS library can be executed transparently over the network as if a local language-compatible library of
Ponweiser, Norbert; Lengauer, Christian L.; Richter, Klaus W.
2011-01-01
The phase equilibria and reaction temperatures in the system Al–Cu were re-investigated by a combination of optical microscopy, powder X-ray diffraction (XRD) at ambient and elevated temperature, differential thermal analysis (DTA) and scanning electron microscopy (SEM). A full description of the phase diagram is given. The phase equilibria and invariant reactions in the Cu-poor part of the phase diagram could be confirmed. The Cu-rich part shows some differences in phase equilibria and invariant reactions compared to the known phase diagram. A two phase field was found between the high temperature phase η1 and the low temperature phase η2 thus indicating a first order transition. In the ζ1/ζ2 region of the phase diagram recent findings on the thermal stability could be widely confirmed. Contrary to previous results, the two phase field between δ and γ1 is very narrow. The results of the current work indicate the absence of the high temperature β0 phase as well as the absence of a two phase field between γ1 and γ0 suggesting a higher order transition between γ1 and γ0. The structure of γ0 (I-43m, Cu5Zn8-type) was confirmed by means of high-temperature XRD. Powder XRD was also used to determine the structure of the high temperature phase η1-Al1−δCu. The phase is orthorhombic (space group Cmmm) and the lattice parameters are a = 4.1450(1) Å, b = 12.3004(4) Å and c = 8.720(1) Å; atomic coordinates are given. PMID:27103761
NASA Astrophysics Data System (ADS)
O'Hara, M. J.; Herzberg, C.
2002-06-01
The concentrations and ratios of the major elements determine the physical properties and the phase equilibria behavior of peridotites and basalts in response to the changing energy contents of the systems. The behavior of the trace elements and isotopic features are influenced in their turn by the phase equilibria, by the physical character of the partial melting and partial crystallization processes, and by the way in which a magma interacts with its wall rocks. Concentrating on the trace element and isotope contents of basalts to the exclusion of the field relations, petrology, major element data, and phase equilibria is as improvident as slaughtering the buffalo for the sake of its tongue. The crust is a cool boundary layer and a density filter, which impedes the upward transfer of hot, dense "primary" picritic and komatiitic liquids. Planetary crusts are sites of large-scale contamination and extensive partial crystallization of primitive melts striving to escape to the surface. Escape of truly unmodified primitive melts to the surface is a rare event, requiring the resolution of daunting problems in chemical and mechanical engineering. Primary status for volumetrically abundant basalts such as mid-ocean ridge basalt, ocean island basalt, and continental flood basalts is denied by their low-pressure cotectic character, first remarked upon on petrological grounds in 1928 and on experimental grounds in 1962. These basalt liquids are products of crystal-liquid separation at low pressure. Primary status for these common basalts is further denied by the phase equilibria of such compositions at elevated pressures, when the required residual mantle mineralogy (magnesian olivine and orthopyroxene) is not stable at the liquidus. It is also denied by the picritic or komatiitic nature of partial melts of candidate upper-mantle compositions at high pressures - a conclusion supported by calculation of the melt composition, which would need to be extracted in order to
Two-population replicator dynamics and number of Nash equilibria in matrix games
NASA Astrophysics Data System (ADS)
Galla, T.
2007-04-01
We study the connection between the evolutionary replicator dynamics and the number of Nash equilibria in large random bi-matrix games. Using techniques of disordered systems theory we compute the statistical properties of both, the fixed points of the dynamics and the Nash equilibria. Except for the special case of zero-sum games, one finds a transition as a function of the so-called co-operation pressure between a phase in which there is a unique stable fixed point of the dynamics coinciding with a unique Nash equilibrium, and an unstable phase in which there are exponentially many Nash equilibria with statistical properties different from the stationary state of the replicator equations. Our analytical results are confirmed by numerical simulations of the replicator dynamics, and by explicit enumeration of Nash equilibria.
Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.
1992-01-01
The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.
NASA Astrophysics Data System (ADS)
Liyana-Arachchi, Thilanga P.; Jamadagni, Sumanth N.; Eike, David; Koenig, Peter H.; Siepmann, J. Ilja
2015-01-01
Three developments are presented that significantly expand the applicability of dissipative particle dynamics (DPD) simulations for symmetric and non-symmetric mixtures, where the former contain particles with equal repulsive parameter for self-interactions but a different repulsive parameter for cross-interactions, and the latter contain particles with different repulsive parameters also for the self-interactions. Monte Carlo and molecular dynamics simulations for unary phases covering a wide range of repulsive parameters and of densities for single-bead DPD particles point to deficiencies of the Groot and Warren equation of state (GW-EOS) [J. Chem. Phys. 107, 4423 (1997)]. A revised version, called rGW-EOS, is proposed here that is significantly more accurate over a wider range of parameters/densities. The second development is the generalization of the relationship between the Flory-Huggins χ parameter and the repulsive cross-interaction parameter when the two particles involved have different molecular volumes. The third aspect is an investigation of Gibbs ensemble Monte Carlo simulation protocols, which demonstrates the importance of volume fluctuations and excess volumes of mixing even for equimolar symmetric mixtures of DPD particles. As an illustrative example, the novel DPD methodology is applied to the prediction of the liquid-liquid equilibria for acetic anhydride/(n-hexane or n-octane) binary mixtures.
Bi, S P; An, S Q; Liu, F
2001-05-01
A practical application of Driscoll's equation for predicting the acid-neutralizing capacity (ANC) in acidic waters equilibria with the mineral phase gibbsite is reported in this paper. Theoretical predication values of ANC are compared with the experimental data obtained from different literatures. The effect of aluminum (Al) on the value of ANC is investigated. It indicates that Al plays an important role in regulating the buffering effects in acidic natural waters. Failure to consider Al in acidic waters may bias assessment results in certain situations so as to overestimate the ANC values in response to increase in atmospheric deposition.
NASA Astrophysics Data System (ADS)
Tramontano, S.; Gualda, G. A. R.; Ghiorso, M. S.; Kennedy, B.
2015-12-01
It is important to understand what triggers silicic eruptions because of the implications for modern-day systems. The goal of this project is to use phase equilibria modeling (i.e. rhyolite-MELTS) to determine to what extent magmas within the crust are induced to erupt due to external triggers (e.g. earthquakes; new magma injection; neighboring eruptions) and to what extent they naturally evolve to a point where eruption is inevitable (e.g. by fluid exsolution and decrease in magma strength and density). Whole-rock compositions from four rhyolite tuffs across the globe associated with large or supereruptions (Mamaku Tuff, New Zealand; Peach Spring Tuff, SW USA; early and late-erupted Bishop Tuff, California; and Toba Tuff, Indonesia) are studied using rhyolite-MELTS modeling. Key physical properties of magma are strongly affected by the initial volatile content due to fluid exsolution. By running simulations with varying water contents, we can track the evolution of fluid exsolution during crystallization. Isobaric (constrained temperature change at constant pressure) and isochoric (constrained temperature change at constant volume) models were run for the four compositions. In constrained-pressure scenarios, fluid is free to exsolve as crystallization proceeds, and the total system volume can increase or decrease accordingly; this would require deformation of the surrounding crust to accommodate the magma volume change. In constrained-volume scenarios, bubble exsolution is limited to the volume change due to crystallization; in this case, pressure can decrease or increase (if bubbles are absent or present). For fixed-pressure scenarios, fluid exsolution is more extensive and leads to internal triggering, at least for fluid-saturated conditions; external triggering is more likely in fluid-undersaturated conditions. For fixed-volume scenarios, none of the systems cross a fragmentation threshold for the crystal contents typically observed in natural pumice. If
NASA Astrophysics Data System (ADS)
Benziane, Mokhtar; Khimeche, Kamel; Dahmani, Abdellah; Nezar, Sawsen; Trache, Djalal
2012-06-01
Solid-liquid equilibria for three binary mixtures, n-Eicosane (1) + Lauric acid (2), n-Tetracosane (1) + Stearic acid (2), and n-Octacosane (1) + Palmitic acid (2), were measured using a differential scanning calorimeter. Simple eutectic behaviour was observed for these systems. The experimental results were correlated by means of the modified UNIFAC (Larsen and Gmehling versions), UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.26 to 3.15 K and depend on the particular model used. The best solubility correlation was obtained with the UNIQUAC model.
Wilson, D Scott; Lee, Lloyd L
2005-07-22
We explore the vapor-liquid phase behavior of binary mixtures of Lennard-Jones-type molecules where one component is supercritical, given the system temperature. We apply the self-consistency approach to the Ornstein-Zernike integral equations to obtain the correlation functions. The consistency checks include not only thermodynamic consistencies (pressure consistency and Gibbs-Duhem consistency), but also pointwise consistencies, such as the zero-separation theorems on the cavity functions. The consistencies are enforced via the bridge functions in the closure which contain adjustable parameters. The full solution requires the values of not only the monomer chemical potentials, but also the dimer chemical potentials present in the zero-separation theorems. These are evaluated by the direct chemical-potential formula [L. L. Lee, J. Chem. Phys. 97, 8606 (1992)] that does not require temperature nor density integration. In order to assess the integral equation accuracy, molecular-dynamics simulations are carried out alongside the states studied. The integral equation results compare well with simulation data. In phase calculations, it is important to have pressure consistency and valid chemical potentials, since the matching of phase boundaries requires the equality of the pressures and chemical potentials of both the liquid and vapor phases. The mixtures studied are methane-type and pentane-type molecules, both characterized by effective Lennard-Jones potentials. Calculations on one isotherm show that the integral equation approach yields valid answers as compared with the experimental data of Sage and Lacey. To study vapor-liquid phase behavior, it is necessary to use consistent theories; any inconsistencies, especially in pressure, will vitiate the phase boundary calculations.
NASA Astrophysics Data System (ADS)
Mick, Jason R.; Soroush Barhaghi, Mohammad; Jackman, Brock; Rushaidat, Kamel; Schwiebert, Loren; Potoff, Jeffrey J.
2015-09-01
Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions.
Mick, Jason R; Soroush Barhaghi, Mohammad; Jackman, Brock; Rushaidat, Kamel; Schwiebert, Loren; Potoff, Jeffrey J
2015-09-21
Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions. PMID:26395716
Mick, Jason R; Soroush Barhaghi, Mohammad; Jackman, Brock; Rushaidat, Kamel; Schwiebert, Loren; Potoff, Jeffrey J
2015-09-21
Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions.
Llanes-Santiago, O.; Sira-Ramirez, H.
1994-12-31
A feedback resetting strategy, exercised on the output of a purposely designed unstable dynamical feedback controller, is shown to yield a robust, and efficient, output voltage stabilization of nonlinear average models of DC-to-DC Power Converters around any non-minimum phase equilibrium point of the system. The technique guarantees, in an average sense, an asymptotically stable behavior of the controlled converter state variables towards their required equilibrium values, while the unstable dynamical compensator output is forcefully kept bounded within an arbitrarily small neighborhood of the required controller operating point.
NASA Astrophysics Data System (ADS)
Gualda, G. A. R.; Pamukcu, A. S.; Wright, K. A.; Ghiorso, M. S.; Miller, C. F.
2014-12-01
Supereruption deposits demonstrate that giant magma bodies sporadically exist within the Earth's crust. We rely on study of such deposits to better understand the underlying magma bodies and their eruptions. We are studying several deposits: Bishop Tuff (BT, CA USA), Peach Spring Tuff (PST, SW USA), and Oruanui Tuff (OT, NZ). We combine quantitative textural characterization in 3D via x-ray tomography (XRT), focusing particularly on CSDs of major and accessory minerals; characterization of mineral zoning, particularly of Ti and CL in quartz, including inferences from diffusion chronometry; documentation of glass inclusion textures in 3D via XRT, with implications to crystallization timescales; and phase equilibria modeling (rhyolite-MELTS), including glass (inclusion and matrix) composition geobarometry, to constrain crystallization conditions. CSDs ubiquitously record a growth-dominated regime, characterized by limited nucleation, consistent with pre-eruptive crystallization under low supersaturation. Phenocryst interiors are largely unzoned, consistent with phase equilibria predictions of nearly invariant, effectively isothermal crystallization. Glass compositions record storage over a large spread of depths (~125-250 MPa) for early and late-erupted BT, while the OT represents multiple magma batches evacuated from different depths. Diffusion chronometry and melt inclusion faceting suggest pre-eruptive crystallization over centennial timescales. CSDs and mineral textures also record syn-eruptive crystallization, which results in huge numbers of small crystals, revealing extensive nucleation prior to eruption. Crystal rims develop on pre-existing phenocrysts, and they can be obvious if compositionally distinct from interiors (BT and PST). In PST, evidence for rim crystallization from hotter magma is very strong. BT contrasts with PST in many ways; evidence for heating is ambiguous, and pumice properties are difficult to reconcile with magma mixing, while the
NASA Astrophysics Data System (ADS)
Frank, Mark R.; Candela, Philip A.; Piccoli, Philip M.
2003-04-01
complex. fH 2Osys and the ASI are the main controls on model NaOH m/ΣNa m in the system, with model NaOH m/ΣNa m increasing with increasing fH 2Osys. This relationship can be used to estimate the C HClb in subaluminous systems, an improvement over previous models. Data for metal partitioning between a volatile phase and melt are commonly presented in the literature as metal-sodium exchange equilibria (i.e., K Cu,Na for the exchange of copper and sodium). However, the variation in K' meas (K, Na) observed in this study implies that the treatment of metal partitioning between a volatile phase and melt as metal-alkali exchange equilibria is complex because alkali partitioning is not constant and suggests that experimental partitioning studies need to carefully control the HCl/NaCl in experimental vapors and brines. This effect may explain discrepancies in metal-alkali exchange equilibria presented in the literature. Therefore, metal-alkali exchange cannot be described fully by a single metal-alkali equilibrium but must be examined by multiple equilibria.
On the topological stability of magnetostatic equilibria
NASA Technical Reports Server (NTRS)
Tsinganos, K. C.; Rosner, R.; Distler, J.
1984-01-01
The topological stability of MHD equilibria is investigated by exploring the formal analogy, in the ideal MHD limit, between the topology of magnetic lines of force in coordinate space and the topology of integral surfaces of one- and two-dimensional Hamiltonian systems in phase space. It is demonstrated that in an astrophysical setting, symmetric magnetostatic equilibria satisfying the ideal MHD equations are exceptional. The principal result of the study is that previous infinitesimal perturbation theory calculations can be generalized to include finite-amplitude and symmetry-breaking effects. The effect of the ergodicity of perturbed symmetric equilibria on heat dispersal in magnetically dominated plasmas is discussed.
NASA Astrophysics Data System (ADS)
Yen, Yee-Wen; Jao, Chien-Chung; Hsiao, Hsien-Ming; Lin, Chung-Yung; Lee, Chiapyng
2007-02-01
The phase equilibria of the Sn-Cu-Au ternary, Ag-Sn-Cu-Au quaternary systems and interfacial reactions between Sn-Cu alloys and Au were experimentally investigated at specific temperatures in this study. The experimental results indicated that there existed three ternary intermetallic compounds (IMCs) and a complete solid solubility between AuSn and Cu6Sn5 phases in the Sn-Cu-Au ternary system at 200°C. No quaternary IMC was found in the isoplethal section of the Ag-Sn-Cu-Au quaternary system. Three IMCs, AuSn, AuSn2, and AuSn4, were found in all couples. The same three IMCs and (Au,Cu)Sn/(Cu,Au)6Sn5 phases were found in all Sn-Cu/Au couples. The thickness of these reaction layers increased with increasing temperature and time. The mechanism of IMC growth can be described by using the parabolic law. In addition, when the reaction time was extended and the Cu content of the alloy was increased, the AuSn4 phase disappeared gradually. The (Au, Cu)Sn and (Cu,Au)6Sn5 layers played roles as diffusion barriers against Sn in Sn-Cu/Au reaction couple systems.
Danov, Krassimir D; Kralchevsky, Peter A; Ananthapadmanabhan, Kavssery P
2014-04-01
On the basis of a detailed physicochemical model, a complete system of equations is formulated that describes the equilibrium between micelles and monomers in solutions of ionic surfactants and their mixtures with nonionic surfactants. The equations of the system express mass balances, chemical and mechanical equilibria. Each nonionic surfactant is characterized by a single thermodynamic parameter--its micellization constant. Each ionic surfactant is characterized by three parameters, including the Stern constant that quantifies the counterion binding. In the case of mixed micelles, each pair of surfactants is characterized with an interaction parameter, β, in terms of the regular solution theory. The comparison of the model with experimental data for surfactant binary mixtures shows that β is constant--independent of the micelle composition and electrolyte concentration. The solution of the system of equations gives the concentrations of all monomeric species, the micelle composition, ionization degree, surface potential and mean area per head group. Upon additional assumptions for the micelle shape, the mean aggregation number can be also estimated. The model gives quantitative theoretical interpretation of the dependence of the critical micellization concentration (CMC) of ionic surfactants on the ionic strength; of the CMC of mixed surfactant solutions, and of the electrolytic conductivity of micellar solutions. It turns out, that in the absence of added salt the conductivity is completely dominated by the contribution of the small ions: monomers and counterions. The theoretical predictions are in good agreement with experimental data.
The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2
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.
Gritti, Fabrice; Guiochon, Georges A
2006-03-01
The extension of the {Psi} function developed by Toth from equilibria taking place at gas-solid interfaces to those taking place at liquid-solid interfaces was investigated. The results were applied to conventional liquid-solid systems used in reversed-phase liquid chromatography (RPLC). The adsorbents in these systems are made of porous silica having a hydrophobic solid surface obtained by chemically bonding C{sub 18} alkyl chains to a porous silica gel then endcapping the surface with trimethylsilyl groups. The liquid is an aqueous solution of an organic solvent, most often methanol or acetonitrile. The probe compound used here is phenol. Adsorption data of phenol were measured using the dynamic frontal analysis (FA) method. The excess adsorption of the organic solvent was measured using the minor disturbance (MD) method. Activity coefficients in the bulk were estimated through the UNIFAC group contributions. The results show that the {Psi} function predicts 90% of the total free energy of immersion, {Delta}F, of the solid when the concentration of phenol is moderate (typically less than 10 g/L). At higher concentrations, the nonideal behavior of the bulk liquid phase becomes significant and it may contribute up to about 30% of {Delta}F. The high concentration of adsorbed molecules of phenol at the interface decreases the interfacial tension, {sigma}, by about 18 mN/m, independently of the structure of the adsorbed phase and of the nature of the organic solvent.
Thermodynamic analysis of the cubic-tetragonal phase equilibria in the system ZrO{sub 2}-YO{sub 1.5}
Katamura, Junji; Sakuma, Taketo
1997-10-01
The cubic-tetragonal (c-t) phase equilibria in the system ZrO{sub 2}-YO{sub 1.5} are thermodynamically analyzed from Landau`s phenomenological theory. The calculated c-t two-phase field is depicted as a miscibility gap with a sharp maximum and the spinodal region as originally predicted by Hillert and Sakuma. However, the observed c-t two-phase field and the spinodal region are better described by the present model. In addition, this model can be used to discuss the nature of the c-t diffusionless transformation from the order parameter in contrast with the original model. The predicted change in the tetragonality of t-ZrO{sub 2} with YO{sub 1.5} content is slightly different from that in the cla axial ratio estimated from X-ray diffraction analysis. The displacement of cations and anions may not take place simultaneously during the c-t transformation.
NASA Astrophysics Data System (ADS)
Vrabec, J.; Fischer, J.
1996-07-01
The NpT + test particle method is used in order to predict vapor-liquid equilibria of the mixtures methane + ethane, methane + carbon dioxide, and carbon dioxide +ethane by molecular simulations. The pure-component molecular models were fitted to the experimental vapor pressures and saturated liquid densities in previous papers, which used the same simulation method for the determination of the phase equilibria. For each binary mixture the two unlike interaction parameters were determined from one experimental excess volume and one excess enthalpy. Based on these molecular models the vapor-liquid phase equilibria were calculated for each mixture at three temperatures. Comparison of the pressure-composition data with experimental results shows the high predictive power of this molecular based procedure. This statement is confirmed by additional comparisons of the pressure-composition diagrams and the pressure-density diagrams with results from equations of state.
NASA Astrophysics Data System (ADS)
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.
NASA Technical Reports Server (NTRS)
Copland, Evan H.; Jacobson, Nathan S.; Ritzert, Frank J.
2001-01-01
A previous study by Ritzert et al. on the formation and prediction of topologically closed packed (TCP) phases in the nickel-base superalloy Rene' N6 is re-examined with computational thermodynamics. The experimental data on phase distribution in forty-four alloys with a composition within the patent limits of the nickel-base superalloy Rene' N6 provide a good basis for comparison to and validation of a commercial nickel superalloy database used with ThermoCalc. Volume fraction of the phases and partitioning of the elements are determined for the forty-four alloys in this dataset. The baseline heat treatment of 400 h at 1366 K was used. This composition set is particularly interesting since small composition differences lead to dramatic changes in phase composition. In general the calculated values follow the experimental trends. However, the calculations indicated no TCP phase formation when the experimental measurements gave a volume percent of TCP phase less than 2 percent. When TCP phases were predicted, the calculations under-predict the volume percent of TCP phases by a factor of 2 to 8. The calculated compositions of the gamma and gamma' phases show fair agreement with the measurements. However, the calculated compositions of the P Phase do not agree with those measured. This may be due to inaccuracies in the model parameters for P phase and/or issues with the microprobe analyses of these phases. In addition, phase fraction diagrams and sigma and P phase solvus temperatures are calculated for each of the alloys. These calculations indicate that P phase is the primary TCP phase formed for the alloys considered here at 1366 K. Finally, a series of isopleths are calculated for each of the seven alloying elements. These show the effect of each alloying element on creating TCP phases.
NASA Astrophysics Data System (ADS)
He, Xiao-Fang; Santosh, M.; Bockmann, Kiara; Kelsey, David E.; Hand, Martin; Hu, Jianmin; Wan, Yusheng
2016-10-01
Among the various Precambrian crustal blocks in the North China Craton (NCC), the geology and evolution of the Ordos Block remain largely enigmatic due to paucity of outcrop. Here we investigate granulite-facies metapelites obtained from deep-penetrating drill holes in the Ordos Block and report petrology, calculated phase equilibria and in-situ monazite LA-ICP-MS geochronology. The rocks we studied are two samples of cordierite-bearing garnet-sillimanite-biotite metapelitic gneisses and one graphite-bearing, two-mica granitic gneiss. The peak metamorphic age from LA-ICP-MS dating of monazite in all three samples is in the range of 1930-1940 Ma. The (U + Pb)-Th chemical ages through EPMA dating reveals that monazite occurring as inclusions in garnet are older than those in the matrix. Calculated metamorphic phase diagrams for the cordierite-bearing metapelite suggest peak P-T conditions ca. 7-9 kbar and 775-825 °C, followed by decompression and evolution along a clockwise P-T path. Our petrologic and age data are consistent with those reported from the Khondalite Belt in the Inner Mongolia Suture Zone in the northern part of the Ordos Block, suggesting that these granulite-facies metasediments represent the largest Paleoproterozoic accretionary belt in the NCC.
NASA Astrophysics Data System (ADS)
Bartoli, Omar; Acosta-Vigil, Antonio; Tajčmanová, Lucie; Cesare, Bernardo; Bodnar, Robert J.
2016-07-01
Anatexis in the crustal footwall of Ronda peridotites (Betic Cordillera, S Spain) is apparently related to the hot emplacement of this mantle slab over metasedimentary rocks. In this study, we combine the analysis of melt inclusions (MI) and phase equilibria calculations on quartzo-feldspathic mylonites (former migmatites) occurring at the contact with the mantle rocks, in the region of Sierra Alpujata (Ojén unit). The goal is to better characterize anatexis in these rocks and to provide new constraints on the geodynamic evolution of the crustal footwall. Such data are important for understanding the mechanisms of crustal emplacement of the mantle slice. The quartzo-feldspathic mylonites are characterized by the mineral assemblage Qtz + Pl + Kfs + Sil + Grt + Ilm + Bt ± Ap ± Gr. Clusters of MI are observed both at the core and toward the rim of peritectic garnet. In each cluster, MI range from totally glassy to nanogranitoids, consisting of Qtz + Kfs + Bt + Ms + Pl aggregates. The trapped melt is leucogranitic and peraluminous with variable Na2O/K2O values and low H2O contents (≈ 2-4 wt%). Phase equilibria modeling in the MnO-Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2-TiO2-O2-C (MnNCaKFMASHTOC) system with graphite-saturated fluid constrains the P-T conditions of melting at ≈ 6 kbar, ≈ 820 °C. MI data support the fluid-absent character of melting. The investigated MI represent the primary anatectic melts produced during prograde anatexis of the host rocks via biotite dehydration melting. Field, compositional, and textural observations indicate that mylonitic migmatites represent strongly deformed former diatexites. The comparison between the new data and some recently published information on migmatites located further from the contact with the peridotites and toward the bottom of the crustal footwall, raises some important issues which question the previously proposed geodynamic models for this region. Among them, (i) the crustal footwall at Sierra Alpujata
Three-phase liquid-liquid-vapor equilibria behavior of certain binary CO/sub 2/-n-paraffin systems
Hottovy, J.D.; Kohn, J.P.; Luks, K.D.
1981-07-01
The 3-phase liquid-liquid-vapor loci of 4 binary CO/sub 2/-n-paraffin systems (n-dodecane, n-tridecane, n-tetradecane, n-pentadecane) are studied, and temperature, pressure, and molar volumes and composition of both liquid phases are reported. It is within this group of n-paraffins that the nature of the upper critical end point for the CO/sub 2/-containing binary systems changes with increasing carbon number from an upper critical solution (temperature) point where L/sub 1/ and L/sub 2/ phases become critical in presence of vapor phase to a K point, where L/sub 2/ and vapor phases become critical in the presence of L/sub 1/ phase. These 4 loci are compared with earlier obtained loci on CO/sub 2/-n-decane and CO/sub 2/-n-elcosane.
Braided magnetic fields: equilibria, relaxation and heating
NASA Astrophysics Data System (ADS)
Pontin, D. I.; Candelaresi, S.; Russell, A. J. B.; Hornig, G.
2016-05-01
We examine the dynamics of magnetic flux tubes containing non-trivial field line braiding (or linkage), using mathematical and computational modelling, in the context of testable predictions for the laboratory and their significance for solar coronal heating. We investigate the existence of braided force-free equilibria, and demonstrate that for a field anchored at perfectly-conducting plates, these equilibria exist and contain current sheets whose thickness scales inversely with the braid complexity—as measured for example by the topological entropy. By contrast, for a periodic domain braided exact equilibria typically do not exist, while approximate equilibria contain thin current sheets. In the presence of resistivity, reconnection is triggered at the current sheets and a turbulent relaxation ensues. We finish by discussing the properties of the turbulent relaxation and the existence of constraints that may mean that the final state is not the linear force-free field predicted by Taylor’s hypothesis.
Miyabe, Kanji; Guiochon, Georges
2005-12-16
The retention behavior on silica gels bonded to C18 and C1 alkyl ligands of different densities was studied in reversed-phase liquid chromatography (RPLC) from the viewpoints of two extrathermodynamic relationships, enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, the four tests proposed by Krug et al. were applied to the values of the retention equilibrium constants (K) normalized by the alkyl ligand density. These tests showed that a real EEC of the retention equilibrium originates from substantial physico-chemical effects. Second, we derived a new model based on the EEC to explain the LFER between the retention equilibria under different RPLC conditions. The new model indicates how the slope and intercept of the LFER are correlated to the compensation temperatures derived from the EEC analyses and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy. Finally, we calculated K under various RPLC conditions from only one original experimental K datum by assuming that the contributions of the C18 and C1 ligands to K are additive and that their contributions are proportional to the density of each ligand. The estimated K values are in agreement with the corresponding experimental data, demonstrating that our model is useful to explain the variations of K due to changes in the RPLC conditions.
Phase equilibria in the system H{sub 2}O-NaCl-KCl-MgCl{sub 2} relevant to salt cake processing
Bodnar, R.J.; Vityk, M.O.; Hryn, J.N.; Mavrogenes, J.
1997-02-01
One waste product in recycling of Al is salt cake, a mixture of Al, salts, and residue oxides. Several methods have been proposed to recycle salt cake, one involving high-temperature leaching of salts from the salt cake. The salt composition can be approximated as a mixture predominantly of NaCl and KCl salts, with lesser amounts of Mg chloride. In order to better assess the feasibility of recycling salt cake, an experimental study was conducted of phase equilibria in the system H{sub 2}O-NaCl-KCl-MgCl{sub 2} at pressure (P), temperature (T), and composition conditions appropriate for high- temperature salt cake recycling. These experiments were designed to evaluate the effect of small amounts (2-10 wt%) of MgCl{sub 2} on solubilities of halite (NaCl) and sylvite (KCl) in saturated solutions (30-50 wt% NaCl+KCl; NaCl:KCl = 1:1 and 3:1) at elevated P and T.
Johnson, J.K.; Rowley, R.L. )
1989-03-01
Mixing rules for an extended Lee-Kesler (ELK) corresponding-states method for prediction of thermodynamic properties are presented. The mixing rules, which do not contain adjustable parameters, permit calculation of vapor-liquid equilibria in mixtures containing one or more polar components. While a single heat-of-mixing datum may be included for strongly associating components, generally only pure component properties are used in the calculations. A comparison of calculated bubble-point pressures and equilibrium vaporization ratios to experimental values is made for 26 ternary mixtures (791 points) and 5 quaternary mixtures (175 points). Bubble-point pressures are predicted quite well with ELK (9.1% AAD for ternaries and 7.9% for quaternaries). Composition predictions are difficult to compare in multicomponent systems, but ELK predictions appear to be acceptable on both a system-by-system and an overall AAD basis.
Nonadditive Mixed State Phases in Neutron Optics
Klepp, J.; Sponar, S.; Filipp, S.; Lettner, M.; Badurek, G.; Hasegawa, Y.
2009-03-10
In a neutron polarimetry experiment mixed neutron spin phases are determined. We consider evolutions leading to purely geometric, purely dynamical and combined phases. It is experimentally demonstrated that the sum of the geometric and dynamical phases--both obtained in separate measurements--is not equal to the associated total phase as obtained from a third measurement, unless the system is in a pure state. In this sense, mixed state phases are not additive.
Kaur, R; Grant, D J; Eaves, T
1980-11-01
Phase equilibrium diagrams were constructed based on hot-stage microscopy and differential scanning calorimetry of solid dispersions of griseofulvin or tolbutamide in polyethylene glycol 2000 or polyoxyethylene 40 stearate. The solid dispersions were prepared by physical mixing, fusion, and coprecipitation from ethanol. The phase diagrams were largely independent of the method of preparation of the dispersion systems. The diagrams were of the monotectic type for polyethylene glycol 2000 with each drug and for griseofulvin with each excipient, with the monotectic species being the pure drug. Polyoxyethylene 40 stearate with tolbutamide gave eutectic systems in which liquid polyoxyethylene 40 stearate dissolved up to 20% of the tolbutamide. The phase diagrams showed greater solubility of tolbutamide in liquid polyoxyethylene 40 stearate than in polyethylene glycol 2000 but showed a similar solubility of griseofulvin in each experiment. Solid solution formation was not detected. PMID:7452463
NASA Astrophysics Data System (ADS)
Degtev, M. I.; Popova, O. N.; Yuminova, A. A.
2014-08-01
The ability of antipyrine and its derivatives (diantipyryl alkanes) to form separating systems in the presence of salicylic (sulfosalicylic) acid and hydrochloric acid and water is studied. The optimum volume of the organic phase, the composition of complexes, and the mechanism for the distribution of metal ions are determined, depending on the concentrations of the main components and the salting-out agent. The complex distribution and extraction constants are calculated.
Phase equilibria and elements partitioning in zirconolite-rich region of Ca-Zr-Ti-Al-Gd-Si-O system
Knyazev, O.A.; Stefanovsky, S.V.; Ioudintsev, S.V.; Nikonov, B.S.; Omelianenko, B.I.; Mokhov, A.V.; Yakushev, A.I.
1997-12-31
Zirconolite-rich ceramics were produced by the cold crucible melting technique in an air atmosphere, at 1550 {+-} 50 C and 1 atm. Four samples with overall composition (in wt.%): 4.9-14.3 CaO; 19.0-41.3 ZrO{sub 2}; 24.1-42.6 TiO{sub 2}; 1.3-11.3 Al{sub 2}O{sub 3}; 6.8-30.0 Gd{sub 2}O{sub 3}; and 1.1-8.5 SiO{sub 2} have been studied. Total phases in the ceramics consist of major zirconolite and minor rutile, perovskite, zirconia, aluminium titanate, and glass. The Gd{sub 2}O{sub 3} content in zirconolite reaches up to 31.4 wt.% corresponding to the formula: (Ca{sub 0.4},Gd{sub 0.7})Zr{sub 1.0}(Ti{sub 1.4},Al{sub 0.5})O{sub 7.0}. The data on the phase composition agree well with coupled Gd incorporation into the mineral structure: Ca(II) + Ti(IV) = Gd(III) + Al(III), and 2Gd(III) = Ca(II) + Zr(IV). The highest Gd contents observed in the other phases are 25.4% for zirconia, 12.6% in glass, 8.8% in perovskite, and 1.4% for rutile. The rest of the elements` distribution in the samples are analyzed.
NASA Astrophysics Data System (ADS)
Thy, P.
1991-01-01
Melting experiments have been performed on a primitive, mildly alkalic glassy lava (10 wt.% MgO) from the 1965 eruption of the Surtsey volcano located at the tip of the south-eastern propagating rift zone of Iceland. At atmospheric pressure, approximately on the FMQ oxygen buffer, olivine (Fo 81) crystallizes from 1240°C, followed by plagioclase (An 70) from 1180°C and augite from 1140°C. The experimental glasses coexisting with olivine, plagioclase and augite are ferrobasaltic enriched in FeO (13.6-14.2 wt.%) and TiO 2 (4.0-4.4 wt.%). In high pressure, piston-cylinder, graphite-controlled runs, olivine occurs as the liquidus phase until 14 kbar, above which augite is the liquidus phase. Low-Ca pyroxene is not a liquidus phase at any pressure. The high pressure liquids are, relative to the one atmosphere liquids, significantly enriched in Al 2O 3 and Na 2O and depleted in CaO as a result of changes in the crystallizing assemblages. Furthermore, liquidus augite is dominantly subcalcic and shows significant enrichment in Al and depletion in Ti. Subliquidus plagioclase is enriched in sodium relative to low pressure phase compositions. Evaluated in normative projections, contrasting liquid lines of descent are revealed as a function of pressure. At one atmosphere, the multisaturated liquids are located close to the thermal divide defined by the plane olivine-plagioclase-augite, but appear, with advanced degrees of crystallization, to be moving away from the thermal divide toward normative quartz. The augites crystallizing in the one atmosphere experiments are calcic and slightly nepheline normative. In the 10 and 12.5 kbar experiments, the augites become subcalcic and dominantly hypersthene normative. Because of this shift in augite compositions, transitional basaltic liquids may at high pressure evolve from the tholeiitic side of the olivine-plagioclase-diopside normative divide onto the alkalic side. With increasing pressure above 15 kbar, the liquidus augite
Phase equilibria in the P(2)O(5)-CaO-CaF(2)-NaF-H(2)O quinary system and the formation of apatite
NASA Astrophysics Data System (ADS)
Martin, Roger Isaac
Phase equilibria among calcium phosphates in the Hsb3POsb4-Ca(OH)sb2-Hsb2O ternary system were determined as a basis for research in the formation of hydroxyapatite, a biomaterial. The acidic portion of the ternary diagram was established. Ca(Hsb2POsb4)sb2 was not stable for temperatures below 100sp°C. The experimental and theoretical dissolution paths of Ca(Hsb2POsb4)sb2{*}Hsb2O were compared. It is possible for the initial dissolution of Ca(Hsb2POsb4)sb2{*}Hsb2O to supersaturate the system with respect to hydroxyapatite because Ca(Hsb2POsb4)sb2{*}Hsb2O is "twice" incongruently soluble. Hydroxyapatite composition is variable with a Ca/P ratio ranging from 1.5 to 1.67. Hydroxyapatite formation from acid-base reactions of CaHPOsb4 and Casb4(POsb4)sb2O was investigated for composition at the terminal limits. The total heats-of-reaction (Delta Hsb{r}) were determined to be 261.3 and 320 kJ/mol for the formation of calcium deficient and stoichiometric hydroxyapatite, respectively. Activation energies of 84.7 and 87.4 kJ/mol were calculated for the formation of calcium deficient and stoichiometric hydroxyapatite, respectively. Heats-of-formation (Delta Hsb{f}) for Casb4(POsb4)sb2O and Casb9HPOsb4(POsb4)sb5OH were calculated to be -4764.1 and -1207.7 kJ/mol, respectively. The effects of magnesium on hydroxyapatite formation in vitro from CaHPOsb4 and Casb4(POsb4)sb2O at 37.4sp°C were investigated. Magnesium is a biological agent with 0.78 mM concentrations in blood. Magnesium inhibited nucleation for 1 mM concentrations and above for a 5 liquid-to-solids ratio. However, a 5 mM concentration of MgClsb2 slightly accelerated the growth rate. The activity of magnesium is approximately 6% of its concentration. Therefore the inorganic chemical activity of magnesium may not significantly inhibit the formation of bioapatites. Phase equilibria in the Psb2Osb5-CaO-CaFsb2-Hsb2O system at 37.4sp°C was determined and dental fluorosis explained. Fluoroapatite dissolves
NASA Astrophysics Data System (ADS)
Koga, K.; Widom, B.
