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

USGS Publications Warehouse

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

2006-01-01

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

Phase Equilibria of Sn-Co-Cu Ternary System

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

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

NASA Astrophysics Data System (ADS)

Shevchenko, M.; Jak, E.

2017-12-01

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

Experimental investigation of the phase equilibria in the carbon dioxide-propane-3 M MDEA system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jou, F.Y.; Mather, A.E.; Otto, F.D.

1995-07-01

The treating of liquefied petroleum gas (LPG) to remove carbon dioxide and hydrogen sulfide using aqueous alkanolamine solutions is an important aspect of gas processing. One of the amines used in the natural gas industry is methyldiethanolamine (MDEA). Measurements of the phase equilibria in the carbon dioxide-propane-3 M MDEA system have been made at 25 and 40 C at pressures up to 15.5 MPa. Vapor-liquid, liquid-liquid, and vapor-liquid-liquid equilibria were determined. The vapor-liquid equilibrium data were compared with the model of Deshmukh and Mather.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

PubMed

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

2017-07-03

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

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

ERIC Educational Resources Information Center

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

2011-01-01

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

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

PubMed Central

Wang, Tian; Kevorkov, Dmytro; Medraj, Mamoun

2016-01-01

Ce-Fe-Co-B is a promising system for permanent magnets. A high-throughput screening method combining diffusion couples, key alloys, Scanning Electron Microscope/Wavelength Dispersive X-ray Spectroscope (SEM/WDS), and Magnetic Force Microscope (MFM) is used in this research to understand the phase equilibria and to explore promising magnetic phases in this system. Three magnetic phases were detected and their homogeneity ranges were determined at 900 °C, which were presented by the formulae: Ce2Fe14−xCoxB (0 ≤ x ≤ 4.76), CeCo4−xFexB (0 ≤ x ≤ 3.18), and Ce3Co11−x FexB4 (0 ≤ x ≤ 6.66). The phase relations among the magnetic phases in this system have been studied. Ce2(Fe, Co)14B appears to have stronger magnetization than Ce(Co, Fe)4B and Ce3(Co, Fe)11B4 from MFM analysis when comparing the magnetic interactions of selected key alloys. Also, a non-magnetic CeCo12−xFexB6 (0 ≤ x ≤ 8.74) phase was detected in this system. A boron-rich solid solution with Ce13FexCoyB45 (32 ≤ x ≤ 39, 3 ≤ y ≤ 10) chemical composition was also observed. However, the crystal structure of this phase could not be found in the literature. Moreover, ternary solid solutions ε1 (Ce2Fe17−xCox (0 ≤ x ≤ 12.35)) and ε2 (Ce2Co17−xFex (0 ≤ x ≤ 3.57)) were found to form between Ce2Fe17 and Ce2Co17 in the Ce-Fe-Co ternary system at 900 °C. PMID:28772374

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.

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.

Experimental study of phase equilibria and thermodynamic optimization of the Fe-Zn-O system

NASA Astrophysics Data System (ADS)

Degterov, Sergei A.; Pelton, Arthur D.; Jak, Evgueni; Hayes, Peter C.

2001-08-01

The Fe-Zn-O phase diagram in air was studied over the temperature range from 900 °C to 1500 °C. The compositions of the phases in quenched samples were obtained by electron probe X-ray microanalysis (EPMA). This experimental technique is not affected by zinc losses resulting from vaporization of zinc at high temperatures. The model for the spinel solid solution was developed within the framework of the compound-energy formalism (CEF). The choice of parameters of the CEF and the sequence of their optimization can have a major influence on the predictions in multicomponent phases. These choices can only be made rationally by reference to the specific model being represented in the CEF. This is discussed for the case of the two-sublattice spinel model. In the limiting case, the proposed model reduces to the model by O’Neill and Navrotsky for spinels. When the CEF is used in combination with the equation of Hillert and Jarl to describe the magnetic contribution to thermodynamic functions of a solution, it is necessary to assign certain values of magnetic properties to all pseudocomponents and to magnetic interaction parameters to obtain the most reasonable approximation of the magnetic properties of a solution. It was shown how this can be done based on very limited experimental data. The same equations can be used when the Murnaghan or the Birch-Murnaghan equation is combined with the CEF to describe the pressure dependence of thermodynamic functions. The polynomial model was used to describe the properties of wustite and zincite, and the modified quasichemical model was used for the liquid slag. All thermodynamic and phase-equilibria data on the Fe-O and Fe-Zn-O systems were critically evaluated, and parameters of the models were optimized to give a self-consistent set of thermodynamic functions of the phases in these systems. All experimental data are reproduced within experimental error limits. These include the thermodynamic properties of phases (such as

Phase Equilibria Modeling of Coesite Eclogite from the Sulu Belt, Eastern China

NASA Astrophysics Data System (ADS)

Xia, B.; Brown, M.; Wang, L.; Wang, S.; Piccoli, P. M.

2016-12-01

Modeling of phase equilibria and tectonic processes are essential components to understand controls on P-T paths of UHPM rocks. However, diffusion at higher temperatures (> 700 °C), and issues with determination of Fe3+ in minerals and estimating H2O contents limit our ability to determine prograde, peak P and retrograde P-T data. Also, the lack of an appropriate activity-composition model for melt in basic rocks has limited the application of phase equilibria modeling to understand partial melting associated with exhumation. Here we apply phase equilibria modeling to coesite eclogite from Yangkou to assess the influence of Fe3+ and fluid during metamorphism, monitor reactions and phase relations in eclogite during deep subduction and exhumation and investigate partial melting at HP conditions. The modeling used the THERMOCALC software and the new internally consistent thermodynamic dataset for basic rocks (http://www.metamorph.geo.uni-mainz.de/thermocalc/dataset6/index.html). Here we investigate bimineralic (gt+omp+coe/qz+ru/ilm), phengite-bearing (gt+omp+phen (2 samples, <5 vol% and >5 vol%) +coe/qz+ru/ilm) and kyanite-bearing (gt+omp+phen+ky+coe/qz+ru/ilm) eclogites. Coesite in the matrix is the hallmark of the Yangkou eclogite. For each sample, we use an iterative process to estimate the H2O and O content in the bulk composition, and then calculate a P-T pseudosection. The results suggest that some prograde information (670-770 °C, > 3.0 GPa) is retained in large garnet cores in bimineralic and phengite-bearing eclogite. The peak P-T conditions are a challenge because in the field of gt+omp+coe/qz±phen+H2O at T > 750 °C and P > 3.5 GPa mode and compositional changes are small. However, isopleths of Si in phengite suggest that the peak P could have been > 5-6 GPa. Re-equilibration of garnet and omphacite compositions occurred during exhumation, yielding P-T conditions of 700-790 °C at 3.1-2.0 GPa. Amphibolite facies metamorphism occurred at 630-710 °C, 1

Determination of pore-scale hydrate phase equilibria in sediments using lab-on-a-chip technology.

PubMed

Almenningen, Stian; Flatlandsmo, Josef; Kovscek, Anthony R; Ersland, Geir; Fernø, Martin A

2017-11-21

We present an experimental protocol for fast determination of hydrate stability in porous media for a range of pressure and temperature (P, T) conditions. Using a lab-on-a-chip approach, we gain direct optical access to dynamic pore-scale hydrate formation and dissociation events to study the hydrate phase equilibria in sediments. Optical pore-scale observations of phase behavior reproduce the theoretical hydrate stability line with methane gas and distilled water, and demonstrate the accuracy of the new method. The procedure is applicable for any kind of hydrate transitions in sediments, and may be used to map gas hydrate stability zones in nature.

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.

A Review and Evaluation of the Phase Equilibria, Liquid-Phase Heats of Mixing and Excess Volumes, and Gas-Phase PVT Measurements for Nitrogen+Methane

NASA Astrophysics Data System (ADS)

Kidnay, A. J.; Miller, R. C.; Sloan, E. D.; Hiza, M. J.

1985-07-01

The available experimental data for vapor-liquid equilibria, heat of mixing, change in volume on mixing for liquid mixtures, and gas-phase PVT measurements for nitrogen+methane have been reviewed and where possible evaluated for consistency. The derived properties chosen for analysis and correlation were liquid mixture excess Gibbs free energies, and Henry's constants.

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

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

Clathrate formation and phase equilibria in the thiourea-bromoform system

NASA Astrophysics Data System (ADS)

Chekhova, G. N.; Shubin, Yu. V.; Pinakov, D. V.; Alferova, N. I.

2008-07-01

Phase equilibria in the thiourea (host)-bromoform (guest) binary system were studied by physicochemical analysis methods over the temperature range 270 455 K. The stoichiometry and stability region were determined for the channel-type compound CHBr3 · 2.40(2)(NH2)2CS; the compound was observed for the first time. When heated, the clathrate incongruently decomposed at 424.0 ± 0.8 K to rhombic thiourea and the guest component. The solubility isotherm of the thiourea-bromoform-acetic acid system was studied to find that the compound was thermodynamically stable at 293 K over the range of guest component concentrations 100 35 wt %. A decrease in its content in an equilibrium mother liquor resulted in the appearance of X-ray diffraction reflections of the initial host α polymorph. Rhombohedral cell parameters were determined (space group R-3 c, a = 15.89(1) Å, c = 12.40(1) Å, V = 2711(6) Å3, d calcd = 2.000 g/cm3, and d expt = 1.98(2) g/cm3). The mode of packing of bromoform molecules was compared with the organization of the guest subsystem in inclusion compounds formed by the substances studied.

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.

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

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.

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

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

2016-12-01

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

The Gibbs free energy of nukundamite (Cu3.38Fe0.62S4): A correction and implications for phase equilibria

USGS Publications Warehouse

Seal, R.R.; Inan, E.E.; Hemingway, B.S.

2001-01-01

The Gibbs free energy of formation of nukundamite (Cu3.38Fe0.62S4) was calculated from published experimental studies of the reaction 3.25 Cu3.38Fe0.62S4 + S2 = 11 CuS + 2 FeS2 in order to correct an erroneous expression in the published record. The correct expression describing the Gibbs free energy of formation (kJ???mol-1) of nukundamite relative to the elements and ideal S2 gas is ??fG?? nukundamite T(K) = -549.75 + 0.23242 T + 3.1284 T0.5, with an uncertainty of 0.6%. An evaluation of the phase equilibria of nukundamite with associated phases in the system Cu-Fe-S as a function of temperature and sulfur fugacity indicates that nukundamite is stable from 224 to 501??C at high sulfidation states. At its greatest extent, at 434??C, the stability field of nukundamite is only 0.4 log f(S2) units wide, which explains its rarity. Equilibria between nukundamite and bornite, which limit the stability of both phases, involve bornite compositions that deviate significantly from stoichiometric Cu5FeS4. Under equilibrium conditions in the system Cu-Fe-S, nukundamite + chalcopyrite is not a stable assemblage at any temperature.

Glass Formation, Phase Equilibria, and Thermodynamic Assessment of the Al-Ce-Co System Assisted by First-Principles Energy Calculations

NASA Astrophysics Data System (ADS)

Gao, Michael C.; Ünlü, Necip; Mihalkovic, Marek; Widom, Michael; Shiflet, G. J.

2007-10-01

This study investigates glass formation, phase equilibria, and thermodynamic descriptions of the Al-rich Al-Ce-Co ternary system using a novel approach that combines critical experiments, CALPHAD modeling, and first-principles (FP) calculations. The glass formation range (GFR) and a partial 500 °C isotherm are determined using a range of experimental techniques including melt spinning, transmission electron microscopy (TEM), electron probe microanalysis (EPMA), X-ray diffraction, and differential thermal analysis (DTA). Three stable ternary phases are confirmed, namely, Al8CeCo2, Al4CeCo, and AlCeCo, while a metastable phase, Al5CeCo2, was discovered. The equilibrium and metastable phases identified by the present and earlier reported experiments, together with many hypothetical ternary compounds, are further studied by FP calculations. Based on new experimental data and FP calculations, the thermodynamics of the Al-rich Al-Co-Ce system is optimized using the CALPHAD method. Application to glass formation is discussed in light of present studies.

Hydrostatic Equilibria of Rotating Stars with Realistic Equation of State

NASA Astrophysics Data System (ADS)

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

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

A reduced basis approach for implementing thermodynamic phase-equilibria information in geophysical and geodynamic studies

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.

Processing, phase equilibria and environmental degradation of molybdenum (silicom,aluminum)(2) intermetallic compound

NASA Astrophysics Data System (ADS)

Eason, Paul Duane

The Mo(Si,Al)2 C40 compound was chosen for investigation as a possible high temperature structural material. To produce the C40 phase, several processing routes were explored with emphasis on obtaining microstructure/property relationships (i.e. control of grain size and minimization of secondary phases). To facilitate processing of single phase material, the phase equilibria of the Mo-Si-Al ternary system were reevaluated with respect to the phases adjacent to the C40 compound. An anomalous environmental degradation appeared to be the primary obstacle to further study of the compound and was investigated accordingly. Several processing routes were assessed for the production of dense, nearly single-phase Mo(Si,Al)2. Hot powder compaction was chosen as the method of sample production as is the case with many refractory silicide based materials. Therefore, variations in the processing techniques came from the choice of precursor materials and methods of powder production. Mechanical alloying, arc-melting and comminution, and blending of both elemental and compound powders were all employed to produce charges for hot uniaxial pressing. The final compacts were compared on the basis of density, grain size and presence of secondary phases. Establishment of a Mo-Si-Al ternary isothermal phase diagram at 1400°C was performed. Multiphase alloy compositions were selected to identify the phase boundaries of the C40, C54, T1 and Mo3Al8 phase fields, as well as to verify the existence of the C54 phase at 1400°C. The alloys were equilibrated by heat treatment and analyzed for phase identification and quantitative compositional information. The environmental degradation phenomenon was approached as a classical "pest" with an emphasis of study on grain boundary chemistry and atmospheric dependence of attack. Both Auger spectroscopy and electron microscopy revealed carbon-impurity-induced grain boundary segregation responsible for the embrittlement and material loss. Means of

An efficient and general approach for implementing thermodynamic phase equilibria information in geophysical and geodynamic studies

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.

Phase equilibria in the Bi 2TeO 5Bi 2SeO 5 system and a high temperature neutron powder diffraction study of Bi 2SeO 5

NASA Astrophysics Data System (ADS)

Dityatyev, Oleg A.; Smidt, Peer; Stefanovich, Sergey Yu; Lightfoot, Philip; Dolgikh, Valery A.; Opperman, Heinrich

2004-09-01

Phase equilibria in the Bi 2TeO 5Bi 2SeO 5 system were studied by X-ray, DTA and second harmonic generation (SHG). The samples were synthesized by solid state reactions of the Bi, Te and Se oxides. The phase diagram is interpreted as a quasibinary peritectic one with wide ranges of solid solutions on the basis of both compounds. The SHG study showed Bi 2SeO 5 to undergo a phase transition at about 250 °C. Neutron diffraction (25-650 °C) showed no major changes in the structure of Bi 2SeO 5 at high temperatures. However, the analysis of the oxygen atom thermal factors and site occupancies suggested that the mechanism of the phase transformation is an order-disorder transition involving reorientation of the SeO 3 group.