2016-06-01
We treat two different density-functional models of the structures and tensions of the interfaces between phases on approach to the tricritical point of three-phase equilibrium. The major objective is to account for some of the results of earlier experimental measurements of these tensions. The thermodynamic background is first reviewed, including representations of the properties near the critical endpoints and tricritical point and of the wetting transitions that may occur on approach to those critical points. The first of the models treated is analytically soluble. Its properties are illuminating but at the price of some artificiality paid for its analytical solubility. The second model, called model T, is in a class of those treated in the past and analyzed numerically. Some of its properties are obtained with sufficient precision to allow one to conclude with near certainty what the analytically exact results would be. This model, too, illuminates the experimental measurements. It is noted where its properties are in accord with those of the analytically soluble model and where the two differ.
Lion, L.W.; Ong, S.K.; Linder, S.R.; Swager, J.L.; Schwager, S.J.
1990-04-01
Most groundwater pollutants are volatile organic compounds; however, there is relatively little understanding of the sorption reactions that control the transport and fate of organic vapors in the vadose zone. This investigation identified the physical/chemical properties of the soil matrix and organic vapors which control vapor-solid phase distribution. The dominant property which regulates vapor sorption in the unsaturated zone is the moisture content of the soil. Under very dry conditions, soil mineral/vapor interactions are regulated by specific surface area, indicating the dominance of a relatively non-specific physical adsorption process. However, at moisture contents exceeding an average surface coverage of four to eight layers of water, vapor uptake is controlled by partitioning reactions into soil moisture and soil organic matter.
Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound
NASA Astrophysics Data System (ADS)
Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian
2015-10-01
In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time.
Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound
Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian
2015-01-01
In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time. PMID:26471964
Romaka, V.V.; Rogl, P.; Romaka, L.; Stadnyk, Yu.; Melnychenko, N.; Grytsiv, A.; Falmbigl, M.; Skryabina, N.
2013-01-15
The phase equilibria of the Ti-Ni-Sn and Ti-Ni-Sb ternary systems have been studied in the whole concentration range by means of X-ray and EPM analyses at 1073 K and 873 K, respectively. Four ternary intermetallic compounds TiNiSn (MgAgAs-type), TiNi{sub 2-x}Sn (MnCu{sub 2}Al-type), Ti{sub 2}Ni{sub 2}Sn (U{sub 2}Pt{sub 2}Sn-type), and Ti{sub 5}NiSn{sub 3} (Hf{sub 5}CuSn{sub 3}-type) are formed in Ti-Ni-Sn system at 1073 K. The TiNi{sub 2}Sn stannide is characterized by homogeneity in the range of 50-47 at% of Ni. The Ti-Ni-Sb ternary system at 873 K is characterized by formation of three ternary intermetallic compounds, Ti{sub 0.8}NiSb (MgAgAs-type), Ti{sub 5}Ni{sub 0.45}Sb{sub 2.55} (W{sub 5}Si{sub 3}-type), and Ti{sub 5}NiSb{sub 3} (Hf{sub 5}CuSn{sub 3}-type). The solubility of Ni in Ti{sub 0.8}NiSb decreases number of vacancies in Ti site up to Ti{sub 0.91}Ni{sub 1.1}Sb composition. - Graphical abstract: Isothermal section of the Ti-Ni-Sn phase diagram and DOS distribution in hypothetical TiNi{sub 1+x}Sn solid solution. Highlights: Black-Right-Pointing-Pointer Ti-Ni-Sn phase diagram was constructed at 1073 K. Black-Right-Pointing-Pointer Four ternary compounds are formed: TiNiSn, TiNi{sub 2-x}Sn, Ti{sub 2}Ni{sub 2}Sn, and Ti{sub 5}NiSn{sub 3}. Black-Right-Pointing-Pointer Three ternary compounds exist in Ti-Ni-Sb system at 873 K. Black-Right-Pointing-Pointer The TiNi{sub 2}Sb compound is absent.
Effect of chlorine on near-liquidus phase equilibria of an Fe-Mg-rich tholeiitic basalt
NASA Astrophysics Data System (ADS)
Filiberto, Justin; Dasgupta, Rajdeep; Gross, Juliane; Treiman, Allan H.
2014-07-01
The importance of Cl in basalt petrogenesis has been recognized, yet constraints on its effect on liquidus crystallization of basalts are scarce. In order to quantify the role of Cl in basaltic systems, we have experimentally determined near-liquidus phase relations of a synthetic Fe-Mg-rich basalt, doped with 0.0-2.5 wt% dissolved Cl, at 0.7, 1.1, and 1.5 GPa. Results have been parameterized and compared with previous data from literature. The effect of Cl on mineral chemistry and liquidus depression is dependent on the starting basaltic composition. The liquidus depression measured for a SiO2-rich, Al2O3-poor basalt is smaller than that observed for a basaltic melt depleted in silica and enriched in FeOT and Al2O3. The effect of Cl on depression of the olivine-orthopyroxene-liquid multiple saturation pressure does not seem to vary with the starting composition of the basaltic liquid. This suggests that Cl may significantly promote the generation of silica-poor, Fe-Al-rich magmas in the Earth, Mars, and the Moon.
Wilczura-Wachnik, Hanna; Jónsdóttir, Svava Osk
2003-04-01
A method for calculating interaction parameters traditionally used in phase-equilibrium computations in low-molecular systems has been extended for the prediction of solvent activities of aromatic polymer solutions (polystyrene+methylcyclohexane). Using ethylbenzene as a model compound for the repeating unit of the polymer, the intermolecular interaction energies between the solvent molecule and the polymer were simulated. The semiempirical quantum chemical method AM1, and a method for sampling relevant internal orientations for a pair of molecules developed previously were used. Interaction energies are determined for three molecular pairs, the solvent and the model molecule, two solvent molecules and two model molecules, and used to calculated UNIQUAC interaction parameters, a(ij) and a(ji). Using these parameters, the solvent activities of the polystyrene 90,000 amu+methylcyclohexane system, and the total vapor pressures of the methylcyclohexane+ethylbenzene system were calculated. The latter system was compared to experimental data, giving qualitative agreement. Figure Solvent activities for the methylcylcohexane(1)+polystyrene(2) system at 316 K. Parameters aij (blue line) obtained with the AM1 method; parameters aij (pink line) from VLE data for the ethylbenzene+methylcyclohexane system. The abscissa is the polymer weight fraction defined as y2(x1)=(1mx1)M2/[x1M1+(1mx1)M2], where x1 is the solvent mole fraction and Mi are the molecular weights of the components.
Phase equilibria investigations and thermodynamic modeling of the system Bi2O3-Al2O3
NASA Astrophysics Data System (ADS)
Oudich, F.; David, N.; Mathieu, S.; Vilasi, M.
2015-02-01
The system Bi2O3-Al2O3 has been experimentally investigated above 600 °C by DTA, XRD and EPMA under air and low oxygen pressure. Only two compounds were found to exist in equilibrium, which are Bi2Al4O9(1Bi2O3:2Al2O3) and Bi25AlO39(25:1). The latter exhibits a sillenite structure and does not contain pentavalent bismuth. A peritectoid decomposition of (25:1) and a peritectic melting of (1:2) occur at 775 °C and 1075 °C respectively, while an eutectic transformation was observed at 815 °C for 97 mol% Bi2O3. On the basis of the results obtained within the present work as well as experimental data provided from literature, a thermodynamic modeling where the liquid phase is described by the two-sublattice ionic liquid model was performed according to the Calphad approach. The resulting thermodynamic optimization yielded good agreement with experimental results in the investigated region.
NASA Astrophysics Data System (ADS)
Siopis, Christos; Kandrup, Henry E.
2000-11-01
This paper focuses on the statistical properties of chaotic orbit ensembles evolved in triaxial generalizations of the Dehnen potential which have been proposed recently to model realistic ellipticals that have a strong density cusp and manifest significant deviations from axisymmetry. Allowance is made for a possible supermassive black hole, as well as low-amplitude friction, noise, and periodic driving which can mimic irregularities associated with discreteness effects and/or an external environment. The chaos exhibited by these potentials is quantified by determining (1) how the relative number of chaotic orbits depends on the steepness of the cusp, as probed by γ, the power-law exponent with which density diverges, and MBH, the black hole mass, (2) how the size of the largest Lyapunov exponent varies with γ and MBH, and (3) the extent to which Arnold webs significantly impede phase-space transport, both with and without perturbations. The most important conclusions dynamically are (1) that, in the absence of irregularities, chaotic orbits tend to be extremely `sticky', so that different pieces of the same chaotic orbit can behave very differently for times ~10000tD or more, but (2) that even very low-amplitude perturbations can prove efficient in erasing many - albeit not all - of these differences. The implications of these facts are discussed both for the structure and evolution of real galaxies and for the possibility of constructing approximate near-equilibrium models using Schwarzschild's method. For example, when trying to use Schwarzschild's method to construct model galaxies containing significant numbers of chaotic orbits, it seems advantageous to build libraries with chaotic orbits evolved in the presence of low-amplitude friction and noise, since such noisy orbits are more likely to represent reasonable approximations to time-independent building blocks. Much of the observed qualitative behaviour can be reproduced with a toy potential given as the
ERIC Educational Resources Information Center
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…
NASA Astrophysics Data System (ADS)
Chou, I.-Ming; Seal, Robert R.
2003-11-01
Epsomite (MgSO4.7H2O) and hexahydrite (MgSO4.6H2O) are common minerals found in marine evaporite deposits, in saline lakes as precipitates, in weathering zones of coal and metallic deposits, in some soils and their efflorescences, and possibly on the surface of Europa as evaporite deposits. Thermodynamic properties of these two minerals reported in the literature are in poor agreement. In this study, epsomite-hexahydrite equilibria were determined along four humidity-buffer curves at 0.1 MPa and between 25 and 45°C. Results obtained for the reaction epsomite = hexahydrite + H2O, as demonstrated by very tight reversals along each humidity buffer, can be represented by ln K(+/- 0.012) = 20.001 - 7182.07/T, where K is the equilibrium constant, and T is temperature in Kelvin. The derived standard Gibbs free energy of reaction is 10.13 +/- 0.07 kJ/mol, which is essentially the same value as that calculated from vapor pressure measurements reported in the literature. However, this value is at least 0.8 kJ/mol lower than those calculated from the data derived mostly from calorimetric measurements.
Chou, I.-Ming; Seal, R.R.
2003-01-01
Epsomite (MgSO(4).7H(2)O) and hexahydrite (MgSO(4).6H(2)O) are common minerals found in marine evaporite deposits, in saline lakes as precipitates, in weathering zones of coal and metallic deposits, in some soils and their efflorescences, and possibly on the surface of Europa as evaporite deposits. Thermodynamic properties of these two minerals reported in the literature are in poor agreement. In this study, epsomite-hexahydrite equilibria were determined along four humidity-buffer curves at 0.1 MPa and between 25 and 45 degrees C. Results obtained for the reaction epsomite = hexahydrite + H(2)O, as demonstrated by very tight reversals along each humidity buffer, can be represented by ln K(+/- 0.012) = 20.001 - 7182.07/T, where K is the equilibrium constant, and T is temperature in Kelvin. The derived standard Gibbs free energy of reaction is 10.13 +/- 0.07 kJ/mol, which is essentially the same value as that calculated from vapor pressure measurements reported in the literature. However, this value is at least 0.8 kJ/mol lower than those calculated from the data derived mostly from calorimetric measurements.
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Kim, Namil; Li, Quan; Kyu, Thein
2011-03-01
Photoisomerization-induced phase transition of neat liquid-crystalline azobenzene chromophore (LCAC) and its effect on phase diagrams of its mixtures with reactive mesogenic diacrylate monomer (RM257) have been investigated experimentally and theoretically. Upon irradiation with ultraviolet light, the nematic phase of LCAC transformed to isotropic, while the crystal phase showed corrugated textures on the surface (i.e., ripples). The phase-transition temperatures and corresponding morphologies of the blends have been investigated by means of differential scanning calorimetry and optical microscopy. A theoretical phase diagram of a binary nematic and crystalline system was constructed by self-consistently solving the combined free energies of Flory-Huggins, Maier-Saupe, and phase-field theory. The calculation revealed various coexistence regions such as nematic + liquid (N1 + L2), crystal + liquid (Cr1 + L2), crystal + nematic (Cr1 + N2), and crystal + crystal (Cr1 + Cr2) over a broad range of compositions including the single-phase nematic (N1, N2) of the corresponding constituents. The calculated liquidus lines were in good accord with the depressed mesophase-isotropic transition points. The present paper demonstrates the effect of trans-cis photoisomerization on the mesophase transitions of neat LCAC and the phase diagram of LCAC-RM257 as well as on the ripple formation (i.e., periodic undulation) on the azobenzene crystals.
Phase Equilibria of the Cu-Ti-Er System at 773 K (500 °C) and Stability of the CuTi3 Phase
NASA Astrophysics Data System (ADS)
Zhan, Yongzhong; Peng, Dan; She, Jia
2012-11-01
The phase relationships of the Cu-Ti-Er ternary phase diagram at 773 K (500 °C) were investigated mainly by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), and differential thermal analysis (DTA). It is confirmed in this work that the binary compounds Cu9Er2 and Cu7Er2 exist in the Cu-Er binary system at 773 K (500 °C). The stability of the CuTi3 phase is confirmed in the Cu-Ti system. After heat treatment at 1023 K (750 °C) for 90 hours, the phase CuTi3 is observed in the microstructure of the alloy 25Cu75Ti. The temperature of the eutectoid transformation, namely, β-Ti ↔ α-Ti + CuTi3, is determined to be 1078 K (805 °C) in this work. The 773 K (500 °C) isothermal section consists of 14 single-phase regions, 25 two-phase regions, and 12 three-phase regions. None of the phases in this system reveals a remarkable homogeneity range at 773 K (500 °C).
NASA Astrophysics Data System (ADS)
Yang, Qiong-Yan; Santosh, M.; Tsunogae, Toshiaki
2016-10-01
Metamorphic regimes in Archean terranes provide important keys to the plate tectonic processes in early Earth. The North China Craton (NCC) is one of the ancient continental nuclei in Asia and recent models propose that the cratonic architecture was built through the assembly of several Archean microcontinental blocks into larger crustal blocks. Here we investigate garnet- and pyroxene-bearing granulite facies rocks along the periphery of the Jiaoliao microcontinental block in the NCC. The garnet-bearing granulites contain peak mineral assemblage of garnet + clinopyroxene + orthopyroxene + magnetite + plagioclase + quartz ± biotite ± ilmenite. Mineral phase equilibria computations using pseudosection and geothermobarometry suggest peak P-T condition of 800-830 °C and 7-8 kbar for metamorphism. Isopleths using XMg of orthopyroxene and XCa of garnet in another sample containing the peak mineral assemblage of garnet + orthopyroxene + quartz + magnetite ± fluid yield peak P-T conditions of 860-920 °C and 11-14 kbar. Geochemical data show tonalitic to granodioritic composition and arc-related tectonic setting for the magmatic protoliths of these rocks. Zircon LA-ICP-MS analyses yield well-defined discordia with upper intercept ages of 2562 ± 20 Ma (MSWD = 0.94) and 2539 ± 21 Ma (MSWD = 0.59) which is correlated with the timing of emplacement of the magmatic protolith. A younger group of zircons with upper intercept ages of 2449 ± 41 Ma (MSWD = 0.83); N = 6 as 2449 ± 41 Ma (MSWD = 0.83; N = 6) and 2480 ± 44 Ma (MSWD = 1.2; N = 9) constrains the timing of metamorphism. Zircon Lu-Hf data show dominantly positive εHf(t) values (up to 8.5), and yield crustal residence ages (TDMC) in the range of 2529 to 2884 Ma, suggesting magma sources from Meso-Neoarchean juvenile components. The high temperature and medium to high pressure metamorphism is considered to have resulted from the subduction-collision tectonics associated with microblock amalgamation in the NCC at
Alfurayj, Ibrahim A; Young, Victor G; Jensen, Michael P
2016-02-15
Consecutive thermochromic lattice distortional and spin crossover equilibria in solid-state Ni(detu)4Cl2 (detu = N,N'-diethylthiourea) are investigated by variable-temperature X-ray crystallography (173-333 K), DFT calculations, and differential scanning calorimetry. Thermochromism and anomalous magnetism were reported previously (S. L. Holt, Jr., et al. J. Am. Chem. Soc. 1964, 86, 519-520); the latter was attributed to equilibration of a singlet ground state and a thermally accessible triplet state, but structural data were not obtained. A crystal structure at 173(2) K revealed [Ni(detu)4](2+) centers with distorted planar ligation of nickel(II) to the four sulfur atoms, with an average Ni-S bond length of 2.226(3) Å. The nickel ion was displaced out-of-plane by 0.334 Å toward a proximal apical chloride at a nonbonding distance of 3.134(1) Å. Asymmetry in the trans S-Ni-S angles was coupled to a monoclinic ↔ tetragonal lattice distortion (T(1/2) = 254 ± 11 K), resulting in thermochromism. Spin crossover occurs by tetragonal modulation of nickel(II) with approach of the proximal chloride at higher temperatures (T(1/2) = 383 ± 18 K), which is consistent with a contraction of -0.096(4) Å in the Ni···Cl separation observed at 293 K. A high-spin (S = 1) square-pyramidal [Ni(dmtu)4Cl](+) model (dmtu = N,N'-dimethylthiourea) was optimized by DFT calculations, which estimated limiting equatorial Ni-S bond lengths of 2.45 Å and an apical Ni-Cl bond of 2.43 Å. Electronic spectra of the spin isomers were calculated by TD-DFT methods. Assignment of the FTIR spectrum was assisted by frequency calculations and isotope substitution. PMID:26836378
Khandkar, A.; Navrotsky, A.; Tare, V.B.; Wagner, J.B.
1984-11-01
The enthalpy of solution of various single- and two-phase AgI-AgBr compositions in AgNO/sub 3/ at 518 K has been determined using a Calvet-type twin microcalorimeter. The enthalpy (H/sub 518/ - H/sub 298/) of melted and unmelted mixtures of AgI and AgBr of various compositions within two-phase regions of the phase diagram has also been obtained using the same calorimeter. The effect of AgBr on the temperature and enthalpy of transformation of ..beta..-AgI to ..cap alpha..AgI has been investigated using a Perkin Elmer Differential Scanning Calorimeter. The terminal compositions at 518 K of the two-phase region of AgI-AgBr system has been found to be AgI /SUB 0.85/ Br /SUB 0.15/ and AgI /SUB 0.3/ Br /SUB 0.7/ . The excess enthalpy, the difference in (H/sub 518/ - H/sub 298/) values of the unmelted and melted mixtures in the two-phase region of the AgI-AgBr system, has been found to be maximum at the equivolume concentration of the two terminal phases and is suggested to be due to the generation of silver ion vacancies at the interfaces due to a space-charge layer.
Luminescence readout of nanoparticle phase state
NASA Astrophysics Data System (ADS)
Denisyuk, A. I.; Jonsson, F.; MacDonald, K. F.; Zheludev, N. I.; García de Abajo, F. J.
2008-03-01
We report that the phase state of bistable gallium nanoparticles, controlled by optical or electron beam excitations, can be identified via measurements of their cathodoluminescent emission, thus offering an innovative conceptual basis for the development of high density nonvolatile phase-change memories. Changes of up to 20% in visible emission intensity are observed following low-fluence optical or electron beam induced phase switching in a monolayer of 60nm particles.
Kwon, Byungsu; Hong, Mei
2016-09-27
The influenza M2 protein is the target of the amantadine family of antiviral drugs, and its transmembrane (TM) domain structure and dynamics have been extensively studied. However, little is known about the structure of the highly conserved N-terminal ectodomain, which contains epitopes targeted by influenza vaccines. In this study, we synthesized an M2 construct containing the N-terminal ectodomain and the TM domain, to understand the site-specific conformation and dynamics of the ectodomain and to investigate the effect of the ectodomain on the TM structure. We incorporated (13)C- and (15)N-labeled residues into both domains and measured their chemical shifts and line widths using solid-state nuclear magnetic resonance. The data indicate that the entire ectodomain is unstructured and dynamic, but the motion is slower for residues closer to the TM domain. (13)C line shapes indicate that this ecto-TM construct undergoes fast uniaxial rotational diffusion, like the isolated TM peptide, but drug binding increases the motional rates of the TM helix while slowing the local motion of the ectodomain residues that are close to the TM domain. Moreover, (13)C and (15)N chemical shifts indicate that the ectodomain shifts the conformational equilibria of the TM residues toward the drug-bound state even in the absence of amantadine, thus providing a molecular structural basis for the lower inhibitory concentration of full-length M2 compared to that of the ectodomain-truncated M2. We propose that this conformational selection may result from electrostatic repulsion between negatively charged ectodomain residues in the tetrameric protein. Together with the recent study of the M2 cytoplasmic domain, these results show that intrinsically disordered extramembrane domains in membrane proteins can regulate the functionally relevant conformation and dynamics of the structurally ordered TM domains.
Phase evolution in spatial dark states
McEndoo, S.; Brophy, J.; Busch, Th.; Croke, S.
2010-04-15
Adiabatic techniques using multilevel systems have recently been generalized from the optical case to settings in atom optics, solid state physics, and even classical electrodynamics. The most well known example of these is the so-called stimulated Raman adiabatic passage (STIRAP) process, which allows transfer of a particle between different states with large fidelity. Here we generalize and examine this process for an atomic center-of-mass state with a nontrivial phase distribution and show that even though dark state dynamics can be achieved for the atomic density, the phase dynamics will still have to be considered as a dynamical process. In particular we show that the combination of adiabatic and nonadiabatic behavior can be used to engineer phase superposition states.
NASA Technical Reports Server (NTRS)
Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.
2007-01-01
Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).
Fu, Dong
2006-10-01
An equation of state (EOS) applicable for both the uniform and nonuniform fluids is established by using the density-gradient theory (DGT). In the bulk phases, the EOS reduces to statistical associating fluid theory (SAFT). By combining the EOS with the renormalization group theory (RGT), the vapor-liquid-phase equilibria and surface tensions for 10 nonpolar chainlike fluids are investigated from low temperature up to the critical point. The obtained results agree well with the experimental data.
Propagating confined states in phase dynamics
NASA Technical Reports Server (NTRS)
Brand, Helmut R.; Deissler, Robert J.
1992-01-01
Theoretical treatment is given to the possibility of the existence of propagating confined states in the nonlinear phase equation by generalizing stationary confined states. The nonlinear phase equation is set forth for the case of propagating patterns with long wavelengths and low-frequency modulation. A large range of parameter values is shown to exist for propagating confined states which have spatially localized regions which travel on a background with unique wavelengths. The theoretical phenomena are shown to correspond to such physical systems as spirals in Taylor instabilities, traveling waves in convective systems, and slot-convection phenomena for binary fluid mixtures.
De Simone, Alfonso; Mote, Kaustubh R.; Veglia, Gianluigi
2014-01-01
Solid-state NMR spectroscopy is emerging as a powerful approach to determine structure, topology, and conformational dynamics of membrane proteins at the atomic level. Conformational dynamics are often inferred and quantified from the motional averaging of the NMR parameters. However, the nature of these motions is difficult to envision based only on spectroscopic data. Here, we utilized restrained molecular dynamics simulations to probe the structural dynamics, topology and conformational transitions of regulatory membrane proteins of the calcium ATPase SERCA, namely sarcolipin and phospholamban, in explicit lipid bilayers. Specifically, we employed oriented solid-state NMR data, such as dipolar couplings and chemical shift anisotropy measured in lipid bicelles, to refine the conformational ensemble of these proteins in lipid membranes. The samplings accurately reproduced the orientations of transmembrane helices and showed a significant degree of convergence with all of the NMR parameters. Unlike the unrestrained simulations, the resulting sarcolipin structures are in agreement with distances and angles for hydrogen bonds in ideal helices. In the case of phospholamban, the restrained ensemble sampled the conformational interconversion between T (helical) and R (unfolded) states for the cytoplasmic region that could not be observed using standard structural refinements with the same experimental data set. This study underscores the importance of implementing NMR data in molecular dynamics protocols to better describe the conformational landscapes of membrane proteins embedded in realistic lipid membranes. PMID:24940774
Hydration states of AFm cement phases
Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Wadsö, Lars
2015-07-15
The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.
NASA Astrophysics Data System (ADS)
Seyfried, W. E., Jr.; Pester, Nicholas J.; Ding, Kang; Rough, Mikaella
2011-03-01
The Rainbow hydrothermal field is located at 36°13.8'N-33°54.15'W at 2300 m depth on the western flank of a non-volcanic ridge between the South AMAR and AMAR segments of the Mid-Atlantic Ridge. The hydrothermal field consists of 10-15 active chimneys that emit high-temperature (˜365 °C) fluid. In July 2008, vent fluids were sampled during cruise KNOX18RR, providing a rich dataset that extends in time information on subseafloor chemical and physical processes controlling vent fluid chemistry at Rainbow. Data suggest that the Mg concentration of the hydrothermal end-member is not zero, but rather 1.5-2 mmol/kg. This surprising result may be caused by a combination of factors including moderately low dissolved silica, low pH, and elevated chloride of the hydrothermal fluid. Combining end-member Mg data with analogous data for dissolved Fe, Si, Al, Ca, and H 2, permits calculation of mineral saturation states for minerals thought appropriate for ultramafic-hosted hydrothermal systems at temperatures and pressures in keeping with constraints imposed by field observations. These data indicate that chlorite solid solution, talc, and magnetite achieve saturation in Rainbow vent fluid at a similar pH (T,P) (400 °C, 500 bar) of approximately 4.95, while higher pH values are indicated for serpentine, suggesting that serpentine may not coexist with the former assemblage at depth at Rainbow. The high Fe/Mg ratio of the Rainbow vent fluid notwithstanding, the mole fraction of clinochlore and chamosite components of chlorite solid solution at depth are predicted to be 0.78 and 0.22, respectively. In situ pH measurements made at Rainbow vents are in good agreement with pH (T,P) values estimated from mineral solubility calculations, when the in situ pH data are adjusted for temperature and pressure. Calculations further indicate that pH (T,P) and dissolved H 2 are extremely sensitive to changes in dissolved silica owing to constraints imposed by chlorite solid solution
Hansen, Poul Erik; Borisov, Eugeny V; Lindon, John C
2015-02-01
The tautomeric equilibria for 2-pyridoyl-, 3-pyridoyl-, and 4-pyridoyl-benzoyl methane have been investigated using deuterium isotope effects on (1)H and (13)C 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((1)H-(13)C) 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 derivatives are in the A-form. In the solid state all three compounds are on the B-form. The 4-pyridoyl derivative shows unusual deuterium isotope effects in the solid, which are ascribed to a change of the crystal structure of the deuteriated compound. PMID:24070650
Instability of magnetic equilibria in barotropic stars
NASA Astrophysics Data System (ADS)
Mitchell, J. P.; Braithwaite, J.; Reisenegger, A.; Spruit, H.; Valdivia, J. A.; Langer, N.
2015-02-01
In stably stratified stars, numerical magnetohydrodynamics simulations have shown that arbitrary initial magnetic fields evolve into stable equilibrium configurations, usually containing nearly axisymmetric, linked poloidal and toroidal fields that stabilize each other. In this work, we test the hypothesis that stable stratification is a requirement for the existence of such stable equilibria. For this purpose, we follow numerically the evolution of magnetic fields in barotropic (and thus neutrally stable) stars, starting from two different types of initial conditions, namely random disordered magnetic fields, as well as linked poloidal-toroidal configurations resembling the previously found equilibria. With many trials, we always find a decay of the magnetic field over a few Alfvén times, never a stable equilibrium. This strongly suggests that there are no stable equilibria in barotropic stars, thus clearly invalidating the assumption of barotropic equations of state often imposed on the search of magnetic equilibria. It also supports the hypothesis that, as dissipative processes erode the stable stratification, they might destabilize previously stable magnetic field configurations, leading to their decay.
Thermodynamic assessment of hydrothermal alkali feldspar-mica-aluminosilicate equilibria
Sverjensky, D.A.; Hemley, J.J.; d'Angelo, W. M.
1991-01-01
The thermodynamic properties of minerals retrieved from consideration of solid-solid and dehydration equilibria with calorimetric reference values, and those of aqueous species derived from studies of electrolytes, are not consistent with experimentally measured high-temperature solubilities in the systems K2O- and Na2O-Al2O3-SiO2-H2O-HCl (e.g., K-fs - Ms - Qtz - K+ - H+). This introduces major inaccuracies into the computation of ionic activity ratios and the acidities of diagenetic, metamorphic, and magmatic hydrothermal fluids buffered by alkali silicate-bearing assemblages. We report a thermodynamic analysis of revised solubility equilibria in these systems that integrates the thermodynamic properties of minerals obtained from phase equilibria studies (Berman, 1988) with the properties of aqueous species calculated from a calibrated equation of state (Shock and Helgeson, 1988). This was achieved in two separate steps. First, new values of the free energies and enthalpies of formation at 25??C and 1 bar for the alkali silicates muscovite and albite were retrieved from the experimental solubility equilibria at 300??C and Psat. Because the latter have stoichiometric reaction coefficients different from those for solid-solid and dehydration equilibria, our procedure preserves exactly the relative thermodynamic properties of the alkali-bearing silicates (Berman, 1988). Only simple arithmetic adjustments of -1,600 and -1,626 (??500) cal/mol to all the K- and Na-bearing silicates, respectively, in Berman (1988) are required. In all cases, the revised values are within ??0.2% of calorimetric values. Similar adjustments were derived for the properties of minerals from Helgeson et al. (1978). Second, new values of the dissociation constant of HCl were retrieved from the solubility equilibria at temperatures and pressures from 300-600??C and 0.5-2.0 kbars using a simple model for aqueous speciation. The results agree well with the conductance-derived dissociation
Higher-order equilibria of temporal soliton molecules in dispersion-managed fibers
NASA Astrophysics Data System (ADS)
Hause, A.; Mitschke, F.
2013-12-01
Bound states of two or three solitons in dispersion-managed fibers (soliton molecules) were experimentally demonstrated recently. We investigate with a modified perturbation analysis whether the binding mechanism creates a unique stable equilibrium of the relative positions of the solitons in the molecule. Indeed, we find a multitude of equilibrium states, alternatingly stable and unstable. This holds for either case: nearest neighbor solitons having the same or the opposite phase. The number of equilibria are limited by the level of the radiation background. The state with the smallest separation and the highest binding energy ("ground state") always occurs for opposite-phase pulses; the lowest-order state for in-phase pulses is always unstable. Stable long-chain molecules can be built with a mixture of different nearest-neighbor equilibrium separations. Our results agree with our numerical simulations and experimental results, and connect well with certain results in the literature.
Sato, Emiko; Miya, Seiko; Saitoh, Kazunori; Saito, Shingo; Shibukawa, Masami
2011-02-18
A reversed-phase ion-pair liquid chromatographic method is presented for the determination of reaction equilibria involving ionic species of the same charge sign as reactant and product compounds. It has been demonstrated that ion-exchange chromatography or reversed-phase ion-pair chromatography is a useful tool for the determination of equilibrium constants of chemical reactions involving ionic species such as metal complexation reactions. Previous work with these methods has been based on the assumption that the limiting retention factors of the reactant and product species are constant independent of concentration of the chemical species (X) in the mobile phase, which reacts with the analyte compound. However, when all the reactant and product species are ions of the same charge sign as that of the species X, it is virtually impossible to apply these methods to the equilibrium constant determination because the retention factors of both the reactant and product species may depend on the concentration of X. In this study, an alternative approach was developed that estimates the limiting retention factors of ionic species from the dependence of the retention factor on the ionic strength of the mobile phase. Ligand substitution reactions of ethylenediaminetetraacetatochromium(III) ion with acetate and phosphate ions were used as model reactions to test this method. The equilibrium constants determined by this method are in good agreement with those obtained by a UV-visible spectrophotometric method.
Self-organized criticality and punctuated equilibria
NASA Astrophysics Data System (ADS)
Bak, Per; Boettcher, Stefan
1997-02-01
Many natural phenomena evolve intermittently, with periods of tranquillity interrupted by bursts of activity, rather than following a smooth gradual path. Examples include earthquakes, volcanic eruptions, solar flares, gamma-ray bursts, and biological evolution. Stephen Jay Gould and Niles Eldredge have coined the term “punctuated equilibria” for this behavior. We argue that punctuated equilibria reflects the tendency of dynamical systems to evolve towards a critical state, and review recent work on simple models. A good metaphoric picture is one where the systems are temporarily trapped in valleys of deformable, interacting landscapes. Similarities with spin glasses are pointed out. Punctuated equilibria are essential for the emergence of complex phenomena. The periods of stasis allow the system to remember its past history; yet the intermittent events permit further change.
Babu, A R; Krishna, D M; Rao, R S
1993-12-01
A detailed study of the species formed in the complex equilibria involving adipic acid dihydrazide (AADH)/2-furoic acid hydrazide (FAH) with Ni(II) using pH titration with glass electrode is performed. The results of modeling studies and effect of errors on the equilibrium constants of AADH/FAH with Ni(II) refined by the non-linear least squares program MINIQUAD75 are reported. Based on the expert system approach developed in our laboratory for the species formed from secondary formation data (n and n (H)), several preliminary chemical models were tested. For the four species identified (MLH, ML, ML(2)H, ML(2)), an exhaustive search of a different combination of models (15) was performed. Then other suspected minor species (ML(2)H(2), ML(3) and ML(3)H) were tested. The final best fit chemical model was found to contain ML(3)H to an extent of 3% along with the other four major species. In order to ascertain the accuracy of the stability constants and consequently distribution of the species, a detailed error analysis is attempted. As the existing least squares procedures cannot suppress the systematic errors, three-dimensional plots of the simultaneous effects of pH and TLO:TMO (1.5:1 to 5:1) on the percentage of species are drawn which are of immense use in arriving at optimum conditions for the preparation of a complex of definite stoichiometry. PMID:18965865
Phase diagram of two interacting helical states
NASA Astrophysics Data System (ADS)
Santos, Raul A.; Gutman, D. B.; Carr, Sam T.
2016-06-01
We consider two coupled time-reversal-invariant helical edge modes of the same helicity, such as would occur on two stacked quantum spin Hall insulators. In the presence of interaction, the low-energy physics is described by two collective modes, one corresponding to the total current flowing around the edge and the other one describing relative fluctuations between the two edges. We find that quite generically, the relative mode becomes gapped at low temperatures, but only when tunneling between the two helical modes is nonzero. There are two distinct possibilities for the gapped state depending on the relative size of different interactions. If the intraedge interaction is stronger than the interedge interaction, the state is characterized as a spin-nematic phase. However, in the opposite limit, when the interaction between the helical edge modes is strong compared to the interaction within each mode, a spin-density wave forms, with emergent topological properties. First, the gap protects the conducting phase against localization by weak nonmagnetic impurities; second, the protected phase hosts localized zero modes on the ends of the edge that may be created by sufficiently strong nonmagnetic impurities.
NASA Astrophysics Data System (ADS)
Brugier, Yann-Aurélien; Pichavant, Michel; di Muro, Andréa
2015-04-01
To understand the petrogenetic relations between the 4 groups of lavas erupted at Piton de la Fournaise (PdF), constrain the structure of the feeding system and the magma storage conditions, experimental phase equilibria have been determined, both at 1 atm and high pressures (HP), on a lava representative of Steady State Basalts (SSB). The lava (SiO2=49.2 wt%, MgO=7.8 wt%, CaO/Al2O3= 0.81) was fused at 1400°C, 1 atm in air. The resulting glass was crushed and the powder directly used as starting material. The 1atm experiments were performed with the wire-loop method in a vertical CO-CO2 gas mixing furnace. To minimize Fe-loss from the charge, experiments were repeated under constant T-fO2 conditions to progressively saturate the suspension wire with Fe. Intermediate charges were dissolved in HF and the charge from the last cycle retained for detailed study. Analyses of experimental products are in progress. The HP experiments were carried out in an internally heated pressure vessel, at 50MPa and 400MPa, between 1100-1200°C and under fluid-present conditions. Glass (30-50 mg) plus 10% in mass of volatiles (H2O or H2O+CO2) were loaded in Au80Pd20 capsules. Distilled water and Ag2C2O4 (CO2 source) were weighted to give charges with xH2O initial (molar H2O / (H2O+CO2)) ranging from 1 to 0. Run durations lasted for 2-14h. Redox conditions were controlled by loading a given proportion of H2 gas in the vessel (3 bar H2 for 50MPa, 5 bar H2 for 400MPa). Experimental fH2 were determined by solid Pd-Co sensors, leading to fO2 conditions approaching NNO-1. All experiments were rapidly drop quenched and products analyzed by SEM, EMPA and µ-FTIR Spectroscopy. To overcome Fe-loss, both capsule Fe pre-saturation and charge Fe pre-enrichment were tested. The first method was shown to be time-consuming and fraught with difficulties while the second is still being developed. Consequently, the experimental data presented here were obtained with no attempt to circumvent Fe loss
Mac Dowell, N; Pereira, F E; Llovell, F; Blas, F J; Adjiman, C S; Jackson, G; Galindo, A
2011-06-30
The amine functional groups are fundamental building blocks of many molecules that are central to life, such as the amino acids, and to industrial processes, such as the alkanolamines, which are used extensively for gas absorption. The modeling of amines and of mixtures of amines with water (H(2)O) and carbon dioxide (CO(2)) is thus relevant to a number of applications. In this contribution, we use the statistical associating fluid theory for potentials of variable range (SAFT-VR) to describe the fluid phase behavior of ammonia + H(2)O + CO(2) and n-alkyl-1-amine + H(2)O + CO(2) mixtures. Models are developed for ammonia (NH(3)) and n-alkyl-1-amines up to n-hexyl-1-amine (CH(3)NH(2) to C(6)H(13)NH(2)). The amines are modeled as homonuclear chain molecules formed from spherical segments with additional association sites incorporated to mediate the effect of hydrogen-bonding interactions. The SAFT-VR approach provides a representation of the pure component fluid phase equilibria, on average, to within 1.48% of the experimental data in relative terms for the saturated liquid densities and vapor pressures. A simple empirical correlation is derived for the SAFT-VR parameters of the n -alkylamine series as a function of molecular weight. Aqueous mixtures of the amines are modeled using a model of water taken from previous work. The models developed for the mixtures are of high fidelity and can be used to calculate the binary fluid phase equilibrium of these systems to within 2.28% in relative terms for the temperature or pressure and 0.027 in absolute terms for the mole fraction. Regions of both vapor-liquid and liquid-liquid equilibria are considered. We also consider the reactive mixtures of amines and CO(2) in aqueous solution. To model the reaction of CO(2) with the amine, an additional site is included on the otherwise nonassociating CO(2) model. The unlike interaction parameters for the NH(3) + H(2)O + CO(2) ternary mixture are obtained by comparison to the
Solid-state phased array (SSPA) performance
NASA Astrophysics Data System (ADS)
Kley, Robert C., Jr.; Hull, W. Porter, Jr.; Lamb, Franklin D.
The solid-state phased-array (SSPA) is an active electronically scanned array (AESA) designed and built for airborne radar applications using transmit/receive module hybrid technology. Details of its subassemblies and results of testing the array and its subassemblies are presented. The SSPA T/R (transmit/receive) modules used a hybrid construction that is labor-intensive and leads to parameter variations. The next generation of modules uses monolithic microwave integrated circuit (MMIC) devices, which will result in more uniform parameters and lower manufacturing cost.
Toroidal equilibria in spherical coordinates
Tsui, K. H.
2008-11-15
The standard Grad-Shafranov equation for axisymmetric toroidal plasma equilibrium is customary expressed in cylindrical coordinates with toroidal contours, and through which benchmark equilibria are solved. An alternative approach to cast the Grad-Shafranov equation in spherical coordinates is presented. This equation, in spherical coordinates, is examined for toroidal solutions to describe low {beta} Solovev and high {beta} plasma equilibria in terms of elementary functions.
Code System to Model Aqueous Geochemical Equilibria.
2001-08-23
Version: 00 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 ofsolid phases. MINTEQ can accept a finite massmore » 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 each compositionally and structurally distinct solid forms a separate phase.« less
Four motional invariants in axisymmetric tori equilibria
A ring gren, O.; Moiseenko, V.E.
2006-05-15
In addition to the standard set ({epsilon},{mu},p{sub {phi}}) of three invariants in axisymmetric tori, there exists a fourth independent radial drift invariant I{sub r}. For confined particles, the net radial drift has to be zero, whereby the drift orbit average I{sub r}=
Phase states of methane in fossil coals
NASA Astrophysics Data System (ADS)
Alexeev, A. D.; Vasylenko, T. A.; Ul'yanova, E. V.
2004-06-01
NMR measurements have revealed that methane can exist in coal samples in the state of solid solution rather than only adsorbed gas, opening new ways to prevention of gas dynamic accidents in underground coal mines and true estimation of coalbed methane resources. Understanding molecular structure of coal constituents and forms of methane occurrence in coal is the only way of extracting safely either coal or methane. We had studied nuclear magnetic resonance lines in various coals at room or low temperatures and have found that there exist three species of methane molecules differing in molecular mobility. Based on estimated diffusion parameters, these species were attributed to free methane, adsorbed methane, and solid solution of methane in crystalline coal substance. While first two phases are well known and can be analyzed by many different techniques, the last one hardly can be studied by methods other than NMR, resulting in inadequate estimations of methane resources.
Wavelength resolved specific optical rotations and homochiral equilibria.
Polavarapu, P L; Covington, C L
2015-09-01
The fundamental expressions governing specific optical rotations (SORs) of homochiral systems exhibiting monomer-dimer equilibria are presented. These equations are then utilized with the experimental measurements of wavelength resolved circular birefringence for (R)-(-)-α-hydroxy-β,β-dimethyl-γ-butyrolactone, to determine the wavelength resolved SORs of monomer and dimer components for the first time. Density functional theory predictions on the corresponding dispersion properties of monomer and dimer are found to match with experimentally determined quantities within a factor of ∼2. The wavelength resolved circular birefringence in the liquid solution phase thus provides a powerful means to investigate the molecular properties involved in homochiral equilibria. PMID:26227210
NASA Astrophysics Data System (ADS)
Henao, Hector M.; Pizarro, Claudio; Font, Jonkion; Moyano, Alex; Hayes, Peter C.; Jak, Evgueni
2010-12-01
Limited data are available on phase equilibria of the multicomponent slag system at the oxygen partial pressures used in the copper smelting, converting, and slag-cleaning processes. Recently, experimental procedures have been developed and have been applied successfully to characterize several complex industrial slags. The experimental procedures involve high-temperature equilibration on a substrate and quenching followed by electron probe X-ray microanalysis. This technique has been used to construct the liquidus for the “Cu2O”-“FeO”-SiO2-based slags with 2 wt pct of CaO, 0.5 wt pct of MgO, and 4.0 wt pct of Al2O3 at controlled oxygen partial pressures in equilibrium with metallic copper. The selected ranges of compositions and temperatures are directly relevant to the copper slag-cleaning processes. The new experimental equilibrium results are presented in the form of ternary sections and as a liquidus temperature vs Fe/SiO2 weight ratio diagram. The experimental results are compared with the FactSage thermodynamic model calculations.
Stable and Metastable Equilibria in the Pb-Cd System
NASA Astrophysics Data System (ADS)
Chuang, Ying-Yu; Paik, J.-S.; Zhang, C.; Perepezko, J. H.; Chang, Y. A.
2013-07-01
Thermodynamic and phase diagram data in the Pb-Cd system are reevaluated. A substitutional solution model is used for the liquid and fcc and hcp phases. The stable and metastable equilibria of this system are calculated using the thermodynamic equations derived from equilibrium data. Besides the well-established eutectic reaction at 521 K (248 °C), one stable monotectic reaction at 548 K (275 °C) is found due to the existence of a stable liquid miscibility gap. The stable monotectic reaction has been missed in all previous evaluations. Experimental verifications of the stable and metastable phase equilibria are provided using droplet samples and undercooled liquid alloys. A differential thermal analysis (DTA) method is applied to determine the phase reaction temperatures using both traditional heating and cooling processes and a specially designed cycling process. Additional microstructural evidence is used to elucidate the nature of the phase reactions. The refined thermodynamic descriptions are based upon both the thermochemical and phase diagram stable and metastable data. The agreement between the calculated and experimental data is good. All experimental stable and metastable results are well explained by the new Pb-Cd phase diagram calculations within the experimental accuracy limits. Combined experimental and thermodynamic modeling procedures developed for determining the stable and metastable phase equilibria yield a highly reliable overall phase diagram assessment and a quantitative basis for the interpretation of non-equilibrium solidification processing.
NASA Astrophysics Data System (ADS)
Anderson, J. L.; Peterson, R. C.
2007-07-01
Careful characterization of minerals present at the martian surface requires a detailed understanding of hydrous sulfate phase relationships. This study explores the effect of metal substitution on the hydration behaviour of hydrous metal sulfates.
Frank, M.R.; Candela, P.A.; Piccoli, P.M.
1998-12-01
Felsic magmas may evolve one or more water or chlorine-rich fluid phases which can transport heat and solutes into associated hydrothermal systems and can contribute to alteration and ore deposition. To understand the role of a high-salinity aqueous phase in the magmatic hydrothermal environment, the composition of a subcritical, vapor-undersaturated high-salinity liquid phase (brine) in equilibrium with K-feldspar-muscovite-quartz and muscovite-andalusite-quartz was determined for pressures and temperatures ranging from 25 MPa and 400 C to 60 MPa and 550 C, with total Cl (NaCl + KCl + HCl) concentrations ranging from 3.42 to 8.56 (moles of solute/kg solution). Comparison of results with previous studies conducted at higher pressures and lower-salinity aqueous phases show that the mineral stability fields in the K-feldspar-muscovite-andalusite-quartz system shift to lower KCl/KCl values with increasing salinity and decreasing pressure.
Ruggiero, Flavia; Netti, Paolo Antonio; Torino, Enza
2015-12-01
Fundamental understanding of thermodynamic of phase separation plays a key role in tuning the desired features of biomedical devices. In particular, phase separation of ternary solution is of remarkable interest in processes to obtain biodegradable and biocompatible architectures applied as artificial devices to repair, replace, or support damaged tissues or organs. In these perspectives, thermally induced phase separation (TIPS) is the most widely used technique to obtained porous morphologies and, in addition, among different ternary systems, polylactic acid (PLLA)/dioxane/water has given promising results and has been largely studied. However, to increase the control of TIPS-based processes and architectures, an investigation of the basic energetic phenomena occurring during phase separation is still required. Here we propose an experimental investigation of the selected ternary system by using isothermal titration calorimetric approach at different solvent/antisolvent ratio and a thermodynamic explanation related to the polymer-solvents interactions in terms of energetic contribution to the phase separation process. Furthermore, relevant information about the phase diagrams and interaction parameters of the studied systems are furnished in terms of liquid-liquid miscibility gap. Indeed, polymer-solvents interactions are responsible for the mechanism of the phase separation process and, therefore, of the final features of the morphologies; the knowledge of such data is fundamental to control processes for the production of membranes, scaffolds and several nanostructures. The behavior of the polymer at different solvent/nonsolvent ratios is discussed in terms of solvation mechanism and a preliminary contribution to the understanding of the role of the hydrogen bonding in the interface phenomena is also reported. It is the first time that thermodynamic data of a ternary system are collected by mean of nano-isothermal titration calorimetry (nano-ITC). Supporting
Berry's phase for coherent states of Landau levels
Yang, Wen-Long; Chen, Jing-Ling
2007-02-15
The Berry phases for coherent states and squeezed coherent states of Landau levels are calculated. Coherent states of Landau levels are interpreted as a result of a magnetic flux moved adiabatically from infinity to a finite place on the plane. The Abelian Berry phase for coherent states of Landau levels is an analog of the Aharonov-Bohm effect. Moreover, the non-Abelian Berry phase is calculated for the adiabatic evolution of the magnetic field B.
Microstructural study of phase equilibria in the Fe-Ca-O system involving CaFe/sub 5/O/sub 7/
Bergman, B.; Song, C. )
1989-08-01
By microscopic studies it is found that CaFe/sub 5/O/sub 7/ (often represented by CW/sub 3/F) does not disappear by decomposition to three solid phases at about 1050{sup 0}C, as suggested by previous phase diagrams. Instead it disappears by melting at about 1100{sup 0}C. On cooling, part of the liquid solidifies to a eutectic structure, wustite + Ca/sub 2/Fe/sub 2/O/sub 5/ (often represented by C/sub 2/F). A revision of Turkdogan's oxygen potential-temperature diagram is proposed in order to account for the new information.
Excited state quantum phase transitions in many-body systems
Caprio, M.A. Cejnar, P.; Iachello, F.
2008-05-15
Phenomena analogous to ground state quantum phase transitions have recently been noted to occur among states throughout the excitation spectra of certain many-body models. These excited state phase transitions are manifested as simultaneous singularities in the eigenvalue spectrum (including the gap or level density), order parameters, and wave function properties. In this article, the characteristics of excited state quantum phase transitions are investigated. The finite-size scaling behavior is determined at the mean-field level. It is found that excited state quantum phase transitions are universal to two-level bosonic and fermionic models with pairing interactions.
Equations of State and Phase Diagrams of Ammonia
ERIC Educational Resources Information Center
Glasser, Leslie
2009-01-01
We present equations of state relating the phases and a three-dimensional phase diagram for ammonia with its solid, liquid, and vapor phases, based on fitted authentic experimental data and including recent information on the high-pressure solid phases. This presentation follows similar articles on carbon dioxide and water published in this…
Equilibria in Quantitative Reachability Games
NASA Astrophysics Data System (ADS)
Brihaye, Thomas; Bruyère, Véronique; de Pril, Julie
In this paper, we study turn-based quantitative multiplayer non zero-sum games played on finite graphs with reachability objectives. In this framework each player aims at reaching his own goal as soon as possible. We prove existence of finite-memory Nash (resp. secure) equilibria in multiplayer (resp. two-player) games.
Holesinger, T.
1993-12-09
The solid solution region and reaction kinetics of the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub y} (2212) superconductor were examined as a function of temperature and oxygen partial pressure. Crystallization studies from the glassy and molten states were undertaken to determine the phase transformation and kinetics associated with the formation of 2212 and other competing phases. Crystallization of nominal 2212 glasses was found to proceed in two steps with the formation of Bi{sub 2}Sr{sub 2{minus}x}Ca{sub x}CuO{sub y} (2201) and Cu{sub 2}O followed by Bi{sub 2}Sr{sub 3{minus}x}Ca{sub x}O{sub y}, CaO, and SrO. The 2212 phase converts from the 2201 phase with increasing temperatures. However, its formation below 800 C was kinetically limited. At 800 C and above, a nearly full conversion to the 2212 phase was achieved after only one minute although considerably longer anneal times were necessary for the system to reach equilibrium. In low oxygen partial pressures, the solidus is reduced to approximately 750 C. Solidification studies revealed an eutectic structure separating the incongruently melting 2212/2201 phases at high oxygen partial pressures from the congruently melting Bi{sub 2}Sr{sub 3{minus}x}Ca{sub x}O{sub y} (23x) and Bi{sub 2}Sr{sub 2{minus}x}Ca{sub x}O{sub y} (22x) phases present at low oxygen partial pressures. During solidification in various oxygen partial pressures, the separation of CaO in the melt and the initial crystallization of alkaline-earth cuprates leaves behind a Bi-rich liquid from which it is impossible to form single-phase 2212. Hence, significant amounts of 2201 were also present in these samples. These problems could be reduced by melt processing in inert atmospheres. Bulk 2212 material produced in this manner was found to possess high transition temperatures, high intergranular critical current densities below 20K, and modest critical current densities at 77K.
NASA Astrophysics Data System (ADS)
Joseph, Kitheri; Sujatha, K.; Nagaraj, S.; Mahendran, K. H.; Sridharan, R.; Periaswami, G.; Gnanasekaran, T.
2005-09-01
Electrochemical meters for measuring hydrogen levels in liquid sodium need thermodynamically stable hydride ion conducting electrolytes. In order to identify electrolytes that have high hydride ion conductivity, phase diagram of systems consisting of low melting compounds such as CaCl 2-LiCl, SrBr 2-LiBr, SrBr 2-SrHBr and CaBr 2-CaHBr were investigated by differential scanning calorimetry and their phase diagrams established. Using these information and supplementary information on effects of addition of alkaline earth hydride to these systems, potential electrolytes were tested for their use in electrochemical meters. Meters were constructed using electrolytes with (i) 22mol%SrCl 2-12.2mol%CaCl 2-54.5mol%LiCl-11.3mol%CaHCl, (ii) 70mol%LiCl-16mol%CaHCl-14mol%CaCl 2 and (iii) 40mol%CaHBr-60mol%CaBr 2 compositions. Output of meters that had Li ions in liquid phase electrolyte showed non-linearity at low hydrogen levels. Output of meters using CaBr 2-40mol%CaHBr solid showed linearity in the concentration range of 50-250 ppb in sodium.
Lenz, T.G.; Vaughan, J.D.
1997-10-01
A long-standing goal of chemical engineers and chemists has been the development of techniques for accurate prediction of the thermodynamic properties of isolated molecules. The thermochemical functions for an ideal gas then provide a means of computing chemical equilibria, and such computations can be extended to condensed phase chemical equilibria with appropriate physical property data. Such capability for predicting diverse chemical equilibria is important in today`s competitive international economic environment, where bringing new products to market rapidly and efficiently is crucial. The purpose of this project has been to develop such computational methods for predicting chemical equilibria.
Spontaneous Decay of Periodic Magnetostatic Equilibria.
East, William E; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D
2015-08-28
In order to understand the conditions that lead to a highly magnetized, relativistic plasma becoming unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria in which the magnetic field satisfies ∇×B=αB, where α is spatially uniform, on a periodic domain. Using numerical solutions, we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones), which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures, and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical time scales and eventually settling into a configuration with the largest allowable wavelength. These properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays. PMID:26371660
Spontaneous decay of periodic magnetostatic equilibria
East, William E.; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D.
2015-08-28
In order to understand the conditions which lead a highly magnetized, relativistic plasma to become unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria where the magnetic field satisfies ∇ x B = αB , where \\alpha is spatially uniform, on a periodic domain. Using numerical solutions we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones) which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures, and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical timescales and eventually settling into a configuration with the largest allowable wavelength. Furthermore, these properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays.
Spontaneous Decay of Periodic Magnetostatic Equilibria.
East, William E; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D
2015-08-28
In order to understand the conditions that lead to a highly magnetized, relativistic plasma becoming unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria in which the magnetic field satisfies ∇×B=αB, where α is spatially uniform, on a periodic domain. Using numerical solutions, we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones), which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures, and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical time scales and eventually settling into a configuration with the largest allowable wavelength. These properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays.
Spontaneous decay of periodic magnetostatic equilibria
East, William E.; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D.
2015-08-28
In order to understand the conditions which lead a highly magnetized, relativistic plasma to become unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria where the magnetic field satisfies ∇ x B = αB , where \\alpha is spatially uniform, on a periodic domain. Using numerical solutions we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones) which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures,more » and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical timescales and eventually settling into a configuration with the largest allowable wavelength. Furthermore, these properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays.« less
NASA Astrophysics Data System (ADS)
Barragán, Rosa María; Núñez, José; Arellano, Víctor Manuel; Nieva, David
2016-03-01
Exploration and exploitation of geothermal resources require the estimation of important physical characteristics of reservoirs including temperatures, pressures and in situ two-phase conditions, in order to evaluate possible uses and/or investigate changes due to exploitation. As at relatively high temperatures (>150 °C) reservoir fluids usually attain chemical equilibrium in contact with hot rocks, different models based on the chemistry of fluids have been developed that allow deep conditions to be estimated. Currently either in water-dominated or steam-dominated reservoirs the chemistry of steam has been useful for working out reservoir conditions. In this context, three methods based on the Fischer-Tropsch (FT) and combined H2S-H2 (HSH) mineral-gas reactions have been developed for estimating temperatures and the quality of the in situ two-phase mixture prevailing in the reservoir. For these methods the mineral buffers considered to be controlling H2S-H2 composition of fluids are as follows. The pyrite-magnetite buffer (FT-HSH1); the pyrite-hematite buffer (FT-HSH2) and the pyrite-pyrrhotite buffer (FT-HSH3). Currently from such models the estimations of both, temperature and steam fraction in the two-phase fluid are obtained graphically by using a blank diagram with a background theoretical solution as reference. Thus large errors are involved since the isotherms are highly nonlinear functions while reservoir steam fractions are taken from a logarithmic scale. In order to facilitate the use of the three FT-HSH methods and minimize visual interpolation errors, the EQUILGAS program that numerically solves the equations of the FT-HSH methods was developed. In this work the FT-HSH methods and the EQUILGAS program are described. Illustrative examples for Mexican fields are also given in order to help the users in deciding which method could be more suitable for every specific data set.
The clathrate Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y}: Phase equilibria and crystal structure
Melnychenko-Koblyuk, Nataliya; Grytsiv, Andriy; Rogl, Peter; Schmid, Harald; Giester, Gerald
2009-07-15
Phase relations at 700 deg. C, 800 deg. C and solidus temperatures have been derived for the clathrate system Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y} via X-ray single crystal and powder diffractometry combined with electron probe micro analysis and differential thermal analysis. The ternary clathrate phase derives from binary Ba{sub 8}Ge{sub 43}square{sub 3} and extends up to x=6. Structure investigations define cubic primitive symmetry with the space group type Pm3-barn consistent with a clathrate type I structure throughout the entire homogeneity region 0
Crystal chemistry and phase equilibria of the CaO-½Eu2O3-CoOz system at 885 °C
NASA Astrophysics Data System (ADS)
Wong-Ng, W.; Laws, W.; Kaduk, J. A.
2016-08-01
The CaO-½Eu2O3-CoOz system prepared at 885 °C in air consists of two calcium cobaltate compounds, namely, the 2D thermoelectric oxide solid solution, (Ca3-xEux)Co4O9-z (0 ≤ x ≤ 0.5) which has a misfit layered structure, and the 1D Ca3Co2O6 compound which consists of chains of alternating CoO6 trigonal prisms and CoO6 octahedra. Ca3Co2O6 was found to be a point compound without the substitution of Eu on the Ca site when prepared at 885 °C. A solid solution region of distorted perovskite, (Eu1-xCax)CoO3-z (0 ≤ x ≤ 0.22, space group Pnma) was established. The (Eu0.91(1)Ca0.09(1))CoO3-z perovskite member has a distorted structure with tilt angles θ (17.37°), ϕ (8.20°), and ω (19.16°) which represent rotations of an octahedron about the pseudo-cubic perovskite [110]p, [001]p and [111]p axes. The reported Eu2CoO4 phase was not observed at 885 °C, but a ternary Ca-doped oxide, (Eu1+xCa1-x)CoO4-z (Bmab) where 0 ≤ x ≤ 0.10 was found to be stable at this temperature. In the peripheral binary systems, Eu was not present in the Ca site of CaO, while a small solid solution region was identified for (Eu1-xCax)O(3-z)/2 (0 ≤ x ≤ 0.05). Seven solid solution tie-line regions and six three-phase regions were determined in the CaO-½Eu2O3-CoOz system in air.
Phase equilibria and crystal chemistry of the CaO-½Sm2O3-CoOz system at 885 °C in air
NASA Astrophysics Data System (ADS)
Wong-Ng, W.; Laws, W.; Lapidus, S. H.; Kaduk, J. A.
2015-10-01
The CaO-½Sm2O3-CoOz system prepared at 885 °C in air consists of two calcium cobaltate compounds, namely, the 2D thermoelectric oxide solid solution, (Ca3-xSmx)Co4O9-z (0 ≤ x ≤ 0.5) which has a misfit layered structure, and the 1D Ca3Co2O6 which consists of chains of alternating CoO6 trigonal prisms and CoO6 octahedra. Ca3Co2O6 was found to be a point compound without the substitution of Sm on the Ca site. A solid solution region of distorted perovskite, (Sm1-xCax)CoO3-z (0 ≤ x ≤ 0.22, space group Pnma) was established. The reported Sm2CoO4 phase was not observed at 885 °C, but a ternary Ca-doped oxide, (Sm1+xCa1-x)CoO4-z (Bmab) where 0 < x ≤ 0.15 was found to be stable at this temperature. In the peripheral binary systems, Sm was not present in the Ca site of CaO, while a small solid solution region was identified for (Sm1-xCax)O(3-z)/2 (0 ≤ x ≤ 0.075). Ten solid solution tie-line regions and six three-phase regions were determined in the CaO-½Sm2O3-CoOz system in air.
Beltrami–Bernoulli equilibria in plasmas with degenerate electrons
Berezhiani, V. I.; Shatashvili, N. L.; Mahajan, S. M.
2015-02-15
A new class of Double Beltrami–Bernoulli equilibria, sustained by electron degeneracy pressure, is investigated. It is shown that due to electron degeneracy, a nontrivial Beltrami–Bernoulli equilibrium state is possible even for a zero temperature plasma. These states are, conceptually, studied to show the existence of new energy transformation pathways converting, for instance, the degeneracy energy into fluid kinetic energy. Such states may be of relevance to compact astrophysical objects like white dwarfs, neutron stars, etc.
Fluorite solubility equilibria in selected geothermal waters
Nordstrom, D.K.; Jenne, E.A.
1977-01-01
Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF2, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions. Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), ??Gof (-280.08 kcal/mole), ??Hof (-292.59 kcal/mole), S?? (16.39 cal/deg/mole) and CoP (16.16 cal/deg/mole) for CaF2 at 25??C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident. ?? 1977.
A Multistep Equilibria-Redox-Complexation Demonstration to Illustrate Le Chatelier's Principle.
ERIC Educational Resources Information Center
Berger, Tomas G.; Mellon, Edward K.
1996-01-01
Describes a process that can be used to illustrate a number of chemical principles including Le Chatelier's principle, redox chemistry, equilibria versus steady state situations, and solubility of species. (JRH)
NASA Astrophysics Data System (ADS)
Shtender, V. V.; Denys, R. V.; Zavaliy, I. Yu.; Zelinska, O. Ya.; Paul-Boncour, V.; Pavlyuk, V. V.
2015-12-01
The isothermal section of the Tb-Mg-Co phase diagram at 500 °C has been built on the basis of XRD analysis of forty samples prepared by powder metallurgy. The existence of two ternary compounds Tb4Mg3Co2 and Tb4MgCo was confirmed. The formation of two solid solutions, Tb1-xMgxCo3 (0≤x≤0.4) and Tb1--xMgxCo2 (0≤x≤0.6), was found for the first time. It is shown that Tb5Mg24 also dissolves a small amount of Co. Other binary compounds do not dissolve the third component. The Tb4MgCo and TbMgCo4 compounds form hydrides (12.7 and 5.3 at.H/f.u. capacity, respectively) that retain the original structure of metallic matrices. Upon thermal desorption the Tb4MgCoH12.7 hydride was stable up to 300 °C and disproportionated at higher temperature. Two other hydrides, Tb4Mg3Co2H∼4 and Tb2MgCo9H12, are unstable in air and decompose into the initial compounds.
Moecher, D.P.
1988-01-01
Scapolite decarbonation reactions and carbon isotope analysis of CO{sub 2} extracted from scapolite are used to determine the presence, composition, and source of fluid components in high grade rocks. Scapolite-plagioclase-garnet-quartz assemblages, common to many lithologies in high grade terranes, monitors CO{sub 2} activity (aCO{sub 2}) by the reaction 2 Meionite + Quarts = 5 Anorthite + Grossular + 2 CO{sub 2}. The P-T-X location of this reaction was calculated using an internally consistent thermodynamic data set for meionite and phases in the CASCH system. Activity-composition relations for meionite in scapolite were calculated from the thermodynamic data set and compositional data on natural scapolite-plagioclase-calcite assemblages. Equilibration pressures of scapolite assemblages were calculated from clinopyroxene-garnet-plagioclass-quartz barometers calibrated for this study. The aCO{sub 2} was calculated for a variety of high grade gneisses from the southwestern Grenville Province and other terranes. Granulites typically yield low to moderate values of aCO{sub 2} (less than 0.5). Calc-silicates and meta-anorthosite yield moderate aCO{sub 2}. Deep crustal xenoliths yield a range of aCO{sub 2}.
Geometric Phase for Adiabatic Evolutions of General Quantum States
Wu, Biao; Liu, Jie; Niu, Qian; Singh, David J
2005-01-01
The concept of a geometric phase (Berry's phase) is generalized to the case of noneigenstates, which is applicable to both linear and nonlinear quantum systems. This is particularly important to nonlinear quantum systems, where, due to the lack of the superposition principle, the adiabatic evolution of a general state cannot be described in terms of eigenstates. For linear quantum systems, our new geometric phase reduces to a statistical average of Berry's phases. Our results are demonstrated with a nonlinear two-level model.
High power phase conjugated solid state lasers
Hackel, L.A.; Dane, C.B.; Zapata, L.E.; Hermann, M.R.
1994-07-01
Three laser systems that are being developed for use in x-ray generation which incorporate SBS phase conjugate mirrors are described. A 25J/pulse Nd:glass laser is being developed for commercial proximity print x-ray lithography; a 0.5J/pulse, 1.3 kHz pulse repetition frequency laser is being built for soft x-ray projection lithography; and a 1 kJ/pulse laser driver for a table top x-ray laser has been designed. The results of prototypical experimental investigations are presented and the basic design principles for high average power phase conjugated laser systems shared by each of these lasers are discussed.
NASA Astrophysics Data System (ADS)
von Nessi, G. T.; Hole, M. J.; The MAST Team
2014-11-01
We present recent results and technical breakthroughs for the Bayesian inference of tokamak equilibria using force-balance as a prior constraint. Issues surrounding model parameter representation and posterior analysis are discussed and addressed. These points motivate the recent advancements embodied in the Bayesian Equilibrium Analysis and Simulation Tool (BEAST) software being presently utilized to study equilibria on the Mega-Ampere Spherical Tokamak (MAST) experiment in the UK (von Nessi et al 2012 J. Phys. A 46 185501). State-of-the-art results of using BEAST to study MAST equilibria are reviewed, with recent code advancements being systematically presented though out the manuscript.
On steady electromagnetic equilibria
NASA Astrophysics Data System (ADS)
Lehnert, B.
1986-12-01
The existence of steady electromagnetic equilibrium states predicted by an extended Lorentz invariant formulation of Maxwell's equations is analyzed. General equilibrium solutions are outlined which lead to integrated field quantities of the system, such as total charge qo, magnetic moment Mo, mass mo and angular momentum so. The quantization of moMo/qo in terms of Bohr magnetons is shown to be equivalent to the proposed resonance condition of circulating self-confined radiation. Exact equilibrium solutions were deduced in two simple cases, thereby leading to a so of the same order as that of the electron, and to a qo one order of magnitude larger than the electronic charge. A variational procedure is suggested in search for states of minimum charge, under the subsidiary quantum conditions on moMo/qo and so, i.e., by varying the profile of the electric space charge distribution.
Equations of state and phase diagrams of hydrogen isotopes
Urlin, V. D.
2013-11-15
A new form of the semiempirical equation of state proposed for the liquid phase of hydrogen isotopes is based on the assumption that its structure is formed by cells some of which contain hydrogen molecules and others contain hydrogen atoms. The values of parameters in the equations of state of the solid (molecular and atomic) phases as well as of the liquid phase of hydrogen isotopes (protium and deuterium) are determined. Phase diagrams, shock adiabats, isentropes, isotherms, and the electrical conductivity of compressed hydrogen are calculated. Comparison of the results of calculations with available experimental data in a wide pressure range demonstrates satisfactory coincidence.
Relativistic Bursian diode equilibria
Ender, A. Y.; Kuznetsov, V. I.; Schamel, H.
2011-03-15
A comprehensive study of steady-states of a planar vacuum diode driven by a cold relativistic electron beam is presented. The emitter electric field as a characteristic function for their existence is evaluated in dependence of the diode length, the applied potential V, and the relativistic beam factor at injection {gamma}{sub 0}. It is used to classify the different branches of possible solutions, which encompass electron flows that are (i) transmitted through the diode completely, (ii) partially reflected from a virtual cathode (VC) either within the diode region or at the collector side, and (iii) reflected totally. As a byproduct, the V and {gamma}{sub 0} dependences of both bifurcation points of the minimum potential and of the transmitted current are obtained and the ultrarelativistic limit, {gamma}{sub 0}>>1, is performed. In this highly relativistic regime, the density of electrons appears to be constant across the diode region except for a small area around the VC.
Estimation of Fluid Properties and Phase Equilibria.
ERIC Educational Resources Information Center
Herskowitz, M.
1985-01-01
Describes a course (given to junior/senior students with strong background in thermodynamics and transport phenomena) that covers the theoretical and practical aspects of properties estimation. An outline for the course is included. (JN)
Gaussian cloning of coherent states with known phases
Alexanian, Moorad
2006-04-15
The fidelity for cloning coherent states is improved over that provided by optimal Gaussian and non-Gaussian cloners for the subset of coherent states that are prepared with known phases. Gaussian quantum cloning duplicates all coherent states with an optimal fidelity of 2/3. Non-Gaussian cloners give optimal single-clone fidelity for a symmetric 1-to-2 cloner of 0.6826. Coherent states that have known phases can be cloned with a fidelity of 4/5. The latter is realized by a combination of two beam splitters and a four-wave mixer operated in the nonlinear regime, all of which are realized by interaction Hamiltonians that are quadratic in the photon operators. Therefore, the known Gaussian devices for cloning coherent states are extended when cloning coherent states with known phases by considering a nonbalanced beam splitter at the input side of the amplifier.
Phase transitions for rotational states within an algebraic cluster model
NASA Astrophysics Data System (ADS)
López Moreno, E.; Morales Hernández, G. E.; Hess, P. O.; Yépez Martínez, H.
2016-07-01
The ground state and excited, rotational phase transitions are investigated within the Semimicroscopic Algebraic Cluster Model (SACM). The catastrophe theory is used to describe these phase transitions. Short introductions to the SACM and the catastrophe theory are given. We apply the formalism to the case of 16O+α→20Ne.
Quantum phase estimation using path-symmetric entangled states
Lee, Su-Yong; Lee, Chang-Woo; Lee, Jaehak; Nha, Hyunchul
2016-01-01
We study the sensitivity of phase estimation using a generic class of path-symmetric entangled states |φ〉|0〉 + |0〉|φ〉, where an arbitrary state |φ〉 occupies one of two modes in quantum superposition. With this generalization, we identify the fundamental limit of phase estimation under energy constraint that is characterized by the photon statistics of the component state |φ〉. We show that quantum Cramer-Rao bound (QCRB) can be indefinitely lowered with super-Poissonianity of the state |φ〉. For possible measurement schemes, we demonstrate that a full photon-counting employing the path-symmetric entangled states achieves the QCRB over the entire range [0, 2π] of unknown phase shift ϕ whereas a parity measurement does so in a certain confined range of ϕ. By introducing a component state of the form , we particularly show that an arbitrarily small QCRB can be achieved even with a finite energy in an ideal situation. This component state also provides the most robust resource against photon loss among considered entangled states over the range of the average input energy Nav > 1. Finally we propose experimental schemes to generate these path-symmetric entangled states for phase estimation. PMID:27457267
Solid state photomultiplier for astronomy, phase 2
NASA Technical Reports Server (NTRS)
Besser, P. J.; Hays, K. M.; Laviolette, R. A.
1989-01-01
Epitaxial layers with varying donor concentration profiles were grown on silicon substrate wafers using chemical vapor deposition (CVD) techniques, and solid state photomultiplier (SSPM) devices were fabricated from the wafers. Representative detectors were tested in a low background photon flux, low temperature environment to determine the device characteristics for comparison to NASA goals for astronomical applications. The SSPM temperatures varied between 6 and 11 K with background fluxes in the range from less than 5 x 10 to the 6th power to 10 to the 13th power photons/square cm per second at wavelengths of 3.2 and 20 cm. Measured parameters included quantum efficiency, dark count rate and bias current. Temperature for optimal performance is 10 K, the highest ever obtained for SSPMs. The devices exhibit a combination of the lowest dark current and highest quantum efficiency yet achieved. Experimental data were reduced, analyzed and used to generate recommendations for future studies. The background and present status of the microscopic theory of SSPM operation were reviewed and summarized. Present emphasis is on modeling of the avalanche process which is the basis for SSPM operation. Approaches to the solution of the Boltzmann transport equation are described and the treatment of electron scattering mechanisms is presented. The microscopic single-electron transport theory is ready to be implemented for large-scale computations.
Colina, Coray M; Gubbins, Keith E
2005-02-24
Perfluoroalkanes have numerous applications (e.g., in the medical field and the chemical industry), and their high affinity for carbon dioxide makes them attractive as surfactants and cosolvents. Although research in this area has grown in the past few years, very little phase-equilibrium data is available in the open literature for these systems. In this work, we present, for the first time, predictions of vapor-liquid and vapor-liquid-liquid equilibria of binary and ternary systems of carbon dioxide/n-perfluoroalkane/n-alkane. Our results are based on the SAFT-VR EOS (statistical associating fluid theory of variable range, equation of state), and we study the influence of temperature, pressure, composition, and chain length on the phase diagram. The predicted phase diagrams are based on temperature-independent binary interaction parameters, and no ternary parameters are introduced. Comparisons to the available experimental and molecular simulation data show that the predicted diagrams should provide a good representation of the phase equilibria.