Stability of Inhomogeneous Equilibria of Hamiltonian Continuous Media Field Theories

NASA Astrophysics Data System (ADS)

Hagstrom, George

2013-10-01

There are a wide variety of 1 + 1 Hamiltonian continuous media field theories that exhibit phase space pattern formation. In plasma physics, the most famous of these is the Vlasov-Poisson equation, but other examples include the incompressible Euler equation in two-dimensions and the Hamiltonian Mean Field (or XY) model. One of the characteristic phenomenon that occurs in systems described by these equations is the formation of cat's eye patterns in phase space as a result of the nonlinear saturation of instabilities. Corresponding to each of these cat's eyes is a spatially inhomogeneous equilibrium solution of the underlying model, in plasma physics these are called BGK modes, but analogous solutions exist in all of the above systems. Here we analyze the stability of inhomogeneous equilibria in the Hamiltonian Mean Field model and in the Single Wave model, which is an equation that was derived to provide a model of the formation of electron holes in plasmas. We use action angle variables and the properties of elliptic functions to analyze the resulting dispersion relation construct linearly stable inhomogeneous equilibria for in the limit of small numbers of particles and study the behavior of solutions near these equilibria. Work supported by USDOE grant no. DE-FG02-ER53223.

Phase equilibria constraints on models of subduction zone magmatism

NASA Astrophysics Data System (ADS)

Myers, James D.; Johnston, Dana A.

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

Postperovskite phase equilibria in the MgSiO3-Al2O3 system.

PubMed

Tsuchiya, Jun; Tsuchiya, Taku

2008-12-09

We investigate high-P,T phase equilibria of the MgSiO(3)-Al(2)O(3) system by means of the density functional ab initio computation methods with multiconfiguration sampling. Being different from earlier studies based on the static substitution properties with no consideration of Rh(2)O(3)(II) phase, present calculations demonstrate that (i) dissolving Al(2)O(3) tends to decrease the postperovskite transition pressure of MgSiO(3) but the effect is not significant ( approximately -0.2 GPa/mol% Al(2)O(3)); (ii) Al(2)O(3) produces the narrow perovskite+postperovskite coexisting P,T area (approximately 1 GPa) for the pyrolitic concentration (x(Al2O3) approximately 6 mol%), which is sufficiently responsible to the deep-mantle D'' seismic discontinuity; (iii) the transition would be smeared (approximately 4 GPa) for the basaltic Al-rich composition (x(Al2O3) approximately 20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh(2)O(3)(II) with increasing the Al concentration involving small displacements of the Mg-site cations.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Interpretation of trace element and isotope features of basalts: relevance of field relations, petrology, major element data, phase equilibria, and magma chamber modeling in basalt petrogenesis

NASA Astrophysics Data System (ADS)

O'Hara, M. J.; Herzberg, C.

2002-06-01

explain the chemical variation between fertile and residual peridotite in natural ultramafic rock suites. The subtleties of magma chamber partial crystallization processes can produce an astounding array of "pseudospidergrams," a small selection of which have been explored here. Major modification of the trace element geochemistry and trace element ratios, even those of the highly incompatible elements, must always be entertained whenever the evidence suggests the possibility of partial crystallization. At one extreme, periodically recharged, periodically tapped magma chambers might undergo partial crystallization by ˜95% consolidation of a succession of small packets of the magma. Refluxing of the 5% residual melts from such a process into the main body of melt would lead to eventual discrimination between highly incompatible elements in that residual liquid comparable with that otherwise achieved by 0.1 to 0.3% liquid extraction in equilibrium partial melting. Great caution needs to be exercised in attempting the reconstruction of more primitive compositions by addition of troctolite, gabbro, and olivine to apparently primitive lava compositions. Special attention is focussed on the phase equilibria involving olivine, plagioclase (i.e., troctolite), and liquid because a high proportion of erupted basalts carry these two phases as phenocrysts, yet the equilibria are restricted to crustal pressures and are only encountered by wide ranges of basaltic compositions at pressures less than 0.5 GPa. The mere presence of plagioclase phenocrysts may be sufficient to disqualify candidate primitive magmas. Determination of the actual contributions of crustal processes to petrogenesis requires a return to detailed field, experimental, and forensic petrologic studies of individual erupted basalt flows; of a multitude of cumulate gabbros and their contacts; and of upper-mantle outcrops.

Spontaneous decay of periodic magnetostatic equilibria

DOE PAGES

East, William E.; Zrake, Jonathan; Yuan, Yajie; ...

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

Phase equilibria and velocity discontinuities across the post-perovskite transition in (Mg,Fe)SiO3

NASA Astrophysics Data System (ADS)

Wentzcovitch, Renata; Shukla, Gaurav; Sarkar, Kanchan

The enigmatic nature of the region above the Earth's core-mantle boundary known as the D'' region, is often characterized by a significant contrast in seismic wave velocities. The perovskite (Pv) to post-perovskite (PPv) transition in bridgmanite ((Mg,Fe)SiO3 perovskite) is one of the keys for understanding this region. In this study, we present DFT + USC calculations of phase equilibria in bridgmanite across the post-perovskite transition. Thermal effects are addressed within the quasi-harmonic approximation. By computing high-pressure and high-temperatures elastic/acoustic properties of Pv and PPv phases, we also investigate seismic signature of the PPv-transition, believed to cause the D'' discontinuity. Aggregate elastic moduli and sound velocities for the Mg-end member are successfully compared with limited experimental data available. Predicted velocity discontinuities across the PPv transition are consistent with seismic observations in some places of the global D'' discontinuity. Our robust estimates of the phase boundary and elastic properties of the perovskite and post-perovskite phases will help to clarify the origin of lateral velocity variations in the deep lower mantle region and constrain its composition and thermal structure. 1This research was supported primarily by NSF Grants EAR 1348066 and DMR 1503084. Computations are performed at the Minnesota Su- percomputing Institute (MSI).

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

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

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

USGS Publications Warehouse

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 relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

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.

Vapor Pressure Plus: An Experiment for Studying Phase Equilibria in Water, with Observation of Supercooling, Spontaneous Freezing, and the Triple Point

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…

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

USGS Publications Warehouse

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.

Postperovskite phase equilibria in the MgSiO3–Al2O3 system

PubMed Central

Tsuchiya, Jun; Tsuchiya, Taku

2008-01-01

We investigate high-P,T phase equilibria of the MgSiO3–Al2O3 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 Rh2O3(II) phase, present calculations demonstrate that (i) dissolving Al2O3 tends to decrease the postperovskite transition pressure of MgSiO3 but the effect is not significant (≈-0.2 GPa/mol% Al2O3); (ii) Al2O3 produces the narrow perovskite+postperovskite coexisting P,T area (≈1 GPa) for the pyrolitic concentration (xAl2O3 ≈6 mol%), which is sufficiently responsible to the deep-mantle D″ seismic discontinuity; (iii) the transition would be smeared (≈4 GPa) for the basaltic Al-rich composition (xAl2O3 ≈20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh2O3(II) with increasing the Al concentration involving small displacements of the Mg-site cations. PMID:19036928

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

2017-02-01

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

Density-functional study on the equilibria in the ThDP activation.

PubMed

Delgado, Eduardo J; Alderete, Joel B; Jaña, Gonzalo A

2011-11-01

The equilibria among the various ionization and tautomeric states involved in the activation of ThDP is addressed using high level density functional theory calculations, X3LYP/6-311++G(d,p)//X3LYP(PB)/6-31++G(d,p). This study provides the first theoretically derived thermodynamic data for the internal equilibria in the activation of ThDP. The role of the medium polarity on the geometry and thermodynamics of the diverse equilibria of ThDP is addressed. The media chosen are cyclohexane and water, as paradigms of apolar and polar media. The results suggest that all ionization and tautomeric states are accessible during the catalytic cycle, even in the absence of substrate, being APH(+) the form required to interconvert the AP and IP tautomers; and the generation of the ylide proceeds via the formation of the IP form. Additionally, the calculated ΔG° values allow to calculate all the equilibrium constants, including the pK(C2) for the thiazolium C2 atom whose ionization is believed to initiate the catalytic cycle.

Static axisymmetric equilibria in general relativistic magnetohydrodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nunez, Manuel

2008-01-15

While the definition of static equilibria is not clear in a general relativistic context, in many cases of astrophysical interest a natural 3+1 split exists which allows us to define physically meaningful spatial and temporal coordinates. We study the possibility of axisymmetric magnetohydrodynamic equilibria in this setting. The presence of a nontrivial shift velocity provides a constraint not present in the Newtonian case, while the momentum equation may be set in a Grad-Shafranov-like form with the presence of additional terms involving the space-time metric coefficients. It is found that whenever the magnetic field or the shift velocity possesses poloidal component,more » the existence of even local static equilibria demands that the metric parameters satisfy such strong conditions that these equilibria are extremely unlikely. Only very particular cases such as purely toroidal fields and shifts yield existence of equilibria, provided we are able to choose arbitrarily the plasma pressure and density.« less

Phase equilibria study of pseudobrookite type minerals

NASA Technical Reports Server (NTRS)

Friel, J. J.

1974-01-01

Pseudobrookite, is found in volcanic rocks, and the mineral armalcolite ((Fe,Mg)Ti2O5) found in the Apollo 11 and subsequent lunar samples seems to be unique to the moon. In plutonic rocks on the earth, ilmenite and rutile were found with what appears to be an equilibrium liquidus texture, while on the moon armalcolite often appears to be the primary liquidus phase among Ti-oxides. This suggests that total pressure may be a factor in the formation of these minerals, and a knowledge of the phase relations in this system yields information about the pressure under which a given magma crystallized.

Phase Equilibria in the ZnO-"FeO"-SiO2 System in Reducing Atmosphere and in the ZnO-"FeO"-SiO2-"Cu2O" System in Equilibrium with Liquid Copper Metal at 1250 °C (1523 K)

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

2018-05-01

Recent experimental studies in the ZnO-"FeO"-SiO2 system in reducing atmosphere demonstrated significant discrepancies with the current FactSage thermodynamic model developed using previous experimental data in this system in equilibrium with metallic iron and air. The present experimental study on phase equilibria in the ZnO-"FeO"-SiO2-"Cu2O" system in equilibrium with liquid copper at 1250 °C (1523 K) at low copper oxide concentrations in slag was initiated and undertaken to resolve these discrepancies. A high-temperature equilibration-rapid quenching-electron-probe X-ray microanalysis (EPMA) technique using a primary phase substrate support and closed system approach with Cu metal introduced to determine effective equilibrium oxygen partial pressure from the Cumetal/Cu2Oslag equilibria was applied to provide accurate information on the liquidus and corresponding solid compositions in the spinel, willemite, and tridymite primary phase fields. The present results confirmed the accuracy of the FactSage model, resolved discrepancies, and demonstrated significant uncertainties in the recent studies by other authors on the system in the open reducing atmosphere. The present study shows how this closed system approach can be used to obtain key thermodynamic data on phase equilibria in systems containing volatile metal species, overcoming the limitations and uncertainties encountered in conventional open gas/condensed phase equilibration with these systems. The study highlights the importance of the focus on obtaining accurate experimental data and the risks of misleading information from inadequate experimental control and analysis. The study also demonstrates that continuing in-depth critical review and analysis of the elemental reactions taking place in complex systems is an essential step in phase equilibrium research.

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

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.

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 in the nominally Al65Cu23Fe12 system at 3, 5 and 21 GPa: Implications for the quasicrystal-bearing Khatyrka meteorite

NASA Astrophysics Data System (ADS)

Stagno, Vincenzo; Bindi, Luca; Steinhardt, Paul J.; Fei, Yingwei

2017-10-01

Two of the three natural quasiperiodic crystals found in the Khatyrka meteorite show a composition within the Al-Cu-Fe system. Icosahedrite, with formula Al63Cu24Fe13, coexists with the new Al62Cu31Fe7 quasicrystal plus additional Al-metallic minerals such as stolperite (AlCu), kryachkoite [(Al,Cu)6(Fe,Cu)], hollisterite (AlFe3), khatyrkite (Al2Cu) and cupalite (AlCu), associated to high-pressure phases like ringwoodite/ahrensite, coesite, and stishovite. These high-pressure minerals represent the evidence that most of the Khatyrka meteoritic fragments formed at least at 5 GPa and 1200 °C, if not at more extreme conditions. On the other hand, experimental studies on phase equilibria within the representative Al-Cu-Fe system appear mostly limited to ambient pressure conditions, yet. This makes the interpretation of the coexisting mineral phases in the meteoritic sample quite difficult. We performed experiments at 3, 5 and 21 GPa and temperatures of 800-1500 °C using the multi-anvil apparatus to investigate the phase equilibria in the Al65Cu23Fe12 system representative of the first natural quasicrystal, icosahedrite. Our results, supported by single-crystal X-ray diffraction and analyses by scanning electron microscopy, confirm the stability of icosahedrite at high pressure and temperature along with additional coexisting Al-bearing phases representative of khatyrkite and stolperite as those found in the natural meteorite. One reversal experiment performed at 5 GPa and 1200 °C shows the formation of the icosahedral quasicrystal from a pure Al, Cu and Fe mixture, a first experimental synthesis of icosahedrite under those conditions. Pressure appears to not play a major role in the distribution of Al, Cu and Fe between the coexisting phases, icosahedrite in particular. Results from this study extend our knowledge on the stability of icosahedral AlCuFe at higher temperature and pressure than previously examined, and provide a new constraint on the stability of

Integrated Modeling of Time Evolving 3D Kinetic MHD Equilibria and NTV Torque

NASA Astrophysics Data System (ADS)

Logan, N. C.; Park, J.-K.; Grierson, B. A.; Haskey, S. R.; Nazikian, R.; Cui, L.; Smith, S. P.; Meneghini, O.

2016-10-01

New analysis tools and integrated modeling of plasma dynamics developed in the OMFIT framework are used to study kinetic MHD equilibria evolution on the transport time scale. The experimentally observed profile dynamics following the application of 3D error fields are described using a new OMFITprofiles workflow that directly addresses the need for rapid and comprehensive analysis of dynamic equilibria for next-step theory validation. The workflow treats all diagnostic data as fundamentally time dependent, provides physics-based manipulations such as ELM phase data selection, and is consistent across multiple machines - including DIII-D and NSTX-U. The seamless integration of tokamak data and simulation is demonstrated by using the self-consistent kinetic EFIT equilibria and profiles as input into 2D particle, momentum and energy transport calculations using TRANSP as well as 3D kinetic MHD equilibrium stability and neoclassical transport modeling using General Perturbed Equilibrium Code (GPEC). The result is a smooth kinetic stability and NTV torque evolution over transport time scales. Work supported by DE-AC02-09CH11466.

An analytical equation of state for describing isotropic-nematic phase equilibria of Lennard-Jones chain fluids with variable degree of molecular flexibility

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

Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.

PubMed

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.

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…

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

NASA Astrophysics Data System (ADS)

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

2004-10-01

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

Phase Equilibria Studies in the System ZnO-``FeO''-Al2O3-CaO-SiO2 Relevant to Imperial Smelting Furnace Slags: Part I

NASA Astrophysics Data System (ADS)

Zhao, Baojun; Hayes, Peter C.; Jak, Evgueni

2010-04-01

The phase equilibria and liquidus temperatures in the system ZnO-“FeO”-Al2O3-CaO-SiO2 in equilibrium with metallic iron have been determined experimentally in the temperature range of 1423 K to 1553 K. The experimental conditions were focused on the composition range relevant to Imperial Smelting Furnace slags. The results are presented in the form of a pseudo-ternary section ZnO-“FeO”-(CaO + SiO2 + Al2O3) in which CaO/SiO2 = 0.93 and (CaO + SiO2)/Al2O3 = 7.0. It was found that wustite and spinel are the major primary phases and that zincite and melilite are also present in the composition range investigated. Wustite (Fe2+,Zn)O and spinel (Fe2+,Zn)O (A1,Fe3+)2O3 solid solutions are formed in this system, and the ZnO concentration in the spinel phase is found to be much greater than in the liquid phase.

Experimental Investigation of Gas/Slag/Matte/Tridymite Equilibria in the Cu-Fe-O-S-Si System in Controlled Atmospheres: Development of Technique

NASA Astrophysics Data System (ADS)

Fallah-Mehrjardi, Ata; Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

2017-12-01

The majority of primary pyrometallurgical copper making processes involve the formation of two immiscible liquid phases, i.e., matte product and the slag phase. There are significant gaps and discrepancies in the phase equilibria data of the slag and the matte systems due to issues and difficulties in performing the experiments and phase analysis. The present study aims to develop an improved experimental methodology for accurate characterisation of gas/slag/matte/tridymite equilibria in the Cu-Fe-O-S-Si system under controlled atmospheres. The experiments involve high-temperature equilibration of synthetic mixtures on silica substrates in CO/CO2/SO2/Ar atmospheres, rapid quenching of samples into water, and direct composition measurement of the equilibrium phases using Electron Probe X-ray Microanalysis (EPMA). A four-point-test procedure was applied to ensure the achievement of equilibrium, which included the following: (i) investigation of equilibration as a function of time, (ii) assessment of phase homogeneity, (iii) confirmation of equilibrium by approaching from different starting conditions, and (iv) systematic analysis of the reactions specific to the system. An iterative improved experimental methodology was developed using this four-point-test approach to characterize the complex multi-component, multi-phase equilibria with high accuracy and precision. The present study is a part of a broader overall research program on the characterisation of the multi-component (Cu-Fe-O-S-Si-Al-Ca-Mg), multi-phase (gas/slag/matte/metal/solids) systems with minor elements (Pb, Zn, As, Bi, Sn, Sb, Ag, and Au).

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

Jump conditions in transonic equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2013-04-15

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

Thermodynamic assessment of hydrothermal alkali feldspar-mica-aluminosilicate equilibria

USGS Publications Warehouse

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

Magnetospheric Reconnection in Modified Current-Sheet Equilibria

NASA Astrophysics Data System (ADS)

Newman, D. L.; Goldman, M. V.; Lapenta, G.; Markidis, S.

2012-10-01

Particle simulations of magnetic reconnection in Earth's magnetosphere are frequently initialized with a current-carrying Harris equilibrium superposed on a current-free uniform background plasma. The Harris equilibrium satisfies local charge neutrality, but requires that the sheet current be dominated by the hotter species -- often the ions in Earth's magnetosphere. This constraint is not necessarily consistent with observations. A modified kinetic equilibrium that relaxes this constraint on the currents was proposed by Yamada et al. [Phys. Plasmas., 7, 1781 (2000)] with no background population. These modified equilibria were characterized by an asymptotic converging or diverging electrostatic field normal to the current sheet. By reintroducing the background plasma, we have developed new families of equilibria where the asymptotic fields are suppressed by Debye shielding. Because the electrostatic potential profiles of these new equilibria contain wells and/or barriers capable of spatially isolating different populations of electrons and/or ions, these solutions can be further generalized to include classes of asymmetric kinetic equilibria. Examples of both symmetric and asymmetric equilibria will be presented. The dynamical evolution of these equilibria, when perturbed, will be further explored by means of implicit 2D PIC reconnection simulations, including comparisons with simulations employing standard Harris-equilibrium initializations.

Equilibria of oligomeric proteins under high pressure - A theoretical description.

PubMed

Ingr, Marek; Kutálková, Eva; Hrnčiřík, Josef; Lange, Reinhard

2016-12-21

High pressure methods have become a useful tool for studying protein structure and stability. Using them, various physico-chemical processes including protein unfolding, aggregation, oligomer dissociation or enzyme-activity decrease were studied on many different proteins. Oligomeric protein dissociation is a process that can perfectly utilize the potential of high-pressure techniques, as the high pressure shifts the equilibria to higher concentrations making them better observable by spectroscopic methods. This can be especially useful when the oligomeric form is highly stable at atmospheric pressure. These applications may be, however, hindered by less intensive experimental response as well as interference of the oligomerization equilibria with unfolding or aggregation of the subunits, but also by more complex theoretical description. In this study we develop mathematical models describing different kinds of oligomerization equilibria, both closed (equilibrium of monomer and the highest possible oligomer without any intermediates) and consecutive. Closed homooligomer equilibria are discussed for any oligomerization degree, while the more complex heterooligomer equilibria and the consecutive equilibria in both homo- and heterooligomers are taken into account only for dimers and trimers. In all the cases, fractions of all the relevant forms are evaluated as functions of pressure and concentration. Significant points (inflection points and extremes) of the resulting transition curves, that can be determined experimentally, are evaluated as functions of pressure and/or concentration. These functions can be further used in order to evaluate the thermodynamic parameters of the system, i.e. atmospheric-pressure equilibrium constants and volume changes of the individual steps of the oligomer-dissociation processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Computation of Phase Equilibria, State Diagrams and Gas/Particle Partitioning of Mixed Organic-Inorganic Aerosols

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

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.

Design of snowflake-diverted equilibria of CFETR

NASA Astrophysics Data System (ADS)

Hang, LI; Xiang, GAO; Guoqiang, LI; Zhengping, LUO; Damao, YAO; Yong, GUO

2018-03-01

The Chinese Fusion Engineering Test Reactor (CFETR) represents the next generation of full superconducting fusion reactors in China. Recently, CFETR was redesigned with a larger size and will be operated in two phases. To reduce the heat flux on the target plate, a snowflake (SF) divertor configuration is proposed. In this paper we show that by adding two dedicated poloidal field (PF) coils, the SF configuration can be achieved in both phases. The equilibria were calculated by TEQ code for a range of self-inductances l i3. The coil currents were calculated at some fiducial points in the flattop phase. The results indicate that the PF coil system has the ability to maintain a long flattop phase in 7.5 and 10 MA inductive scenarios for the single null divertor (SND) and SF divertor configurations. The properties of the SF configuration were also analyzed. The connection length and flux expansion of the SF divertor were both increased significantly over the SND.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frolov, T., E-mail: timfrol@berkeley.edu; Mishin, Y., E-mail: ymishin@gmu.edu

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 phasemore » 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.« less

Characterizing the Nash equilibria of three-player Bayesian quantum games

NASA Astrophysics Data System (ADS)

Solmeyer, Neal; Balu, Radhakrishnan

2017-05-01

Quantum games with incomplete information can be studied within a Bayesian framework. We analyze games quantized within the EWL framework [Eisert, Wilkens, and Lewenstein, Phys Rev. Lett. 83, 3077 (1999)]. We solve for the Nash equilibria of a variety of two-player quantum games and compare the results to the solutions of the corresponding classical games. We then analyze Bayesian games where there is uncertainty about the player types in two-player conflicting interest games. The solutions to the Bayesian games are found to have a phase diagram-like structure where different equilibria exist in different parameter regions, depending both on the amount of uncertainty and the degree of entanglement. We find that in games where a Pareto-optimal solution is not a Nash equilibrium, it is possible for the quantized game to have an advantage over the classical version. In addition, we analyze the behavior of the solutions as the strategy choices approach an unrestricted operation. We find that some games have a continuum of solutions, bounded by the solutions of a simpler restricted game. A deeper understanding of Bayesian quantum game theory could lead to novel quantum applications in a multi-agent setting.

Computing Nash equilibria through computational intelligence methods

NASA Astrophysics Data System (ADS)

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

2005-03-01

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

Phase equilibria in the KFeS2-Fe-S system at 300-600 °C and bartonite stability

NASA Astrophysics Data System (ADS)

Osadchii, Valentin O.; Voronin, Mikhail V.; Baranov, Alexander V.

2018-05-01

The article deals with phase relations in the KFeS2-Fe-S system studied by the dry synthesis method in the range of 300-600 °C and at a pressure of 1 bar. At the temperature below 513 ± 3 °C, pyrite coexists with rasvumite and there are pyrite-rasvumite-KFeS2 and pyrite-rasvumite-pyrrhotite equilibria established. Above 513 ± 3 °C pyrite and rasvumite react to form KFeS2 and pyrrhotite, limiting the pyrite-rasvumite association to temperatures below this in nature. The experiments also outline the compositional stability range of the copper-free analog of murunskite (K x Fe2- y S2) and suggest that mineral called bartonite is not stable in the Cl-free system, at least at atmospheric pressure and the temperature in the experiments. Chlorbartonite could be easily produced after adding KCl in the experiment. Possible parageneses in the quaternary K-Fe-S-Cl system were described based on the data obtained in this research and found in the previous studies. The factors affecting the formation of potassium-iron sulfides in nature were discussed.

Sulfur in Hydrous, Oxidized Basaltic Magmas: Phase Equilibria and Melt Solubilities

NASA Astrophysics Data System (ADS)

Pichavant, M.; Scaillet, B.; di Carlo, I.; Rotolo, S.; Metrich, N.

2006-05-01

Basaltic magmas from subduction zone settings are typically S-rich and may be the ultimate source of sulfur in vapor phases emitted during eruptions of more silicic systems. To understand processes of sulfur recycling in subduction zones, the behaviour of S in hydrous, oxidized, mafic arc magmas must be known. Although experimental data on S-bearing basaltic melts are available for dry conditions, and under both reduced and oxidized fO2, no study has yet examined the effect of S in hydrous mafic melts. In this work, 3 starting compositions were investigated, a basaltic andesite, a K basalt and a picritic basalt. For each composition, experimental data for S-added (1 wt % elemental sulfur) and S-free charges were obtained under similar P-T- H2O-fO2. All experiments were performed at 4 kbar and at either 950 ° C (basaltic andesite), 1100 ° C (K basalt) or 1150 ° C (picritic basalt). These were carried out in an internally heated vessel pressurized with Ar-H2 mixtures and fitted with a drop-quench device, and lasted for between 15 and 99 h. Either Au (950 ° C) or AuPd alloys (1100 and 1150 ° C) were used as containers. These latter perform satisfactorily under strongly oxidizing conditions, i.e., for fO2 above NNO+1 at 1100 and 1150 ° C. Below NNO+1, Pd- Au-S-Fe phases appear in the charges, suggesting extensive interaction between S and the capsule material. Experimental redox conditions, determined from Ni-Pd-O sensors, ranged between NNO+1.3 to +4.1 (basaltic andesite), +0.6 to +2.0 (K basalt), and +0.3 to +3.6 (picritic basalt). H2O concentrations in melt ranged from 8.2 wt % (basaltic andesite), decreasing to 2.2-3.9 wt % (K basalt) and 2.5-5.0 wt % (picritic basalt). All 3 compositions studied crystallize anhydrite and Fe-Ni-S-O sulphide as saturating S-bearing phases, anhydrite at high fO2 and sulphide at lower fO2, although melt composition also influences their stability. Anhydrite is present at a fO2 as low as NNO+1.5 in the K basalt. In the picritic

Morse Theory and Relative Equilibria in the Planar n-Vortex Problem

NASA Astrophysics Data System (ADS)

Roberts, Gareth E.

2018-04-01

Morse theoretical ideas are applied to the study of relative equilibria in the planar n-vortex problem. For the case of positive circulations, we prove that the Morse index of a critical point of the Hamiltonian restricted to a level surface of the angular impulse is equal to the number of pairs of real eigenvalues of the corresponding relative equilibrium periodic solution. The Morse inequalities are then used to prove the instability of some families of relative equilibria in the four-vortex problem with two pairs of equal vorticities. We also show that, for positive circulations, relative equilibria cannot accumulate on the collision set.

The Effect of CaO on Gas/Slag/Matte/Tridymite Equilibria in Fayalite-Based Copper Smelting Slags at 1473 K (1200 °C) and P(SO2) = 0.25 Atm

NASA Astrophysics Data System (ADS)

Fallah-Mehrjardi, Ata; Hayes, Peter C.; Jak, Evgueni

2018-04-01

Fundamental experimental studies have been undertaken to determine the effect of CaO on the equilibria between the gas phase (CO/CO2/SO2/Ar) and slag/matte/tridymite phases in the Cu-Fe-O-S-Si-Ca system at 1473 K (1200 °C) and P(SO2) = 0.25 atm. The experimental methodology developed in the Pyrometallurgy Innovation Centre was used. New experimental data have been obtained for the four-phase equilibria system for fixed concentrations of CaO (up to 4 wt pct) in the slag phase as a function of copper concentration in matte, including the concentrations of dissolved sulfur and copper in slag, and Fe/SiO2 ratios in slag at tridymite saturation. The new data provided in the present study are of direct relevance to the pyrometallurgical processing of copper and will be used as an input to optimize the thermodynamic database for the copper-containing multi-component multi-phase system.

On Nash-Equilibria of Approximation-Stable Games

NASA Astrophysics Data System (ADS)

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

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

Phase equilibria, crystal structure and properties of complex oxides in the Nd{sub 2}O{sub 3}–SrO–CoO system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aksenova, T.V.; Efimova, T.G.; Lebedev, O.I.

2017-04-15

The phase equilibria in the ½Nd{sub 2}O{sub 3}–SrO–CoO system were systematically studied at 1373 K in air. The intermediate phases formed in the ½Nd{sub 2}O{sub 3}–SrO–CoO system at 1373 K in air are: Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} (0.0≤x≤0.5 with orthorhombic structure, sp. gr. Pbnm and 0.6≤x≤0.95 whose structure was detected as cubic according to XRD sp. gr. Pm3m, but shown to be tetragonal by TEM due to the oxygen vacancy ordering), Nd{sub 2-y}Sr{sub y}CoO{sub 4-δ} (0.6≤y≤1.1 with tetragonal K{sub 2}NiF{sub 4}-type structure, sp. gr. I4/mmm) and Nd{sub 2-z}Sr{sub z}O{sub 3} (0.0≤z≤0.15 with hexagonal structure, sp. gr. P-3m1). The unit cellmore » parameters for the single phase samples were refined by the Rietveld analysis. The changes of oxygen content in Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} (0.6≤x≤0.95) and Ruddlesden-Popper oxide Nd{sub 2-y}Sr{sub y}CoO{sub 4-δ} were examined by TGA. All were found to be oxygen deficient phases. High-temperature dilatometry allows calculating the thermal expansion coefficient and evaluating the chemical expansion coefficient at high temperature. The projection of isothermal-isobaric phase diagram for the Nd–Sr–Co–O system at 1373 K in air to the compositional triangle of metallic components has been constructed. The phase equilibria in the studied Nd–Sr–Co–O system were compared to La–Sr–Co–O and Nd–M–Co–O (M=Ca and Ba). - Graphical abstract: Crystal structure of vacancy ordered supercell for Nd{sub 0.2}Sr{sub 0.8}CoO{sub 3-δ} and projection of phase diagram for the Nd–Sr–Co–O system onto the triangle edge of metallic components at 1373 K in air. - Highlights: • The diagram for the Nd–Sr–Co–O system at 1373 K in air has been constructed. • The crystal structure of Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} and Nd{sub 2-y}Sr{sub y}CoO{sub 4±δ} was refined. • The formation of superstructure due to the oxygen vacancy ordering was proved. • The changes of

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

USGS Publications Warehouse

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.