MHD equilibria with diamagnetic effects
NASA Astrophysics Data System (ADS)
Tessarotto, M.; Zorat, R.; Johnson, J. L.; White, R. B.
1997-11-01
An outstanding issue in magnetic confinement is the establishment of MHD equilibria with enhanced flow shear profiles for which turbulence (and transport) may be locally effectively suppressed or at least substantially reduced with respect to standard weak turbulence models. Strong flows develop in the presence of equilibrium E× B-drifts produced by a strong radial electric field, as well as due to diamagnetic contributions produced by steep equilibrium radial profiles of number density, temperature and the flow velocity itself. In the framework of a kinetic description, this generally requires the construction of guiding-center variables correct to second order in the relevant expansion parameter. For this purpose, the Lagrangian approach developed recently by Tessarotto et al. [1] is adopted. In this paper the conditions of existence of such equilibria are analyzed and their basic physical properties are investigated in detail. 1 - M. Pozzo, M. Tessarotto and R. Zorat, in Theory of fusion Plasmas, E.Sindoni et al. eds. (Societá Italiana di Fisica, Editrice Compositori, Bologna, 1996), p.295.
Signaling equilibria in sensorimotor interactions.
Leibfried, Felix; Grau-Moya, Jordi; Braun, Daniel A
2015-08-01
Although complex forms of communication like human language are often assumed to have evolved out of more simple forms of sensorimotor signaling, less attention has been devoted to investigate the latter. Here, we study communicative sensorimotor behavior of humans in a two-person joint motor task where each player controls one dimension of a planar motion. We designed this joint task as a game where one player (the sender) possesses private information about a hidden target the other player (the receiver) wants to know about, and where the sender's actions are costly signals that influence the receiver's control strategy. We developed a game-theoretic model within the framework of signaling games to investigate whether subjects' behavior could be adequately described by the corresponding equilibrium solutions. The model predicts both separating and pooling equilibria, in which signaling does and does not occur respectively. We observed both kinds of equilibria in subjects and found that, in line with model predictions, the propensity of signaling decreased with increasing signaling costs and decreasing uncertainty on the part of the receiver. Our study demonstrates that signaling games, which have previously been applied to economic decision-making and animal communication, provide a framework for human signaling behavior arising during sensorimotor interactions in continuous and dynamic environments. PMID:25935748
Topological superconducting phase and Majorana bound states in Shiba chains
NASA Astrophysics Data System (ADS)
Pientka, Falko; Peng, Yang; Glazman, Leonid; von Oppen, Felix
2015-12-01
Chains of magnetic adatoms on a conventional superconducting substrate constitute a promising venue for realizing topological superconductivity and Majorana end states. Here, we give a brief overview over recent attempts to describe these systems theoretically, emphasizing how the topological phase emerges from the physics of individual magnetic impurities and their associated Shiba states.
Universal and phase-covariant superbroadcasting for mixed qubit states
Buscemi, Francesco; D'Ariano, Giacomo Mauro; Macchiavello, Chiara; Perinotti, Paolo
2006-10-15
We describe a general framework to study covariant symmetric broadcasting maps for mixed qubit states. We explicitly derive the optimal N{yields}M superbroadcasting maps, achieving optimal purification of the single-site output copy, in both the universal and phase-covariant cases. We also study the bipartite entanglement properties of the superbroadcast states.
Phase diagram of the ground states of DNA condensates
NASA Astrophysics Data System (ADS)
Hoang, Trinh X.; Trinh, Hoa Lan; Giacometti, Achille; Podgornik, Rudolf; Banavar, Jayanth R.; Maritan, Amos
2015-12-01
The phase diagram of the ground states of DNA in a bad solvent is studied for a semiflexible polymer model with a generalized local elastic bending potential characterized by a nonlinearity parameter x and effective self-attraction promoting compaction. x =1 corresponds to the wormlike chain model. Surprisingly, the phase diagram as well as the transition lines between the ground states are found to be a function of x . The model provides a simple explanation for the results of prior experimental and computational studies and makes predictions for the specific geometries of the ground states. The results underscore the impact of the form of the microscopic bending energy at macroscopic observable scales.
Quantum phase estimation for nonlinear phase shifts with entangled spin coherent states of two modes
NASA Astrophysics Data System (ADS)
Berrada, K.; Abdel Khalek, S.
2013-10-01
Recently, we presented (Berrada K, Abdel-Khalek S and Raymond Ooi C H 2012 Phys. Rev. A 86 033823) an improved phase estimation scheme employing entangled spin coherent states (ESCSs) using the Holstein-Primakoff realization of angular momentum algebra. Here, we study the nonlinear phase enhancement from a generalized nonlinearity on ESCSs under perfect and lossy conditions with the same mean photon number and nonlinearity order. The results show that an increase in the spin number gives the smallest variance in the phase parameter in comparison to N00N states for different orders of nonlinearity. Finally, we study the physical properties of the input optical field and explore a connection between this quantity and the output state phase uncertainty. In particular, we show that the Mandel parameter may be used as an indicator of the phase estimation behavior in this interferometric setting.
Edge states and phase diagram for graphene under polarized light
Wang, Yi -Xiang; Li, Fuxiang
2016-03-22
In this paper, we investigate the topological phase transitions in graphene under the modulation of circularly polarized light, by analyzing the changes of edge states and its topological structures. A full phase diagram, with several different topological phases, is presented in the parameter space spanned by the driving frequency and light strength. We find that the high-Chern number behavior is very common in the driven system. While the one-photon resonance can create the chiral edge states in the π-gap, the two-photon resonance will induce the counter-propagating edge modes in the zero-energy gap. When the driving light strength is strong, themore » number and even the chirality of the edge states may change in the π-gap. The robustness of the edge states to disorder potential is also examined. We close by discussing the feasibility of experimental proposals.« less
Edge states and phase diagram for graphene under polarized light
NASA Astrophysics Data System (ADS)
Wang, Yi-Xiang; Li, Fuxiang
2016-07-01
In this work, we investigate the topological phase transitions in graphene under the modulation of circularly polarized light, by analyzing the changes of edge states and its topological structures. A full phase diagram, with several different topological phases, is presented in the parameter space spanned by the driving frequency and light strength. We find that the high-Chern number behavior is very common in the driven system. While the one-photon resonance can create the chiral edge states in the π-gap, the two-photon resonance will induce the counter-propagating edge modes in the zero-energy gap. When the driving light strength is strong, the number and even the chirality of the edge states may change in the π-gap. The robustness of the edge states to disorder potential is also examined. We close by discussing the feasibility of experimental proposals.
Persistent chimera states in nonlocally coupled phase oscillators
NASA Astrophysics Data System (ADS)
Suda, Yusuke; Okuda, Koji
2015-12-01
Chimera states in the systems of nonlocally coupled phase oscillators are considered stable in the continuous limit of spatially distributed oscillators. However, it is reported that in the numerical simulations without taking such limit, chimera states are chaotic transient and finally collapse into the completely synchronous solution. In this Rapid Communication, we numerically study chimera states by using the coupling function different from the previous studies and obtain the result that chimera states can be stable even without taking the continuous limit, which we call the persistent chimera state.
Persistent chimera states in nonlocally coupled phase oscillators.
Suda, Yusuke; Okuda, Koji
2015-12-01
Chimera states in the systems of nonlocally coupled phase oscillators are considered stable in the continuous limit of spatially distributed oscillators. However, it is reported that in the numerical simulations without taking such limit, chimera states are chaotic transient and finally collapse into the completely synchronous solution. In this Rapid Communication, we numerically study chimera states by using the coupling function different from the previous studies and obtain the result that chimera states can be stable even without taking the continuous limit, which we call the persistent chimera state.
Vlasov tokamak equilibria with shearad toroidal flow and anisotropic pressure
NASA Astrophysics Data System (ADS)
Throumoulopoulos, George; Kuiroukidis, Apostolos; Tasso, Henri
2015-11-01
By choosing appropriate deformed Maxwellian ion and electron distribution functions depending on the two particle constants of motion, i.e. the energy and toroidal angular momentum, we reduce the Vlasov axisymmetric equilibrium problem for quasineutral plasmas to a transcendental Grad-Shafranov-like equation. This equation is then solved numerically under the Dirichlet boundary condition for an analytically prescribed boundary possessing a lower X-point to construct tokamak equilibria with toroidal sheared ion flow and anisotropic pressure. Depending on the deformation of the distribution functions these steady states can have toroidal current densities either peaked on the magnetic axis or hollow. These two kinds of equilibria may be regarded as a bifurcation in connection with symmetry properties of the distribution functions on the magnetic axis. This work has received funding from (a) the National Programme for the Controlled Thermonuclear Fusion, Hellenic Republic, (b) Euratom research and training programme 2014-2018 under grant agreement No 633053.
Vlasov tokamak equilibria with sheared toroidal flow and anisotropic pressure
Kuiroukidis, Ap; Throumoulopoulos, G. N.; Tasso, H.
2015-08-15
By choosing appropriate deformed Maxwellian ion and electron distribution functions depending on the two particle constants of motion, i.e., the energy and toroidal angular momentum, we reduce the Vlasov axisymmetric equilibrium problem for quasineutral plasmas to a transcendental Grad-Shafranov-like equation. This equation is then solved numerically under the Dirichlet boundary condition for an analytically prescribed boundary possessing a lower X-point to construct tokamak equilibria with toroidal sheared ion flow and anisotropic pressure. Depending on the deformation of the distribution functions, these steady states can have toroidal current densities either peaked on the magnetic axis or hollow. These two kinds of equilibria may be regarded as a bifurcation in connection with symmetry properties of the distribution functions on the magnetic axis.
Vapor-Liquid Equilibria Using the Gibbs Energy and the Common Tangent Plane Criterion
ERIC Educational Resources Information Center
Olaya, Maria del Mar; Reyes-Labarta, Juan A.; Serrano, Maria Dolores; Marcilla, Antonio
2010-01-01
Phase thermodynamics is often perceived as a difficult subject with which many students never become fully comfortable. The Gibbsian geometrical framework can help students to gain a better understanding of phase equilibria. An exercise to interpret the vapor-liquid equilibrium of a binary azeotropic mixture, using the equilibrium condition based…
Hydrogen exchange equilibria in thiols.
Hofstetter, Dustin; Thalmann, Basil; Nauser, Thomas; Koppenol, Willem H
2012-09-17
Cysteine, cysteinyl-glycine, glutathione, phenylalanyl-cysteinyl-glycine, and histidyl-cysteinyl-glycine were dissolved in acidic and neutral D(2)O in the presence of the radical generator 2,2'-azobis(2-methylpropionamidine) dihydrochloride and radical mediator compounds (benzyl alcohol and 2-propanol). An exchange of H-atoms by D-atoms took place in these peptides due to intramolecular H-abstraction equilibria. NMR measurements allow one to follow the extent of H-D exchanges and to identify the sites where these exchanges take place. Significant exchanges occur in acidic media in GSH at positions Glu-β and Glu-γ, in Phe-Cys-Gly at positions Phe ortho, Phe-β, Cys-α, Cys-β, and Gly-α, and in His-Cys-Gly at positions His H1, His H2, His β, Cys β, and Gly α. In neutral media, exchanges occur in Cys-Gly at position Cys β and in GSH at position Cys α. Phe-Cys-Gly and His-Cys-Gly were not examined in neutral media. Sites participating in the radical exchange equilibria are highly dependent on structure and pH; the availability of electron density in the form of lone pairs appears to increase the extent of exchange. Interestingly, and unexpectedly, 2D NMR experiments show that GSH rearranges itself in acidic solution: the signals shift, but their patterns do not change. The formation of a thiolactone from Gly and Cys residues matches the changes observed.
Efficient computations of quantum canonical Gibbs state in phase space
NASA Astrophysics Data System (ADS)
Bondar, Denys I.; Campos, Andre G.; Cabrera, Renan; Rabitz, Herschel A.
2016-06-01
The Gibbs canonical state, as a maximum entropy density matrix, represents a quantum system in equilibrium with a thermostat. This state plays an essential role in thermodynamics and serves as the initial condition for nonequilibrium dynamical simulations. We solve a long standing problem for computing the Gibbs state Wigner function with nearly machine accuracy by solving the Bloch equation directly in the phase space. Furthermore, the algorithms are provided yielding high quality Wigner distributions for pure stationary states as well as for Thomas-Fermi and Bose-Einstein distributions. The developed numerical methods furnish a long-sought efficient computation framework for nonequilibrium quantum simulations directly in the Wigner representation.
Efficient computations of quantum canonical Gibbs state in phase space.
Bondar, Denys I; Campos, Andre G; Cabrera, Renan; Rabitz, Herschel A
2016-06-01
The Gibbs canonical state, as a maximum entropy density matrix, represents a quantum system in equilibrium with a thermostat. This state plays an essential role in thermodynamics and serves as the initial condition for nonequilibrium dynamical simulations. We solve a long standing problem for computing the Gibbs state Wigner function with nearly machine accuracy by solving the Bloch equation directly in the phase space. Furthermore, the algorithms are provided yielding high quality Wigner distributions for pure stationary states as well as for Thomas-Fermi and Bose-Einstein distributions. The developed numerical methods furnish a long-sought efficient computation framework for nonequilibrium quantum simulations directly in the Wigner representation. PMID:27415384
Emerging single-phase state in small manganite nanodisks.
Shao, Jian; Liu, Hao; Zhang, Kai; Yu, Yang; Yu, Weichao; Lin, Hanxuan; Niu, Jiebin; Du, Kai; Kou, Yunfang; Wei, Wengang; Lan, Fanli; Zhu, Yinyan; Wang, Wenbin; Xiao, Jiang; Yin, Lifeng; Plummer, E W; Shen, Jian
2016-08-16
In complex oxides systems such as manganites, electronic phase separation (EPS), a consequence of strong electronic correlations, dictates the exotic electrical and magnetic properties of these materials. A fundamental yet unresolved issue is how EPS responds to spatial confinement; will EPS just scale with size of an object, or will the one of the phases be pinned? Understanding this behavior is critical for future oxides electronics and spintronics because scaling down of the system is unavoidable for these applications. In this work, we use La0.325Pr0.3Ca0.375MnO3 (LPCMO) single crystalline disks to study the effect of spatial confinement on EPS. The EPS state featuring coexistence of ferromagnetic metallic and charge order insulating phases appears to be the low-temperature ground state in bulk, thin films, and large disks, a previously unidentified ground state (i.e., a single ferromagnetic phase state emerges in smaller disks). The critical size is between 500 nm and 800 nm, which is similar to the characteristic length scale of EPS in the LPCMO system. The ability to create a pure ferromagnetic phase in manganite nanodisks is highly desirable for spintronic applications. PMID:27482108
Emerging single-phase state in small manganite nanodisks
NASA Astrophysics Data System (ADS)
Shao, Jian; Liu, Hao; Zhang, Kai; Yu, Yang; Yu, Weichao; Lin, Hanxuan; Niu, Jiebin; Du, Kai; Kou, Yunfang; Wei, Wengang; Lan, Fanli; Zhu, Yinyan; Wang, Wenbin; Xiao, Jiang; Yin, Lifeng; Plummer, E. W.; Shen, Jian
2016-08-01
In complex oxides systems such as manganites, electronic phase separation (EPS), a consequence of strong electronic correlations, dictates the exotic electrical and magnetic properties of these materials. A fundamental yet unresolved issue is how EPS responds to spatial confinement; will EPS just scale with size of an object, or will the one of the phases be pinned? Understanding this behavior is critical for future oxides electronics and spintronics because scaling down of the system is unavoidable for these applications. In this work, we use La0.325Pr0.3Ca0.375MnO3 (LPCMO) single crystalline disks to study the effect of spatial confinement on EPS. The EPS state featuring coexistence of ferromagnetic metallic and charge order insulating phases appears to be the low-temperature ground state in bulk, thin films, and large disks, a previously unidentified ground state (i.e., a single ferromagnetic phase state emerges in smaller disks). The critical size is between 500 nm and 800 nm, which is similar to the characteristic length scale of EPS in the LPCMO system. The ability to create a pure ferromagnetic phase in manganite nanodisks is highly desirable for spintronic applications.
Emerging single-phase state in small manganite nanodisks
Shao, Jian; Liu, Hao; Zhang, Kai; Yu, Yang; Yu, Weichao; Lin, Hanxuan; Niu, Jiebin; Du, Kai; Kou, Yunfang; Wei, Wengang; Lan, Fanli; Zhu, Yinyan; Wang, Wenbin; Xiao, Jiang; Yin, Lifeng; Plummer, E. W.; Shen, Jian
2016-01-01
In complex oxides systems such as manganites, electronic phase separation (EPS), a consequence of strong electronic correlations, dictates the exotic electrical and magnetic properties of these materials. A fundamental yet unresolved issue is how EPS responds to spatial confinement; will EPS just scale with size of an object, or will the one of the phases be pinned? Understanding this behavior is critical for future oxides electronics and spintronics because scaling down of the system is unavoidable for these applications. In this work, we use La0.325Pr0.3Ca0.375MnO3 (LPCMO) single crystalline disks to study the effect of spatial confinement on EPS. The EPS state featuring coexistence of ferromagnetic metallic and charge order insulating phases appears to be the low-temperature ground state in bulk, thin films, and large disks, a previously unidentified ground state (i.e., a single ferromagnetic phase state emerges in smaller disks). The critical size is between 500 nm and 800 nm, which is similar to the characteristic length scale of EPS in the LPCMO system. The ability to create a pure ferromagnetic phase in manganite nanodisks is highly desirable for spintronic applications. PMID:27482108
Doorway states in the random-phase approximation
De Pace, A.; Molinari, A.; Weidenmüller, H.A.
2014-12-15
By coupling a doorway state to a sea of random background states, we develop the theory of doorway states in the framework of the random-phase approximation (RPA). Because of the symmetry of the RPA equations, that theory is radically different from the standard description of doorway states in the shell model. We derive the Pastur equation in the limit of large matrix dimension and show that the results agree with those of matrix diagonalization in large spaces. The complexity of the Pastur equation does not allow for an analytical approach that would approximately describe the doorway state. Our numerical results display unexpected features: The coupling of the doorway state with states of opposite energy leads to strong mutual attraction.
Topological phase states of the SU(3) QCD
NASA Astrophysics Data System (ADS)
Protogenov, Alexander P.; Chulkov, Evgueni V.; Teo, Jeffrey C. Y.
2014-03-01
We consider the topologically nontrivial phase states and the corresponding topological defects in the SU(3) d-dimensional quantum chromodynamics (QCD). The homotopy groups for topological classes of such defects are calculated explicitly. We have shown that the three nontrivial groups are π3SU(3) = Bbb Z, π5SU(3) = Bbb Z, and π6SU(3) = Bbb Z6 if 3 <= d <= 6. The latter result means that we are dealing exactly with six topologically different phase states. The topological invariants for d=3,5,6 are described in detail.
Accelerated Superposition State Molecular Dynamics for Condensed Phase Systems.
Ceotto, Michele; Ayton, Gary S; Voth, Gregory A
2008-04-01
An extension of superposition state molecular dynamics (SSMD) [Venkatnathan and Voth J. Chem. Theory Comput. 2005, 1, 36] is presented with the goal to accelerate timescales and enable the study of "long-time" phenomena for condensed phase systems. It does not require any a priori knowledge about final and transition state configurations, or specific topologies. The system is induced to explore new configurations by virtue of a fictitious (free-particle-like) accelerating potential. The acceleration method can be applied to all degrees of freedom in the system and can be applied to condensed phases and fluids. PMID:26620930
Excited-state quantum phase transition in the Rabi model
NASA Astrophysics Data System (ADS)
Puebla, Ricardo; Hwang, Myung-Joong; Plenio, Martin B.
2016-08-01
The Rabi model, a two-level atom coupled to a harmonic oscillator, can undergo a second-order quantum phase transition (QPT) [M.-J. Hwang et al., Phys. Rev. Lett. 115, 180404 (2015), 10.1103/PhysRevLett.115.180404]. Here we show that the Rabi QPT accompanies critical behavior in the higher-energy excited states, i.e., the excited-state QPT (ESQPT). We derive analytic expressions for the semiclassical density of states, which show a logarithmic divergence at a critical energy eigenvalue in the broken symmetry (superradiant) phase. Moreover, we find that the logarithmic singularities in the density of states lead to singularities in the relevant observables in the system such as photon number and atomic polarization. We corroborate our analytical semiclassical prediction of the ESQPT in the Rabi model with its numerically exact quantum mechanical solution.
Symmetry transforms for ideal magnetohydrodynamics equilibria.
Bogoyavlenskij, Oleg I
2002-11-01
A method for constructing ideal magnetohydrodynamics (MHD) equilibria is introduced. The method consists of the application of symmetry transforms to any known MHD equilibrium [ O. I. Bogoyavlenskij, Phys. Rev. E. 62, 8616, (2000)]. The transforms break the geometrical symmetries of the field-aligned solutions and produce continuous families of the nonsymmetric MHD equilibria. The method of symmetry transforms also allows to obtain MHD equilibria with current sheets and exact solutions with noncollinear vector fields B and V. A model of the nonsymmetric astrophysical jets outside of their accretion disks is developed. The total magnetic and kinetic energy of the jet is finite in any layer c(1)
Symmetry transforms for ideal magnetohydrodynamics equilibria.
Bogoyavlenskij, Oleg I
2002-11-01
A method for constructing ideal magnetohydrodynamics (MHD) equilibria is introduced. The method consists of the application of symmetry transforms to any known MHD equilibrium [ O. I. Bogoyavlenskij, Phys. Rev. E. 62, 8616, (2000)]. The transforms break the geometrical symmetries of the field-aligned solutions and produce continuous families of the nonsymmetric MHD equilibria. The method of symmetry transforms also allows to obtain MHD equilibria with current sheets and exact solutions with noncollinear vector fields B and V. A model of the nonsymmetric astrophysical jets outside of their accretion disks is developed. The total magnetic and kinetic energy of the jet is finite in any layer c(1)
Stability analysis of cylindrical Vlasov equilibria
Short, R W
1980-02-01
A method is presented for the fully kinetic, nonlocal stability analysis of cylindrically symmetric equilibria. Applications to the lower hybrid drift instability and the modes associated with a finite-width relativistic E-layer are discussed.
Equilibria of Constantin Popovici's Photogravitational Model Revisited
NASA Astrophysics Data System (ADS)
Mioc, Vasile
The equilibria of the two-body problem associated to Constantin Popovici's photogravitational model are tackled again. We consider the motion in the infinity-blow-up coordinates provided by McGehee-type transformations. Then we study the vector field expressed in collision-regularizing Levi-Civita coordinates. This new framework provides the same location of the equilibria and the same information about their nature as the previous approaches.
Equilibria of Seeliger's Problem. Analytic Approach
NASA Astrophysics Data System (ADS)
Popescu, E.; Pasca, D.; Mioc, V.; Popescu, N. A.
2010-09-01
We offer a deeper insight into the two-body problem associated to Seeliger's potential. We resort to McGehee-type transformations to write the motion equations and the integrals of energy and angular momentum. Then we search for equilibria, considering the whole interplay among the parameter A of the field, the constant K of the field, and the integration constants of energy h and angular momentum C. We find the number of equilibria for each such situation.
Excited-state quantum phase transitions in Dicke superradiance models.
Brandes, Tobias
2013-09-01
We derive analytical results for various quantities related to the excited-state quantum phase transitions in a class of Dicke superradiance models in the semiclassical limit. Based on a calculation of a partition sum restricted to Dicke states, we discuss the singular behavior of the derivative of the density of states and find observables such as the mean (atomic) inversion and the boson (photon) number and its fluctuations at arbitrary energies. Criticality depends on energy and a parameter that quantifies the relative weight of rotating versus counterrotating terms, and we find a close analogy to the logarithmic and jump-type nonanalyticities known from the Lipkin-Meshkov-Glick model. PMID:24125239
Hydrogen bond symmetrization and equation of state of phase D
Hushur, Anwar; Manghnani, Murli H.; Smyth, Joseph R.; Williams, Quentin; Hellebrand, Eric; Lonappan, Dayana; Ye, Yu; Dera, Przemyslaw; Frost, Daniel J.
2012-10-09
We have synthesized phase D at 24 GPa and at temperatures of 1250-1100 C in a multianvil press under conditions of high silica activity. The compressibility of this high-silica-activity phase D (Mg{sub 1.0}Si{sub 1.7}H{sub 3.0}O{sub 6}) has been measured up to 55.8 GPa at ambient temperature by powder X-ray diffraction. The volume (V) decreases smoothly with increasing pressure up to 40 GPa, consistent with the results reported in earlier studies. However, a kink is observed in the trend of V versus pressure above {approx}40 GPa, reflecting a change in the compression behavior. The data to 30 GPa fit well to a third-order Birch-Murnaghan equation of state (EoS), yielding V{sub o} = 85.1 {+-} 0.2 {angstrom}{sup 3}; K{sub o} = 167.9 {+-} 8.6 GPa; and K{prime}{sub o} = 4.3 {+-} 0.5, similar to results for Fe-Al-free phase D reported by Frost and Fei (1999). However, these parameters are larger than those reported for Fe-Al-bearing phase D and for Fe-Al-free phase D. The abnormal volume change in this study may be attributed to the reported hydrogen bond symmetrization in phase D. Fitting a third-order Birch-Murnaghan EoS to the data below 30 GPa yields a bulk modulus K{sub o} = 173 (2) GPa for the hydrogen-off-centered (HOC) phase and K{sub o} = 212 (15) GPa for the data above 40 GPa for the hydrogen-centered (HC) phase, assuming K{prime}{sub o} is 4. The calculated bulk modulus K{sub o} of the HC phase is 18% larger than the bulk modulus K{sub o} of the HOC phase.
Strain glass state as the boundary of two phase transitions
Zhou, Zhijian; Cui, Jian; Ren, Xiaobing
2015-01-01
A strain glass state was found to be located between B2-B19’ (cubic to monoclinic) phase transition and B2-R (cubic to rhombohedral) phase transition in Ti49Ni51 alloys after aging process. After a short time aging, strong strain glass transition was observed, because the size of the precipitates is small, which means the strain field induced by the precipitates is isotropic and point-defect-like, and the distribution of the precipitates is random. After a long time aging, the average size of the precipitates increases. The strong strain field induced by the precipitates around them forces the symmetry of the matrix materials to conform to the symmetry of the crystalline structure of the precipitates, which results in the new phase transition. The experiment shows that there exists no well-defined boundary in the evolution from the strain glass transition to the new phase transition. Due to its generality, this glass mediated phase transition divergence scheme can be applied to other proper material systems to induce a more important new phase transition path, which can be useful in the field of phase transition engineering. PMID:26307500
All solid-state SBS phase conjugate mirror
Dane, C.B.; Hackel, L.A.
1999-03-09
A stimulated Brillouin scattering (SBS) phase conjugate laser mirror uses a solid-state nonlinear gain medium instead of the conventional liquid or high pressure gas medium. The concept has been effectively demonstrated using common optical-grade fused silica. An energy threshold of 2.5 mJ and a slope efficiency of over 90% were achieved, resulting in an overall energy reflectivity of >80% for 15 ns, 1 um laser pulses. The use of solid-state materials is enabled by a multi-pass resonant architecture which suppresses transient fluctuations that would otherwise result in damage to the SBS medium. This all solid state phase conjugator is safer, more reliable, and more easily manufactured than prior art designs. It allows nonlinear wavefront correction to be implemented in industrial and defense laser systems whose operating environments would preclude the introduction of potentially hazardous liquids or high pressure gases. 8 figs.
All solid-state SBS phase conjugate mirror
Dane, Clifford B.; Hackel, Lloyd A.
1999-01-01
A stimulated Brillouin scattering (SBS) phase conjugate laser mirror uses a solid-state nonlinear gain medium instead of the conventional liquid or high pressure gas medium. The concept has been effectively demonstrated using common optical-grade fused silica. An energy threshold of 2.5 mJ and a slope efficiency of over 90% were achieved, resulting in an overall energy reflectivity of >80% for 15 ns, 1 um laser pulses. The use of solid-state materials is enabled by a multi-pass resonant architecture which suppresses transient fluctuations that would otherwise result in damage to the SBS medium. This all solid state phase conjugator is safer, more reliable, and more easily manufactured than prior art designs. It allows nonlinear wavefront correction to be implemented in industrial and defense laser systems whose operating environments would preclude the introduction of potentially hazardous liquids or high pressure gases.
Classification scheme of pure multipartite states based on topological phases
NASA Astrophysics Data System (ADS)
Johansson, Markus; Ericsson, Marie; Sjöqvist, Erik; Osterloh, Andreas
2014-01-01
We investigate the connection between the concept of affine balancedness (a-balancedness) introduced by M. Johansson et al. [Phys. Rev. A 85, 032112 (2012), 10.1103/PhysRevA.85.032112] and polynomial local SU invariants and the appearance of topological phases, respectively. It is found that different types of a-balancedness correspond to different types of local SU invariants analogously to how different types of balancedness, as defined by A. Osterloh and J. Siewert, [New J. Phys. 12, 075025 (2010), 10.1088/1367-2630/12/7/075025], correspond to different types of local special linear (SL) invariants. These different types of SU invariants distinguish between states exhibiting different topological phases. In the case of three qubits, the different kinds of topological phases are fully distinguished by the three-tangle together with one more invariant. Using this, we present a qualitative classification scheme based on balancedness of a state. While balancedness and local SL invariants of bidegree (2n,0) classify the SL-semistable states [A. Osterloh and J. Siewert, New J. Phys. 12, 075025 (2010), 10.1088/1367-2630/12/7/075025; O. Viehmann et al., Phys. Rev. A 83, 052330 (2011), 10.1103/PhysRevA.83.052330], a-balancedness and local SU invariants of bidegree (2n-m,m) give a more fine-grained classification. In this scheme, the a-balanced states form a bridge from the genuine entanglement of balanced states, invariant under the SL group, towards the entanglement of unbalanced states characterized by U invariants of bidegree (n,n). As a byproduct, we obtain generalizations to the W state, i.e., states that are entangled, but contain only globally distributed entanglement of parts of the system.
A method to resolve the phase state of aerosol particles
NASA Astrophysics Data System (ADS)
Saukko, E.; Kuuluvainen, H.; Virtanen, A.
2012-01-01
The phase state of atmospheric aerosols has an impact on their chemical aging and their deliquescence and thus their ability to act as cloud condensation nuclei (CCN). The phase change of particles can be induced by the deliquescence or efflorescence of water or by chemical aging. Existing methods, such as tandem differential mobility analysis rely on the size change of particles related to the water uptake or release. To address the need to study the phase change induced by mass-preserving and nearly mass-preserving processes a new method has been developed. The method relies on the physical impaction of particles on a smooth substrate and subsequent counting of bounced particles by a condensation particle counter (CPC). The connection between the bounce probability and physical properties of particles is so far qualitative. To evaluate the performance of this method, the phase state of ammonium sulfate and levoglucosan, crystalline and amorphous solid, in the presence of water vapor was studied. The results show a marked difference in particle bouncing properties between substances - not only at the critical relative humidity level, but also on the slope of the bouncing probability with respect to humidity. This suggests that the method can be used to differentiate between amorphous and crystalline substances as well as to differentiate between liquid and solid phases.
A method to resolve the phase state of aerosol particles
NASA Astrophysics Data System (ADS)
Saukko, E.; Kuuluvainen, H.; Virtanen, A.
2011-10-01
The phase state of atmospheric aerosols has impact on their chemical aging and their deliquescence and thus their ability to act as cloud condensation nuclei (CCN). The phase change of particles can be induced by the deliquescence or efflorescence of water or by chemical aging. Existing methods, such as tandem differential mobility analysis rely on the size change of particles related to the water uptake or release related to deliquescence and efflorescence. To address the need to study the phase change induced by mass-preserving and nearly mass-preserving processes a new method has been developed. The method relies on the physical impaction of particles on a smooth substrate and subsequent counting of bounced particles by condensation particle counter (CPC). The connection between the bounce probability and physical properties of particles is so far qualitative. To evaluate the performance of this method, the phase state of ammonium sulfate and levoglucosan, crystalline and amorphous solid, in the presence of water vapor was studied. The results show a marked difference in particle bouncing properties between substances - not only at the critical relative humidity level, but also on the slope of the bouncing probability with respect to humidity. This suggests that the method can be used to differentiate between amorphous and crystalline substances as well as to differentiate between liquid and solid phases.
Dispersion cancellation with phase-sensitive Gaussian-state light
Shapiro, Jeffrey H.
2010-02-15
Franson's paradigm for nonlocal dispersion cancellation [J. D. Franson, Phys. Rev. A 45, 3126 (1992)] is studied using two kinds of jointly Gaussian-state signal and reference beams with phase-sensitive cross correlations. The first joint signal-reference state is nonclassical, with a phase-sensitive cross correlation that is at the ultimate quantum-mechanical limit. It models the outputs obtained from continuous-wave spontaneous parametric down-conversion. The second joint signal-reference state is classical--it has a proper P representation--with a phase-sensitive cross correlation that is at the limit set by classical physics. Using these states we show that a version of Franson's nonlocal dispersion cancellation configuration has essentially identical quantum and classical explanations except for the contrast obtained, which is much higher in the quantum case than it is in the classical case. This work bears on Franson's recent article [J. D. Franson, Phys. Rev. A 80, 032119 (2009)], which asserts that there is no classical explanation for all the features seen in quantum nonlocal dispersion cancellation.
Solid State NMR Studies of the Aluminum Hydride Phases
NASA Technical Reports Server (NTRS)
Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.
2006-01-01
Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.
Thermodynamics and phase coexistence in nonequilibrium steady states
NASA Astrophysics Data System (ADS)
Dickman, Ronald
2016-09-01
I review recent work focussing on whether thermodynamics can be extended to nonequilibrium steady states (NESS), in particular, the possibility of consistent definitions of temperature T and chemical potential μ for NESS. The testing-grounds are simple lattice models with stochastic dynamics. Each model includes a drive that maintains the system far from equilibrium, provoking particle and/or energy flows; for zero drive the system relaxes to equilibrium. Analysis and numerical simulation show that for spatially uniform NESS, consistent definitions of T and μ are possible via coexistence with an appropriate reservoir, if (and in general only if) a particular kind of rate (that proposed by Sasa and Tasaki) is used for exchanges of particles and energy between systems. The program fails, however, for nonuniform systems. The functions T and μ describing isolated phases cannot be used to predict the properties of coexisting phases in a single, phase-separated system.
Engineering aspects of solid-state phase conjugate lasers
NASA Astrophysics Data System (ADS)
Gregor, Eduard; Mordaunt, David W.; Matthews, Steven C.; Kahan, Osher; Muir, Alexander R.; Palombo, Mario
1992-06-01
An engineering approach for the development of laser hardware that takes advantage of the special properties of phase conjugation is reported. The principal advantages of conjugate solid-state lasers are alignment stability and passive compensation of thermal distortion in a double pass laser amplifier chain. Attention is given to the application of phase conjugation techniques to the design, fabrication, and field testing of an Nd:YAG second harmonic 0.5 Joule, 30 Hertz flashlamp pumped laser in a master oscillator power amplifier configuration. The double pass amplifier featured a phase conjugate mirror and a second harmonic crystal within the amplifier chain. The basic Nd:YAG laser produced a doubling efficiency of 75 percent from 1064 to 532 nm. This output was subsequently used as the source, and a conversion efficiency of 80 percent into six wavelengths in the visible spectrum was obtained using stimulated rotational Raman scattering.
Connection between decoherence and excited state quantum phase transitions
Perez-Fernandez, P.; Arias, J. M.; Relano, A.; Dukelsky, J.; Garcia-Ramos, J. E.
2010-04-26
In this work we explore the relationship between an excited state quantum phase transition (ESQPT) and the phenomenon of quantum decoherence. For this purpose, we study how the decoherence is affected by the presence of a continuous ESQPT in the environment. This one is modeled as a two level boson system described by a Lipkin Hamiltonian. We will show that the decoherence of the system is maximal when the environment undergoes a continuous ESQPT.
Phenomena of solid state grain boundaries phase transition in technology
Minaev, Y. A.
2015-03-30
The results of study the phenomenon, discovered by author (1971), of the phase transition of grain boundary by the formation of two-dimensional liquid or quasi-liquid films have been done. The described phenomena of the first order phase transition (two-dimensional melting) at temperatures 0.6 – 0.9 T{sub S0} (of the solid state melting point) is a fundamental property of solid crystalline materials, which has allowed to revise radically scientific representations about a solid state of substance. Using the mathematical tools of the film thermodynamics it has been obtained the generalized equation of Clausius - Clapeyron type for two-dimensional phase transition. The generalized equation has been used for calculating grain boundary phase transition temperature T{sub Sf} of any metal, which value lies in the range of (0.55…0.86) T{sub S0}. Based on these works conclusions the develop strategies for effective forming of coatings (by thermo-chemical processing) on surface layers of functional alloys and hard metals have been made. The short overview of the results of some graded alloys characterization has been done.