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

DOE PAGES

Wingen, Andreas; Wilcox, Robert S.; Cianciosa, Mark R.; ...

2016-10-13

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

Experimental Investigation of Gas/Slag/Matte/Tridymite Equilibria in the Cu-Fe-O-S-Si System in Controlled Gas Atmosphere: Experimental Results at 1523 K (1250 °C) and P(SO2) = 0.25 atm

NASA Astrophysics Data System (ADS)

Fallah-Mehrjardi, Ata; Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

2018-04-01

To assist in the optimization of copper smelting and converting processes, accurate new measurements of the phase equilibria of the Cu-Fe-O-S-Si system have been undertaken. The experimental investigation was focused on the characterization of gas/slag/matte/tridymite equilibria in the Cu-Fe-O-S-Si system at 1523 K (1250 °C), P(SO2) = 0.25 atm, and a range of P(O2)s. The experimental methodology, developed in PYROSEARCH, includes high-temperature equilibration of samples on substrate made from the silica primary phase in controlled gas atmospheres (CO/CO2/SO2/Ar) followed by rapid quenching of the equilibrium condensed phases and direct measurement of the phase compositions with electron-probe X-ray microanalysis (EPMA). The data provided in the present study at 1523 K (1250 °C) and the previous study by the authors at 1473 K (1200 °C) has enabled the determination of the effects of temperature on the phase equilibria of the multicomponent multiphase system, including such characteristics as the chemically dissolved copper in slag and Fe/SiO2 ratio at silica saturation as a function of copper concentration in matte. The new data will be used in the optimization of the thermodynamic database for the copper-containing systems.

Selective adsorption and phase equilibria of confined fluids: Density-functional theory and Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Sowers, Susanne Lynn

1997-11-01

Microporous sorbents such as carbons, silicas and aluminas are used commercially in a variety of separation, purification and selective reaction applications. A detailed study of the effects of the porous material characteristics on the adsorption equilibrium properties such as selectivity and phase equilibria of fluid mixtures can enhance our understanding of adsorption on a molecular level. Such knowledge will improve our utilization of such adsorbents and provide a tool for directing the future of tailoring sorbents for particular separation processes. The effect of pore size, shape and pressure on the selective adsorption of trace pollutants from an inert gas was studied using prototype mixtures of Lennard-Tones (LJ) N2/CCl4, CF4, and SO2. Both nonlocal density functional theory (DFT) and grand canonical Monte Carlo (GCMC) molecular simulations were used in order to investigate the validity of the theory, which is much quicker and easier to use. Our results indicate that there is an optimal pore size and shape for which the pollutant selectivity is greatly enhanced. In many industrial adsorption processes relative humidity can greatly affect the life of an adsorbent bed, as seen in breakthrough curves. Therefore, the influence of water vapor on the selective adsorption of CCl4 from a mixture of N2/CCl4/H20 in activated carbon was studied using GCMC simulations. The equilibrium adsorption properties are found to be dependent upon both the density of active sites on the pore walls and the relative humidity. Liquid-liquid transitions in porous materials are of interest in connection with oil recovery, lubrication, coating technology and pollution control. The results of a study on the effect of confinement on the liquid-liquid equilibrium of binary LJ mixtures using DFT are compared with those of molecular simulation and experiments. Our findings show that the phase coexistence for the confined mixture is in general decreased and shifted toward the component which

Thermodynamic analysis of reaction equilibria in ionic and molecular liquid systems by high-temperature Raman spectroscopy.

PubMed

Kalampounias, Angelos G; Boghosian, Soghomon

2009-09-01

A formalism for correlating relative Raman band intensities with the stoichiometric coefficients, the equilibrium constant, and the thermodynamics of reaction equilibria in solution is derived. The proposed method is used for studying: (1) the thermal dissociation of molten KHSO(4) in the temperature range 240-450 degrees C; (2) the dinuclear complex formation in molten TaCl(5)-AlCl(3) mixtures at temperatures between 125 and 235 degrees C. The experimental and calculational procedures for exploiting the temperature-dependent Raman band intensities in the molten phase as well as (if applicable) in the vapors thereof are described and used for determining the enthalpy of the equilibria: (1) 2HSO(4)(-)(l) <--> S(2)O(7)(2-)(l) + H(2)O(g), DeltaH(0)=64.9 +/- 2.9 kJ mol(-1); and (2) 1/2Ta(2)Cl(10)(l) + 1/2Al(2)Cl(6)(l) <--> TaAlCl(8)(l), DeltaH(0)=-12.1 +/- 1.5 kJ mol(-1).

Phase equilibria, crystal structures, and dielectric anomaly in the BaZrO 3-CaZrO 3 system

NASA Astrophysics Data System (ADS)

Levin, Igor; Amos, Tammy G.; Bell, Steven M.; Farber, Leon; Vanderah, Terrell A.; Roth, Robert S.; Toby, Brian H.

2003-11-01

Phase equilibria in the (1- x)BaZrO 3- xCaZrO 3 system were analyzed using a combination of X-ray and neutron powder diffraction, and transmission electron microscopy. The proposed phase diagram features two extended two-phase fields containing mixtures of a Ba-rich cubic phase and a tetragonal, or orthorhombic Ca-rich phase, all having perovskite-related structures. The symmetry differences in the Ca-rich phases are caused by different tilting patterns of the [ZrO 6] octahedra. In specimens quenched from 1650°C, CaZrO 3 dissolves only a few percent of Ba, whereas the solubility of Ca in BaZrO 3 is approximately 30 at% . The BaZrO 3-CaZrO 3 system features at least two tilting phase transitions, Pm3 m→ I4/ mcm and I4/ mcm→ Pbnm. Rietveld refinements of the Ba 0.8Ca 0.2ZrO 3 structure using variable-temperature neutron powder diffraction data confirmed that the Pm3 m→ I4/ mcm transition corresponds to a rotation of octahedra about one of the cubic axes; successive octahedra along this axis rotate in opposite directions. In situ variable-temperature electron diffraction studies indicated that the transition temperature increases with increasing Ca-substitution on the A-sites, from approximately -120°C at 5 at% Ca to 225°C at 20 at% Ca. Dielectric measurements revealed that the permittivity increases monotonically from 36 for BaZrO 3 to 53 for Ba 0.9Ca 0.1ZrO 3, and then decreases to 50 for Ba 0.8Ca 0.2ZrO 3. This later specimen was the Ca-richest composition for which pellets could be quenched from the single-phase cubic field with presently available equipment. Strongly non-monotonic behavior was also observed for the temperature coefficient of resonant frequency; however, in this case, the maximum occurred at a lower Ca concentration, 0.05⩽ x⩽0.1. The non-linear behavior of the dielectric properties was attributed to two competing structural effects: a positive effect associated with substitution of relatively small Ca cations on the A-sites, resulting

Heat capacity and phase equilibria of almandine, Fe3Al2Si3O12

USGS Publications Warehouse

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.

Stability of Poisson Equilibria and Hamiltonian Relative Equilibria by Energy Methods

NASA Astrophysics Data System (ADS)

Patrick, George W.; Roberts, Mark; Wulff, Claudia

2004-12-01

We develop a general stability theory for equilibrium points of Poisson dynamical systems and relative equilibria of Hamiltonian systems with symmetries, including several generalisations of the Energy-Casimir and Energy-Momentum Methods. Using a topological generalisation of Lyapunov’s result that an extremal critical point of a conserved quantity is stable, we show that a Poisson equilibrium is stable if it is an isolated point in the intersection of a level set of a conserved function with a subset of the phase space that is related to the topology of the symplectic leaf space at that point. This criterion is applied to generalise the energy-momentum method to Hamiltonian systems which are invariant under non-compact symmetry groups for which the coadjoint orbit space is not Hausdorff. We also show that a G-stable relative equilibrium satisfies the stronger condition of being A-stable, where A is a specific group-theoretically defined subset of G which contains the momentum isotropy subgroup of the relative equilibrium. The results are illustrated by an application to the stability of a rigid body in an ideal irrotational fluid.

Phase Equilibria and Crystal Chemistry in Portions of the System SrO-CaO-Bi2O3-CuO, Part IV— The System CaO-Bi2O3-CuO

PubMed Central

Burton, B. P.; Rawn, C. J.; Roth, R. S.; Hwang, N. M.

1993-01-01

New data are presented on the phase equilibria and crystal chemistry of the binary systems CaO-Bi2O3 and CaO-CuO and the ternary CaO-Bi2O3-CuO. Symmetry data and unit cell dimensions based on single crystal and powder x-ray diffraction measurements are reported for several of the binary CaO-Bi2O3 phases, including corrected compositions for Ca4Bi6O13 and Ca2Bi2O5. The ternary system contains no new ternary phases which can be formed in air at ~700–900 °C. PMID:28053484

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

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.

A new transiently chaotic flow with ellipsoid equilibria

NASA Astrophysics Data System (ADS)

Panahi, Shirin; Aram, Zainab; Jafari, Sajad; Pham, Viet-Thanh; Volos, Christos; Rajagopal, Karthikeyan

2018-03-01

In this article, a simple autonomous transiently chaotic flow with cubic nonlinearities is proposed. This system represents some unusual features such as having a surface of equilibria. We shall describe some dynamical properties and behaviours of this system in terms of eigenvalue structures, bifurcation diagrams, time series, and phase portraits. Various behaviours of this system such as periodic and transiently chaotic dynamics can be shown by setting special parameters in proper values. Our system belongs to a newly introduced category of transiently chaotic systems: systems with hidden attractors. Transiently chaotic behaviour of our proposed system has been implemented and tested by the OrCAD-PSpise software. We have found a proper qualitative similarity between circuit and simulation results.

Phase equilibria in the lysozyme-ammonium sulfate-water system.

PubMed

Moretti, J J; Sandler, S I; Lenhoff, A M

2000-12-05

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. Copyright 2000 John Wiley & Sons, Inc.

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

NASA Astrophysics Data System (ADS)

Glampedakis, Kostas; Lasky, Paul D.

2016-12-01

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

Relative equilibria in quasi-homogeneous planar three body problems

NASA Astrophysics Data System (ADS)

Arredondo, John A.

2018-01-01

In this paper we find the families of relative equilibria for the three body problem in the plane, when the interaction between the bodies is given by a quasi-homogeneous potential. The number of the relative equilibria depends on the values of the masses and on the size of the system, measured by the moment of inertia.

The Cu-Li-Sn Phase Diagram: Isopleths, Liquidus Projection and Reaction Scheme

PubMed Central

Flandorfer, Hans

2016-01-01

The Cu-Li-Sn phase diagram was constructed based on XRD and DTA data of 60 different alloy compositions. Eight ternary phases and 14 binary solid phases form 44 invariant ternary reactions, which are illustrated by a Scheil-Schulz reaction scheme and a liquidus projection. Phase equilibria as a function of concentration and temperature are shown along nine isopleths. This report together with an earlier publication of our group provides for the first time comprehensive investigations of phase equilibria and respective phase diagrams. Most of the phase equilibria could be established based on our experimental results. Only in the Li-rich part where many binary and ternary compounds are present estimations had to be done which are all indicated by dashed lines. A stable ternary miscibility gap could be found which was predicted by modelling the liquid ternary phase in a recent work. The phase diagrams are a crucial input for material databases and thermodynamic optimizations regarding new anode materials for high-power Li-ion batteries. PMID:27788175

Signaling equilibria in sensorimotor interactions.

PubMed

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

Theoretical features of MHD equilibria with flow

NASA Astrophysics Data System (ADS)

Beklemishev, Alexei; Tessarotto, Massimo

2002-11-01

The effect produced on plasma dynamics by plasma flows, especially those produced by strong E× B-drifts represent an important theoretical issue in magnetic confinement. These include in particular Stellarator equilibria in the presence of weak flows, with velocity much smaller in magnitude than the ion thermal velocity [1]. Strong flows, however, more generally can be produced locally in a variety of physical situations (for example due to strong radial electric fields, neutral beams, RF heating, etc.). These flows can be important in establishing advanced operational regimes, such as the recently discovered HDH mode in the W7-AS Stellarator [2]. Goal of this work is to investigate theoretical features of the MHD equilibria in the presence of strong flows, with particular reference to conditions of existence of kinetic equilibria, particle adiabatic and/or bounce-averaged invariants. References 1 - M. Tessarotto, J.L. Johnson, R.B. White and L.J. Zheng, Phys. Plasmas 3, 2653 (1996); 2 - K. McCormick et al., Phys. Rev. Lett. 89, 15001 (2002).

Discovering the Thermodynamics of Simultaneous Equilibria: An Entropy Analysis Activity Involving Consecutive Equilibria

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…

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

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-05-01

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

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

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-08-01

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

Free boundary skin current magnetohydrodynamic equilibria

NASA Astrophysics Data System (ADS)

Reusch, Michael F.

1988-10-01

Function theoretic methods in the complex plane are used to develop simple parametric hodograph formulas that generate sharp boundary equilibria of arbitrary shape. The related method of Gorenflo [Z. Angew. Math. Phys. 16, 279 (1965)] and Merkel (Ph.D. thesis, University of Munich, 1965) is discussed. A numerical technique for the construction of solutions, based on one of the methods, is presented. A study is made of the bifurcations of an equilibrium of general form.

Computational Thermodynamic Study to Predict Complex Phase Equilibria in the Nickel-Base Superalloy Rene N6

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.

Quantum Nash Equilibria and Quantum Computing

NASA Astrophysics Data System (ADS)

Fellman, Philip Vos; Post, Jonathan Vos

In 2004, At the Fifth International Conference on Complex Systems, we drew attention to some remarkable findings by researchers at the Santa Fe Institute (Sato, Farmer and Akiyama, 2001) about hitherto unsuspected complexity in the Nash Equilibrium. As we progressed from these findings about heteroclinic Hamiltonians and chaotic transients hidden within the learning patterns of the simple rock-paper-scissors game to some related findings on the theory of quantum computing, one of the arguments we put forward was just as in the late 1990's a number of new Nash equilibria were discovered in simple bi-matrix games (Shubik and Quint, 1996; Von Stengel, 1997, 2000; and McLennan and Park, 1999) we would begin to see new Nash equilibria discovered as the result of quantum computation. While actual quantum computers remain rather primitive (Toibman, 2004), and the theory of quantum computation seems to be advancing perhaps a bit more slowly than originally expected, there have, nonetheless, been a number of advances in computation and some more radical advances in an allied field, quantum game theory (Huberman and Hogg, 2004) which are quite significant. In the course of this paper we will review a few of these discoveries and illustrate some of the characteristics of these new "Quantum Nash Equilibria". The full text of this research can be found at http://necsi.org/events/iccs6/viewpaper.php?id-234

Correct Representation of Conformational Equilibria.

ERIC Educational Resources Information Center

Fulop, F.; And Others

1983-01-01

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

Free boundary skin current MHD (magnetohydrodynamic) equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reusch, M.F.

1988-02-01

Function theoretic methods in the complex plane are used to develop simple parametric hodograph formulae which generate sharp boundary equilibria of arbitrary shape. The related method of Gorenflo and Merkel is discussed. A numerical technique for the construction of solutions, based on one of the methods is presented. A study is made of the bifurcations of an equilibrium of general form. 28 refs., 9 figs.

Theoretical study on the vibrational spectra of methoxy- and formyl-dihydroxy- trans-stilbenes and their hydrolytic equilibria

NASA Astrophysics Data System (ADS)

Molnár, Viktor; Billes, Ferenc; Tyihák, Ernő; Mikosch, Hans

2008-02-01

Compounds formed by exchanging one of the resveratrol hydroxy groups to methoxy or formyl groups are biologically important. Quantum chemical DFT calculations were applied for the simulation of some of their properties. Their optimized structures and charge distributions were computed. Based on the calculated vibrational force constants and optimized molecular structure infrared and Raman spectra were calculated. The characteristics of the vibrational modes were determined by normal coordinate analysis. Applying the calculated thermodynamic functions also for resveratrol, methanol, formaldehyde and water, thermodynamic equilibria were calculated for the equilibria between resveratrol and its methyl and formyl substituted derivatives, respectively.

Mixed Nash equilibria in Eisert-Lewenstein-Wilkens (ELW) games

NASA Astrophysics Data System (ADS)

Bolonek-Lasoń, Katarzyna; Kosiński, Piotr

2017-01-01

The classification of all mixed Nash equilibria for the original ELW game is presented. It is based on the quaternionic form of the game proposed by Landsburg (Proc. Am. Math. Soc. 139 (2011), 4423; Rochester Working Paper No 524 (2006); Wiley Encyclopedia of Operations Research and Management Science (Wiley and Sons, New York, (2011)). This approach allows to reduce the problem of finding the Nash equilibria to relatively simple analysis of the extrema of certain quadratic forms.

Protonation linked equilibria and apparent affinity constants: the thermodynamic profile of the alpha-chymotrypsin-proflavin interaction.

PubMed

Bruylants, Gilles; Wintjens, René; Looze, Yvan; Redfield, Christina; Bartik, Kristin

2007-12-01

Protonation/deprotonation equilibria are frequently linked to binding processes involving proteins. The presence of these thermodynamically linked equilibria affects the observable thermodynamic parameters of the interaction (K(obs), DeltaH(obs)(0) ). In order to try and elucidate the energetic factors that govern these binding processes, a complete thermodynamic characterisation of each intrinsic equilibrium linked to the complexation event is needed and should furthermore be correlated to structural information. We present here a detailed study, using NMR and ITC, of the interaction between alpha-chymotrypsin and one of its competitive inhibitors, proflavin. By performing proflavin titrations of the enzyme, at different pH values, we were able to highlight by NMR the effect of the complexation of the inhibitor on the ionisable residues of the catalytic triad of the enzyme. Using ITC we determined the intrinsic thermodynamic parameters of the different equilibria linked to the binding process. The possible driving forces of the interaction between alpha-chymotrypsin and proflavin are discussed in the light of the experimental data and on the basis of a model of the complex. This study emphasises the complementarities between ITC and NMR for the study of binding processes involving protonation/deprotonation equilibria.

Phase Equilibria in the System "FeO"-CaO-SiO2-Al2O3-MgO at Different CaO/SiO2 Ratios

NASA Astrophysics Data System (ADS)

Jang, Kyoung-oh; Ma, Xiaodong; Zhu, Jinming; Xu, Haifa; Wang, Geoff; Zhao, Baojun

2017-06-01

The "FeO"-containing slags play an important role in the operation of an ironmaking blast furnace (BF), in particular the primary slags such as the system "FeO"-CaO-SiO2-Al2O3-2 mass pct MgO with CaO/SiO2 weight ratios of 1.3, 1.5, and 1.8 saturated with metallic iron. To investigate the characteristics of such a slag system and its behavior in BF, the phase equilibria and liquidus temperatures in the slag system have been experimentally determined using the high-temperature equilibration and quenching technique followed by an electron probe X-ray microanalysis (EPMA). Isotherms between 1553 K and 1603 K (1280 °C and 1330 °C) were determined in the primary phase fields of dicalcium silicate, melilite, spinel, and monoxide [(Mg,Fe2+)O]. Pseudo-ternary phase diagrams of (CaO + SiO2)-Al2O3-"FeO" with a fixed MgO concentration at 2 mass pct and at CaO/SiO2 ratios of 1.3, 1.5, and 1.8 have been discussed, respectively, simplifying the complexity of the slag system for easy understanding and applying in BF operation. It was found that the liquidus temperatures increase in melilite and spinel primary phase fields, but decrease in dicalcium silicate and monoxide primary phase fields with increasing Al2O3/(CaO + SiO2) ratio. In addition, the liquidus temperatures decrease with increasing "FeO" concentration in dicalcium silicate and melilite primary phase fields, while showing an increasing trend in the spinel and monoxide primary phase fields. The data resulted from this study can be used to improve and optimize currently available database of thermodynamic models used in FactSage.

Determination of 3D Equilibria from Flux Surface Knowledge Only

DOE Office of Scientific and Technical Information (OSTI.GOV)

H.E. Mynick; N. Pomphrey

We show that the method of Christiansen and Taylor, from which complete tokamak equilibria can be determined given only knowledge of the shape of the flux surfaces, can be extended to 3-dimensional equilibria, such as those of stellarators. As for the tokamak case, the given geometric knowledge has a high degree of redundancy, so that the full equilibrium can be obtained using only a small portion of that information.

Phase equilibria in polymer-blend thin films

NASA Astrophysics Data System (ADS)

Clarke, Nigel; Souche, Mireille

2010-03-01

To describe equilibrium concentration profiles in thin films of polymer mixtures, we propose a Hamiltonian formulation of the Flory-Huggins-de Gennes theory describing a polymer blend thin film. We first focus on the case of 50:50 polymer blends confined between anti-symmetric walls. The different phases of the system and the transitions between them, including finite size effects, are systematically studied through their relation with the geometry of the Hamiltonian flow in phase space. This method provides an easy and efficient way, with strong graphical insight, to infer the qualitative physical behavior of polymer blend thin films. The addition of a further degree of freedom in the system, namely a solvent, may result in a chaotic behavior of the system, characterized by the existence of solutions with exponential sensitivity to initial conditions. Such solutions and there subsequent contribution to the out-of-equilibrium dynamics of the system are well described in Hamiltonian formalism. A fully consistent treatment of the Flory-Huggins-de Gennes theory of thin film polymer blend solutions, in the spirit of the Hamiltonian approach will be presented. 1. M. Souche and N. Clarke, J. Chem. Phys., submitted.

Calculating phase diagrams using PANDAT and panengine

NASA Astrophysics Data System (ADS)

Chen, S.-L.; Zhang, F.; Xie, F.-Y.; Daniel, S.; Yan, X.-Y.; Chang, Y. A.; Schmid-Fetzer, R.; Oates, W. A.

2003-12-01

Knowledge of phase equilibria or phase diagrams and thermodynamic properties is important in alloy design and materials-processing simulation. In principle, stable phase equilibrium is uniquely determined by the thermodynamic properties of the system, such as the Gibbs energy functions of the phases. PANDAT, a new computer software package for multicomponent phase-diagram calculation, was developed under the guidance of this principle.

A note on two-dimensional asymptotic magnetotail equilibria

NASA Technical Reports Server (NTRS)

Voigt, Gerd-Hannes; Moore, Brian D.

1994-01-01

In order to understand, on the fluid level, the structure, the time evolution, and the stability of current sheets, such as the magnetotail plasma sheet in Earth's magnetosphere, one has to consider magnetic field configurations that are in magnetohydrodynamic (MHD) force equilibrium. Any reasonable MHD current sheet model has to be two-dimensional, at least in an asymptotic sense (B(sub z)/B (sub x)) = epsilon much less than 1. The necessary two-dimensionality is described by a rather arbitrary function f(x). We utilize the free function f(x) to construct two-dimensional magnetotail equilibria are 'equivalent' to current sheets in empirical three-dimensional models. We obtain a class of asymptotic magnetotail equilibria ordered with respect to the magnetic disturbance index Kp. For low Kp values the two-dimensional MHD equilibria reflect some of the realistic, observation-based, aspects of three-dimensional models. For high Kp values the three-dimensional models do not fit the asymptotic MHD equlibria, which is indicative of their inconsistency with the assumed pressure function. This, in turn, implies that high magnetic activity levels of the real magnetosphere might be ruled by thermodynamic conditions different from local thermodynamic equilibrium.

LEPER: Library of Experimental PhasE Relations

NASA Astrophysics Data System (ADS)

Davis, F.; Gordon, S.; Mukherjee, S.; Hirschmann, M.; Ghiorso, M.

2006-12-01

The Library of Experimental PhasE Relations (LEPER) seeks to compile published experimental determinations of magmatic phase equilibria and provide those data on the web with a searchable and downloadable interface. Compiled experimental data include the conditions and durations of experiments, the bulk compositions of experimental charges, and the identity, compositions and proportions of phases observed, and, where available, estimates of experimental and analytical uncertainties. Also included are metadata such as the type of experimental device, capsule material, and method(s) of quantitative analysis. The database may be of use to practicing experimentalists as well as the wider Earth science community. Experimentalists may find the data useful for planning new experiments and will easily be able to compare their results to the full body of previous experimentnal data. Geologists may use LEPER to compare rocks sampled in the field with experiments performed on similar bulk composition or with experiments that produced similar-composition product phases. Modelers may use LEPER to parameterize partial melting of various lithologies. One motivation for compiling LEPER is for calibration of updated and revised versions of MELTS, however, it is hoped that the availability of LEPER will facilitate formulation and calibration of additional thermodynamic or empirical models of magmatic phase relations and phase equilibria, geothermometers and more. Data entry for LEPER is occuring presently: As of August, 2006, >6200 experiments have been entered, chiefly from work published between 1997 and 2005. A prototype web interface has been written and beta release on the web is anticipated in Fall, 2006. Eventually, experimentalists will be able to submit their new experimental data to the database via the web. At present, the database contains only data pertaining to the phase equilibria of silicate melts, but extension to other experimental data involving other fluids or

Gyrokinetic magnetohydrodynamics and the associated equilibria

NASA Astrophysics Data System (ADS)

Lee, W. W.; Hudson, S. R.; Ma, C. H.

2017-12-01

The gyrokinetic magnetohydrodynamic (MHD) equations, related to the recent paper by W. W. Lee ["Magnetohydrodynamics for collisionless plasmas from the gyrokinetic perspective," Phys. Plasmas 23, 070705 (2016)], and their associated equilibria properties are discussed. This set of equations consists of the time-dependent gyrokinetic vorticity equation, the gyrokinetic parallel Ohm's law, and the gyrokinetic Ampere's law as well as the equations of state, which are expressed in terms of the electrostatic potential, ϕ, and the vector potential, A , and support both spatially varying perpendicular and parallel pressure gradients and the associated currents. The corresponding gyrokinetic MHD equilibria can be reached when ϕ→0 and A becomes constant in time, which, in turn, gives ∇.(J∥+J⊥)=0 and the associated magnetic islands, if they exist. Examples of simple cylindrical geometry are given. These gyrokinetic MHD equations look quite different from the conventional MHD equations, and their comparisons will be an interesting topic in the future.

Gyrokinetic magnetohydrodynamics and the associated equilibria

DOE PAGES

Lee, W. W.; Hudson, S. R.; Ma, C. H.

2017-12-27

The gyrokinetic magnetohydrodynamic (MHD) equations, related to the recent paper by W. W. Lee, and their associated equilibria properties are discussed. This set of equations consists of the time-dependent gyrokinetic vorticity equation, the gyrokinetic parallel Ohm's law, and the gyrokinetic Ampere's law as well as the equations of state, which are expressed in terms of the electrostatic potential, Φ, and the vector potential, A, and support both spatially varying perpendicular and parallel pressure gradients and the associated currents. The corresponding gyrokinetic MHD equilibria can be reached when Φ → 0 and A becomes constant in time, which, in turn, givesmore » ∇· (J ∥+J ⊥) = 0 and the associated magnetic islands, if they exist. Examples of simple cylindrical geometry are given. In conclusion, these gyrokinetic MHD equations look quite different from the conventional MHD equations, and their comparisons will be an interesting topic in the future.« less

Gyrokinetic magnetohydrodynamics and the associated equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, W. W.; Hudson, S. R.; Ma, C. H.

The gyrokinetic magnetohydrodynamic (MHD) equations, related to the recent paper by W. W. Lee, and their associated equilibria properties are discussed. This set of equations consists of the time-dependent gyrokinetic vorticity equation, the gyrokinetic parallel Ohm's law, and the gyrokinetic Ampere's law as well as the equations of state, which are expressed in terms of the electrostatic potential, Φ, and the vector potential, A, and support both spatially varying perpendicular and parallel pressure gradients and the associated currents. The corresponding gyrokinetic MHD equilibria can be reached when Φ → 0 and A becomes constant in time, which, in turn, givesmore » ∇· (J ∥+J ⊥) = 0 and the associated magnetic islands, if they exist. Examples of simple cylindrical geometry are given. In conclusion, these gyrokinetic MHD equations look quite different from the conventional MHD equations, and their comparisons will be an interesting topic in the future.« less

Solution influence on biomolecular equilibria - Nucleic acid base associations

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Thermodynamic characteristics of protolytic equilibria in aqueous solutions of glycyl peptides

NASA Astrophysics Data System (ADS)

Gridchin, S. N.

2016-11-01

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

A stochastic cellular automata model of tautomer equilibria

NASA Astrophysics Data System (ADS)

Bowers, Gregory A.; Seybold, Paul G.

2018-03-01

Many chemical substances, including drugs and biomolecules, exist in solution not as a single species, but as a collection of tautomers and related species. Importantly, each of these species is an independent compoundwith its own specific biochemical and physicochemical properties. The species interconvert in a dynamic and often complicated manner, making modelling the overall species composition difficult. Agent-based cellular automata models are uniquely suited to meet this challenge, allowing the equilibria to be simulated using simple rulesand at the same time capturing the inherent stochasticity of the natural phenomenon. In the present example a stochastic cellular automata model is employed to simulate the tautomer equilibria of 9-anthrone and 9-anthrol in the presence of their common anion. The observed KE of the 9-anthrone ⇌ 9-anthrol tautomerisation along with the measured tautomer pKa values were used to model the equilibria at pH values 4, 7 and 10. At pH 4 and 7, the anthrone comprises >99% of the total species population, while at pH 10the anthrone and the anion each represent just under half of the total population. The advantages of the cellular automata approach over the customary coupled differential equation approach are discussed.