Effect of temperature on acid-base equilibria in separation techniques. A review.
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.
Phase sensitivity in deformed-state superposition considering nonlinear phase shifts
NASA Astrophysics Data System (ADS)
Berrada, K.
2016-07-01
We study the problem of the phase estimation for the deformation-state superposition (DSS) under perfect and lossy (due to a dissipative interaction of DSS with their environment) regimes. The study is also devoted to the phase enhancement of the quantum states resulting from a generalized non-linearity of the phase shifts, both without and with losses. We find that such a kind of superposition can give the smallest variance in the phase parameter in comparison with usual Schrödinger cat states in different order of non-linearity even if for a larger average number of photons. Due to the significance of how a system is quantum correlated with its environment in the construction of a scalable quantum computer, the entanglement between the DSS and its environment is investigated during the dissipation. We show that partial entanglement trapping occurs during the dynamics depending on the kind of deformation and mean photon number. These features make the DSS with a larger average number of photons a good candidate for implementation of schemes of quantum optics and information with high precision.
On Nash equilibria in Eisert-Lewenstein-Wilkens game
NASA Astrophysics Data System (ADS)
Bolonek-Lasoń, Katarzyna; Kosiński, Piotr
2015-12-01
Landsburg method of classifying mixed Nash equilibria for maximally entangled Eisert-Lewenstein-Wilkens (ELW) game is analyzed with special emphasis on symmetries inherent to the problem. Nash equilibria for the original ELW game are determined.
Kang, Y.W.; Cho, S.Y.; Nah, I.W.
1998-07-01
Isothermal vapor-liquid equilibria for difluoromethane + chlorine, chlorodifluoromethane + chlorine, and dichlorodifluoromethane + chlorine have been measured. The experimental data are correlated with the Peng-Robinson equation of state, and the relevant parameters are presented. All of the binary systems form minimum boiling homogeneous azeotropes at the experimental conditions. The correlation of the vapor-liquid equilibria was found to be in good agreement with the experimental data.
NASA Astrophysics Data System (ADS)
Moroz, M. V.; Prokhorenko, M. V.
2016-07-01
The phase equilibria of the Ag-Bi-Te-I system in the part AgI-Bi-Bi2Te3-BiTeI is studied in the interval of 500-540 K by means of physicochemical analysis. Thermodynamic properties of phases are determined via EMF. Potential-forming processes occur in electrochemical cells (ECCs) of the C|Ag|glass Ag3GeS3I|D|C structure (where C denotes inert (graphite) electrodes; Ag, D denotes ECC electrodes; D denotes four-phase alloys of the AgI-Bi-Bi2Te3-BiTeI system; and Ag3GeS3I glass is the selective Ag+ conducting membrane). Linear dependences of the EMFs of cells E(T) in the interval of 505-535 K are used to calculate the values of the thermodynamic functions of BiTeI, Bi2TeI, and Bi4TeI1.25 phases saturated over silver.
Finding Plasma Equilibria with Magnetic Islands
NASA Astrophysics Data System (ADS)
Miller, G.; Faber, V.; White, A. B., Jr.
1988-12-01
The traditional method of solving the helically symmetric plasma equilibrium equation, of the form L[ G] = F( G, r) where L is an elliptic linear operator, has been the simple iteration L[ Gn + 1 ]= F( Gn, r). A model of a Tokomak equilibrium is constructed and used to illustrate the divergence of the simple iteration for plasma equilibria with magnetic islands. Although the problem of equilibria with magnetic islands is two dimensional, for small islands the numerical stability of the simple iteration may be analyzed using a one-dimensional equation similar to the linearized equilibrium equation used to analyze physical (resistive) instability. This analysis is used to prove that any equilibria of the Tokamak type with small islands cannot be obtained by the simple iteration and to illustrate the superlinear convergence of Newton's method on these problems. The implementation of Newton's method is discussed and examples are given.
Partially coherent twisted states in arrays of coupled phase oscillators
Omel'chenko, Oleh E.; Wolfrum, Matthias; Laing, Carlo R.
2014-06-15
We consider a one-dimensional array of phase oscillators with non-local coupling and a Lorentzian distribution of natural frequencies. The primary objects of interest are partially coherent states that are uniformly “twisted” in space. To analyze these, we take the continuum limit, perform an Ott/Antonsen reduction, integrate over the natural frequencies, and study the resulting spatio-temporal system on an unbounded domain. We show that these twisted states and their stability can be calculated explicitly. We find that stable twisted states with different wave numbers appear for increasing coupling strength in the well-known Eckhaus scenario. Simulations of finite arrays of oscillators show good agreement with results of the analysis of the infinite system.
Partially coherent twisted states in arrays of coupled phase oscillators.
Omel'chenko, Oleh E; Wolfrum, Matthias; Laing, Carlo R
2014-06-01
We consider a one-dimensional array of phase oscillators with non-local coupling and a Lorentzian distribution of natural frequencies. The primary objects of interest are partially coherent states that are uniformly "twisted" in space. To analyze these, we take the continuum limit, perform an Ott/Antonsen reduction, integrate over the natural frequencies, and study the resulting spatio-temporal system on an unbounded domain. We show that these twisted states and their stability can be calculated explicitly. We find that stable twisted states with different wave numbers appear for increasing coupling strength in the well-known Eckhaus scenario. Simulations of finite arrays of oscillators show good agreement with results of the analysis of the infinite system.
Dimensionless Equation of State to Predict Microemulsion Phase Behavior.
Ghosh, Soumyadeep; Johns, Russell T
2016-09-01
Prediction of microemulsion phase behavior for changing state variables is critical to formulation design of surfactant-oil-brine (SOB) systems. SOB systems find applications in various chemical and petroleum processes, including enhanced oil recovery. A dimensional equation-of-state (EoS) was recently presented by Ghosh and Johns1 that relied on estimation of the surfactant tail length and surface area. We give an algorithm for flash calculations for estimation of three-phase Winsor regions that is more robust, simpler, and noniterative by making the equations dimensionless so that estimates of tail length and surface area are no longer needed. We predict phase behavior as a function temperature, pressure, volume, salinity, oil type, oil-water ratio, and surfactant/alcohol concentration. The dimensionless EoS is based on coupling the HLD-NAC (Hydrophilic Lipophilic Difference-Net Average Curvature) equations with new relationships between optimum salinity and solubility. An updated HLD expression that includes pressure is also used to complete the state description. A significant advantage of the dimensionless form of the EoS over the dimensional version is that salinity scans are tuned based only on one parameter, the interfacial volume ratio. Further, stability conditions are developed in a simplified way to predict whether an overall compositions lies within the single, two-, or three-phase regions. Important new microemulsion relationships are also found, the most important of which is that optimum solubilization ratio is equal to the harmonic mean of the oil and water solubilization ratios in the type III region. Thus, only one experimental measurement is needed in the three-phase zone to estimate the optimum solubilization ratio, a result which can aid experimental design and improve estimates of optimum from noisy data. Predictions with changing state variables are illustrated by comparison to experimental data using standard diagrams including a new type
Dimensionless Equation of State to Predict Microemulsion Phase Behavior.
Ghosh, Soumyadeep; Johns, Russell T
2016-09-01
Prediction of microemulsion phase behavior for changing state variables is critical to formulation design of surfactant-oil-brine (SOB) systems. SOB systems find applications in various chemical and petroleum processes, including enhanced oil recovery. A dimensional equation-of-state (EoS) was recently presented by Ghosh and Johns1 that relied on estimation of the surfactant tail length and surface area. We give an algorithm for flash calculations for estimation of three-phase Winsor regions that is more robust, simpler, and noniterative by making the equations dimensionless so that estimates of tail length and surface area are no longer needed. We predict phase behavior as a function temperature, pressure, volume, salinity, oil type, oil-water ratio, and surfactant/alcohol concentration. The dimensionless EoS is based on coupling the HLD-NAC (Hydrophilic Lipophilic Difference-Net Average Curvature) equations with new relationships between optimum salinity and solubility. An updated HLD expression that includes pressure is also used to complete the state description. A significant advantage of the dimensionless form of the EoS over the dimensional version is that salinity scans are tuned based only on one parameter, the interfacial volume ratio. Further, stability conditions are developed in a simplified way to predict whether an overall compositions lies within the single, two-, or three-phase regions. Important new microemulsion relationships are also found, the most important of which is that optimum solubilization ratio is equal to the harmonic mean of the oil and water solubilization ratios in the type III region. Thus, only one experimental measurement is needed in the three-phase zone to estimate the optimum solubilization ratio, a result which can aid experimental design and improve estimates of optimum from noisy data. Predictions with changing state variables are illustrated by comparison to experimental data using standard diagrams including a new type
Equation of state and phase diagram of FeO
Fischer, Rebecca A.; Campbell, Andrew J.; Shofner, Gregory A.; Lord, Oliver T.; Dera, Przemyslaw; Prakapenka, Vitali B.
2012-04-11
Wuestite, Fe{sub 1-x}O, is an important component in the mineralogy of Earth's lower mantle and may also be a component in the core. Therefore the high pressure, high temperature behavior of FeO, including its phase diagram and equation of state, is essential knowledge for understanding the properties and evolution of Earth's deep interior. We performed X-ray diffraction measurements using a laser-heated diamond anvil cell to achieve simultaneous high pressures and temperatures. Wuestite was mixed with iron metal, which served as our pressure standard, under the assumption that negligible oxygen dissolved into the iron. Our data show a positive slope for the subsolidus phase boundary between the B1 and B8 structures, indicating that the B1 phase is stable at the P-T conditions of the lower mantle and core. We have determined the thermal equation of state of B1 FeO to 156 GPa and 3100 K, finding an isothermal bulk modulus K{sub 0} = 149.4 {+-} 1.0 GPa and its pressure derivative K'{sub 0} = 3.60 {+-} 0.4. This implies that 7.7 {+-} 1.1 wt.% oxygen is required in the outer core to match the seismologically-determined density, under the simplifying assumption of a purely Fe-O outer core.
Steady-state phase error for a phase-locked loop subjected to periodic Doppler inputs
NASA Technical Reports Server (NTRS)
Chen, C.-C.; Win, M. Z.
1991-01-01
The performance of a carrier phase locked loop (PLL) driven by a periodic Doppler input is studied. By expanding the Doppler input into a Fourier series and applying the linearized PLL approximations, it is easy to show that, for periodic frequency disturbances, the resulting steady state phase error is also periodic. Compared to the method of expanding frequency excursion into a power series, the Fourier expansion method can be used to predict the maximum phase error excursion for a periodic Doppler input. For systems with a large Doppler rate fluctuation, such as an optical transponder aboard an Earth orbiting spacecraft, the method can be applied to test whether a lower order tracking loop can provide satisfactory tracking and thereby save the effect of a higher order loop design.
Relativistic nuclear hydrodynamics and phase transition to the deconfinement state
Barz, H.W.; Kaempfer, B.; Lukacs, B.
1987-11-01
The possible formation of nuclear matter in the phase of a quark--gluon plasma in relativistic heavy-ion collisions is considered in the framework of a hydrodynamic approach. The main results are obtained in a single-fluid model of the formation of a baryon-enriched plasma and relate to nuclear collisions at energies up to 10 GeV/nucleon. At higher energies, a two-fluid model predicts the formation of a plasma in the fragmentation region, but the baryon density is much lower. In all the investigations, including scaling hydrodynamics in the baryon-depleted region of intermediate rapidities, allowance is made for a delayed phase transition to the deconfinement state. A generally covariant formulation of relativistic hydrodynamics is presented as a useful numerical method, together with some extensions of the methods of the standard theory (selection of comoving coordinates, allowance for sink terms, and two-fluid interaction).
Parameter estimation of qubit states with unknown phase parameter
NASA Astrophysics Data System (ADS)
Suzuki, Jun
2015-02-01
We discuss a problem of parameter estimation for quantum two-level system, qubit system, in presence of unknown phase parameter. We analyze trade-off relations for mean square errors (MSEs) when estimating relevant parameters with separable measurements based on known precision bounds; the symmetric logarithmic derivative (SLD) Cramér-Rao (CR) bound and Hayashi-Gill-Massar (HGM) bound. We investigate the optimal measurement which attains the HGM bound and discuss its properties. We show that the HGM bound for relevant parameters can be attained asymptotically by using some fraction of given n quantum states to estimate the phase parameter. We also discuss the Holevo bound which can be attained asymptotically by a collective measurement.
Particle Rebound and Phase State of Secondary Organic Material
NASA Astrophysics Data System (ADS)
Bateman, A.; Bertram, A. K.; Martin, S. T.
2014-12-01
Secondary organic material (SOM) is produced in the atmosphere from the oxidation of volatile organic compounds emitted from anthropogenic and biogenic sources. Aerosol particles, composed in part of SOM, play important roles in climate and air quality by scattering/absorbing radiation and serving as cloud condensation nuclei (CCN). The magnitude of climate-relevant perturbations depends on particle chemical composition, hygroscopic growth, and phase state, among other factors. Herein, the hygroscopic influence on particle rebound and the phase state of particles composed of isoprene, toluene, and α-pinene secondary organic material (SOM) was studied. Particle rebound measurements were obtained from 5 to 95% RH using a three-arm impaction apparatus. The experimentally determined rebound fractions were compared with results from a model of the rebound process that took into account the particle kinetic energy, van der Waals forces, and RH-dependent capillary forces. Comparison of the experimental and modeled indicated particles softened due to water uptake. For low RH values, the model explained the rebound behavior for all studied SOMs. At higher RH values specific to each SOM, however, particle rebound was no longer observed, and the model did not capture this behavior. Calibration experiments using sucrose particles of variable known viscosities showed the transition from non-rebounding to rebounding particles occurred for viscosity values from 100 to 1 Pa s, corresponding to a transition from semisolid to liquid material. The implication of the differing RH-dependent behaviors among the SOMs is that each SOM has a specific and quantitatively different interaction with water. A linear correlation between rebound fraction and hygroscopic growth factor was demonstrated, implying that absorbed water volume is the governing factor of viscosity for the studied classes of SOM. The findings of this study suggest that both the chemical composition and the ambient
Economical Gaussian cloning of coherent states with known phase
Dong Yuli; Zou Xubo; Guo Guangcan; Li Shangbin
2007-07-15
We investigate the economical Gaussian cloning of coherent states with the known phase, which produces M copies from N input replica and can be implemented with degenerate parametric amplifiers and beam splitters.The achievable fidelity of single copy is given by 2M{radical}(N)/[{radical}(N)(M-1)+{radical}((1+N)(M{sup 2}+N))], which is bigger than the optimal fidelity of the universal Gaussian cloning. The cloning machine presented here works without ancillary optical modes and can be regarded as the continuous variable generalization of the economical cloning machine for qudits.
Geometric phases causing lifetime modifications of metastable states of hydrogen
NASA Astrophysics Data System (ADS)
Trappe, Martin-Isbjörn; Augenstein, Peter; DeKieviet, Maarten; Gasenzer, Thomas; Nachtmann, Otto
2016-04-01
Externally applied electromagnetic fields in general have an influence on the width of atomic spectral lines. The decay rates of atomic states can also be affected by the geometry of an applied field configuration giving rise to an imaginary geometric phase. A specific chiral electromagnetic field configuration is presented which geometrically modifies the lifetimes of metastable states of hydrogen. We propose to extract the relevant observables in a realistic longitudinal atomic beam spin-echo apparatus which allows the initial and final fluxes of the metastable atoms to be compared with each other interferometrically. A geometry-induced change in lifetimes at the 5%-level is found, an effect large enough to be observed in an available experiment.
Semiclassical Dynamics of Electron Wave Packet States with Phase Vortices
Bliokh, Konstantin Yu.; Bliokh, Yury P.; Savel'ev, Sergey; Nori, Franco
2007-11-09
We consider semiclassical higher-order wave packet solutions of the Schroedinger equation with phase vortices. The vortex line is aligned with the propagation direction, and the wave packet carries a well-defined orbital angular momentum (OAM) ({Dirac_h}/2{pi})l (l is the vortex strength) along its main linear momentum. The probability current coils around the momentum in such OAM states of electrons. In an electric field, these states evolve like massless particles with spin l. The magnetic-monopole Berry curvature appears in momentum space, which results in a spin-orbit-type interaction and a Berry/Magnus transverse force acting on the wave packet. This brings about the OAM Hall effect. In a magnetic field, there is a Zeeman interaction, which, can lead to more complicated dynamics.
Absorbing State Phase Transition with Competing Quantum and Classical Fluctuations
NASA Astrophysics Data System (ADS)
Marcuzzi, Matteo; Buchhold, Michael; Diehl, Sebastian; Lesanovsky, Igor
2016-06-01
Stochastic processes with absorbing states feature examples of nonequilibrium universal phenomena. While the classical regime has been thoroughly investigated in the past, relatively little is known about the behavior of these nonequilibrium systems in the presence of quantum fluctuations. Here, we theoretically address such a scenario in an open quantum spin model which, in its classical limit, undergoes a directed percolation phase transition. By mapping the problem to a nonequilibrium field theory, we show that the introduction of quantum fluctuations stemming from coherent, rather than statistical, spin flips alters the nature of the transition such that it becomes first order. In the intermediate regime, where classical and quantum dynamics compete on equal terms, we highlight the presence of a bicritical point with universal features different from the directed percolation class in a low dimension. We finally propose how this physics could be explored within gases of interacting atoms excited to Rydberg states.
Absorbing State Phase Transition with Competing Quantum and Classical Fluctuations.
Marcuzzi, Matteo; Buchhold, Michael; Diehl, Sebastian; Lesanovsky, Igor
2016-06-17
Stochastic processes with absorbing states feature examples of nonequilibrium universal phenomena. While the classical regime has been thoroughly investigated in the past, relatively little is known about the behavior of these nonequilibrium systems in the presence of quantum fluctuations. Here, we theoretically address such a scenario in an open quantum spin model which, in its classical limit, undergoes a directed percolation phase transition. By mapping the problem to a nonequilibrium field theory, we show that the introduction of quantum fluctuations stemming from coherent, rather than statistical, spin flips alters the nature of the transition such that it becomes first order. In the intermediate regime, where classical and quantum dynamics compete on equal terms, we highlight the presence of a bicritical point with universal features different from the directed percolation class in a low dimension. We finally propose how this physics could be explored within gases of interacting atoms excited to Rydberg states. PMID:27367395
Equilibrator: Modeling Chemical Equilibria with Excel
ERIC Educational Resources Information Center
Vander Griend, Douglas A.
2011-01-01
Equilibrator is a Microsoft Excel program for learning about chemical equilibria through modeling, similar in function to EQS4WIN, which is no longer supported and does not work well with newer Windows operating systems. Similar to EQS4WIN, Equilibrator allows the user to define a system with temperature, initial moles, and then either total…
Equilibria with incompressible flows from symmetry analysis
Kuiroukidis, Ap E-mail: gthroum@cc.uoi.gr; Throumoulopoulos, G. N. E-mail: gthroum@cc.uoi.gr
2015-08-15
We identify and study new nonlinear axisymmetric equilibria with incompressible flow of arbitrary direction satisfying a generalized Grad Shafranov equation by extending the symmetry analysis presented by Cicogna and Pegoraro [Phys. Plasmas 22, 022520 (2015)]. In particular, we construct a typical tokamak D-shaped equilibrium with peaked toroidal current density, monotonically varying safety factor, and sheared electric field.
Equations of state and phase transitions in stellar matter
Raduta, Ad. R.; Gulminelli, F.; Aymard, F.; Oertel, M.; Margueron, J.
2014-05-09
Realistic description of core-collapsing supernovae evolution and structure of proto-neutron stars chiefly depends on microphysics input in terms of equations of state, chemical composition and weak interaction rates. At sub-saturation densities the main uncertainty comes from the symmetry energy. Within a nuclear statistical equilibrium (NSE) model with consistent treatment of clusterized and unbound components we investigate the meaning of symmetry energy in the case of dis-homogeneous systems, as the one thought to constitute the neutron star crust, and its sensitivity to the isovector properties of the effective interaction. At supra-saturation densities the situation is much more difficult because of the poor knowledge of nucleon-hyperon and hyperon-hyperon interactions and thermodynamic behavior in terms of phase transitions. Within a simple (npΛ) model we show that compressed baryonic matter with strangeness manifests a complex phase diagram with first and second order phase transitions. The fact that both are explored under strangeness chemical equilibrium and survive Coulomb suggests that they might have sizable consequences on star evolution. An example in this sense is the drastic reduction of the neutrino-mean free path in the vicinity of the critical point obtained within RPA which would lead to a less rapid star cooling.
Metastable Equilibria Among Aqueous Organic Compounds
NASA Astrophysics Data System (ADS)
Shock, E.; Shipp, J.; Yang, Z.; Gould, I. R.
2011-12-01
Metastable equilibrium states exist when reactions among a subset of compounds in a chemical system are reversible even though other irreversible reactions exist in the same system. The existence of metastable equilibrium among organic compounds was initially detected by comparing ratios of organic acid concentrations reported for oil-field brines (Shock, 1988, Geology 16, 886-890; Shock, 1989, Geology 17, 572-573), and calculating the same ratios for likely oxidation states determined by mineral assemblages and mixtures of hydrocarbons in coexisting petroleum (Shock, 1994, in: The Role of Organic Acids in Geological Processes, Springer). This led to the notion of extending the concept of metastable equilibrium states to explicitly account for petroleum compositions (Helgeson et al., 1993, GCA, 57, 3295-3339), which eventually yielded the concept of hydrolytic disproportionation of kerogens to produce petroleum and CO2(g) (Helgeson et al., 2009, GCA, 73, 594-695). Experimental tests of metastable equilibrium among organic compounds began with the identification of reversible reactions between alkanes and alkenes that are dependent on the H2 fugacity of the experimental system (Seewald, 1994, Nature 370, 285-287). These were followed with a comprehensive series of long-term experiments leading to the hypothesis that reversible reactions include alkanes, alkenes, alcohol, aldehydes, ketones and carboxylic acids (e.g., Seewald, 2001, GCA 65, 1641-1664; 2003, Nature 426, 327-333; McCollom & Seewald, 2003, GCA 67, 3645-3664). We have conducted sets of hydrothermal organic transformation experiments that test the extent to which these reactions are indeed reversible using aromatic and cyclic compounds. Results demonstrate reversibility for reactions among dibenzyl ketone, 1,3-diphenyl-2-propanol, 1,3-diphenylpropene and 1,3-diphenylpropane, as well as among methylcyclohexanes, methylcyclohexenes, methylcyclohexanols, methylcyclohexanones and methylcyclohexadienes. The
Metastable states in calcium phosphate - aqueous phase equilibrations
NASA Astrophysics Data System (ADS)
Driessens, F. C. M.; Verbeeck, R. M. H.
1981-05-01
A critical evaluation of the literature reveals that during equilibration of well crystallized hydroxyapatite in aqueous solutions metastable states can occur. They are characterized by a persistent supersaturation with respect to hydroxyapatite and a systematical dependence of the ion activity product of this compound on the solution composition. For products synthesized by thermal treatment it is known that they are transformed into oxyhydroxyapatite so that the theoretical solubility behaviour could be predicted from the extrapolated value of the free energy of oxyapatite at room temperature: the negative logarithm of the ionic product for hydroxyapatite should become close to that of oxyapatite during equilibration. The discrepancy with experimental data is probably due to the formation of thin layers seeming dicalcium phosphate dihydrate, octocalcium phosphate or defective hydroxyapatite as coatings on the apatite crystals. This is derived from the apparent Ca/P ratio of the solubility controlling phase. According to chemical potential plots this apparent Ca/P ratio can have values close to 1, 1.33, 1.50 or 1.67. The aqueous solutions are clearly undersaturated with respect to the more acidic calcium phosphates so that the coatings must deviate from the compositions of these compounds in their pure state. The formation of these metastable states during equilibration of oxyhydroxyapatites is compared with others occuring during precipitation and crystal growth of calcium phosphates. A model is proposed which explains the observations qualitatively.
Structural-phase state and creep of mixed nitride fuel
NASA Astrophysics Data System (ADS)
Konovalov, I. I.; Tarasov, B. A.; Glagovsky, E. M.
2016-04-01
By the analysis of thermal creep data in conjunction with structural-phase state the most likely mechanisms of UN creep are considered. An equation relating the thermal and radiation creep of nitride fuel with such important parameters as plutonium content, porosity, grain size, the content of impurities of transition metals and oxygen, the carbon content has been suggested. At stationary operating parameters in reactor the creep of nitride fuel with technical purity is defined by the thermal component at mechanism of intergranular slip and by the radiation component, which plays a significant role at temperatures below 1100°C. Both types of creep in a first approximation have a linear dependence on the stress.
Stability of Hall equilibria in neutron star crusts
Marchant, Pablo; Reisenegger, Andreas; Valdivia, Juan Alejandro; Hoyos, Jaime H.
2014-12-01
In the solid crusts of neutron stars, the advection of the magnetic field by the current-carrying electrons, an effect known as Hall drift, should play a very important role as the ions remain essentially fixed (as long as the solid does not break). Although Hall drift preserves the magnetic field energy, it has been argued that it may drive a turbulent cascade to scales at which ohmic dissipation becomes effective, allowing a much faster decay in objects with very strong fields. On the other hand, it has been found that there are 'Hall equilibria', i.e., field configurations that are unaffected by Hall drift. Here we address the crucial question of the stability of these equilibria through axially symmetric (two-dimensional (2D)) numerical simulations of Hall drift and ohmic diffusion, with the simplifying assumption of uniform electron density and conductivity. We demonstrate the 2D stability of a purely poloidal equilibrium, for which ohmic dissipation makes the field evolve toward an attractor state through adjacent stable configurations, around which damped oscillations occur. For this field, the decay scales with the ohmic timescale. We also study the case of an unstable equilibrium consisting of both poloidal and toroidal field components that are confined within the crust. This field evolves into a stable configuration, which undergoes damped oscillations superimposed on a slow evolution toward an attractor, just as the purely poloidal one.
Symmetry breaking of quasihelical stellarator equilibria
Weening, R.H. )
1993-04-01
A mean-field Ohm's law is used to determine the effects of the bootstrap current on quasihelically symmetric stellarator equilibria. The Ohm's law leads to the conclusion that the effects of the bootstrap current break the quasihelical stellarator symmetry at second order in an inverse aspect ratio expansion of the magnetic field strength. The level of symmetry breaking suggests that good approximations to quasihelical stellarator fusion reactors may not be attainable.
Magnetohydrodynamic equilibria with incompressible flows: Symmetry approach
Cicogna, G.; Pegoraro, F.
2015-02-15
We identify and discuss a family of azimuthally symmetric, incompressible, magnetohydrodynamic plasma equilibria with poloidal and toroidal flows in terms of solutions of the Generalized Grad Shafranov (GGS) equation. These solutions are derived by exploiting the incompressibility assumption, in order to rewrite the GGS equation in terms of a different dependent variable, and the continuous Lie symmetry properties of the resulting equation and, in particular, a special type of “weak” symmetries.
ON MAGNETIC EQUILIBRIA IN BAROTROPIC STARS
Armaza, Cristóbal; Reisenegger, Andreas; Valdivia, Juan Alejandro
2015-04-01
Upper main-sequence stars, white dwarfs, and neutron stars are known to possess stable, large-scale magnetic fields. Numerical works have confirmed that stable magnetohydrodynamic equilibria can exist in non-barotropic, stably stratified stars. On the other hand, it is unclear whether stable equilibria are possible in barotropic stars, although the existing evidence suggests that they are all unstable. This work aims to construct barotropic equilibria in order to study their properties, as a first step to test their stability. We have assumed that the star is a perfectly conducting, axially symmetric fluid, allowing for both poloidal and toroidal components of the magnetic field. In addition, we made the astrophysically justified assumption that the magnetic force has a negligible influence on the fluid structure, in which case the equilibrium is governed by the Grad–Shafranov equation, involving two arbitrary functions of the poloidal flux. We built a numerical code to solve this equation, allowing for an arbitrary prescription for these functions. Taking particularly simple, but physically reasonable choices for these functions with a couple of adjustable parameters, all of the equilibria found present only a small (≲10%) fraction of the magnetic energy stored in the toroidal component, confirming previous results. We developed an analytical model in order to study in more detail the behavior of the magnetic energy over the full range of parameters. The model confirms that the toroidal fraction of the energy and the ratio of toroidal to poloidal flux are bounded from above for the whole range of parameters.
Relative Equilibria in Continuous Stellar Dynamics
NASA Astrophysics Data System (ADS)
Campos, Juan; Del Pino, Manuel; Dolbeault, Jean
2010-12-01
We study a three dimensional continuous model of gravitating matter rotating at constant angular velocity. In the rotating reference frame, by a finite dimensional reduction, we prove the existence of non-radial stationary solutions whose supports are made of an arbitrarily large number of disjoint compact sets, in the low angular velocity and large scale limit. At first order, the solutions behave like point particles, thus making the link with the relative equilibria in N-body dynamics.
Close relative equilibria of identical point vortices
NASA Astrophysics Data System (ADS)
Dirksen, Tobias; Aref, Hassan
2011-11-01
Via numerical solution of the classical problem of relative equilibria for identical point vortices on the unbounded plane we have found configurations that are very close to the analytically known, centered, symmetrically arranged, nested equilateral triangles. Numerical solutions of this kind were found for 3 n + 1 vortices, where n = 2 , 3 , ... , 30 . A sufficient, although apparently not necessary, condition for this phenomenon of close solutions is that the ``core'' of the configuration is marginally stable, as occurs for a central vortex surrounded by an equilateral triangle. The open, regular heptagon also has this property, and new relative equilibria close to the nested, symmetrically arranged, regular heptagons have been found. The centered regular nonagon is also marginally stable. Again, a new family of close relative equilibria has been found. The closest relative equilibrium pairs occur, however, for symmetrically nested equilateral triangles. The numerical evidence is surveyed and related recent work mentioned. A Letter in Physics of Fluids 23 (2011) 051706 is available. Supported in part by the Danish National Research Foundation through a Niels Bohr visiting professorship.
Extended MHD Stabiliy Calculations of Spheromak Equilibria
NASA Astrophysics Data System (ADS)
Howell, E. C.; Sovinec, C. R.
2013-10-01
Linear extended MHD calculations of spheromak equilibria in a cylindrical flux conserver are performed using the NIMROD code (Sovinec et al., JCP 195, 2004). A series of Grad-Sharfranov equilibria are generated with β ranging from 0 . 4 % to 4 . 2 % , corresponding to peak electron temperatures ranging 50 to 300 eV. These equilibria use a λ profile representative of SSPX shot 14590, which measured a peak electron temperature of 325 eV (McLean et al., POP 13, 2006). Resistive MHD calculations find that the β = 0 . 4 % case is unstable to resonant resistive interchange modes with γτA <= 2 . 3 % . These modes transition to ideal interchange as the equilibrium pressure is increased. Growth rates as large as γτA = 20 % are calculated for the 4 . 2 % β case. Calculations including ion-gyroviscosity show a minimal reduction of growth rate. Effects from including the Hall and Electron pressure terms in Ohm's Law and the cross-field diamagnetic heat flux are investigated. Results of related nonlinear simulations are also presented. Work Supported by US DOE.
Finding plasma equilibria with magnetic islands
Miller, G.; Faber, V.; White A.B. Jr.
1988-12-01
The traditional method of solving the helically symmetric plasma equilibrium equation, of the form L(G) = F(G, r) where L is an elliptic linear operator, has been the simple iteration L(G/sup n//sup +1/) = F(G/sup n/, r). A model of a Tokomak equilibrium is constructed and used to illustrate the divergence of the simple iteration for plasma equilibria with magnetic islands. Although the problem of equilibria with magnetic islands is two dimensional, for small islands the numerical stability of the simple iteration may be analyzed using a one-dimensional equation similar to the linearized equilibrium equation used to analyze physical (resistive) instability. This analysis is used to prove that any equilibria of the Tokamak type with small islands cannot be obtained by the simple iteration and to illustrate the superlinear convergence of Newton's method on these problems. The implementation of Newton's method is discussed and examples are given. copyright 1988 Academic Press, Inc.
Fixed boundary toroidal plasma equilibria with toroidal flows
NASA Astrophysics Data System (ADS)
Hu, Yanqiang; Hu, Yemin; Xiang, Nong
2016-04-01
The fixed boundary toroidal plasma equilibria with toroidal flows are investigated by solving the modified Grad-Shafranov equation numerically in the cylindrical coordinate system. For normal equilibrium configurations with geometry and profiles similar to usual tokamaks with no flow, it is found that the effect of flow is to lead to an outward shift of the magnetic flux surfaces, together with the profiles of pressure, and mass and current densities. The shifts could become significant when the toroidal flow Mach number exceeds 0.5. For non-conventional current profiles, even for the usual tokamak geometry, novel current reversal equilibrium configurations may result, sometimes with changed topology in the poloidal flux function. This change in the topology of plasma equilibrium can be attributed to the large toroidal flow. The computed results may correspond to situations of intense tangential injection during the low toroidal current phase in expected experimental situations.
NASA Astrophysics Data System (ADS)
Kahlenberg, Volker; Maier, Matthias
2016-06-01
Singe crystals of a new high-temperature polymorph of Na2Ca6Si4O15 have been obtained from solid state reactions performed at 1300 °C. The basic crystallographic data of this so-called β-phase at ambient conditions are as follows: space group P1c1, a = 9.0112(5) Å, b = 7.3171(5) Å, c = 10.9723(6) Å, β = 107.720(14)°, V = 689.14(7) Å3, Z = 2. The crystals showed twinning by reticular merohedry (mimicking an orthorhombic C-centred unit cell) which was accounted for during data processing and structure solution. Structure determination was accomplished by direct methods. Least-squares refinements resulted in a residual of R(|F|) = 0.043 for 5811 observed reflections with I > 2σ(I). From a structural point of view β-Na2Ca6Si4O15 can be attributed to the group of mixed-anion silicates containing [Si2O7]-dimers as well as isolated [SiO4]-tetrahedra in the ratio 1:2, i.e. more precisely the formula can be written as Na2Ca6[SiO4]2[Si2O7]. The tetrahedral groups are arranged in layers parallel to (100). Sodium and calcium cations are located between the silicate anions for charge compensation and are coordinated by six to eight nearest oxygen ligands. Alternatively, the structure can be described as a mixed tetrahedral-octahedral framework based on kröhnkite-type [Ca(SiO4)2O2]-chains in which the CaO6-octahedra are corner-linked to bridging SiO4-tetrahedra. The infinite chains are running parallel to [001] and are concentrated in layers parallel to (010). Adjacent layers are shifted relative to each other by an amount of +δ or -δ along a*. Consequently, a …ABABAB… stacking sequence is created. A detailed comparison with related structures such as α-Na2Ca6Si4O15 and other A2B6Si4O15 representatives including topological as well as group theoretical aspects is presented. There are strong indications that monoclinic Na2Ca3Si2O8 mentioned in earlier studies is actually misinterpreted β-Na2Ca6Si4O15. In addition to the detailed crystallographic analysis of the
Social Interactions under Incomplete Information: Games, Equilibria, and Expectations
NASA Astrophysics Data System (ADS)
Yang, Chao
Interactions under Incomplete Information", is an application of the first chapter to censored outcomes, corresponding to the situation when agents" behaviors are subjected to some binding restrictions. In an interesting empirical analysis for property tax rates set by North Carolina municipal governments, it is found that there is a significant positive correlation among near-by municipalities. Additionally, some private information about its own residents is used by a municipal government to predict others' tax rates, which enriches current empirical work about tax competition. The third chapter, "Social Interactions under Incomplete Information with Multiple Equilibria", extends the first chapter by investigating effective estimation methods when the condition for a unique equilibrium may not be satisfied. With multiple equilibria, the previous model is incomplete due to the unobservable equilibrium selection. Neither conventional likelihoods nor moment conditions can be used to estimate parameters without further specifications. Although there are some solutions to this issue in the current literature, they are based on strong assumptions such as agents with the same observable characteristics play the same strategy. This paper relaxes those assumptions and extends the all-solution method used to estimate discrete choice games to a setting with both discrete and continuous choices, bounded and unbounded outcomes, and a general form of incomplete information, where the existence of a pure strategy equilibrium has been an open question for a long time. By the use of differential topology and functional analysis, it is found that when all exogenous characteristics are public information, there are a finite number of equilibria. With privately known exogenous characteristics, the equilbria can be represented by a compact set in a Banach space and be approximated by a finite set. As a result, a finite-state probability mass function can be used to specify a probability measure
Geometric phase of mixed states for three-level open systems
Jiang Yanyan; Ji, Y. H.; Wang, Z. S.; Xu Hualan; Hu Liyun; Chen, Z. Q.; Guo, L. P.