Phase equilibria in the Tb-Mg-Co system at 500 °C, crystal structure and hydrogenation properties of selected compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shtender, V.V.; Denys, R.V.; Zavaliy, I.Yu., E-mail: zavaliy@ipm.lviv.ua

2015-12-15

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 Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo was confirmed. The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} (0≤x≤0.4) and Tb{sub 1-−x}Mg{sub x}Co{sub 2} (0≤x≤0.6), was found for the first time. It is shown that Tb{sub 5}Mg{sub 24} also dissolves a small amount of Co. Other binary compounds do not dissolve the third component. The Tb{sub 4}MgCo and TbMgCo{sub 4} compounds form hydrides (12.7 and 5.3more » at.H/f.u. capacity, respectively) that retain the original structure of metallic matrices. Upon thermal desorption the Tb{sub 4}MgCoH{sub 12.7} hydride was stable up to 300 °C and disproportionated at higher temperature. Two other hydrides, Tb{sub 4}Mg{sub 3}Co{sub 2}H{sub ∼4} and Tb{sub 2}MgCo{sub 9}H{sub 12}, are unstable in air and decompose into the initial compounds. - Highlights: • The phase equilibria at 500 °°C in the Tb–Mg–Co system has been studied. • The existence of two ternary compounds, Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo, was confirmed. • The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} and Tb{sub 1−x}Mg{sub x}Co{sub 2}, was found. • Hydrogen sorption–desorption properties have been studied for the selected alloys.« less

Reduction and relative equilibria for the two-body problem on spaces of constant curvature

NASA Astrophysics Data System (ADS)

Borisov, A. V.; García-Naranjo, L. C.; Mamaev, I. S.; Montaldi, J.

2018-06-01

We consider the two-body problem on surfaces of constant nonzero curvature and classify the relative equilibria and their stability. On the hyperbolic plane, for each q>0 we show there are two relative equilibria where the masses are separated by a distance q. One of these is geometrically of elliptic type and the other of hyperbolic type. The hyperbolic ones are always unstable, while the elliptic ones are stable when sufficiently close, but unstable when far apart. On the sphere of positive curvature, if the masses are different, there is a unique relative equilibrium (RE) for every angular separation except π /2. When the angle is acute, the RE is elliptic, and when it is obtuse the RE can be either elliptic or linearly unstable. We show using a KAM argument that the acute ones are almost always nonlinearly stable. If the masses are equal, there are two families of relative equilibria: one where the masses are at equal angles with the axis of rotation (`isosceles RE') and the other when the two masses subtend a right angle at the centre of the sphere. The isosceles RE are elliptic if the angle subtended by the particles is acute and is unstable if it is obtuse. At π /2, the two families meet and a pitchfork bifurcation takes place. Right-angled RE are elliptic away from the bifurcation point. In each of the two geometric settings, we use a global reduction to eliminate the group of symmetries and analyse the resulting reduced equations which live on a five-dimensional phase space and possess one Casimir function.

Liquid-liquid equilibria for 2,3-butanediol + water + organic solvents at 303. 15 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, S.; Pandya, G.; Chakrabarti, T.

1994-10-01

2, 3-Butanediol, an important industrial chemical, is of interest because of its application as a solvent and liquid fuel additive. Liquid-liquid equilibria at 303.15 [+-] 0.5 K were measured for water + 2, 3-butanediol + butan-1-ol, + 3-methyl-1-butanol, + 4-methyl-2-pentanone, + tributyl phosphate, and + butyl acetate. Complete phase diagrams were obtained by evaluating the solubility and tie-line results for each ternary mixture. The consistency of the tie-line results was ascertained using an Othmer-Tobias plot. The distribution coefficient and separation factors were evaluated over the immiscibility region. Among the solvents studied, butan-1-ol is the most effective one though tributyl phosphatemore » and 3-methyl-1-butanol may be preferred because of their low solubility and high selectivity.« less

Phase Equilibria and Crystal Chemistry in Portions of the System SrO-CaO-Bi2O3-CuO, Part II—The System SrO-Bi2O3-CuO

PubMed Central

Roth, R. S.; Rawn, C. J.; Burton, B. P.; Beech, F.

1990-01-01

New data are presented on the phase equilibria and crystal chemistry of the binary systems Sr0-Bi203 and SrO-CuO and the ternary system SrO-Bi2O3-CuO. Symmetry data and unit cell dimensions based on single crystal and powder x-ray diffraction measurements are reported for all the binary SrO-Bi2O3 phases, including a new phase identified as Sr6Bi2O9. The ternary system contains at least four ternary phases which can be formed in air at ~900 °C. These are identified as Sr2Bi2CuO6, Sr8Bi4Cu5O19+x, Sr3Bi2Cu2O8 and a solid solution (the Raveau phase) which, for equilibrium conditions at ~900 °C, corresponds approximately to the formula Sr1.8−xBi2.2+xCu1±x/2Oz.(0.0⩽x⩽~0.15). Superconductivity in this phase apparently occurs only in compositions that correspond to negative values of x. Compositions that lie outside the equilibrium Raveau-phase field often form nearly homogeneous Raveau-phase products. Typically this occurs after relatively brief heat treatments, or in crystallization of a quenched melt. PMID:28179779

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canale, Eduardo A., E-mail: ecanale@pol.una.py; Monzón, Pablo, E-mail: monzon@fing.edu.uy

2015-02-15

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

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…

Acid-Base and Precipitation Equilibria in Wine

ERIC Educational Resources Information Center

Palma, Miguel; Barroso, Carmelo G.

2004-01-01

Experiments are performed to establish the changes of pH during the precipitation of potassium hydrogen tartrate, with its unfavorable impact on the stability of wine. Students, thus, obtain a clearer understanding of the interplay between a variety of chemical equilibria within a single medium.

An Introduction to Multivariate Curve Resolution-Alternating Least Squares: Spectrophotometric Study of the Acid-Base Equilibria of 8-Hydroxyquinoline-5-Sulfonic Acid

ERIC Educational Resources Information Center

Rodriguez-Rodriguez, Cristina; Amigo, Jose Manuel; Coello, Jordi; Maspoch, Santiago

2007-01-01

A spectrophotometric study of the acid-base equilibria of 8-hydroxyquinoline-5-sulfonic acid to describe the multivariate curve resolution-alternating least squares algorithm (MCR-ALS) is described. The algorithm provides a lot of information and hence is of great importance for the chemometrics research.

Finding Bounded Rational Equilibria. Part 1; Iterative Focusing

NASA Technical Reports Server (NTRS)

Wolpert, David H.

2004-01-01

A long-running difficulty with conventional game theory has been how to modify it to accommodate the bounded rationality characterizing all real-world players. A recurring issue in statistical physics is how best to approximate joint probability distributions with decoupled (and therefore far more tractable) distributions. It has recently been shown that the same information theoretic mathematical structure, known as Probability Collectives (PC) underlies both issues. This relationship between statistical physics and game theory allows techniques and insights from the one field to be applied to the other. In particular, PC provides a formal model-independent definition of the degree of rationality of a player and of bounded rationality equilibria. This pair of papers extends previous work on PC by introducing new computational approaches to effectively find bounded rationality equilibria of common-interest (team) games.

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

PubMed

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

2012-05-14

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

Beltrami–Bernoulli equilibria in plasmas with degenerate electrons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berezhiani, V. I., E-mail: vazhab@yahoo.com; Shatashvili, N. L., E-mail: shatash@ictp.it; Mahajan, S. M., E-mail: mahajan@mail.utexas.edu

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.

Using Computer-Based "Experiments" in the Analysis of Chemical Reaction Equilibria

ERIC Educational Resources Information Center

Li, Zhao; Corti, David S.

2018-01-01

The application of the Reaction Monte Carlo (RxMC) algorithm to standard textbook problems in chemical reaction equilibria is discussed. The RxMC method is a molecular simulation algorithm for studying the equilibrium properties of reactive systems, and therefore provides the opportunity to develop computer-based "experiments" for the…

Phase equilibria in polymer blend thin films: A Hamiltonian approach

NASA Astrophysics Data System (ADS)

Souche, M.; Clarke, N.

2009-12-01

We propose a Hamiltonian formulation of the Flory-Huggins-de Gennes theory describing a polymer blend thin film. We then focus on the case of 50:50 polymer blends confined between antisymmetric walls. The different phases of the system and the transitions between them, including finite-size effects, are systematically studied through their relation with the geometry of the Hamiltonian flow in phase space. This method provides an easy and efficient way, with strong graphical insight, to infer the qualitative physical behavior of polymer blend thin films.

Roto-orbital dynamics of a triaxial rigid body around a sphere. Relative equilibria and stability

NASA Astrophysics Data System (ADS)

Crespo, F.; Ferrer, S.

2018-06-01

We study the roto-orbital motion of a triaxial rigid body around a sphere, which is assumed to be much more massive than the triaxial body. The associated dynamics of this system, which consists of a normalized Hamiltonian with respect to the fast angles (partial averaging), is investigated making use of variables referred to the total angular momentum. The first order approximation of this model is integrable. We carry out the analysis of the relative equilibria, which hinges principally in the dihedral angle between the orbital and rotational planes and the ratio among the moments of inertia ρ = (B - A) / (2 C - B - A) . In particular, the dynamics of the body frame, though formally given by the classical Euler equations, experiences changes of stability in the principal directions related to the roto-orbital coupling. When ρ = 1 / 3 , we find a family of relative equilibria connected to the unstable equilibria of the free rigid body.

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

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

A decentralized process for finding equilibria given by linear equations.

PubMed Central

Reiter, S

1994-01-01

I present a decentralized process for finding the equilibria of an economy characterized by a finite number of linear equilibrium conditions. The process finds all equilibria or, if there are none, reports that, in a finite number of steps at most equal to the number of equations. The communication and computational complexity compare favorably with other decentralized processes. The process may also be interpreted as an algorithm for solving a distributed system of linear equations. Comparisons with the Linpack program for LU (lower and upper triangular decomposition of the matrix of the equation system, a version of Gaussian elimination) are presented. PMID:11607486

Textbook Forum: Equilibrium Constants of Chemical Reactions Involving Condensed Phases: Pressure Dependence and Choice of Standard State.

ERIC Educational Resources Information Center

Perlmutter-Hayman, Berta

1984-01-01

Problems of equilibria in condensed phases (particularly those involving solutes in dilute solutions) are encountered by students in their laboratory work; the thermodynamics of these equilibria is neglected in many textbooks. Therefore, several aspects of this topic are explored, focusing on pressure dependence and choice of standard state. (JN)

A Computer Algebra Approach to Solving Chemical Equilibria in General Chemistry

ERIC Educational Resources Information Center

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

2012-01-01

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

Biparametric equilibria bifurcations of the Pierce diode: A one-dimensional plasma-filled device

DOE Office of Scientific and Technical Information (OSTI.GOV)

Terra, Maisa O.

2011-03-15

The equilibria bifurcations of the biparametric version of the classical Pierce diode, a one-dimensional plasma-filled device, are analyzed in detail. Our investigation reveals that this spatiotemporal model is not structurally stable in relation to a second control parameter, the ratio of the plasma ion density to the injected electron beam density. For the first time, we relate the existence of one-fluid chaotic regions with specific biparametric equilibria bifurcations, identifying the restricted regions in the parametric plane where they occur. We show that the system presents several biparametric scenarios involving codimension-two transcritical bifurcations. Finally, we provide the spatial profile of themore » stable and unstable one-fluid equilibria in order to describe their metamorphoses.« less

Initial condition-dependent dynamics and transient period in memristor-based hypogenetic jerk system with four line equilibria

NASA Astrophysics Data System (ADS)

Bao, Han; Wang, Ning; Bao, Bocheng; Chen, Mo; Jin, Peipei; Wang, Guangyi

2018-04-01

Memristor-based nonlinear dynamical system easily presents the initial condition-dependent dynamical phenomenon of extreme multistability, i.e., coexisting infinitely many attractors, which has been received much attention in recent years. By introducing an ideal and active flux-controlled memristor into an existing hypogenetic chaotic jerk system, an interesting memristor-based chaotic system with hypogenetic jerk equation and circuit forms is proposed. The most striking feature is that this system has four line equilibria and exhibits the extreme multistability phenomenon of coexisting infinitely many attractors. Stability of these line equilibria are analyzed, and coexisting infinitely many attractors' behaviors with the variations of the initial conditions are investigated by bifurcation diagrams, Lyapunov exponent spectra, attraction basins, and phased portraits, upon which the forming mechanism of extreme multistablity in the memristor-based hypogenetic jerk system is explored. Specially, unusual transition behavior of long term transient period with steady chaos, completely different from the phenomenon of transient chaos, can be also found for some initial conditions. Moreover, a hardware circuit is design and fabricated and its experimental results effectively verify the truth of extreme multistablity.

Multi-region approach to free-boundary three-dimensional tokamak equilibria and resistive wall instabilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferraro, N. M.; Jardin, S. C.; Lao, L. L.

Free-boundary 3D tokamak equilibria and resistive wall instabilities are calculated using a new resistive wall model in the two-fluid M3D-C1 code. In this model, the resistive wall and surround- ing vacuum region are included within the computational domain. Our implementation contrasts with the method typically used in fluid codes in which the resistive wall is treated as a boundary condition on the computational domain boundary and has the advantage of maintaining purely local coupling of mesh elements. We use this new capability to simulate perturbed, free-boundary non- axisymmetric equilibria; the linear evolution of resistive wall modes; and the linear andmore » nonlinear evolution of axisymmetric vertical displacement events (VDEs). Calculated growth rates for a resistive wall mode with arbitrary wall thickness are shown to agree well with the analytic theory. Equilibrium and VDE calculations are performed in diverted tokamak geometry, at physically real- istic values of dissipation, and with resistive walls of finite width. Simulations of a VDE disruption extend into the current-quench phase, in which the plasma becomes limited by the first wall, and strong currents are observed to flow in the wall, in the SOL, and from the plasma to the wall.« less

Multi-region approach to free-boundary three-dimensional tokamak equilibria and resistive wall instabilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferraro, N. M., E-mail: nferraro@pppl.gov; Lao, L. L.; Jardin, S. C.

Free-boundary 3D tokamak equilibria and resistive wall instabilities are calculated using a new resistive wall model in the two-fluid M3D-C1 code. In this model, the resistive wall and surrounding vacuum region are included within the computational domain. This implementation contrasts with the method typically used in fluid codes in which the resistive wall is treated as a boundary condition on the computational domain boundary and has the advantage of maintaining purely local coupling of mesh elements. This new capability is used to simulate perturbed, free-boundary non-axisymmetric equilibria; the linear evolution of resistive wall modes; and the linear and nonlinear evolutionmore » of axisymmetric vertical displacement events (VDEs). Calculated growth rates for a resistive wall mode with arbitrary wall thickness are shown to agree well with the analytic theory. Equilibrium and VDE calculations are performed in diverted tokamak geometry, at physically realistic values of dissipation, and with resistive walls of finite width. Simulations of a VDE disruption extend into the current-quench phase, in which the plasma becomes limited by the first wall, and strong currents are observed to flow in the wall, in the SOL, and from the plasma to the wall.« less

Multi-region approach to free-boundary three-dimensional tokamak equilibria and resistive wall instabilities

NASA Astrophysics Data System (ADS)

Ferraro, N. M.; Jardin, S. C.; Lao, L. L.; Shephard, M. S.; Zhang, F.

2016-05-01

Free-boundary 3D tokamak equilibria and resistive wall instabilities are calculated using a new resistive wall model in the two-fluid M3D-C1 code. In this model, the resistive wall and surrounding vacuum region are included within the computational domain. This implementation contrasts with the method typically used in fluid codes in which the resistive wall is treated as a boundary condition on the computational domain boundary and has the advantage of maintaining purely local coupling of mesh elements. This new capability is used to simulate perturbed, free-boundary non-axisymmetric equilibria; the linear evolution of resistive wall modes; and the linear and nonlinear evolution of axisymmetric vertical displacement events (VDEs). Calculated growth rates for a resistive wall mode with arbitrary wall thickness are shown to agree well with the analytic theory. Equilibrium and VDE calculations are performed in diverted tokamak geometry, at physically realistic values of dissipation, and with resistive walls of finite width. Simulations of a VDE disruption extend into the current-quench phase, in which the plasma becomes limited by the first wall, and strong currents are observed to flow in the wall, in the SOL, and from the plasma to the wall.

Multi-region approach to free-boundary three-dimensional tokamak equilibria and resistive wall instabilities

DOE PAGES

Ferraro, N. M.; Jardin, S. C.; Lao, L. L.; ...

2016-05-20

Free-boundary 3D tokamak equilibria and resistive wall instabilities are calculated using a new resistive wall model in the two-fluid M3D-C1 code. In this model, the resistive wall and surround- ing vacuum region are included within the computational domain. Our implementation contrasts with the method typically used in fluid codes in which the resistive wall is treated as a boundary condition on the computational domain boundary and has the advantage of maintaining purely local coupling of mesh elements. We use this new capability to simulate perturbed, free-boundary non- axisymmetric equilibria; the linear evolution of resistive wall modes; and the linear andmore » nonlinear evolution of axisymmetric vertical displacement events (VDEs). Calculated growth rates for a resistive wall mode with arbitrary wall thickness are shown to agree well with the analytic theory. Equilibrium and VDE calculations are performed in diverted tokamak geometry, at physically real- istic values of dissipation, and with resistive walls of finite width. Simulations of a VDE disruption extend into the current-quench phase, in which the plasma becomes limited by the first wall, and strong currents are observed to flow in the wall, in the SOL, and from the plasma to the wall.« less

Plasma Equilibria With Stochastic Magnetic Fields

NASA Astrophysics Data System (ADS)

Krommes, J. A.; Reiman, A. H.

2009-05-01

Plasma equilibria that include regions of stochastic magnetic fields are of interest in a variety of applications, including tokamaks with ergodic limiters and high-pressure stellarators. Such equilibria are examined theoretically, and a numerical algorithm for their construction is described.^2,3 % The balance between stochastic diffusion of magnetic lines and small effects^2 omitted from the simplest MHD description can support pressure and current profiles that need not be flattened in stochastic regions. The diffusion can be described analytically by renormalizing stochastic Langevin equations for pressure and parallel current j, with particular attention being paid to the satisfaction of the periodicity constraints in toroidal configurations with sheared magnetic fields. The equilibrium field configuration can then be constructed by coupling the prediction for j to Amp'ere's law, which is solved numerically. A. Reiman et al., Pressure-induced breaking of equilibrium flux surfaces in the W7AS stellarator, Nucl. Fusion 47, 572--8 (2007). J. A. Krommes and A. H. Reiman, Plasma equilibrium in a magnetic field with stochastic regions, submitted to Phys. Plasmas. J. A. Krommes, Fundamental statistical theories of plasma turbulence in magnetic fields, Phys. Reports 360, 1--351.

A Closer Look at Phase Diagrams for the General Chemistry Course.

ERIC Educational Resources Information Center

Gramsch, Stephen A.

2000-01-01

Information concerning structural chemistry and phase equilibria contained in the full phase diagrams of common substances is a great deal richer than the general chemistry students are given to believe. Discusses ways of enriching the traditional presentation of phase diagrams in general chemistry courses. (Contains over 20 references.) (WRM)

Phase diagrams for understanding gold-seeded growth of GaAs and InAs nanowires

NASA Astrophysics Data System (ADS)

Ghasemi, Masoomeh; Johansson, Jonas

2017-04-01

Phase diagrams are useful tools to study the phase equilibria of nanowire materials systems because the growth of nanowires is accompanied by phase formation and phase transition. We have modeled the phase equilibria of the As-Au-Ga ternary system by means of the CALPHAD method. This method is a well-established semi-empirical technique for thermodynamic modeling in which Gibbs energy functions with free parameters are defined for all phases in a system followed by adjusting these parameters to the experimental data. Using the resulting As-Au-Ga thermodynamic database, four vertical cuts of this ternary system are calculated and all show good agreement with experiments. This ternary system is particularly useful for predicting the state of the Au seed alloys when growing GaAs nanowires and we discuss such predictions. Similar calculations are performed for Au-seeded InAs nanowires. We show that the vapor-liquid-solid (VLS) growth fails for InAs nanowires, while GaAs nanowires can grow from a liquid particle. Our calculations are in agreement with experimental data on the growth of Au-seeded GaAs and InAs nanowires.

Multiple Reaction Equilibria--With Pencil and Paper: A Class Problem on Coal Methanation.

ERIC Educational Resources Information Center

Helfferich, Friedrich G.

1989-01-01

Points out a different and much simpler approach for the study of equilibria of multiple and heterogeneous chemical reactions. A simulation on coal methanation is used to teach the technique. An example and the methodology used are provided. (MVL)

Two-fluid flowing equilibria of spherical torus sustained by coaxial helicity injection

NASA Astrophysics Data System (ADS)

Kanki, Takashi; Steinhauer, Loren; Nagata, Masayoshi

2007-11-01

Two-dimensional equilibria in helicity-driven systems using two-fluid model were previously computed, showing the existence of an ultra-low-q spherical torus (ST) configuration with diamagnetism and higher beta. However, this computation assumed purely toroidal ion flow and uniform density. The purpose of the present study is to apply the two-fluid model to the two-dimensional equilibria of helicity-driven ST with non-uniform density and both toroidal and poloidal flows for each species by means of the nearby-fluids procedure, and to explore their properties. We focus our attention on the equilibria relevant to the HIST device, which are characterized by either driven or decaying λ profiles. The equilibrium for the driven λ profile has a diamagnetic toroidal field, high-β (βt = 32%), and centrally broad density. By contrast, the decaying equilibrium has a paramagnetic toroidal field, low-β (βt = 10%), and centrally peaked density with a steep gradient in the outer edge region. In the driven case, the toroidal ion and electron flows are in the same direction, and two-fluid effects are less important since the ExB drift is dominant. In the decaying case, the toroidal ion and electron flows are opposite in the outer edge region, and two-fluid effects are significant locally in the edge due to the ion diamagnetic drift.

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.

Idealized modeling of convective organization with changing sea surface temperatures using multiple equilibria in weak temperature gradient simulations

NASA Astrophysics Data System (ADS)

Sentić, Stipo; Sessions, Sharon L.

2017-06-01

The weak temperature gradient (WTG) approximation is a method of parameterizing the influences of the large scale on local convection in limited domain simulations. WTG simulations exhibit multiple equilibria in precipitation; depending on the initial moisture content, simulations can precipitate or remain dry for otherwise identical boundary conditions. We use a hypothesized analogy between multiple equilibria in precipitation in WTG simulations, and dry and moist regions of organized convection to study tropical convective organization. We find that the range of wind speeds that support multiple equilibria depends on sea surface temperature (SST). Compared to the present SST, low SSTs support a narrower range of multiple equilibria at higher wind speeds. In contrast, high SSTs exhibit a narrower range of multiple equilibria at low wind speeds. This suggests that at high SSTs, organized convection might occur with lower surface forcing. To characterize convection at different SSTs, we analyze the change in relationships between precipitation rate, atmospheric stability, moisture content, and the large-scale transport of moist entropy and moisture with increasing SSTs. We find an increase in large-scale export of moisture and moist entropy from dry simulations with increasing SST, which is consistent with a strengthening of the up-gradient transport of moisture from dry regions to moist regions in organized convection. Furthermore, the changes in diagnostic relationships with SST are consistent with more intense convection in precipitating regions of organized convection for higher SSTs.

Predicting vapor liquid equilibria using density functional theory: A case study of argon

NASA Astrophysics Data System (ADS)

Goel, Himanshu; Ling, Sanliang; Ellis, Breanna Nicole; Taconi, Anna; Slater, Ben; Rai, Neeraj

2018-06-01

Predicting vapor liquid equilibria (VLE) of molecules governed by weak van der Waals (vdW) interactions using the first principles approach is a significant challenge. Due to the poor scaling of the post Hartree-Fock wave function theory with system size/basis functions, the Kohn-Sham density functional theory (DFT) is preferred for systems with a large number of molecules. However, traditional DFT cannot adequately account for medium to long range correlations which are necessary for modeling vdW interactions. Recent developments in DFT such as dispersion corrected models and nonlocal van der Waals functionals have attempted to address this weakness with a varying degree of success. In this work, we predict the VLE of argon and assess the performance of several density functionals and the second order Møller-Plesset perturbation theory (MP2) by determining critical and structural properties via first principles Monte Carlo simulations. PBE-D3, BLYP-D3, and rVV10 functionals were used to compute vapor liquid coexistence curves, while PBE0-D3, M06-2X-D3, and MP2 were used for computing liquid density at a single state point. The performance of the PBE-D3 functional for VLE is superior to other functionals (BLYP-D3 and rVV10). At T = 85 K and P = 1 bar, MP2 performs well for the density and structural features of the first solvation shell in the liquid phase.

Rapid nondestructive spectrometric measurement of temperature-dependent gas-liquid solubility equilibria.

PubMed

Ma, Jian; Dasgupta, Purnendu K; Yang, Bingcheng

2011-02-01

Gas-liquid solubility equilibria (Henry's Law behavior) are of basic interest to many different areas. Temperature-dependent aqueous solubilities of various organic compounds are of fundamental importance in many branches of environmental science. In a number of situations, the gas/dissolved solute of interest has characteristic spectroscopic absorption that is distinct from that of the solvent. For such cases, we report facile nondestructive rapid measurement of the temperature-dependent Henry's law constant (K(H)) in a static sealed spectrometric cell. Combined with a special cell design, multiwavelength measurement permits a large range of K(H) to be spanned. It is possible to derive the K(H) values from the absorbance measured in the gas phase only, the liquid phase only (preferred), and both phases. Underlying principles are developed, and all three approaches are illustrated for a solute like acetone in water. A thermostatic spectrophotometer cell compartment, widely used and available, facilitates rapid temperature changes and allows rapid temperature-dependent equilibrium measurements. Applicability is shown for both acetone and methyl isobutyl ketone. Very little sample is required for the measurement; the K(H) for 4-hydroxynonenal, a marker for oxidative stress, is measured to be 56.9 ± 2.6 M/atm (n = 3) at 37.4 °C with 1 mg of the material available.

Microbial control of mineral–groundwater equilibria:Macroscale to microscale

USGS Publications Warehouse

Bennett, Philip C.; Hiebert, Franz K.; Roger, Jennifer Roberts

2000-01-01

macroscaleprocesses that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral.In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loizu, J.; Princeton Plasma Physics Laboratory, PO Box 451, Princeton, New Jersey 08543; Hudson, S. R.

2015-09-15

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

An Introductory Idea for Teaching Two-Component Phase Diagrams

ERIC Educational Resources Information Center

Peckham, Gavin D.; McNaught, Ian J.

2011-01-01

The teaching of two-component phase diagrams has attracted little attention in this "Journal," and it is hoped that this article will make a useful contribution. Current physical chemistry textbooks describe two-component phase diagrams adequately, but do so in a piecemeal fashion one section at a time; first solid-liquid equilibria, then…

Hydrogen exchange equilibria in thiols.

PubMed

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.

Multiple Equilibria and Endogenous Cycles in a Non-Linear Harrodian Growth Model

NASA Astrophysics Data System (ADS)

Commendatore, Pasquale; Michetti, Elisabetta; Pinto, Antonio

The standard result of Harrod's growth model is that, because investors react more strongly than savers to a change in income, the long run equilibrium of the economy is unstable. We re-interpret the Harrodian instability puzzle as a local instability problem and integrate his model with a nonlinear investment function. Multiple equilibria and different types of complex behaviour emerge. Moreover, even in the presence of locally unstable equilibria, for a large set of initial conditions the time path of the economy is not diverging, providing a solution to the instability puzzle.

Generalized thermodynamics of phase equilibria in scalar active matter

NASA Astrophysics Data System (ADS)

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

2018-02-01

Motility-induced phase separation (MIPS) arises generically in fluids of self-propelled particles when interactions lead to a kinetic slowdown at high densities. Starting from a continuum description of scalar active matter akin to a generalized Cahn-Hilliard equation, we give a general prescription for the mean densities of coexisting phases in flux-free steady states that amounts, at a hydrodynamics scale, to extremizing an effective free energy. We illustrate our approach on two well-known models: self-propelled particles interacting either through a density-dependent propulsion speed or via direct pairwise forces. Our theory accounts quantitatively for their phase diagrams, providing a unified description of MIPS.

The Tautomeric Equilibria of Thio-Analogues of Nucleic Acid Bases. Part 1. 2-Thiouracil: Background, Preparation of Model Compounds, and Gas Phase Proton Affinities

DTIC Science & Technology

1989-05-11

complilmentary publication for the present paper has studied the tautomeric equilibria by infrared spectroscopy . (Scheme 2 ) 5 Preparation of Compounds...4 6 292-2940C). 14 2 -Methylthio-4- pyrimidone (6).- To 2 -thiouracil (4) (12.8 g, 0.1 mol) and NaOH (7.6 g, 0.19 mol) in 200 ml of H20-EtOH (I : 1... pyrimidone (1i).- To a solution of 5N NaOH (44 ml, 220 mmol) containing 2 -thiouracil (4) (10.0 g, 78.0 mmol) at 0 CC was added dropwise dimethyl

Vapor-liquid equilibria for hydrogen fluoride + 1,1-difluoroethane at 288.23 and 298.35 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.; Kim, H.; Lim, J.S.

1997-07-01

Isothermal vapor-liquid equilibria for hydrogen fluoride + 1,1-difluoroethane at 288.23 and 298.35 K were measured using a circulation type apparatus equipped with an equilibrium view cell. The compositions of both vapor and liquid phases were analyzed by an on-line gas chromatographic method. They were compared with PTx equilibrium data measured by the total pressure method. The experimental data were correlated with Anderko`s equation of state using the Wong-Sandler mixing rule as well as the van der Waals one-fluid mixing rule. The Wong-Sandler mixing rule gives better results, and the relevant parameters are presented.