2010-12-15
Geometric phase of mixed state for three-level open system is defined by establishing in connecting density matrix with nonunit vector ray in a three-dimensional complex Hilbert space. Because the geometric phase depends only on the smooth curve on this space, it is formulated entirely in terms of geometric structures. Under the limiting of pure state, our approach is in agreement with the Berry phase, Pantcharatnam phase, and Aharonov and Anandan phase. We find that, furthermore, the Berry phase of mixed state correlated to population inversions of three-level open system.
A Magnetic Diagnostic Code for 3D Fusion Equilibria
Samuel A. Lazerson, S. Sakakibara and Y. Suzuki
2013-03-12
A synthetic magnetic diagnostics code for fusion equilibria is presented. This code calculates the response of various magnetic diagnostics to the equilibria produced by the VMEC and PIES codes. This allows for treatment of equilibria with both good nested flux surfaces and those with stochastic regions. DIAGNO v2.0 builds upon previous codes through the implementation of a virtual casing principle. The code is validated against a vacuum shot on the Large Helical Device (LHD) where the vertical field was ramped. As an exercise of the code, the diagnostic response for various equilibria are calculated on the LHD.
A Magnetic Diagnostic Code for 3D Fusion Equilibria
Samuel Aaron Lazerson
2012-07-27
A synthetic magnetic diagnostics code for fusion equilibria is presented. This code calculates the response of various magnetic diagnostics to the equilibria produced by the VMEC and PIES codes. This allows for treatment of equilibria with both good nested flux surfaces and those with stochastic regions. DIAGNO v2.0 builds upon previous codes through the implementation of a virtual casing principle. The codes is validated against a vacuum shot on the Large Helical Device where the vertical field was ramped. As an exercise of the code, the diagnostic response for various equilibria are calculated on the Large Helical Device (LHD).
Phases of non-extremal multi-centered bound states
NASA Astrophysics Data System (ADS)
Chowdhury, Borun D.; Mayerson, Daniel R.; Vercnocke, Bert
2013-12-01
We investigate the phase space of multi-centered near-extremal configurations previously studied in arXiv:1108.5821 [1] and arXiv:1110.5641 [2] in the probe limit. We confirm that in general the energetically favored ground state of the multi-center potential, which can be a single or multi-center configuration, has the most entropy and is thus thermodynamically stable. However, we find the surprising result that for a subset of configurations, even though a single center black hole seems to be energetically favored, it is entropically not allowed (the resulting black hole would violate cosmic censorship). This disproves classical intuition that everything would just fall into the black hole if energetically favored. Along the way we highlight a shortcoming in the literature regarding the computation of the angular momentum coming from electromagnetic interaction in the probe limit and rectify it. We also demonstrate that static supertubes can exist inside ergoregions where ordinary point particles would be frame dragged.
Phase-Conjugate Receiver for Gaussian-State Quantum Illumination
NASA Technical Reports Server (NTRS)
Erkmen, Baris I.; Guha, Saikat
2010-01-01
An active optical sensor probes a region of free space that is engulfed in bright thermal noise to determine the presence (or absence) of a weakly reflecting target. The returned light (which is just thermal noise if no target is present, and thermal noise plus a weak reflection of the probe beam if a target is present) is measured and processed by a receiver and a decision is made on whether a target is present. It has been shown that generating an entangled pair of photons (which is a highly nonclassical state of light), using one photon as the probe beam and storing the other photon for comparison to the returned light, has superior performance to the traditional classical-light (coherent-state) target detection sensors. An entangled-photon transmitter and optimal receiver combination can yield up to a factor of 4 (i.e., 6 dB) gain in the error-probability exponent over a coherent state transmitter and optimal receiver combination, in a highly lossy and noisy scenario (when both sensors have the same number of transmitted photons). However, the receiver that achieves this advantage is not known. One structured receiver can close half of the 6-dB gap (i.e., a 3-dB improvement). It is based on phase-conjugating the returned light, then performing dual-balanced difference detection with the stored half of the entangled-photon pair. Active optical sensors are of tremendous value to NASA s missions. Although this work focuses on target detection, it can be extended to imaging (2D, 3D, hyperspectral, etc.) scenarios as well, where the image quality can be better than that offered by traditional active sensors. Although the current work is theoretical, NASA s future missions could benefit significantly from developing and demonstrating this capability. This is an optical receiver design whose components are, in principle, all implementable. However, the work is currently entirely theoretical. It is necessary to: 1. Demonstrate a bench-top proof of the theoretical
Quantum theory of the smectic metal state in stripe phases
Emery; Fradkin; Kivelson; Lubensky
2000-09-01
We present a theory of the electron smectic fixed point of the stripe phases of doped layered Mott insulators. We show that in the presence of a spin gap three phases generally arise: (a) a smectic superconductor, (b) an insulating stripe crystal, and (c) a smectic metal. The latter phase is a stable two-dimensional anisotropic non-Fermi liquid. In the absence of a spin gap there is also a more conventional Fermi-liquid-like phase. The smectic superconductor and smectic metal phases (or glassy versions thereof) may have already been seen in Nd-doped La2-xSrxCuO4.
Bootstrap currents in radio-frequency-driven tokamak equilibria
Hsiao, Ming-Yuan; Ehst, D.A.; Evans, K. Jr.
1988-05-01
Interest in the bootstrap current arising from neoclassical transport in tokamaks has increased recently in view of certain experimental observations. In this study, the bootstrap current is calculated for a number of rf current-driven tokamaks. Two-dimensional, self-consistent, steady-state tokamak MHD equilibria are obtained by including both the transport-driven bootstrap current and the externally driven rf current. The self-consistency is acomplished by iterating between two-dimensional MHD equilibrium calculations and the current calculations (including bootstrap and rf ray-tracing). Calculations for other reactor parameters of interest are also carried out. It is found that for reactor-grade plasmas, the bootstrap current contribution to the toroidal current is, in general, important. An approxiamte scaling law for GAMMA, based on parametric survey performed, is also obtained. 16 refs., 8 figs., 1 tab.
NASA Astrophysics Data System (ADS)
Ban, Masashi
1999-08-01
Phase-space representation of quantum state vectors has been recently formulated by means of the relative-state method developed by the present author [J. Math. Phys. 39, 1744 (1998)]. It is, however, pointed out by Mo/ller that the displacement-operator method provides another basis of phase-space representation of quantum state vectors [J. Math. Phys. (to appear)]. Hence the relation between the relative-state approach and the displacement-operator approach is discussed, both of which yield equivalent phase-space representations.
ERIC Educational Resources Information Center
Bindel, Thomas H.
2007-01-01
An activity is presented in which the thermodynamics of simultaneous, consecutive equilibria are explored. The activity is appropriate for second-year high school or AP chemistry. Students discover that a reactant-favored (entropy-diminishing or endergonic) reaction can be caused to happen if it is coupled with a product-favored reaction of…
Phase correlation of ensemble of quantum emitters and timed Dicke state
NASA Astrophysics Data System (ADS)
Yoon, Jae Seok; Hong, Suc-Kyoung; Nam, Seog Woo; Yang, Hyung Jin
2016-06-01
We study the phase-correlated state which is introduced by the instantaneous excitation of an ensemble of identical two-level quantum emitters and its relation with the Dicke states. Under weak coupling regime, the time evolution of the phase-correlated system of the emitters is also derived to see the characteristics of the collective spontaneous emission of the emitters. It is found that the effective coupling of the ensemble in the phase-correlated state with the emitted field is directly determined by the collective phase of the system. Hence, the collective phase is considered for several specified distributions in brief.
Hydrolysis of iodine: equilibria at high temperatures
Palmer, D.A.; Ramette, R.W.; Mesmer, R.E.
1984-01-01
The hydrolysis (or disproportionation) of molecular iodine to form iodate and iodide ions has been studied by emf measurements over the temperature range, 3.8/sup 0/ to 209.0/sup 0/C. The interpretation of these results required a knowledge of the formation constant for triiodide ion and the acid dissociation constant of iodic acid, both of which were measured as a function of temperature. The resulting thermodynamic data have been incorporated into a general computer model describing the hydrolysis equilibria of iodine as a function of initial concentration, pH and temperature.
Metal biosorption equilibria in a ternary system
Chong, K.H.; Volesky, B.
1996-03-20
Equilibrium metal uptake performance of a biosorbent prepared from Ascophyllum nodosum seaweed biomass was studied using aqueous solutions containing copper, cadmium, and zinc ions in binary and ternary mixtures. Triangular equilibrium diagrams can graphically represent all the ternary equilibrium sorption data. Application of the multicomponent Langmuir model to describe the three-metal system revealed its nonideal characteristics, whereby the value of apparent dissociation constants for the respective metals differed for each system. This restricted the prediction of the ternary equilibria from the binary systems. However, some predictions of the ternary system behavior from the model were consistent with experimental data and with conclusions postulated from the three possible binary subsystems.
Inverse moments equilibria for helical anisotropic systems
NASA Astrophysics Data System (ADS)
Cooper, W. A.; Hirshman, S. P.; Depassier, M. C.
1987-11-01
An energy functional is devised for magnetic confinement schemes that have anisotropic plasma pressure. The minimization of this energy functional is demonstrated to reproduce components of the magnetohydrodynamic (MHD) force balance relation in systems with helical symmetry. An iterative steepest descent procedure is applied to the Fourier moments of the inverse magnetic flux coordinates to minimize the total energy and thus generate anisotropic pressure MHD equilibria. Applications to straight ELMO Snaky Torus (NTIS Document No. DE-84002406) configurations that have a magnetic well on the outermost flux surfaces have been obtained.
NASA Astrophysics Data System (ADS)
Yang, Ji-min; Zhang, Rui-zhi; Liu, Hong; Ma, Si-hong
2013-12-01
The solubilities in the NaCl-MgCl2-H2O system were determined at 50 and 75°C and the phase diagrams were constructed on the base of experimental data. One invariant point, two univariant curves, and two crystallization zones, corresponding to sodium chloride and dihydrate (MgCl2 · 6H2O) showed up in the phase diagrams of the ternary system, The mixing parameters θNa,Mg and ΨNa,Mg, Cl and equilibrium constant K sp were evaluated in NaCl-MgCl2-H2O system by least-squares optimization procedure, in which the single-salt Pitzer parameters of NaCl and MgCl2β(0), β(1), and C φ were directly calculated from the literature. The results obtained were in good agreement with the experimental data.
Quantum Theory of the Smectic Metal State in Stripe Phases
Emery, V. J.; Fradkin, E.; Kivelson, S. A.; Lubensky, T. C.
2000-09-04
We present a theory of the electron smectic fixed point of the stripe phases of doped layered Mott insulators. We show that in the presence of a spin gap three phases generally arise: (a) a smectic superconductor, (b) an insulating stripe crystal, and (c) a smectic metal. The latter phase is a stable two-dimensional anisotropic non-Fermi liquid. In the absence of a spin gap there is also a more conventional Fermi-liquid-like phase. The smectic superconductor and smectic metal phases (or glassy versions thereof) may have already been seen in Nd-doped La{sub 2-x}Sr {sub x}CuO{sub 4} . (c) 2000 The American Physical Society.
Demonstrating the Possibility of Pareto Inferior Nash Equilibria.
ERIC Educational Resources Information Center
Vriend, Nicolaas J.
2000-01-01
Describes a classroom game that demonstrates to students that equilibria can occur naturally in order to encourage students to take unreasonable equilibria more seriously. Discusses the game, how to organize it in the classroom for a game theory course, and the results. (CMK)
Wong-Ng, W.; Laws, W.; Talley, K.R.; Huang, Q.; Yan, Y.; Martin, J.; Kaduk, J.A.
2014-07-01
The phase diagram of the CaO–1/2 Nd{sub 2}O{sub 3}–CoO{sub z} system at 885 °C in air has been determined. The system consists of two calcium cobaltate compounds that have promising thermoelectric properties, namely, the 2D thermoelectric oxide solid solution, (Ca{sub 3−x}Nd{sub x})Co{sub 4}O{sub 9−z} (0≤x≤0.5), which has a misfit layered structure, and Ca{sub 3}Co{sub 2}O{sub 6} which consists of 1D chains of alternating CoO{sub 6} trigonal prisms and CoO{sub 6} octahedra. Ca{sub 3}Co{sub 2}O{sub 6} was found to be a point compound without the substitution of Nd on the Ca site. The reported Nd{sub 2}CoO{sub 4} phase was not observed at 885 °C. A ternary (Ca{sub 1−x}Nd{sub 1+x})CoO{sub 4−z} (x=0) phase, or (CaNdCo)O{sub 4−z}, was found to be stable at this temperature. A solid solution region of distorted perovskite (Nd{sub 1−x}Ca{sub x})CoO{sub 3−z} (0≤x≤0.25, space group Pnma) was established. In the peripheral binary systems, while a solid solution region was identified for (Nd{sub 1−x}Ca{sub x}){sub 2}O{sub 3−z} (0≤x≤0.2), Nd was not found to substitute in the Ca site of CaO. Six solid solution tie-line regions and six three-phase regions were determined in the CaO–Nd{sub 2}O{sub 3}–CoO{sub z} system in air. - Graphical abstract: Phase diagram of the 1/2 Nd{sub 2}O{sub 3}–CaO–CoO{sub x} system at 885 °C, showing the limits of various solid solutions, and the tie-line relationships of various phases. - Highlights: • Phase diagram of the CaO–1/2 Nd{sub 2}O{sub 3}–CoO{sub z} system constructed. • System consists of thermoelectric oxide (Ca{sub 3−x}Nd{sub x})Co{sub 4}O{sub 9−z} (0≤x≤0.5). • Structures of (Nd{sub 1−x}Ca{sub x})CoO{sub 3−z} and (CaNdCo)O{sub 4−z} determined.
Robust Light State by Quantum Phase Transition in Non-Hermitian Optical Materials.
Zhao, Han; Longhi, Stefano; Feng, Liang
2015-11-23
Robust light transport is the heart of optical information processing, leading to the search for robust light states by topological engineering of material properties. Here, it is shown that quantum phase transition, rather than topology, can be strategically exploited to design a novel robust light state. We consider an interface between parity-time (PT) symmetric media with different quantum phases and use complex Berry phase to reveal the associated quantum phase transition and topological nature. While the system possesses the same topological order within different quantum phases, phase transition from PT symmetry to PT breaking across the interface in the synthetic non-Hermitian metamaterial system facilitates novel interface states, which are robust against a variety of gain/loss perturbations and topological impurities and disorder. The discovery of the robust light state by quantum phase transition may promise fault-tolerant light transport in optical communications and computing.
Robust Light State by Quantum Phase Transition in Non-Hermitian Optical Materials
Zhao, Han; Longhi, Stefano; Feng, Liang
2015-01-01
Robust light transport is the heart of optical information processing, leading to the search for robust light states by topological engineering of material properties. Here, it is shown that quantum phase transition, rather than topology, can be strategically exploited to design a novel robust light state. We consider an interface between parity-time (PT) symmetric media with different quantum phases and use complex Berry phase to reveal the associated quantum phase transition and topological nature. While the system possesses the same topological order within different quantum phases, phase transition from PT symmetry to PT breaking across the interface in the synthetic non-Hermitian metamaterial system facilitates novel interface states, which are robust against a variety of gain/loss perturbations and topological impurities and disorder. The discovery of the robust light state by quantum phase transition may promise fault-tolerant light transport in optical communications and computing. PMID:26592765
Robust Light State by Quantum Phase Transition in Non-Hermitian Optical Materials
NASA Astrophysics Data System (ADS)
Zhao, Han; Longhi, Stefano; Feng, Liang
2015-11-01
Robust light transport is the heart of optical information processing, leading to the search for robust light states by topological engineering of material properties. Here, it is shown that quantum phase transition, rather than topology, can be strategically exploited to design a novel robust light state. We consider an interface between parity-time (PT) symmetric media with different quantum phases and use complex Berry phase to reveal the associated quantum phase transition and topological nature. While the system possesses the same topological order within different quantum phases, phase transition from PT symmetry to PT breaking across the interface in the synthetic non-Hermitian metamaterial system facilitates novel interface states, which are robust against a variety of gain/loss perturbations and topological impurities and disorder. The discovery of the robust light state by quantum phase transition may promise fault-tolerant light transport in optical communications and computing.
NASA Astrophysics Data System (ADS)
Zabolotnykh, S. A.; Lesnov, A. E.; Denisova, S. A.
2016-10-01
Solubility isotherms of water-sulfonol-hydrochloric (or sulfuric) acid and water-sodium dodecyl sulfate-hydrochloric acid systems at 75°C and a water-sodium dodecyl sulfate-sulfuric acid system at 50°C are constructed. Regions of two-phase liquid equilibrium suitable for use in extraction are found. Concentration parameters for extraction are determined. The interfacial distribution of a series of metal ions with and without such additional complexing reagents as diantipyrylmethane and diantipyrylheptane is studied.
NASA Astrophysics Data System (ADS)
Furukawa, Shunsuke; Sato, Masahiro; Onoda, Shigeki; Furusaki, Akira
2012-09-01
The ground-state phase diagram of a spin-(1)/(2) XXZ chain with competing ferromagnetic nearest-neighbor (J1<0) and antiferromagnetic second-neighbor (J2>0) exchange couplings is studied by means of the infinite time evolving block decimation algorithm and effective field theories. For the SU(2)-symmetric (Heisenberg) case, we show that the nonmagnetic phase in the range -4
Phase stability in the Cd-Mg system
Asta, M.; McCormack, R.; de Fontaine, D.
1993-12-31
This paper reports on results of a theoretical study of solid-state phase equilibria and short-range order in Cd-Mg alloys. Results of first-principles linear muffin-tin orbital method total-energy calculations for seven hcp-based superstructures have been combined with cluster-variation-method calculations of thermodynamic properties in order to compute the Cd-Mg phase diagram. Effect on the calculated phase diagram of contributions to the alloy free energy arising from atomic vibrations and structural relaxations are assessed using available experimental information for ordered and disordered alloys in the Cd-Mg system.
Nonambipolar Transport and Torque in Perturbed Equilibria
NASA Astrophysics Data System (ADS)
Logan, N. C.; Park, J.-K.; Wang, Z. R.; Berkery, J. W.; Kim, K.; Menard, J. E.
2013-10-01
A new Perturbed Equilibrium Nonambipolar Transport (PENT) code has been developed to calculate the neoclassical toroidal torque from radial current composed of both passing and trapped particles in perturbed equilibria. This presentation outlines the physics approach used in the development of the PENT code, with emphasis on the effects of retaining general aspect-ratio geometric effects. First, nonambipolar transport coefficients and corresponding neoclassical toroidal viscous (NTV) torque in perturbed equilibria are re-derived from the first order gyro-drift-kinetic equation in the ``combined-NTV'' PENT formalism. The equivalence of NTV torque and change in potential energy due to kinetic effects [J-K. Park, Phys. Plas., 2011] is then used to showcase computational challenges shared between PENT and stability codes MISK and MARS-K. Extensive comparisons to a reduced model, which makes numerous large aspect ratio approximations, are used throughout to emphasize geometry dependent physics such as pitch angle resonances. These applications make extensive use of the PENT code's native interfacing with the Ideal Perturbed Equilibrium Code (IPEC), and the combination of these codes is a key step towards an iterative solver for self-consistent perturbed equilibrium torque. Supported by US DOE contract #DE-AC02-09CH11466 and the DOE Office of Science Graduate Fellowship administered by the Oak Ridge Institute for Science & Education under contract #DE-AC05-06OR23100.
On Learning Algorithms for Nash Equilibria
NASA Astrophysics Data System (ADS)
Daskalakis, Constantinos; Frongillo, Rafael; Papadimitriou, Christos H.; Pierrakos, George; Valiant, Gregory
Can learning algorithms find a Nash equilibrium? This is a natural question for several reasons. Learning algorithms resemble the behavior of players in many naturally arising games, and thus results on the convergence or non-convergence properties of such dynamics may inform our understanding of the applicability of Nash equilibria as a plausible solution concept in some settings. A second reason for asking this question is in the hope of being able to prove an impossibility result, not dependent on complexity assumptions, for computing Nash equilibria via a restricted class of reasonable algorithms. In this work, we begin to answer this question by considering the dynamics of the standard multiplicative weights update learning algorithms (which are known to converge to a Nash equilibrium for zero-sum games). We revisit a 3×3 game defined by Shapley [10] in the 1950s in order to establish that fictitious play does not converge in general games. For this simple game, we show via a potential function argument that in a variety of settings the multiplicative updates algorithm impressively fails to find the unique Nash equilibrium, in that the cumulative distributions of players produced by learning dynamics actually drift away from the equilibrium.
A Multi-Phase Equation of State and Strength Model for Tin
Cox, G. A.
2006-07-28
This paper considers a multi-phase equation of state and a multi-phase strength model for tin in the {beta}, {gamma} and liquid phases. At a phase transition there are changes in volume, energy, and properties of a material that should be included in an accurate model. The strength model will also be affected by a solid-solid phase transition. For many materials there is a lack of experimental data for strength at high pressures making the derivation of strength parameters for some phases difficult. In the case of tin there are longitudinal sound speed data on the Hugoniot available that have been used here in conjunction with a multi-phase equation of state to derive strength parameters for the {gamma} phase, a phase which does not exist at room temperature and pressure.
NASA Astrophysics Data System (ADS)
Leung, Mary Ann
2004-03-01
We propose a model for the generation of Schrödinger cat states of BEC in multiple wells, and also show how squeezed states can be produced nonadiabatically. The condensate in the multiple well evolves, starting with a certain initial phase difference between the neighboring wells, to a state with a well defined entanglement. We propose a general formula for the initial phase difference: j 2 pi/N where j=1,2,..,N-1, and N is the number of wells. We show the generation of cat states for these different phase configurations in two, three and four wells, and thus generalize this method to any number of wells, even or odd. In addition to the macroscopic superposition states, the method can also be used to generate squeezed states in a nonadiabatic fashion. This work was supported by NSF grant PHY-0140091 and the Computational Science Graduate Fellowship program.
Chemical equilibria of rare earth oxides in glow-discharge mass spectrometry
Mei, Y.
1992-01-01
This research centers around method development and fundamental exploration of the rare earth elements (REE) in glow discharge mass spectrometry (GDMS). The capability of GDMS to analyze directly solids materials eliminates the sample dissolution and preconcentration steps required by many other methods. The simplicity of sample preparation and instrumental operation makes GDMS a promising analytical technique for the field of earth science. Initial studies were dedicated to improving the detection sensitivity of GDMS in analyzing the REE. This was accomplished by eliminating water contamination, a factor that was found to prevent the conversion of the rare earth oxidized to their atomic form in the glow discharge plasma. Methods experimented for water elimination included the uses of both a cryogenic cooling device and getter reagents. When used to determine the REE concentrations in a standard rock sample, the chemical elimination approach yielded comparable results to that obtained by other analytical methods. Further studies focused on probing the chemical reactions involving the REE and other plasma constituents in the glow discharge. It is proposed that the availability of the atomic REE in the glow discharge is strongly influenced by the oxidant and reductant contents in the plasma. Species that contain oxygen tend to shift the redox equilibria of REE toward the formation of their oxides, whereas species that compete for oxygen help reduce the oxidant content in the plasma, and shift the REE redox equilibria toward the formation of the REE atoms. Factors that govern the reaction processes of the REE equilibria were investigated by means of plasma reagent introduction and time-resolved discharge operation. Results indicate that while redox equilibria between the elemental REE and their monoxides exist on the cathode surface and in the gas phase, interactions occurring in the gas phase are probably the main paths for this equilibration in the glow discharge.
NASA Astrophysics Data System (ADS)
Wu, Changjun; Su, Xuping; Peng, Haoping; Liu, Ya; Tu, Hao; Wang, Jianhua
2015-10-01
Ternary Sn-Ni-V alloys were prepared and annealed at 980°C, 600°C, and 300°C for 15, 60 and 60 days, respectively. The annealed alloys were metallographically examined and the equilibrium phases formed were identified on the basis of determination of composition and x-ray diffraction analysis. The isothermal region of the ternary Sn-Ni-V system at 980°C was studied. Nine three-phase regions and more than 20 conjugate lines were detected at 980°C. The range of composition of VNi2Sn at 980°C spans 24.5-59.2 at.% V, 52.1-25.5 at.% Ni, and 15.3-23.4 at.% Sn. Its lattice constant increases with increasing V content. A sharp increase near 40.4 at.% V is indicative of a second-order transition. It is believed that atomic site occupation changed when the V content was >40.4 at.%. The maximum solubility of V in Ni3Sn2 can reach 23.3 at.%; that in Ni3Sn is below 0.6 at.%. Up to 3.4 at.% Ni dissolves in V3Sn. The Sn-rich corner of the Sn-Ni-V system at 600°C and 300°C was also investigated experimentally. The solubility of Ni in VSn2 and V in Ni3Sn4 at 600°C and 300°C are both less than 0.5 at.%.
The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.
ERIC Educational Resources Information Center
Long, Gary J.; Leighly, H. P., Jr.
1982-01-01
Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)
40 CFR 72.73 - State issuance of Phase II permits.
Code of Federal Regulations, 2013 CFR
2013-07-01
... (CONTINUED) PERMITS REGULATION Acid Rain Phase II Implementation § 72.73 State issuance of Phase II permits... permit program under part 70 of this chapter and that has a State Acid Rain program accepted by the Administrator under § 72.71 shall be responsible for administering and enforcing Acid Rain permits effective...
40 CFR 72.73 - State issuance of Phase II permits.
Code of Federal Regulations, 2010 CFR
2010-07-01
... (CONTINUED) PERMITS REGULATION Acid Rain Phase II Implementation § 72.73 State issuance of Phase II permits... permit program under part 70 of this chapter and that has a State Acid Rain program accepted by the Administrator under § 72.71 shall be responsible for administering and enforcing Acid Rain permits effective...
40 CFR 72.73 - State issuance of Phase II permits.
Code of Federal Regulations, 2012 CFR
2012-07-01
... (CONTINUED) PERMITS REGULATION Acid Rain Phase II Implementation § 72.73 State issuance of Phase II permits... permit program under part 70 of this chapter and that has a State Acid Rain program accepted by the Administrator under § 72.71 shall be responsible for administering and enforcing Acid Rain permits effective...
40 CFR 72.73 - State issuance of Phase II permits.
Code of Federal Regulations, 2011 CFR
2011-07-01
... (CONTINUED) PERMITS REGULATION Acid Rain Phase II Implementation § 72.73 State issuance of Phase II permits... permit program under part 70 of this chapter and that has a State Acid Rain program accepted by the Administrator under § 72.71 shall be responsible for administering and enforcing Acid Rain permits effective...
40 CFR 72.73 - State issuance of Phase II permits.
Code of Federal Regulations, 2014 CFR
2014-07-01
... (CONTINUED) PERMITS REGULATION Acid Rain Phase II Implementation § 72.73 State issuance of Phase II permits... permit program under part 70 of this chapter and that has a State Acid Rain program accepted by the Administrator under § 72.71 shall be responsible for administering and enforcing Acid Rain permits effective...
NASA Astrophysics Data System (ADS)
Yuan, Haojie
1992-09-01
Thin films of pure germanium-carbon alloys (Ge _{rm x}C _{rm 1-x} with 0 <=q x <=q 1) have been grown on Si and Al_2O_3 substrates by pulsed laser ablation in a high vacuum chamber. The films were analyzed by x-ray 0-20 diffraction (XRD), x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), conductivity measurements and optical absorption spectroscopy. The analyses of these new materials showed that films of all compositions were amorphous, free of contamination and uniform in composition. By changing the film composition, the optical band gap of these semiconducting films was varied from 0.00 eV to 0.85 eV for x = 0.0 to 1.0 respectively. According to the AES results, the carbon atoms in the Ge-C alloy thin film samples have a bonding structure that is a mixture of sp^2 and sp^3 hybridizations. The presence of the sp^2 C is apparently what causes the bandgap of amorphous Ge-C alloys to decrease with increasing carbon concentration. The solidus portion of the ternary phase diagrams of the type M-Si-O, where M = Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr and Hf have been derived at 298K and 1 atm oxygen partial pressure by investigating the bulk reactions possible in these systems. These phase diagrams, which have been determined by experiments and by calculations using thermodynamic data available, can be used to predict the occurrence of the reaction products or the stability of the phases present at the interfaces between different solid materials. Hence, they provide guides in designing thin film structures and in selecting candidate materials to form chemically stable interfaces. A research effort has been made on the investigation of the growth of diamond thin films from a carbon containing solid-CI_4, using laser ablation technique. The film grown by laser ablation from CI _4 is mainly composed of carbon with very small amount of oxygen and iodine as indicated by x-ray photoelectron spectroscopy data. The Auger electron spectroscopy result shows
Phase coexistence in partially symmetric q-state models
NASA Astrophysics Data System (ADS)
Laanait, Lahoussine; Masaif, Noureddine; Ruiz, Jean
1993-08-01
We consider a lattice model whose spins may assume a finite number q of values. The interaction energy between two nearest-neighbor spins takes on the value J 1 + J 2 or J 2, depending on whether the two spins coincide or are different but coincide modulo q1, and it is zero otherwise. This model is a generalization of the Ashkin-Teller model and exhibits the multilayer wetting phenomenon, that is, wetting by one or two or three interfacial layers, depending on the number of phases in coexistence. While we plan to consider interface properties in such a case, here we study the phase diagram of the model. We show that for large values of q 1 and q/q 1, it exhibits, according the value of J 2/ J 1, either a unique first-order temperature-driven phase transition at some point β t where q ordered phases coexist with the disordered one, or two transition temperatures β{t/(1)} and β{t/(2)}, where q1 partially ordered phases coexist with the ordered ones (β{t/(1)}) or with the disordered one (β{t/(2)}), or for a particular value of J 2/ J 1 there is a unique transition temperature where all the previous phases coexist. Proofs are based on the Pirogov-Sinai theory: we perform a random cluster representation of the model (allowing us to consider noninteger values of q 1 and q/q 1) to which we adapt this theory.
Background field functional renormalization group for absorbing state phase transitions.
Buchhold, Michael; Diehl, Sebastian
2016-07-01
We present a functional renormalization group approach for the active to inactive phase transition in directed percolation-type systems, in which the transition is approached from the active, finite density phase. By expanding the effective potential for the density field around its minimum, we obtain a background field action functional, which serves as a starting point for the functional renormalization group approach. Due to the presence of the background field, the corresponding nonperturbative flow equations yield remarkably good estimates for the critical exponents of the directed percolation universality class, even in low dimensions. PMID:27575107
Background field functional renormalization group for absorbing state phase transitions
NASA Astrophysics Data System (ADS)
Buchhold, Michael; Diehl, Sebastian
2016-07-01
We present a functional renormalization group approach for the active to inactive phase transition in directed percolation-type systems, in which the transition is approached from the active, finite density phase. By expanding the effective potential for the density field around its minimum, we obtain a background field action functional, which serves as a starting point for the functional renormalization group approach. Due to the presence of the background field, the corresponding nonperturbative flow equations yield remarkably good estimates for the critical exponents of the directed percolation universality class, even in low dimensions.
Ternary liquid-liquid equilibria measurement for epoxidized soybean oil + acetic acid + water.
Cai, Shuang-Fei; Wang, Li-Sheng; Yan, Guo-Qing; Li, Yi; Feng, Yun-Xia; Linghu, Rong-Gang
2012-01-01
Liquid-liquid equilibria (LLE) data were measured for ternary system epoxidized soybean oil (ESO) + acetic acid + water at 313.15, 323.15 and 333.15 K, respectively. The consistency of the measured LLE data was tested, using Othmer-Tobias correlation and root-mean-square deviation (sigma) in mass fraction of water in the lower phase and average value of the absolute difference (AAD) between experimental mass fraction of epoxidized soybean oil in the upper phase and that calculated using Othmer-Tobias correlation.
NASA Astrophysics Data System (ADS)
Weller, O. M.; St-Onge, M. R.; Rayner, N.; Waters, D. J.; Searle, M. P.; Palin, R. M.
2016-10-01
The Sumdo complex is a Permian-Triassic eclogitic metamorphic belt in south-east Tibet, which marks the location of a suture zone that separates the northern and southern Lhasa terranes. An integrated geochronological and petrological study of a mafic eclogite from the complex has constrained its tectonometamorphic history and provides a case study of zircon growth in eclogite as a product of prograde dissolution-precipitation. In situ U-Pb geochronology indicates that the eclogite contains a single population of zircon with a crystallisation age of 273.6 ± 2.8 Ma. The morphology and chemistry of the zircon grains are consistent with growth by dissolution-precipitation of protolith magmatic zircon. The presence of zircon grains as inclusions in the cores of peak phases indicates that zircon dissolution-precipitation occurred during prograde metamorphism, and calculated pressure and temperature conditions over which mineral inclusions in zircon are stable suggest that the zircon most likely precipitated at ~15.5-16.5 kbar and 500-560 °C. Subsequent peak metamorphism is calculated to have reached pressure-temperature conditions of 27 ± 1 kbar and 670 ± 50 °C. Previous studies, which have documented a range of peak metamorphic conditions from high- to ultrahigh-pressure at c. 266-230 Ma, indicate that the Sumdo complex is a composite belt that experienced protracted eclogite exhumation. The results of this study are consistent with this interpretation, and extend the age range of high-pressure metamorphism in the complex to over 40 Myr. Analysis of published pressure-temperature-time data indicates two systematic behaviours within this spread. First, peak metamorphic temperatures declined over time. Second, eclogite exhumation occurred in two discrete intervals: soon after formation, and during the demise of the subduction zone. The latter behaviour serves as a reminder that eclogite exhumation is the exception rather than the rule.
Thermodynamic Calibration of Cr-Al Exchange Equilibria for Garnet and Spinel
NASA Astrophysics Data System (ADS)
Hamecher, E. A.; Antoshechkina, P. M.; Ghiorso, M. S.; Asimow, P. D.
2009-12-01
xMELTS is a new thermodynamic model of igneous phase equilibria (Ghiorso et al., 2007, Eos 88, V31C-0608) that extends MELTS (Ghiorso and Sack, 1995, CMP 119, 197-212) and pMELTS (Ghiorso et al., 2002, G3, 10.1029/2001GC000217) to a broader range of bulk compositions and to pressure and temperature conditions spanning from the shallow crust to the top of Earth’s lower mantle. To complete xMELTS, comprehensive garnet and pyroxene solid solution models that include Cr and other minor components must be developed. Garnet is an important phase involved in partial melting of the upper mantle because it controls partitioning of major and minor elements at pressures greater than 3 GPa. Chromium is a minor but significant component of mantle rocks as its presence increases the stability of spinel relative to plagioclase at low pressure and to garnet at high pressure. Thermodynamic models incorporating Cr into garnet solid solutions have been absent from the MELTS packages, motivating simulations for Cr-free bulk compositions and preventing accurate modeling of the spinel-garnet phase transition. The extension of the garnet model to include energetics of mixing on the Y-site is the first step in a planned calibration that will also include the majorite component needed for transition zone garnets. Initially, standard state properties and phase equilibria experiments for a Cr-bearing garnet endmember were compiled. Internally consistent thermodynamic properties of the endmember species were found by examination of reversal experiments on pure systems. We used the reversal experiments of Klemme (2004, Lithos 77, 639-646) to fix the enthalpy and entropy of knorringite (Mg3Cr2Si3O12), but were unable to fit the reversals using the standard state values given by Klemme and instead re-optimized these parameters. Although a Cr-bearing garnet model is included in the PERPLEX package (Connolly, 1990, AJS 290, 666-718; Connolly and Petrini, 2002, J.Met.Pet. 20, 697-708), the Y
Kang, Y.W.
1998-01-01
Isothermal vapor-liquid equilibria for difluoromethane + hydrogen fluoride, dichlorodifluoromethane + hydrogen fluoride, and chlorine + hydrogen fluoride have been measured. The experimental data for the binary systems are correlated with the NRTL equation with the vapor-phase association model for the mixtures containing hydrogen fluoride, and the relevant parameters are presented. The binary system difluoromethane + hydrogen fluoride forms a homogeneous liquid phase, and the others form minimum boiling heterogeneous azeotropes at the experimental conditions.
Isothermal Multiphase Flash Calculations with the PC-SAFT Equation of State
Justo-Garcia, Daimler N.; Garcia-Sanchez, Fernando; Romero-Martinez, Ascencion
2008-03-05
A computational approach for isothermal multiphase flash calculations with the PC-SAFT (Perturbed-Chain Statistical Associating Fluid Theory) equation of state is presented. In the framework of the study of fluid phase equilibria of multicomponent systems, the general multiphase problem is the single most important calculation which consists of finding the correct number and types of phases and their corresponding equilibrium compositions such that the Gibbs energy of the system is a minimum. For solving this problem, the system Gibbs energy was minimized using a rigorous method for thermodynamic stability analysis to find the most stable state of the system. The efficiency and reliability of the approach to predict and calculate complex phase equilibria are illustrated by solving three typical problems encountered in the petroleum industry.
NASA Astrophysics Data System (ADS)
Thy, P.
1991-01-01
The south-eastern propagating rift zone of Iceland shows a progression from tholeiitic, to transitional, and mildly alkalic basalts going toward the front of the propagator. A petrogenetic model has been formulated based on low and high pressure melting experiments. The evolution of the magmas behind the front of the propagating rift is dominated by near surface processes (e.g., Katla and Hekla volcanic systems). Compared with the one atmosphere liquid line of descent, the Vestmannaeyjar lavas, erupted at the front of the propagating rift, have systematically higher Al 2O 3 and Na 2O contents consistent with the experimentally determined effects of high pressure, Labradoritic plagioclase megacrysts, which occur in the early phase of the Surtsey eruption at the front of the propagator, are consistent with the predicted effect of high pressure on plagioclase composition. On the other hand, augites similar to those of the high pressure experiments are unknown among the phenocryst and xenolith assemblages of the Vestmannaeyjar lavas (and other Icelandic lavas). Petrographic evidence points toward a high water content in the evolved lavas of the Vestmannaeyjar. A relatively high water activity and high pressure in the magma chambers at the front of the propagator could have caused a significant suppression of the liquids temperature, in particular for plagioclase. Seismic and magnetotelluric evidence suggest that magma chambers behind the propagating front occur at the depth equivalent to 2-3 kbar of pressure. At the front, magma chambers have been located by geophysical evidence at significantly greater depths equivalent to 3-8 kbar. The lavas erupted at the front of the propagator are located to the alkalic side of the thermal divide and, therefore, can be expected to evolve toward nepheline saturation under slightly hydrous conditions. The most evolved of these lavas are of ferrobasaltic compositions and may be saturated with augite. The lavas erupted behind the
Relative equilibria of vortices in two dimensions.
Palmore, J I
1982-01-01
An old problem of the evolution of finitely many interacting point vortices in the plane is shown to be amenable to investigation by critical point theory in a way that is identical to the study of the planar n-body problem of celestial mechanics. For any choice of positive circulations of the vortices it is shown by critical point theory applied to Kirchhoff's function that there are many relative equilibria configurations. Each of these configurations gives rise to a stationary configuration of the vortices in a suitably chosen rotating coordinate system. A sharp lower bound on the number of stationary vortex configurations for the problem of point vortices interacting in the plane is given. The problem of point vortices in a circular disk is defined and it is shown that these estimates hold for stationary configurations of small size. PMID:16593155
Relative equilibria of vortices in two dimensions.
Palmore, J I
1982-01-01
An old problem of the evolution of finitely many interacting point vortices in the plane is shown to be amenable to investigation by critical point theory in a way that is identical to the study of the planar n-body problem of celestial mechanics. For any choice of positive circulations of the vortices it is shown by critical point theory applied to Kirchhoff's function that there are many relative equilibria configurations. Each of these configurations gives rise to a stationary configuration of the vortices in a suitably chosen rotating coordinate system. A sharp lower bound on the number of stationary vortex configurations for the problem of point vortices interacting in the plane is given. The problem of point vortices in a circular disk is defined and it is shown that these estimates hold for stationary configurations of small size.
Simulating Dynamic Equilibria: A Class Experiment
NASA Astrophysics Data System (ADS)
Harrison, John A.; Buckley, Paul D.
2000-08-01
A first-order reversible reaction is simulated on an overhead projector using small coins or discs. A simulation is carried out in which initially there are 24 discs representing reactant A and none representing reactant B. At the end of each minute half of the reactant A discs get converted to reactant B, and one quarter of the reactant B discs get converted to reactant A discs. Equilibrium is established with 8 A discs and 16 B discs, and no further net change is observed as the simulation continues. Another simulation beginning with 48 A discs and 0 B discs leads at equilibrium to 16 A discs and 32 B discs. These results illustrate how dynamic equilibria are established and allow the introduction of the concept of an equilibrium constant. Le Châtelier's principle is illustrated by further simulations.
Ultrafast electronic relaxation of excited state vitamin B 12 in the gas phase
NASA Astrophysics Data System (ADS)
Shafizadeh, Niloufar; Poisson, Lionel; Soep, Benoıˆt
2008-06-01
The time evolution of electronically excited vitamin B 12 (cyanocobalamin) has been observed for the first time in the gas phase. It reveals an ultrafast decay to a state corresponding to metal excitation. This decay is interpreted as resulting from a ring to metal electron transfer. This opens the observation of the excited state of other complex biomimetic systems in the gas phase, the key to the characterisation of their complex evolution through excited electronic states.
Pressure induced phase transitions and equation of state of adamantane
NASA Astrophysics Data System (ADS)
Vijayakumar, V.; Garg, Alka B.; Godwal, B. K.; Sikka, S. K.
2001-03-01
Results of angle dispersive x-ray powder diffraction measurements under pressure up to 25 GPa on adamantane carried out at the synchrotron source SPRING-8 are reported. The disorder-order transition at 0.5 GPa in adamantane known earlier is reproduced with detailed structural information. For this ordered tetragonal (Pφ) of the two molecules within the cell about the c-axis increases from 8.5° to 10.5°. This is consistent with values determined from energy minimization in this pressure region. The anomaly in the pressure variation of c/a, and the failure of the constrained Rietveld refinement, occurring close to 9 GPa, are interpreted as due to distortion of the adamantane molecule when H...H distance decreases below the critical value of 1.9 Å. Above 16 GPa there is a subtle change in the diffraction pattern that indicates a transition to a closely related phase. Beyond 22 GPa, a monoclinic phase with one molecule per cell could only index the patterns. The ambient cubic phase is recovered on unloading indicating the absence of decomposition or polymerization. The results of high pressure x-ray diffraction experiments confirm the changes in the Raman spectra observed in the earlier measurements.
Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.
Zhou, Xiao-Peng; Su, Xue-Li; Sun, Yan
2007-01-01
The statistical thermodynamic (ST) model was used to study nonlinear binary protein adsorption equilibria on an anion exchanger. Single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin (BSA) on DEAE Spherodex M were determined by batch adsorption experiments in 10 mM Tris-HCl buffer containing a specific NaCl concentration (0.05, 0.10, and 0.15 M) at pH 7.40. The ST model was found to depict the effect of ionic strength on the single-component equilibria well, with model parameters depending on ionic strength. Moreover, the ST model gave acceptable fitting to the binary adsorption data with the fitted single-component model parameters, leading to the estimation of the binary ST model parameter. The effects of ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories. The effective charge of protein in adsorption phase can be separately calculated from the two categories of the model parameters, and the values obtained from the two methods are consistent. The results demonstrate the utility of the ST model for describing nonlinear binary protein adsorption equilibria.
Q-band 4-state phase shifter in planar technology: Circuit design and performance analysis
NASA Astrophysics Data System (ADS)
Villa, E.; Cagigas, J.; Aja, B.; de la Fuente, L.; Artal, E.
2016-09-01
A 30% bandwidth phase shifter with four phase states is designed to be integrated in a radio astronomy receiver. The circuit has two 90° out-of-phase microwave phase-shifting branches which are combined by Wilkinson power dividers. Each branch is composed of a 180° phase shifter and a band-pass filter. The 180° phase shifter is made of cascaded hybrid rings with microwave PIN diodes as switching devices. The 90° phase shift is achieved with the two band-pass filters. Experimental characterization has shown significant results, with average phase shift values of -90.7°, -181.7°, and 88.5° within the operation band, 35-47 GHz, and mean insertion loss of 7.4 dB. The performance of its integration in a polarimetric receiver for radio astronomy is analyzed, which validates the use of the presented phase shifter in such type of receiver.
Discontinuous phase transition in an annealed multi-state majority-vote model
NASA Astrophysics Data System (ADS)
Li, Guofeng; Chen, Hanshuang; Huang, Feng; Shen, Chuansheng
2016-07-01
In this paper, we generalize the original majority-vote (MV) model with noise from two states to arbitrary q states, where q is an integer no less than two. The main emphasis is paid to the comparison on the nature of phase transitions between the two-state MV (MV2) model and the three-state MV (MV3) model. By extensive Monte Carlo simulation and mean-field analysis, we find that the MV3 model undergoes a discontinuous order-disorder phase transition, in contrast to a continuous phase transition in the MV2 model. A central feature of such a discontinuous transition is a strong hysteresis behavior as noise intensity goes forward and backward. Within the hysteresis region, the disordered phase and ordered phase are coexisting.
Amplitude-phase coupling drives chimera states in globally coupled laser networks.
Böhm, Fabian; Zakharova, Anna; Schöll, Eckehard; Lüdge, Kathy
2015-04-01
For a globally coupled network of semiconductor lasers with delayed optical feedback, we demonstrate the existence of chimera states. The domains of coherence and incoherence that are typical for chimera states are found to exist for the amplitude, phase, and inversion of the coupled lasers. These chimera states defy several of the previously established existence criteria. While chimera states in phase oscillators generally demand nonlocal coupling, large system sizes, and specially prepared initial conditions, we find chimera states that are stable for global coupling in a network of only four coupled lasers for random initial conditions. The existence is linked to a regime of multistability between the synchronous steady state and asynchronous periodic solutions. We show that amplitude-phase coupling, a concept common in different fields, is necessary for the formation of the chimera states.
Phase diagram of quantum critical system via local convertibility of ground state
Liu, Si-Yuan; Quan, Quan; Chen, Jin-Jun; Zhang, Yu-Ran; Yang, Wen-Li; Fan, Heng
2016-01-01
We investigate the relationship between two kinds of ground-state local convertibility and quantum phase transitions in XY model. The local operations and classical communications (LOCC) convertibility is examined by the majorization relations and the entanglement-assisted local operations and classical communications (ELOCC) via Rényi entropy interception. In the phase diagram of XY model, LOCC convertibility and ELOCC convertibility of ground-states are presented and compared. It is shown that different phases in the phase diagram of XY model can have different LOCC or ELOCC convertibility, which can be used to detect the quantum phase transition. This study will enlighten extensive studies of quantum phase transitions from the perspective of local convertibility, e.g., finite-temperature phase transitions and other quantum many-body models. PMID:27381284
Phase diagram of quantum critical system via local convertibility of ground state.
Liu, Si-Yuan; Quan, Quan; Chen, Jin-Jun; Zhang, Yu-Ran; Yang, Wen-Li; Fan, Heng
2016-01-01
We investigate the relationship between two kinds of ground-state local convertibility and quantum phase transitions in XY model. The local operations and classical communications (LOCC) convertibility is examined by the majorization relations and the entanglement-assisted local operations and classical communications (ELOCC) via Rényi entropy interception. In the phase diagram of XY model, LOCC convertibility and ELOCC convertibility of ground-states are presented and compared. It is shown that different phases in the phase diagram of XY model can have different LOCC or ELOCC convertibility, which can be used to detect the quantum phase transition. This study will enlighten extensive studies of quantum phase transitions from the perspective of local convertibility, e.g., finite-temperature phase transitions and other quantum many-body models.
Loss resilience for two-qubit state transmission using distributed phase sensitive amplification
Dailey, James; Agarwal, Anjali; Toliver, Paul; Peters, Nicholas A.
2015-11-12
We transmit phase-encoded non-orthogonal quantum states through a 5-km long fibre-based distributed optical phase-sensitive amplifier (OPSA) using telecom-wavelength photonic qubit pairs. The gain is set to equal the transmission loss to probabilistically preserve input states during transmission. While neither state is optimally aligned to the OPSA, each input state is equally amplified with no measurable degradation in state quality. These results promise a new approach to reduce the effects of loss by encoding quantum information in a two-qubit Hilbert space which is designed to benefit from transmission through an OPSA.
Semiclassical States Associated with Isotropic Submanifolds of Phase Space
NASA Astrophysics Data System (ADS)
Guillemin, V.; Uribe, A.; Wang, Z.
2016-05-01
We define classes of quantum states associated with isotropic submanifolds of cotangent bundles. The classes are stable under the action of semiclassical pseudo-differential operators and covariant under the action of semiclassical Fourier integral operators. We develop a symbol calculus for them; the symbols are symplectic spinors. We outline various applications.
Entropy, chaos, and excited-state quantum phase transitions in the Dicke model.
Lóbez, C M; Relaño, A
2016-07-01
We study nonequilibrium processes in an isolated quantum system-the Dicke model-focusing on the role played by the transition from integrability to chaos and the presence of excited-state quantum phase transitions. We show that both diagonal and entanglement entropies are abruptly increased by the onset of chaos. Also, this increase ends in both cases just after the system crosses the critical energy of the excited-state quantum phase transition. The link between entropy production, the development of chaos, and the excited-state quantum phase transition is more clear for the entanglement entropy. PMID:27575109
Entropy, chaos, and excited-state quantum phase transitions in the Dicke model
NASA Astrophysics Data System (ADS)
Lóbez, C. M.; Relaño, A.
2016-07-01
We study nonequilibrium processes in an isolated quantum system—the Dicke model—focusing on the role played by the transition from integrability to chaos and the presence of excited-state quantum phase transitions. We show that both diagonal and entanglement entropies are abruptly increased by the onset of chaos. Also, this increase ends in both cases just after the system crosses the critical energy of the excited-state quantum phase transition. The link between entropy production, the development of chaos, and the excited-state quantum phase transition is more clear for the entanglement entropy.
Stable equilibria of elliptic roly-poly toys
NASA Astrophysics Data System (ADS)
Hong, Seok-In
2016-11-01
As an instructive (gravitational potential) energy approach, we show that the elliptic roly-poly has a richer and more useful profile (including the tilted configuration) of stable equilibria than conventional spherical or cylindrical roly-polys.
Variational Principle and Stability of Nonmonotonic Vlasov-Poisson Equilibria
NASA Astrophysics Data System (ADS)
Morrison, P. J.
1987-10-01
The stability of nonmonotonic equilibria of the Vlasov-Poisson equation is assessed by using nonlinear constants of motion . The constants of motion make up the free energy of the system , which upon variation yields nonmonotonic equilibria. Such equilibria have not previously been obtainable from a variation principle, but here this is accomplished by the inclusion of a passively advected tracer field. Definiteness of the second variation of the free energy gives a sufficient condition for stability in agreement with Gardner's theorem [5], Previously, we have argued that indefiniteness implies either spectral in stability or negative energy modes, which are generically unstable when one adds dissipation or nonlinearity [6]. Such is the case for the nonmonotonic equilibria considered.
The freedom to choose neutron star magnetic field equilibria
NASA Astrophysics Data System (ADS)
Glampedakis, Kostas; Lasky, Paul D.
2016-08-01
Our ability to interpret and glean useful information from the large body of observations of strongly magnetised neutron stars rests largely on our theoretical understanding of magnetic field equilibria. We answer the following question: is one free to arbitrarily prescribe magnetic equilibria such that fluid degrees of freedom can balance the equilibrium equations? We examine this question for various models for neutron star matter; from the simplest single-fluid barotrope to more realistic non-barotropic multifluid models with superfluid/superconducting components, muons and entropy. We do this for both axi- and non-axisymmetric equilibria, and in Newtonian gravity and general relativity. We show that, in axisymmetry, the most realistic model allows complete freedom in choosing a magnetic field equilibrium whereas non-axisymmetric equilibria are never completely arbitrary.
Edge states at phase boundaries and their stability
NASA Astrophysics Data System (ADS)
Asorey, M.; Balachandran, A. P.; Pérez-Pardo, J. M.
2016-10-01
We analyze the effects of Robin-like boundary conditions on different quantum field theories of spin 0, 1/2 and 1 on manifolds with boundaries. In particular, we show that these conditions often lead to the appearance of edge states. These states play a significant role in physical phenomena like quantum Hall effect and topological insulators. We prove in a rigorous way the existence of spectral lower bounds on the kinetic term of different Hamiltonians, even in the case of Abelian gauge fields where it is a non-elliptic differential operator. This guarantees the stability and consistency of massive field theories with masses larger than the lower bound of the kinetic term. Moreover, we find an upper bound for the deepest edge state. In the case of Abelian gauge theories, we analyze a generalization of Robin boundary conditions. For Dirac fermions, we analyze the cases of Atiyah-Patodi-Singer and chiral bag boundary conditions. The explicit dependence of the bounds on the boundary conditions and the size of the system is derived under general assumptions.
Ground-state phase diagram of the one-dimensional half-filled extended Hubbard model
NASA Astrophysics Data System (ADS)
Tsuchiizu, M.; Furusaki, A.
2004-01-01
We revisit the ground-state phase diagram of the one-dimensional half-filled extended Hubbard model with on-site (U) and nearest-neighbor (V) repulsive interactions. In the first half of the paper, using the weak-coupling renormalization-group approach (g-ology) including second-order corrections to the coupling constants, we show that bond-charge-density-wave (BCDW) phase exists for U≈2V in between charge-density-wave (CDW) and spin-density-wave (SDW) phases. We find that the umklapp scattering of parallel-spin electrons disfavors the BCDW state and leads to a bicritical point where the CDW-BCDW and SDW-BCDW continuous-transition lines merge into the CDW-SDW first-order transition line. In the second half of the paper, we investigate the phase diagram of the extended Hubbard model with either additional staggered site potential Δ or bond alternation δ. Although the alternating site potential Δ strongly favors the CDW state (that is, a band insulator), the BCDW state is not destroyed completely and occupies a finite region in the phase diagram. Our result is a natural generalization of the work by Fabrizio, Gogolin, and Nersesyan [Phys. Rev. Lett. 83, 2014 (1999)], who predicted the existence of a spontaneously dimerized insulating state between a band insulator and a Mott insulator in the phase diagram of the ionic Hubbard model. The bond alternation δ destroys the SDW state and changes it into the BCDW state (or Peierls insulating state). As a result the phase diagram of the model with δ contains only a single critical line separating the Peierls insulator phase and the CDW phase. The addition of Δ or δ changes the universality class of the CDW-BCDW transition from the Gaussian transition into the Ising transition.
Molecular equilibria and condensation sequences in carbon rich gases
NASA Technical Reports Server (NTRS)
Sharp, C. M.; Wasserburg, G. J.
1993-01-01
Chemical equilibria in stellar atmospheres have been investigated by many authors. Lattimer, Schramm, and Grossman presented calculations in both O rich and C rich environments and predicted possible presolar condensates. A recent paper by Cherchneff and Barker considered a C rich composition with PAH's included in the calculations. However, the condensation sequences of C bearing species have not been investigated in detail. In a carbon rich gas surrounding an AGB star, it is often assumed that graphite (or diamond) condenses out before TiC and SiC. However, Lattimer et al. found some conditions under which TiC condenses before graphite. We have performed molecular equilibrium calculations to establish the stability fields of C(s), TiC(s), and SiC(s) and other high temperature phases under conditions of different pressures and C/O. The preserved presolar interstellar dust grains so far discovered in meteorites are graphite, diamond, SiC, TiC, and possibly Al2O3.
Emanuelsson, Eva U; Tschiskale, Morten; Bilde, Merete
2016-09-15
meso-Erythritol is a sugar alcohol identified in atmospheric aerosol particles. In this work, evaporation of submicron-sized particles of meso-erythritol was studied in a TDMA system including a laminar flow tube under dry conditions at five temperatures (278-308 K) and ambient pressure. A complex behavior was observed and attributed to the formation of particles of three different phase states: (1) crystalline, (2) subcooled liquid or amorphous, and (3) mixed. With respect to saturation vapor pressure, the subcooled liquid and amorphous states are treated to be the same. The particle phase state was linked to initial particle size and flow tube temperature. Saturation vapor pressures of two phase states attributed to the crystalline and subcooled liquid state respectively are reported. Our results suggest a mass accommodation coefficient close to one for both states. PMID:27525492
Emanuelsson, Eva U; Tschiskale, Morten; Bilde, Merete
2016-09-15
meso-Erythritol is a sugar alcohol identified in atmospheric aerosol particles. In this work, evaporation of submicron-sized particles of meso-erythritol was studied in a TDMA system including a laminar flow tube under dry conditions at five temperatures (278-308 K) and ambient pressure. A complex behavior was observed and attributed to the formation of particles of three different phase states: (1) crystalline, (2) subcooled liquid or amorphous, and (3) mixed. With respect to saturation vapor pressure, the subcooled liquid and amorphous states are treated to be the same. The particle phase state was linked to initial particle size and flow tube temperature. Saturation vapor pressures of two phase states attributed to the crystalline and subcooled liquid state respectively are reported. Our results suggest a mass accommodation coefficient close to one for both states.
Ground states of stealthy hyperuniform potentials. II. Stacked-slider phases
NASA Astrophysics Data System (ADS)
Zhang, G.; Stillinger, F. H.; Torquato, S.
2015-08-01
Stealthy potentials, a family of long-range isotropic pair potentials, produce infinitely degenerate disordered ground states at high densities and crystalline ground states at low densities in d -dimensional Euclidean space Rd. In the previous paper in this series, we numerically studied the entropically favored ground states in the canonical ensemble in the zero-temperature limit across the first three Euclidean space dimensions. In this paper, we investigate using both numerical and theoretical techniques metastable stacked-slider phases, which are part of the ground-state manifold of stealthy potentials at densities in which crystal ground states are favored entropically. Our numerical results enable us to devise analytical models of this phase in two, three, and higher dimensions. Utilizing this model, we estimated the size of the feasible region in configuration space of the stacked-slider phase, finding it to be smaller than that of crystal structures in the infinite-system-size limit, which is consistent with our recent previous work. In two dimensions, we also determine exact expressions for the pair correlation function and structure factor of the analytical model of stacked-slider phases and analyze the connectedness of the ground-state manifold of stealthy potentials in this density regime. We demonstrate that stacked-slider phases are distinguishable states of matter; they are nonperiodic, statistically anisotropic structures that possess long-range orientational order but have zero shear modulus. We outline some possible future avenues of research to elucidate our understanding of this unusual phase of matter.
Ye Jinwu; Zhang Cunlin
2011-08-15
Recently, strong-coupling regimes of superconducting qubits or quantum dots inside a microwave circuit cavity and BEC atoms inside an optical cavity were achieved experimentally. The strong-coupling regimes in these systems were described by the Dicke model. Here, we solve the Dicke model by a 1/N expansion. In the normal state, we find a {radical}(N) behavior of the collective Rabi splitting. In the superradiant phase, we identify an important Berry phase term that has dramatic effects on both the ground state and the excitation spectra of the strongly interacting system. The single photon excitation spectrum has a low-energy quantum phase diffusion mode in imaginary time with a large spectral weight and also a high-energy optical mode with a low spectral weight. The photons are in a number squeezed state that may have wide applications in high sensitive measurements and quantum-information processing. Comparisons with exact diagonalization studies are made. Possible experimental schemes to realize the superradiant phase are briefly discussed.
Experimental Studies of Phase Equilibria of Meteorites and Planetary Bodies
NASA Technical Reports Server (NTRS)
Stolper, Edward M.
2005-01-01
The primary theme of this project was the application of experimental petrology and geochemistry to a variety of problems in meteoritics and planetary geology. The studies were designed to help develop constraints on the histories of primitive meteorites and their components, the environments in which they formed and evolved, and to understand quantitatively the processes involved in the evolution of igneous rocks on the earth and other planetary bodies. We undertook several projects relating to the origin of CAIs and chondrules. Systematics in the thermodynamic properties of CAI-like liquids were investigated and used to elucidate speciation of multi-valent cations and sulfide capacity of silicate melts and to constrain redox conditions and the vapor pressures of volatile species over molten chondrules. We experimentally determined vanadium speciation in meteoritic pyroxenes and in pyroxenes crystallized from CAI-like melts under very reducing conditions. We also found that bulk oxygen isotope compositions of chondrules in the moderately unequilibrated LL chondrites are related to the relative timing of plagioclase crystallization. We completed an experimental study on the vaporization of beta-SiC and SiO2 (glass or cristobalite) in reducing gases and established the conditions under which these presolar grains could have survived in the solar nebula. We expanded our technique for determining the thermodynamic properties of minerals and liquids to iron-bearing systems. We determined activity-composition relationships in Pt-Fe, Pt-Cr and Pt-Fe-Cr alloys. Results were used to determine the thermodynamic properties of chromite-picrochromite spinels including the free energy of formation of end-member FeCr2O4. We also established a new approach for evaluating Pt-Fe saturation experiments. We calculated the T-fO2 relationships in equilibrated ordinary chondrites and thereby constrained the conditions of metamorphism in their parent bodies.
MOLECULAR SIMULATION OF PHASE EQUILIBRIA FOR COMPLEX FLUIDS
Athanassios Z. Panagiotopoulos
2009-09-09
The general area of this project was the development and application of novel molecular simulation methods for prediction of thermodynamic and structural properties of complex polymeric, surfactant and ionic fluids. Over this project period, we have made considerable progress in developing novel algorithms to meet the computational challenges presented by the strong or long-range interactions in these systems and have generated data for well-defined mod-els that can be used to test theories and compare to experimental data. Overall, 42 archival papers and many invited and contributed presentations and lectures have been based on work supported by this project. 6 PhD, 1 M.S. and 2 postdoctoral students have been associated with this work, as listed in the body of the report.
Phase equilibria in systems of formates with isobutyl alcohol
Seselkin, I.V.; Garber, Y.N.; Mironenko, V.F.
1985-09-01
The borate method, based on esterification with boric acid, was proposed for isolation of isobutyl alchohol. The method inv olves formation and hydrolysis of alkyl borate esters; in particular, formation and hydrolysis of triisobutyl borate. Esterification of isobutyl alcohol with boric acid is a reversible equilibrium reaction, and therefore in order to obtain high yields the water formed in the reaction must be removed. The presence of other organic compounds, which do not react with boric acid, in the mixture does not affect esterification of the alcohol. The reaction proceeds at 95-100/sup 0/ under atmospheric pressure. It was found that up to 97% of the isobutyl alcohol combines with boric acid. The resultant triisobutyl borate is isolated by ordinary distillation and then hydrolyzed to form boric acid and isobutyl alcohol.
High-pressure phase equilibria with compressed gases.
Ren, Wei; Scurto, Aaron M
2007-12-01
An apparatus is described that is capable of determining high-pressure vapor-liquid equilibrium, liquid-liquid equilibrium, solid-liquid-vapor equilibrium, vapor-liquid-liquid equilibrium, and mixture critical points and transitions. The device is capable of temperatures to 150 degrees C and pressures to 300 bars (higher with slight modifications). The construction and operation are described in detail and do not require the use of mercury. This method requires very low sample volumes and no analytical equipment nor system-specific calibration. The apparatus was verified by comparison with literature data for the decane-CO(2) mixture and CO(2)-ionic liquid [1-hexyl-3-methyl-imidazolium bis(trifyl)imide)] systems. The experimental data have excellent agreement with the literature data that used different experimental methods. A rigorous error analysis of the system is also presented.
Fingerprint of topological Andreev bound states in phase-dependent heat transport
NASA Astrophysics Data System (ADS)
Sothmann, Björn; Hankiewicz, Ewelina M.
2016-08-01
We demonstrate that phase-dependent heat currents through superconductor-topological insulator Josephson junctions provide a useful tool to probe the existence of topological Andreev bound states, even for multichannel surface states. We predict that in the tunneling regime topological Andreev bound states lead to a minimum of the thermal conductance for a phase difference ϕ =π , in clear contrast to a maximum of the thermal conductance at ϕ =π that occurs for trivial Andreev bound states in superconductor-normal-metal tunnel junctions. This opens up the possibility that phase-dependent heat transport can distinguish between topologically trivial and nontrivial 4 π modes. Furthermore, we propose a superconducting quantum interference device geometry where phase-dependent heat currents can be measured using available experimental technology.
Detecting critical state before phase transition of complex systems by hidden Markov model
NASA Astrophysics Data System (ADS)
Liu, Rui; Chen, Pei; Li, Yongjun; Chen, Luonan
Identifying the critical state or pre-transition state just before the occurrence of a phase transition is a challenging task, because the state of the system may show little apparent change before this critical transition during the gradual parameter variations. Such dynamics of phase transition is generally composed of three stages, i.e., before-transition state, pre-transition state, and after-transition state, which can be considered as three different Markov processes. Thus, based on this dynamical feature, we present a novel computational method, i.e., hidden Markov model (HMM), to detect the switching point of the two Markov processes from the before-transition state (a stationary Markov process) to the pre-transition state (a time-varying Markov process), thereby identifying the pre-transition state or early-warning signals of the phase transition. To validate the effectiveness, we apply this method to detect the signals of the imminent phase transitions of complex systems based on the simulated datasets, and further identify the pre-transition states as well as their critical modules for three real datasets, i.e., the acute lung injury triggered by phosgene inhalation, MCF-7 human breast cancer caused by heregulin, and HCV-induced dysplasia and hepatocellular carcinoma.
Simplified formula for mean cycle-slip time of phase-locked loops with steady-state phase error.
NASA Technical Reports Server (NTRS)
Tausworthe, R. C.
1972-01-01
Previous work shows that the mean time from lock to a slipped cycle of a phase-locked loop is given by a certain double integral. Accurate numerical evaluation of this formula for the second-order loop is extremely vexing because the difference between exponentially large quantities is involved. The presented article demonstrates a method in which a much-reduced precision program can be used to obtain the mean first-cycle slip time for a loop of arbitrary degree tracking at a specified SNR and steady-state phase error. It also presents a simple approximate formula that is asymptotically tight at higher loop SNR.
Ritter, James A; Bhadra, Shubhra J; Ebner, Armin D
2011-04-19
A new model has been developed for predicting mixed-gas adsorption equilibria from multicomponent gas mixtures based on the dual-process Langmuir (DPL) formulation. It predicts ideal, nonideal, and azeotropic adsorbed solution behavior from a knowledge of only single-component adsorption isotherms and the assertion that each binary pair in the gas mixture correlates in either a perfect positive (PP) or perfect negative (PN) fashion on each of the two Langmuir sites. The strictly PP and strictly PN formulations thus provide a simple means for determining distinct and absolute bounds of the behavior of each binary pair, and the PP or PN behavior can be confirmed by comparing predictions to binary experimental adsorption equilibria or from intuitive knowledge of binary pairwise adsorbate-adsorbent interactions. The extension to ternary and higher-order systems is straightforward on the basis of the pairwise additivity of the binary adsorbent-adsorbate interactions and two rules that logically restrict the combinations of PP and PN behaviors between binary pairs in a multicomponent system. Many ideal and nonideal binary systems and two ternary systems were tested against the DPL model. Each binary adsorbate-adsorbent pair exhibited either PP or PN behavior but nothing in between. This binary information was used successfully to predict ternary adsorption equilibria based on binary pairwise additivity. Overall, predictions from the DPL model were comparable to or significantly better than those from other models in the literature, revealing that its correlative and predictive powers are universally applicable. Because it is loading-explicit, simple to use, and also accurate, the DPL model may be one of the best equilibrium models to use in gas-phase adsorption process simulation.
Hybrid phase transition into an absorbing state: Percolation and avalanches
NASA Astrophysics Data System (ADS)
Lee, Deokjae; Choi, S.; Stippinger, M.; Kertész, J.; Kahng, B.
2016-04-01
Interdependent networks are more fragile under random attacks than simplex networks, because interlayer dependencies lead to cascading failures and finally to a sudden collapse. This is a hybrid phase transition (HPT), meaning that at the transition point the order parameter has a jump but there are also critical phenomena related to it. Here we study these phenomena on the Erdős-Rényi and the two-dimensional interdependent networks and show that the hybrid percolation transition exhibits two kinds of critical behaviors: divergence of the fluctuations of the order parameter and power-law size distribution of finite avalanches at a transition point. At the transition point global or "infinite" avalanches occur, while the finite ones have a power law size distribution; thus the avalanche statistics also has the nature of a HPT. The exponent βm of the order parameter is 1 /2 under general conditions, while the value of the exponent γm characterizing the fluctuations of the order parameter depends on the system. The critical behavior of the finite avalanches can be described by another set of exponents, βa and γa. These two critical behaviors are coupled by a scaling law: 1 -βm=γa .
Density and Phase State of a Confined Nonpolar Fluid
NASA Astrophysics Data System (ADS)
Kienle, Daniel F.; Kuhl, Tonya L.
2016-07-01
Measurements of the mean refractive index of a spherelike nonpolar fluid, octamethytetracylclosiloxane (OMCTS), confined between mica sheets, demonstrate direct and conclusive experimental evidence of the absence of a first-order liquid-to-solid phase transition in the fluid when confined, which has been suggested to occur from previous experimental and simulation results. The results also show that the density remains constant throughout confinement, and that the fluid is incompressible. This, along with the observation of very large increases (many orders of magnitude) in viscosity during confinement from the literature, demonstrate that the molecular motion is limited by the confining wall and not the molecular packing. In addition, the recently developed refractive index profile correction method, which enables the structural perturbation inherent at a solid-liquid interface and that of a liquid in confinement to be determined independently, was used to show that there was no measurable excess or depleted mass of OMCTS near the mica surface in bulk films or confined films of only two molecular layers.
Density and Phase State of a Confined Nonpolar Fluid.
Kienle, Daniel F; Kuhl, Tonya L
2016-07-15
Measurements of the mean refractive index of a spherelike nonpolar fluid, octamethytetracylclosiloxane (OMCTS), confined between mica sheets, demonstrate direct and conclusive experimental evidence of the absence of a first-order liquid-to-solid phase transition in the fluid when confined, which has been suggested to occur from previous experimental and simulation results. The results also show that the density remains constant throughout confinement, and that the fluid is incompressible. This, along with the observation of very large increases (many orders of magnitude) in viscosity during confinement from the literature, demonstrate that the molecular motion is limited by the confining wall and not the molecular packing. In addition, the recently developed refractive index profile correction method, which enables the structural perturbation inherent at a solid-liquid interface and that of a liquid in confinement to be determined independently, was used to show that there was no measurable excess or depleted mass of OMCTS near the mica surface in bulk films or confined films of only two molecular layers. PMID:27472123
Hybrid phase transition into an absorbing state: Percolation and avalanches.
Lee, Deokjae; Choi, S; Stippinger, M; Kertész, J; Kahng, B
2016-04-01
Interdependent networks are more fragile under random attacks than simplex networks, because interlayer dependencies lead to cascading failures and finally to a sudden collapse. This is a hybrid phase transition (HPT), meaning that at the transition point the order parameter has a jump but there are also critical phenomena related to it. Here we study these phenomena on the Erdős-Rényi and the two-dimensional interdependent networks and show that the hybrid percolation transition exhibits two kinds of critical behaviors: divergence of the fluctuations of the order parameter and power-law size distribution of finite avalanches at a transition point. At the transition point global or "infinite" avalanches occur, while the finite ones have a power law size distribution; thus the avalanche statistics also has the nature of a HPT. The exponent β_{m} of the order parameter is 1/2 under general conditions, while the value of the exponent γ_{m} characterizing the fluctuations of the order parameter depends on the system. The critical behavior of the finite avalanches can be described by another set of exponents, β_{a} and γ_{a}. These two critical behaviors are coupled by a scaling law: 1-β_{m}=γ_{a}.
Hybrid phase transition into an absorbing state: Percolation and avalanches.
Lee, Deokjae; Choi, S; Stippinger, M; Kertész, J; Kahng, B
2016-04-01
Interdependent networks are more fragile under random attacks than simplex networks, because interlayer dependencies lead to cascading failures and finally to a sudden collapse. This is a hybrid phase transition (HPT), meaning that at the transition point the order parameter has a jump but there are also critical phenomena related to it. Here we study these phenomena on the Erdős-Rényi and the two-dimensional interdependent networks and show that the hybrid percolation transition exhibits two kinds of critical behaviors: divergence of the fluctuations of the order parameter and power-law size distribution of finite avalanches at a transition point. At the transition point global or "infinite" avalanches occur, while the finite ones have a power law size distribution; thus the avalanche statistics also has the nature of a HPT. The exponent β_{m} of the order parameter is 1/2 under general conditions, while the value of the exponent γ_{m} characterizing the fluctuations of the order parameter depends on the system. The critical behavior of the finite avalanches can be described by another set of exponents, β_{a} and γ_{a}. These two critical behaviors are coupled by a scaling law: 1-β_{m}=γ_{a}. PMID:27176256
One-Dimensional Three-State Quantum Walk with Single-Point Phase Defects
NASA Astrophysics Data System (ADS)
Xu, Yong-Zhen; Guo, Gong-De; Lin, Song
2016-09-01
In this paper, we study a three-state quantum walk with a phase defect at a designated position. The coin operator is a parametrization of the eigenvectors of the Grover matrix. We numerically investigate the properties of the proposed model via the position probability distribution, the position standard deviation, and the time-averaged probability at the designated position. It is shown that the localization effect can be governed by the phase defect's position and strength, coin parameter and initial state.
Phase states of a 2D easy-plane ferromagnet with strong inclined anisotropy
Fridman, Yu. A. Klevets, F. N.; Gorelikov, G. A.; Meleshko, A. G.
2012-12-15
We investigate the spin states of a 2D film exhibiting easy-axis anisotropy and a strong single-ion inclined anisotropy whose axis forms a certain angle with the normal to the film surface. Such a system may have an angular ferromagnetic phase, a spatially inhomogeneous state, and a quadrupole phase, whose realization depends substantially on the inclined anisotropy and the orientation of the wavevector in the film plane.
Two-dimensional magnetohydrodynamic equilibria with flow and studies of equilibria fluctuations
Agim, Y.Z.
1989-08-01
A set of reduced ideal MHD equations is derived to investigate equilibria of plasmas with mass flow in general two-dimensional geometry. These equations provide a means of investigating the effects of flow on self-consistent equilibria in a number of new two-dimensional configurations such as helically symmetric configurations with helical axis, which are relevant to stellarators, as well as axisymmetric configurations. It is found that as in the axisymmetric case, general two-dimensional flow equilibria are governed by a second-order quasi-linear partial differential equation for a magnetic flux function, which is coupled to a Bernoulli-type equation for the density. The equation for the magnetic flux function becomes hyperbolic at certain critical flow speeds which follow from its characteristic equation. When the equation is hyperbolic, shock phenomena may exist. As a particular example, unidirectional flow along the lines of symmetry is considered. In this case, the equation mentioned above is always elliptic. An exact solution for the case of helically symmetric unidirectional flow is found and studied to determine flow effects on the magnetic topology. In second part of this thesis, magnetic fluctuations due to the thermally excited MHD waves are investigated using fluid and kinetic models to describe stable, uniform, compressible plasma in the range above the drift wave frequency and below the ion cyclotron frequency. It is shown that the fluid model with resistivity yields spectral densities which are roughly Lorentzian, exhibit equipartition with no apparent cutoff in wavenumber space and a Bohm-type diffusion coefficient. Under certain conditions, the ensuing transport may be comparable to classical values. For a phenomenological cutoff imposed on the spectrum, the typical fluctuating-to-equilibrium magnetic field ratio is found to be of the order of 10 {sup {minus}10}.
SESAME 96171, a three-phase equation of state for CeO2
Chisolm, Eric D.; Day, Christy M.
2014-06-25
We describe an equation of state (EOS) for cerium (IV) oxide, CeO_{2}, that includes two solid phases and the liquid. The models and parameters used to calculate the EOS are presented in detail, and we compare with data for both crystal phases and ambient melt. We discuss complications that arise when making multiphase EOS.
Geometric phases for laser-induced aligned pendular states of linear molecules
Aleynikov, Dmitriy V.
2006-02-15
Geometric phases may arise in a linear molecule interacting via its anisotropic polarizability with a strong nonresonant laser field. When the polarization vector of laser radiation undergoes cyclic evolution, the molecule returns to its original state but may acquire a Berry or Aharonov-Anandan phase factor.
On the Finiteness of Collisions and Phase-Locked States for the Kuramoto Model
NASA Astrophysics Data System (ADS)
Ha, Seung-Yeal; Kim, Hwa Kil; Ryoo, Sang Woo
2016-06-01
Synchronization phenomenon is ubiquitous in our complex systems, and many phenomenological models have been proposed and studied analytically and numerically. Among them, the Kuramoto model serves as a prototype model for the phase synchronization of weakly coupled oscillators. In this paper, we study the finiteness of collisions (crossings) among Kuramoto oscillators in the relaxation process toward the phase-locked states and the total number of phase-locked states with positive (Kuramoto) order parameters. For identical oscillators, it is well known that collisions between distinct oscillators cannot occur in finite-time, and we show that there are only a finite number of phase-locked states with positive order parameters. However, for non-identical oscillators, oscillators with different natural frequencies can cross each other in their relaxation process, and estimating the total number of phase-locked states is a nontrivial matter. We show that, for the non-identical case, asymptotic phase-locking is equivalent to the finiteness of collisions, and the total number of phase-locked states with positive order parameters is bounded above by 2^N, where N is the number of oscillators.
The in-phase states of Josephson junctions stacks as attractors
Hristov, I.; Dimova, S.; Hristova, R.
2014-11-12
The aim of this investigation is to show that the coherent, in-phase states of intrinsic Josephson junctions stacks are attractors of the stacks' states when the applied external magnetic field h{sub e} and the external current γ vary within certain domains. Mathematically the problem is to find the solutions of the system of perturbed sine-Gordon equations for fixed other parameters and zero or random initial conditions. We determine the region in the plane (h{sub e}, γ), where the in-phase states are attractors of the stack's states for arbitrary initial perturbations. This is important, because the in-phase states are required for achieving terahertz radiation from the Josephson stacks.
Comparison of time/phase lags in the hard state and plateau state of GRS 1915+105
Pahari, Mayukh; Yadav, J. S.; Neilsen, Joseph; Misra, Ranjeev; Uttley, Phil
2013-12-01
We investigate the complex behavior of energy- and frequency-dependent time/phase lags in the plateau state and the radio-quiet hard (χ) state of GRS 1915+105. In our timing analysis, we find that when the source is faint in the radio, quasi-periodic oscillations (QPOs) are observed above 2 Hz and typically exhibit soft lags (soft photons lag hard photons), whereas QPOs in the radio-bright plateau state are found below 2.2 Hz and consistently show hard lags. The phase lag at the QPO frequency is strongly anti-correlated with that frequency, changing sign at 2.2 Hz. However, the phase lag at the frequency of the first harmonic is positive and nearly independent of that frequency at ∼0.172 rad, regardless of the radio emission. The lag energy dependence at the first harmonic is also independent of radio flux. However, the lags at the QPO frequency are negative at all energies during the radio-quiet state, but lags at the QPO frequency during the plateau state are positive at all energies and show a 'reflection-type' evolution of the lag energy spectra with respect to the radio-quiet state. The lag energy dependence is roughly logarithmic, but there is some evidence for a break around 4-6 keV. Finally, the Fourier-frequency-dependent phase lag spectra are fairly flat during the plateau state, but increase from negative to positive during the radio-quiet state. We discuss the implications of our results in light of some generic models.
Tearing Mode Stability of Evolving Toroidal Equilibria
NASA Astrophysics Data System (ADS)
Pletzer, A.; McCune, D.; Manickam, J.; Jardin, S. C.
2000-10-01
There are a number of toroidal equilibrium (such as JSOLVER, ESC, EFIT, and VMEC) and transport codes (such as TRANSP, BALDUR, and TSC) in our community that utilize differing equilibrium representations. There are also many heating and current drive (LSC and TORRAY), and stability (PEST1-3, GATO, NOVA, MARS, DCON, M3D) codes that require this equilibrium information. In an effort to provide seamless compatibility between the codes that produce and need these equilibria, we have developed two Fortran 90 modules, MEQ and XPLASMA, that serve as common interfaces between these two classes of codes. XPLASMA provides a common equilibrium representation for the heating and current drive applications while MEQ provides common equilibrium and associated metric information needed by MHD stability codes. We illustrate the utility of this approach by presenting results of PEST-3 tearing stability calculations of an NSTX discharge performed on profiles provided by the TRANSP code. Using the MEQ module, the TRANSP equilibrium data are stored in a Fortran 90 derived type and passed to PEST3 as a subroutine argument. All calculations are performed on the fly, as the profiles evolve.
Unifying dynamical and structural stability of equilibria
NASA Astrophysics Data System (ADS)
Arnoldi, Jean-François; Haegeman, Bart
2016-09-01
We exhibit a fundamental relationship between measures of dynamical and structural stability of linear dynamical systems-e.g. linearized models in the vicinity of equilibria. We show that dynamical stability, quantified via the response to external perturbations (i.e. perturbation of dynamical variables), coincides with the minimal internal perturbation (i.e. perturbations of interactions between variables) able to render the system unstable. First, by reformulating a result of control theory, we explain that harmonic external perturbations reflect the spectral sensitivity of the Jacobian matrix at the equilibrium, with respect to constant changes of its coefficients. However, for this equivalence to hold, imaginary changes of the Jacobian's coefficients have to be allowed. The connection with dynamical stability is thus lost for real dynamical systems. We show that this issue can be avoided, thus recovering the fundamental link between dynamical and structural stability, by considering stochastic noise as external and internal perturbations. More precisely, we demonstrate that a linear system's response to white-noise perturbations directly reflects the intensity of internal white-noise disturbance that it can accommodate before becoming stochastically unstable.
Singular Isothermal Disks. Paper 2; Nonaxiymmetric Bifurcations and Equilibria
NASA Technical Reports Server (NTRS)
Galli, Danielle; Shu, Frank H.; Laughlin, Gregory; Lizano, Susana
2000-01-01
We review the difficulties of the classical fission and fragmentation hypotheses for the formation of binary and multiple stars. A crucial missing ingredient in previous theoretical studies is the inclusion of dynamically important levels of magnetic fields. As a minimal model for a candidate presursor to the formation of binary and multiple stars, we therefore formulate and solve the problem of the equilibria of isopedically magnetized, singular isothermal disks, without the assumption of axial symmetry. Considerable analytical progress can be made if we restrict our attention to models that are scale-free, i.e., that have surface densities that vary inversely with distance omega from the rotation axis of the system. In agreement with earlier analysis by Syer and Tremaine, we find that lopsided (M = 1) configurations exist at any dimensionless rotation rate, including zero. Multiple-lobed (M = 2, 3, 4, ...) configurations bifurcate from an underlying axisymmetric sequence at progressively higher dimensionless rates of rotation, but such nonaxisymmetric sequences always terminate in shockwaves before they have a chance to fission into M = 2, 3, 4, ... separate bodies. On the basis of our experience in this paper, we advance the hypothesis that binary and multiple star-formation from smooth (i.e., not highly turbulent) starting states that are supercritical but in unstable mechanical balance requires the rapid (i.e., dynamical) loss of magnetic flux at some stage of the ensuing gravitational collapse.
Phase boundary of spin-polarized-current state of electrons in bilayer graphene
NASA Astrophysics Data System (ADS)
Yan, Xin-Zhong; Ma, Yinfeng; Ting, C. S.
2016-06-01
Using a four-band Hamiltonian, we study the phase boundary of spin-polarized-current state (SPCS) of interacting electrons in bilayer graphene. The model of spin-polarized-current state has previously been shown to resolve a number of experimental puzzles in bilayer graphene. The phase boundaries of the SPCS with and without the external voltage between the two layers are obtained in this work. An unusual phase boundary where there are two transition temperatures for a given carrier concentration is found at finite external voltage. The physics of this phenomenon is explained.
Chou, I.-Ming; Sterner, S.M.; Pitzer, Kenneth S.
1992-01-01
The sylvite liquidus in the binary system KCl-H2O and the liquidus in the ternary system NaCl-KCl-H2O were determined by using isobaric differential thermal analysis (DTA) cooling scans at pressures up to 2 kbars. Sylvite solubilities along the three-phase curve in the binary system KCl-H2O were obtained by the intersection of sylvite-liquidus isopleths with the three-phase curve in a P-T plot. These solubility data can be represented by the equation Wt.% KCl (??0.2) = 12.19 + 0.1557T - 5.4071 ?? 10-5 T2, where 400 ??? T ??? 770??C. These data are consistent with previous experimental observations. The solidus in the binary system NaCl-KCl was determined by using isobaric DTA heating scans at pressures up to 2 kbars. Using these liquidus and solidus data and other published information, a thermodynamic-PTX analysis of solid-liquid equilibria at high pressures and temperatures for the ternary system has been performed and is presented in an accompanying paper (Part V of this series). However, all experimental liquidus, solidus, and solvus data used in this analysis are summarized in this report (Part IV) and they are compared with the calculated values based on the analysis. ?? 1992.
Some Phase Equilibrium Systematics of Martian Volatiles
NASA Astrophysics Data System (ADS)
Longhi, J.
2010-03-01
Binary pressure (P) - temperature (T) phase diagrams were constructed for the N2-, CH4-, and SO2-H2O systems making use of published triple points, critical points, and limited experimental determination of univariant equilibria.
Eutectic equilibria in the quaternary system Fe-Cr-Mn-C
NASA Technical Reports Server (NTRS)
Nowotny, H.; Wayne, S.; Schuster, J. C.
1982-01-01
The constitution of the quaternary system, Fe-Cr-Mn-C and to a lesser extent of the quinary system, Fe-Cr-Mn-Al-C were examined for in situ composite alloy candidates. Multivariant eutectic compositions were determined from phase equilibria studies wherein M7C3 carbides (approximately 30% by volume) formed from the melt within gamma iron. An extended field of the hexagonal carbide, (Cr, Fe, Mn)7 C3, was found without undergoing transformation to the orthorhombic structure. Increasing stability for this carbide was found for higher ratios of Cr/Fe(+) Cr + Mn. Aluminum additions promoted a ferritic matrix while manganese favored the desired gamma austenitic matrix. In coexistence with the matrix phase, chromium enters preferentially the carbide phase while manganese distributes equally between the gamma matrix and the M7C3 carbide. The composition and lattice parameters of the carbide and matrix phases were determined to establish their respective stabilities.
Canted antiferromagnetic phase of the ν=0 quantum Hall state in bilayer graphene.
Kharitonov, Maxim
2012-07-27
Motivated to understand the nature of the strongly insulating ν=0 quantum Hall state in bilayer graphene, we develop the theory of the state in the framework of quantum Hall ferromagnetism. The generic phase diagram, obtained in the presence of the isospin anisotropy, perpendicular electric field, and Zeeman effect, consists of the spin-polarized ferromagnetic (F), canted antiferromagnetic (CAF), and partially (PLP) and fully (FLP) layer-polarized phases. We address the edge transport properties of the phases. Comparing our findings with the recent data on suspended dual-gated devices, we conclude that the insulating ν=0 state realized in bilayer graphene at lower electric field is the CAF phase. We also predict a continuous and a sharp insulator-metal phase transition upon tilting the magnetic field from the insulating CAF and FLP phases, respectively, to the F phase with metallic edge conductance 2e(2)/h, which could be within the reach of available fields and could allow one to identify and distinguish the phases experimentally.
Bilayer quantum Hall phase transitions and the orbifold non-Abelian fractional quantum Hall states
NASA Astrophysics Data System (ADS)
Barkeshli, Maissam; Wen, Xiao-Gang
2011-09-01
We study continuous quantum phase transitions that can occur in bilayer fractional quantum Hall (FQH) systems as the interlayer tunneling and interlayer repulsion are tuned. We introduce a slave-particle gauge theory description of a series of continuous transitions from the (ppq) Abelian bilayer states to a set of non-Abelian FQH states, which we dub orbifold FQH states, of which the Z4 parafermion (Read-Rezayi) state is a special case. This provides an example in which Z2 electron fractionalization leads to non-Abelian topological phases. The naive “ideal” wave functions and ideal Hamiltonians associated with these orbifold states do not in general correspond to incompressible phases but, instead, lie at a nearby critical point. We discuss this unusual situation from the perspective of the pattern-of-zeros/vertex algebra frameworks and discuss implications for the conceptual foundations of these approaches. Due to the proximity in the phase diagram of these non-Abelian states to the (ppq) bilayer states, they may be experimentally relevant, both as candidates for describing the plateaus in single-layer systems at filling fractions 8/3 and 12/5 and as a way to tune to non-Abelian states in double-layer or wide quantum wells.
Geometric quantum phase for displaced states for a particle with an induced electric dipole moment
NASA Astrophysics Data System (ADS)
Lemos de Melo, J.; Bakke, K.; Furtado, C.
2016-07-01
Basing on the analogue Landau levels for a neutral particle possessing an induced electric dipole moment, we show that displaced states can be built in the presence of electric and magnetic fields. Besides, the Berry phase associated with these displaced quantum states is obtained by performing an adiabatic cyclic evolution in series of paths in parameter space.
Bilayer quantum Hall phase transitions and the orbifold non-Abelian fractional quantum Hall states
Barkeshli, Maissam; Wen Xiaogang
2011-09-15
We study continuous quantum phase transitions that can occur in bilayer fractional quantum Hall (FQH) systems as the interlayer tunneling and interlayer repulsion are tuned. We introduce a slave-particle gauge theory description of a series of continuous transitions from the (ppq) Abelian bilayer states to a set of non-Abelian FQH states, which we dub orbifold FQH states, of which the Z{sub 4} parafermion (Read-Rezayi) state is a special case. This provides an example in which Z{sub 2} electron fractionalization leads to non-Abelian topological phases. The naive ''ideal'' wave functions and ideal Hamiltonians associated with these orbifold states do not in general correspond to incompressible phases but, instead, lie at a nearby critical point. We discuss this unusual situation from the perspective of the pattern-of-zeros/vertex algebra frameworks and discuss implications for the conceptual foundations of these approaches. Due to the proximity in the phase diagram of these non-Abelian states to the (ppq) bilayer states, they may be experimentally relevant, both as candidates for describing the plateaus in single-layer systems at filling fractions 8/3 and 12/5 and as a way to tune to non-Abelian states in double-layer or wide quantum wells.
Chemical equilibria model analysis of Hope Creek eastern oil shale lysimeter leachate data
Essington, M.E.
1989-09-01
Leachates from field lysimeters containing an eastern oil shale, a retorted eastern oil shale, and an oil shale fines/retorted oil shale mixture were subjected to chemical equilibria analysis by the GEOCHEM model. Results of the chemical equilibria model analysis provided a more detailed characterization of the chemistry of oil shale materials. The aqueous chemistry of the lysimeter leachates is dominated by free ionic metal species and metal sulfate ion pairs. Activity diagrams shows that free metal ion activities (with the exception of Ca{sup 2+}) are directly related to SO{sub 4}{sup 2{minus}} activities. This suggests that the aqueous activities of the metals examined are not supported by metal sulfate solid phases. However, an examination of metal sulfate ion activity products (IAPs) as a function of time shows that the IAPs approach constant values after approximately 800 days of the field study. For the great majority of the metals examined, the IAP values suggest leachate undersaturation with respect to even the most stable metal sulfate phases. Leachates from all three materials are predicted by GEOCHEM to approach equilibrium with respect to gypsum and goethite. In addition, leachates from the oil shale lysimeter are predicted by GEOCHEM to approach equilibrium with respect to melanterite, Fe-jurbanite, franklinite, molybdite, and molybdic acid. Aluminum activities in all three lysimeter leachates fall within the stability region of several basic aluminum sulfates. However, Al{sup 3+} activities in the lysimeter leachates are not supported by sulfate phases. 34 refs., 15 figs., 2 tabs.
NASA Technical Reports Server (NTRS)
Han, D.; Kim, Y. S.; Noz, Marilyn E.
1990-01-01
It is shown that the basic symmetry of two-mode squeezed states is governed by the group SP(4) in the Wigner phase space which is locally isomorphic to the (3 + 2)-dimensional Lorentz group. This symmetry, in the Schroedinger picture, appears as Dirac's two-oscillator representation of O(3,2). It is shown that the SU(2) and SU(1,1) interferometers exhibit the symmetry of this higher-dimensional Lorentz group. The mathematics of two-mode squeezed states is shown to be applicable to other branches of physics including thermally excited states in statistical mechanics and relativistic extended hadrons in the quark model.
Exploring the phase space of multiple states in highly turbulent Taylor-Couette flow
NASA Astrophysics Data System (ADS)
van der Veen, Roeland C. A.; Huisman, Sander G.; Dung, On-Yu; Tang, Ho L.; Sun, Chao; Lohse, Detlef
2016-06-01
We investigate the existence of multiple turbulent states in highly turbulent Taylor-Couette flow in the range of Ta =1011 to 9 ×1012 by measuring the global torques and the local velocities while probing the phase space spanned by the rotation rates of the inner and outer cylinders. The multiple states are found to be very robust and are expected to persist beyond Ta =1013 . The rotation ratio is the parameter that most strongly controls the transitions between the flow states; the transitional values only weakly depend on the Taylor number. However, complex paths in the phase space are necessary to unlock the full region of multiple states. By mapping the flow structures for various rotation ratios in a Taylor-Couette setup with an equal radius ratio but a larger aspect ratio than before, multiple states are again observed. Here they are characterized by even richer roll structure phenomena, including an antisymmetrical roll state.
The steady-state phase distribution of the motor switch complex model of Halobacterium salinarum.
del Rosario, Ricardo C H; Diener, Francine; Diener, Marc; Oesterhelt, Dieter
2009-12-01
Steady-state analysis is performed on the kinetic model for the switch complex of the flagellar motor of Halobacterium salinarum (Nutsch et al.). The existence and uniqueness of a positive steady-state of the system is established and it is demonstrated why the steady-state is centered around the competent phase, a state of the motor in which it is able to respond to light stimuli. It is also demonstrated why the steady-state shifts to the refractory phase when the steady-state value of the response regulator CheYP increases. This work is one aspect of modeling in systems biology wherein the mathematical properties of a model are established. PMID:19857501
Dynamical phase transitions, time-integrated observables, and geometry of states
NASA Astrophysics Data System (ADS)
Hickey, James M.; Genway, Sam; Garrahan, Juan P.
2014-02-01
We show that there exist dynamical phase transitions (DPTs), as defined by Heyl et al. [Phys. Rev. Lett. 110, 135704 (2013), 10.1103/PhysRevLett.110.135704], in the transverse-field Ising model (TFIM) away from the static quantum critical points. We study a class of special states associated with singularities in the generating functions of time-integrated observables as found by Hickey et al. [Phys. Rev. B 87, 184303 (2013)], 10.1103/PhysRevB.87.184303. Studying the dynamics of these special states under the evolution of the TFIM Hamiltonian, we find temporal nonanalyticities in the initial-state return probability associated with dynamical phase transitions. By calculating the Berry phase and Chern number we show the set of special states have interesting geometric features similar to those associated with static quantum critical points.
Faraldo-Gómez, José D; Roux, Benoît
2007-07-30
Molecular dynamics simulations based on the replica-exchange framework (REMD) are emerging as a useful tool to characterize the conformational variability that is intrinsic to most chemical and biological systems. In this work, it is shown that a simple extension of the replica-exchange method, known as Hamiltonian REMD, greatly facilitates the characterization of conformational equilibria across large energetic barriers, or in the presence of substantial entropic effects, overcoming some of the difficulties of REMD based on temperature alone. In particular, a comparative assessment of the HREMD and TREMD approaches was made, through computation of the gas-phase free-energy difference between the so-called D(2d) and S(4) states of tetrabutylammonium (TBA), an ionic compound of frequently used in biophysical studies of ion channels. Taking advantage of the greater efficiency of the HREMD scheme, the conformational equilibrium of TBA was characterized in a variety of conditions. Simulation of the gas-phase equilibrium in the 100-300 K range allowed us to compute the entropy difference between these states as well as to describe its temperature dependence. Through HREMD simulations of TBA in a water droplet, the effect of solvation on the conformational equilibrium was determined. Finally, the equilibrium of TBA in the context of a simplified model of the binding cavity of the KcsA potassium channel was simulated, and density maps for D(2d) and S(4) states analogous to those derived from X-ray crystallography were constructed. Overall, this work illustrates the potential of the HREMD approach in the context of computational drug design, ligand-receptor structural prediction and more generally, molecular recognition, where one of the most challenging issues remains to account for conformational flexibility as well for the solvation and entropic effects thereon.
Phase transitions and isothermal equations of state of epsilon hexanitrohexaazaisowurtzitane (CL-20)
NASA Astrophysics Data System (ADS)
Gump, Jared C.; Peiris, Suhithi M.
2008-10-01
The phase stability of epsilon hexanitrohexaazaisowurtzitane at high pressure and temperature was investigated using synchrotron angle-dispersive x-ray diffraction experiments. The samples were compressed at room temperature using a Merrill-Bassett diamond anvil cell. For high-temperature compression experiments a hydrothermal diamond anvil cell developed by Bassett was used. Pressures and temperatures of around 5 GPa and 175 °C, respectively, were achieved. The epsilon phase was determined to be stable under ambient pressure to a temperature of 120 °C. A phase transition to the gamma phase was seen at 125 °C and the gamma phase remained stable until thermal decomposition above 150 °C. Pressure-volume data for the epsilon phase at ambient and 75 °C were fitted to the Birch-Murnaghan formalism to obtain isothermal equations of state.
Bilinear relative equilibria of identical point vortices
NASA Astrophysics Data System (ADS)
Aref, Hassan; Beelen, Peter; Brøns, Morten
2011-11-01
A new class of bilinear relative equilibria of identical point vortices in which the vortices are constrained to be on two perpendicular lines, taken to be the x- and y-axes of a cartesian coordinate system, is introduced and studied. In general we have m vortices on the y-axis and n on the x- axis. We define generating polynomials q (z) and p (z) , respectively, for each set of vortices. A second order, linear ODE for p (z) given q (z) is derived. Several results relating the general solution of the ODE to relative equilibrium configurations are established. Our strongest result, obtained using Sturm's comparison theorem, is that if p (z) satisfies the ODE for a given q (z) with its imaginary zeros symmetric relative to the x-axis, then it must have at least n - m + 2 simple, real zeros. For m = 2 this provides a complete characterization of all zeros, and we study this case in some detail. In particular, we show that given q (z) =z2 +η2 , where η is real, there is a unique p (z) of degree n, and a unique value of η2 =An , such that the zeros of q (z) and p (z) form a relative equilibrium of n + 2 point vortices. We show that An ~2/3 n +1/2 , as n --> ∞ , where the coefficient of n is determined analytically, the next order term numerically. Supported in part by the Danish National Research Foundation through a Niels Bohr visiting professorship.
Yu-Shiba-Rusinov states in phase-biased superconductor-quantum dot-superconductor junctions
NASA Astrophysics Data System (ADS)
Kiršanskas, Gediminas; Goldstein, Moshe; Flensberg, Karsten; Glazman, Leonid I.; Paaske, Jens
2015-12-01
We study the effects of a phase difference on Yu-Shiba-Rusinov (YSR) states in a spinful Coulomb-blockaded quantum dot contacted by a superconducting loop. In the limit where charging energy is larger than the superconducting gap, we determine the subgap excitation spectrum, the corresponding supercurrent, and the differential conductance as measured by a normal-metal tunnel probe. In absence of a phase difference only one linear combination of the superconductor lead electrons couples to the spin, which gives a single YSR state. With finite phase difference, however, it is effectively a two-channel scattering problem and therefore an additional state emerges from the gap edge. The energy of the phase-dependent YSR states depend on the gate voltage and one state can cross zero energy twice inside the valley with odd occupancy. These crossings are shifted by the phase difference towards the charge degeneracy points, corresponding to larger exchange couplings. Moreover, the zero-energy crossings give rise to resonant peaks in the differential conductance with magnitude 4 e2/h . Finally, we demonstrate that the quantum fluctuations of the dot spin do not alter qualitatively any of the results.
Role of the aerosol phase state in ammonia/amines exchange reactions.
Chan, Lap P; Chan, Chak K
2013-06-01
The exchange reaction of ammonia in (NH4)2SO4 with an amine and the corresponding reverse reaction of amines in aminium sulfates with ammonia were investigated using an electrodynamic balance coupled with a Raman spectrometer. The temporal changes in particle mass, chemical composition, and phase state were simultaneously monitored. When the salt particles were in an aqueous state at elevated relative humidities (RHs), the exchange of ammonia/amine vapors in the particle phase was reversible. The exchange rates of aqueous particles were in general higher than those of their corresponding solid counterparts. An aqueous phase was essential for the effective displacement of ammonia and amines. Aminium salts in different phase states and with different evaporation characteristics showed remarkably different reaction behaviors in ammonia vapor. The less compact amorphous aminium sulfate solids were more susceptible to ammonia exchange than the crystalline solids. The aminium salts in a liquid state exhibited substantial amine evaporation at <3% RH and formed acidic bisulfate. Under ammonia exposure, these acidic aminium droplets underwent both neutralization and displacement reactions. Stable solid salts containing ammonium, aminium, sulfate, and bisulfate were formed and hindered further reactions. The result suggests that ambient aminium sulfates may be acidic. Overall, the phase states of the ammonium and aminium salt particles crucially determine the heterogeneous reaction rates and final product properties and identities. PMID:23668831
NASA Astrophysics Data System (ADS)
Kobayashi, Kazumichi; Hori, Kazumasa; Kon, Misaki; Sasaki, Kiyofumi; Watanabe, Masao
2016-09-01
Using molecular dynamics simulations, the present study investigates the precise characteristics of evaporating and reflecting monatomic molecules (argon) composing a kinetic boundary condition (KBC) in a vapor-liquid equilibria. We counted the evaporating and reflecting molecules utilizing two boundaries (vapor and liquid boundaries) proposed by the previous studies (Meland et al. in Phys Fluids 16:223-243, 2004; Gu et al. in Fluid Phase Equilib 297:77-89, 2010). In the present study, we improved the method using the two boundaries incorporating the concept of the spontaneously evaporating molecular mass flux. The present method allows us to count the evaporating and reflecting molecules easily, to investigate the detail motion of the evaporating and reflecting molecules, and also to evaluate the velocity distribution function of the KBC at the vapor-liquid interface, appropriately. From the results, we confirm that the evaporating and reflecting molecules in the normal direction to the interface have slightly faster and significantly slower average velocities than that of the Maxwell distribution at the liquid temperature, respectively. Also, the stall time of the reflecting molecules at the interphase that is the region in the vicinity of the vapor-liquid interface is much shorter than those of the evaporating molecules. Furthermore, we discuss our method for constructing the KBC that incorporates condensation and evaporation coefficients. Based on these results, we suggest that the proposed method is appropriate for investigating KBC in various nonequilibrium states or multi-component systems.
Cerri, S. S.; Pegoraro, F.; Califano, F.; Jenko, F.
2014-11-15
Observations and numerical simulations of laboratory and space plasmas in almost collisionless regimes reveal anisotropic and non-gyrotropic particle distribution functions. We investigate how such states can persist in the presence of a sheared flow. We focus our attention on the pressure tensor equation in a magnetized plasma and derive analytical self-consistent plasma equilibria which exhibit a novel asymmetry with respect to the magnetic field direction. These results are relevant for investigating, within fluid models that retain the full pressure tensor dynamics, plasma configurations where a background shear flow is present.
Ballooning mode second stability region for sequences of tokamak equilibria
Sugiyama, L.; Mark, J. W-K.
1980-01-01
A numerical study of several sequences of tokamak equilibria derived from two flux conserving sequences confirms the tendency of high n ideal MHD ballooning modes to stabilize for values of the plasma beta greater than a second critical beta, for sufficiently favorable equilibria. The major stabilizing effect of increasing the inverse rotational transform profile q(Psi) for equilibria with the same flux surface geometry is shown. The unstable region shifts toward larger shear d ln q/d ln ..gamma.. and the width of the region measured in terms of the poloidal beta or a pressure gradient parameter, for fixed shear, decreases. The smaller aspect ratio sequences are more sensitive to changes in q and have less stringent limits on the attainable value of the plasma beta in the high beta stable region. Finally, the disconnected mode approximation is shown to provide a reasonable description of the second high beta stability boundary.
Extended fluid models: Pressure tensor effects and equilibria
Cerri, S. S.; Henri, P.; Califano, F.; Pegoraro, F.; Del Sarto, D.; Faganello, M.
2013-11-15
We consider the use of “extended fluid models” as a viable alternative to computationally demanding kinetic simulations in order to manage the global large scale evolution of a collisionless plasma while accounting for the main effects that come into play when spatial micro-scales of the order of the ion inertial scale d{sub i} and of the thermal ion Larmor radius ρ{sub i} are formed. We present an extended two-fluid model that retains finite Larmor radius (FLR) corrections to the ion pressure tensor while electron inertia terms and heat fluxes are neglected. Within this model we calculate analytic FLR plasma equilibria in the presence of a shear flow and elucidate the role of the magnetic field asymmetry. Using a Hybrid Vlasov code, we show that these analytic equilibria offer a significant improvement with respect to conventional magnetohydrodynamic shear-flow equilibria when initializing kinetic simulations.
Predictions of adsorption equilibria of nonpolar hydrocarbons onto activated carbon
Do, D.D.; Wang, K.
1998-12-08
This paper presents a new approach to analyze the adsorption equilibria of nonpolar hydrocarbons onto activated carbon. The kinetic theory of gases and the 10-4-3 potential energy were employed to describe the adsorption process inside micropores. On the basis of this theory, a general isotherm model was proposed which possesses the potential capability of predicting the adsorption equilibria of an adsorbent by using the knowledge of its microporous structure and molecular properties of adsorbates. Experimental data of gases and vapors on Ajax activated carbon were employed to examine the model. Adsorption equilibria of binary mixtures were also investigated with the model, and it is shown that the model is capable of simulating the nonideal, or azeotropic, adsorption behaviors resulting from the structural heterogeneity of the adsorbent.
Three-dimensional force-free looplike magnetohydrodynamic equilibria
NASA Technical Reports Server (NTRS)
Finn, John M.; Guzdar, Parvez N.; Usikov, Daniel
1994-01-01
Computations of three-dimensional force-free magnetohydrodynamic (MHD) equilibria, del x B = lambdaB with lambda = lambda(sub 0), a constant are presented. These equilibria are determined by boundary conditions on a surface corresponding to the solar photosphere. The specific boundary conditions used correspond to looplike magnetic fields in the corona. It is found that as lambda(sub 0) is increased, the loops of flux become kinked, and for sufficiently large lambda(sub 0), develop knots. The relationship between the kinking and knotting properties of these equilibria and the presence of a kink instability and related loss of equilibrium is explored. Clearly, magnetic reconnection must be involved for an unknotted loop equilibrium to become knotted, and speculations are made about the creation of a closed hyperbolic field line (X-line) about which this reconnection creating knotted field lines is centered.
Water-Nafion equilibria. absence of Schroeder's paradox.
Onishi, Lisa M; Prausnitz, John M; Newman, John
2007-08-30
Water-Nafion phase equilibria and proton conductivities were measured in two ways. First, Nafion was in contact with saturated water vapor. Second, Nafion was in contact with liquid water at the same temperature. At 29 degrees C, for preboiled, vapor-equilibrated Nafion exposed to water with an activity = 1 and air pressures ranging from 0 to 0.96 bar, the water content was lambda = 23 +/- 1 mol H(2)O/mol SO3-. For the preboiled, liquid-equilibrated membrane, lambda = 24 +/- 2. At 100% relative humidity (RH), the water content of preboiled Nafion decreased as the temperature rose from 30 to 80 degrees C but did not recover its initial water content when the temperature returned to 30 degrees C. The water content of predried Nafion at 1 atm and 30 degrees C was lambda = 13.7 +/- 0.2 when vapor-equilibrated and lambda = 13.1 +/- 0.5 when liquid-equilibrated. A Nafion membrane originally boiled in water had much higher liquid- and 100% RH vapor-equilibrated proton conductivities than the same membrane originally dried at 110 degrees C with a RH less than 2%. The liquid-equilibrated and 100% RH vapor-equilibrated membrane conductivities were the same when the membrane had the same thermal history. The conductivity data was fit to a model, and the water content was determined at different temperatures. The predried membrane water content increased with temperature, and the preboiled membrane's water content changed slightly with temperature. Both water sorption and proton-conductivity data do not exhibit Schroeder's paradox. These studies and previous results suggest that Schroeder's paradox is resolved when attention is given to the thermal history of the absorbing polymer.
Solid–liquid equilibria of binary mixtures of fluorinated ionic liquids†
Teles, Ana Rita R.; Correia, Helga; Maximo, Guilherme J.; Rebelo, Luís P. N.; Freire, Mara G.; Pereiro, Ana B.; Coutinho, João A. P.
2016-01-01
Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid–liquid and solid–solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid–liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid–solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures. PMID:27603428
Solid-liquid equilibria of binary mixtures of fluorinated ionic liquids.
Teles, Ana Rita R; Correia, Helga; Maximo, Guilherme J; Rebelo, Luís P N; Freire, Mara G; Pereiro, Ana B; Coutinho, João A P
2016-09-28
Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid-liquid and solid-solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid-liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid-solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures. PMID:27603428
Solid-liquid equilibria of binary mixtures of fluorinated ionic liquids.
Teles, Ana Rita R; Correia, Helga; Maximo, Guilherme J; Rebelo, Luís P N; Freire, Mara G; Pereiro, Ana B; Coutinho, João A P
2016-09-28
Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid-liquid and solid-solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid-liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid-solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures.
Cluster Mean-Field Approach to the Steady-State Phase Diagram of Dissipative Spin Systems
NASA Astrophysics Data System (ADS)
Jin, Jiasen; Biella, Alberto; Viyuela, Oscar; Mazza, Leonardo; Keeling, Jonathan; Fazio, Rosario; Rossini, Davide
2016-07-01
We show that short-range correlations have a dramatic impact on the steady-state phase diagram of quantum driven-dissipative systems. This effect, never observed in equilibrium, follows from the fact that ordering in the steady state is of dynamical origin, and is established only at very long times, whereas in thermodynamic equilibrium it arises from the properties of the (free) energy. To this end, by combining the cluster methods extensively used in equilibrium phase transitions to quantum trajectories and tensor-network techniques, we extend them to nonequilibrium phase transitions in dissipative many-body systems. We analyze in detail a model of spin-1 /2 on a lattice interacting through an X Y Z Hamiltonian, each of them coupled to an independent environment that induces incoherent spin flips. In the steady-state phase diagram derived from our cluster approach, the location of the phase boundaries and even its topology radically change, introducing reentrance of the paramagnetic phase as compared to the single-site mean field where correlations are neglected. Furthermore, a stability analysis of the cluster mean field indicates a susceptibility towards a possible incommensurate ordering, not present if short-range correlations are ignored.