Determination of epsomite-hexahydrite equilibria by the humidity-buffer technique at 0.1 MPa with implications for phase equilibria in the system MgSO4-H2O.

USGS Publications Warehouse

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.

Dynamics of Perturbed Relative Equilibria of Point Vortices on the Sphere or Plane

NASA Astrophysics Data System (ADS)

Patrick, G. W.

2000-06-01

, and there are stable relative equilibria of four point vortices, where three identical point vortices form an equilateral triangle circling a central vortex. These relative equilibria have zero (nongeneric) momentum and form a family that extends to arbitrarily small diameters. Using the energy-momentum method, I show their shape is stable while their location on the sphere is unstable, and they move, after perturbation to nonzero momentum, on the sphere as point particles move under the influence of a magnetic monopole. In the analysis the internal and external degrees of freedom are separated and the mass of these point particles determined. In addition, two identical such relative equilibria attract one another, while opposites repel, and in energetic collisions, opposites disintegrate to vortex pairs while identicals interact by exchanging a vortex. An analogous situation also occurs for the planar system with its noncompact SE(2) symmetry.

Modeling Complex Equilibria in ITC Experiments: Thermodynamic Parameters Estimation for a Three Binding Site Model

PubMed Central

Le, Vu H.; Buscaglia, Robert; Chaires, Jonathan B.; Lewis, Edwin A.

2013-01-01

Isothermal Titration Calorimetry, ITC, is a powerful technique that can be used to estimate a complete set of thermodynamic parameters (e.g. Keq (or ΔG), ΔH, ΔS, and n) for a ligand binding interaction described by a thermodynamic model. Thermodynamic models are constructed by combination of equilibrium constant, mass balance, and charge balance equations for the system under study. Commercial ITC instruments are supplied with software that includes a number of simple interaction models, for example one binding site, two binding sites, sequential sites, and n-independent binding sites. More complex models for example, three or more binding sites, one site with multiple binding mechanisms, linked equilibria, or equilibria involving macromolecular conformational selection through ligand binding need to be developed on a case by case basis by the ITC user. In this paper we provide an algorithm (and a link to our MATLAB program) for the non-linear regression analysis of a multiple binding site model with up to four overlapping binding equilibria. Error analysis demonstrates that fitting ITC data for multiple parameters (e.g. up to nine parameters in the three binding site model) yields thermodynamic parameters with acceptable accuracy. PMID:23262283

Equilibria of perceptrons for simple contingency problems.

PubMed

Dawson, Michael R W; Dupuis, Brian

2012-08-01

The contingency between cues and outcomes is fundamentally important to theories of causal reasoning and to theories of associative learning. Researchers have computed the equilibria of Rescorla-Wagner models for a variety of contingency problems, and have used these equilibria to identify situations in which the Rescorla-Wagner model is consistent, or inconsistent, with normative models of contingency. Mathematical analyses that directly compare artificial neural networks to contingency theory have not been performed, because of the assumed equivalence between the Rescorla-Wagner learning rule and the delta rule training of artificial neural networks. However, recent results indicate that this equivalence is not as straightforward as typically assumed, suggesting a strong need for mathematical accounts of how networks deal with contingency problems. One such analysis is presented here, where it is proven that the structure of the equilibrium for a simple network trained on a basic contingency problem is quite different from the structure of the equilibrium for a Rescorla-Wagner model faced with the same problem. However, these structural differences lead to functionally equivalent behavior. The implications of this result for the relationships between associative learning, contingency theory, and connectionism are discussed.

Phase equilibria of CFC alternative refrigerant mixtures: Binary systems of isobutane + 1,1,1,2-tetrafluoroethane, + 1,1-difluoroethane, and + difluoromethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, J.S.; Park, J.Y.; Lee, B.G.

1999-12-01

Isothermal vapor-liquid equilibria were measured in the binary systems 1,1,1,2-tetrafluoroethane + isobutane at 303.2 and 323.2 K, 1,1-difluoroethane + isobutane at 303.2, 313.2, 323.2, and 333.2 K, and difluoromethane + isobutane at 301.8 and 321.8 K in a circulation-type equilibrium apparatus. The experimental data were well correlated with the Peng-Robinson equation of state using the Wong and Sandler mixing rules.

Metal biosorption equilibria in a ternary system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chong, K.H.; Volesky, B.

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 andmore » with conclusions postulated from the three possible binary subsystems.« less

Theoretical models of non-Maxwellian equilibria for one-dimensional collisionless plasmas

NASA Astrophysics Data System (ADS)

Allanson, O.; Neukirch, T.; Wilson, F.; Troscheit, S.

2016-12-01

It is ideal to use exact equilibrium solutions of the steady state Vlasov-Maxwell system to intialise collsionless simulations. However, exact equilibrium distribution functions (DFs) for a given macroscopic configuration are typically unknown, and it is common to resort to using `flow-shifted' Maxwellian DFs in their stead. These DFs may be consistent with a macrosopic system with the target number density and current density, but could well have inaccurate higher order moments. We present recent theoretical work on the `inverse problem in Vlasov-Maxwell equilibria', namely calculating an exact solution of the Vlasov equation for a specific given magnetic field. In particular, we focus on one-dimensional geometries in Cartesian (current sheets) coordinates.1. From 1D fields to Vlasov equilibria: Theory and application of Hermite Polynomials: (O. Allanson, T. Neukirch, S. Troscheit and F. Wilson, Journal of Plasma Physics, 82, 905820306 (2016) [28 pages, Open Access] )2. An exact collisionless equilibrium for the Force-Free Harris Sheet with low plasma beta: (O. Allanson, T. Neukirch, F. Wilson and S. Troscheit, Physics of Plasmas, 22, 102116 (2015) [11 pages, Open Access])3. Neutral and non-neutral collisionless plasma equilibria for twisted flux tubes: The Gold-Hoyle model in a background field (O. Allanson, F. Wilson and T. Neukirch, (2016)) (accepted, Physics of Plasmas)

Polymer-induced phase separation and crystallization in immunoglobulin G solutions.

PubMed

Li, Jianguo; Rajagopalan, Raj; Jiang, Jianwen

2008-05-28

We study the effects of the size of polymer additives and ionic strength on the phase behavior of a nonglobular protein-immunoglobulin G (IgG)-by using a simple four-site model to mimic the shape of IgG. The interaction potential between the protein molecules consists of a Derjaguin-Landau-Verwey-Overbeek-type colloidal potential and an Asakura-Oosawa depletion potential arising from the addition of polymer. Liquid-liquid equilibria and fluid-solid equilibria are calculated by using the Gibbs ensemble Monte Carlo technique and the Gibbs-Duhem integration (GDI) method, respectively. Absolute Helmholtz energy is also calculated to get an initial coexisting point as required by GDI. The results reveal a nonmonotonic dependence of the critical polymer concentration rho(PEG) (*) (i.e., the minimum polymer concentration needed to induce liquid-liquid phase separation) on the polymer-to-protein size ratio q (equivalently, the range of the polymer-induced depletion interaction potential). We have developed a simple equation for estimating the minimum amount of polymer needed to induce the liquid-liquid phase separation and show that rho(PEG) (*) approximately [q(1+q)(3)]. The results also show that the liquid-liquid phase separation is metastable for low-molecular weight polymers (q=0.2) but stable at large molecular weights (q=1.0), thereby indicating that small sizes of polymer are required for protein crystallization. The simulation results provide practical guidelines for the selection of polymer size and ionic strength for protein phase separation and crystallization.

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

Crystallization history of lunar picritic basalt sample 12002 - Phase-equilibria and cooling-rate studies

NASA Technical Reports Server (NTRS)

Walker, D.; Kirkpatrick, R. J.; Longhi, J.; Hays, J. F.

1976-01-01

Experimental crystallization of a lunar picrite composition (sample 12002) at controlled linear cooling rates produces systematic changes in the temperature at which crystalline phases appear, in the texture, and in crystal morphology as a function of cooling rate. Phases crystallize in the order olivine, chromium spinel, pyroxene, plagioclase, and ilmenite during equilibrium crystallization, but ilmenite and plagioclase reverse their order of appearance and silica crystallizes in the groundmass during controlled cooling experiments. The partition of iron and magnesium between olivine and liquid is independent of cooling rate, temperature, and pressure. Comparison of the olivine nucleation densities in the lunar sample and in the experiments indicates that the sample began cooling at about 1 deg C/hr. Pyroxene size, chemistry, and growth instability spacings, as well as groundmass coarseness, all suggest that the cooling rate subsequently decreased by as much as a factor of 10 or more. The porphyritic texture of this sample, then, is produced at a decreasing, rather than a discontinuously increasing, cooling rate.

Extrathermodynamic interpretation of retention equilibria in reversed-phase liquid chromatography using octadecylsilyl-silica gels bonded to C1 and C18 ligands of different densities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miyabe, Kanji; Guiochon, Georges A

2005-09-01

The retention behavior on silica gels bonded to C{sub 18} and C{sub 1} 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 retentionmore » 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 C{sub 18} and C{sub 1} 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.« less

Optimal Equilibria and Plasma Parameter Evolutions for the Ignitor Experiment*

NASA Astrophysics Data System (ADS)

Airoldi, A.; Cenacchi, G.; Coppi, B.

2011-10-01

In view of the operation of the Ignitor machine in both the H and the I-regime, optimal equilibrium configurations that can sustain plasma currents Ip up to 10 MA with a double X-point have been identified. In fact, the emergence of the I-regime in double X-point configurations has not been observed experimentally yet. The characteristics of the magnetic equilibrium configurations that can be produced play a crucial role in the performance of the machine. Therefore, particular care has been devoted to the study of plasma equilibria relevant to the main phases of the discharge evolution. A series of simulations to be utilized for the control of the relevant (sub-ignited) plasma parameters has been carried out using the JETTO transport code considering different values of the plasma current and, correspondingly, of the magnetic field. Special attention has been devoted to non-igniting experiments with Ip = 5 MA and BT = 8 T, where BT is the toroidal magnetic field, as they can be performed with much better duty cycles and longer duration than experiments aimed at reaching the most extreme plasma parameters and ignition in particular. The results of the relevant analyses with a discussion of the adopted transport coefficients is presented. * Sponsored in part by ENEA and the U.S. DOE.

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)

On subgame perfect equilibria in quantum Stackelberg duopoly

NASA Astrophysics Data System (ADS)

Frąckiewicz, Piotr; Pykacz, Jarosław

2018-02-01

Our purpose is to study the Stackelberg duopoly with the use of the Li-Du-Massar quantum duopoly scheme. The result of Lo and Kiang has shown that the correlation of players's quantities caused by the quantum entanglement enlarges the first-mover advantage in the quantum Stackelberg duopoly. However, the interval of entanglement parameters for which this result is valid is bounded from above. It has been an open question what the equilibrium result is over the upper bound, in particular when the entanglement parameter goes to infinity. Our work provides complete analysis of subgame perfect equilibria of the game for all the values of the entanglement parameter.

A Petrogenetic Evaluation of Clinopyroxene-hosted Melt Inclusions from an Enriched Submarine Lava of the Samoan Hotspot Track: A Phase Equilibria and Diffusion Modeling Study

NASA Astrophysics Data System (ADS)

Adams, J.; Spera, F. J.; Jackson, M. G.; Schmidt, J.

2017-12-01

The Samoan hotspot track hosts lavas that are representative of the Enriched Mantle II (EMII) geochemical signature, long thought to result from incorporation of recycled upper continental crust. Silicic (66-69 wt% SiO2) clinopyroxene (cpx)-hosted melt inclusions (MI) from isotopically enriched lavas from Samoa provide a window into their petrogenetic evolution. Enriched Samoan submarine lava, ALIA-115-18, from Savai'i Island, Samoa contains clinopyroxene (cpx) antecrysts that host uniformly trachydacitic MI's. The cpx's are more radiogenic (87Sr/86Sr=0.720232-0.720830) than the host whole rock (WR) (87Sr/86Sr=0.718592) providing evidence of cpx antecryst-WR disequilibrium (Jackson et al., 2007, 2009). Phase equilibria calculations using the Magma Chamber Simulator (Bohrson et al., 2014) have corroborated a lack of relationship by fractional crystallization (FC) between the antecrysts and WR composition as well as the cpx's and MI's. Cpx thermobarometry reveals cpx antecryst-WR disequilibrium is not a pressure effect but rather reflects cpx crystallization from a more magnesian parental melt (similar to the most mafic WR of the Samoan submarine lavas; SiO2=49 wt%, MgO=9 wt%), different than the ALIA-115-18 WR. The cpx antecrysts (Mg#72-86), and the rest of the antecryst population show a crystallization range of 1-5 kbar. Cpx groundmass phenocrysts (Mg#70-75) are consistent with ALIA-115-18 WR (SiO2=55 wt%, MgO=5 wt%) composition by FC in the 1-5 kbar range. The more mafic parent may represent the magma that mixed with evolved magmas, giving rise to radiogenic ALIA-115-18, and possibly the silicic MI's. Thus, studying the petrogenesis of the MI's is essential to understanding the evolution of EMII. Many cpx antecrysts with MI's are characterized by compositional halos; transects across the halos exhibit major and trace element gradients. Modeling of diffusive exchange (Cottrell et al., 2002) between the MI's and their host lavas, mediated by diffusion through cpx

Predominance Diagrams, a Useful Tool for the Correlation of the Precipitation-Solubility Equilibrium with Other Ionic Equilibria

ERIC Educational Resources Information Center

Pereira, Constantino Fernandez; Alcalde, Manuel; Villegas, Rosario; Vale, Jose

2007-01-01

The four types of ionic equilibria--acid-base, redox, precipitation, and complexation--have certain similarities, which has led some authors to develop a unified treatment of them. These authors have highlighted the common aspects and tried to find a systemization of the equilibria that would facilitate learning them. In this unified treatment,…

Phase transition thermodynamics of bisphenols.

PubMed

Costa, José C S; Dávalos, Juan Z; Santos, Luís M N B F

2014-10-16

Herein we have studied, presented, and analyzed the phase equilibria thermodynamics of a bisphenols (BP-A, BP-E, BP-F, BP-AP, and BP-S) series. In particular, the heat capacities, melting temperatures, and vapor pressures at different temperatures as well as the standard enthalpies, entropies, and Gibbs energies of phase transition (fusion and sublimation) were experimentally determined. Also, we have presented the phase diagrams of each bisphenol derivative and investigated the key parameters related to the thermodynamic stability of the condensed phases. When all the bisphenol derivatives are compared at the same conditions, solids BP-AP and BP-S present lower volatilities (higher Gibbs energy of sublimation) and high melting temperatures due to the higher stability of their solid phases. Solids BP-A and BP-F present similar stabilities, whereas BP-E is more volatile. The introduction of -CH3 groups in BP-F (giving BP-E and BP-A) leads an entropic differentiation in the solid phase, whereas in the isotropic liquids the enthalpic and entropic differentiations are negligible.

Phase Diagram for a Four-Component System of Pentanedioic, Hexanedioic, Nonanedioic, and Decanedioic Acids

NASA Astrophysics Data System (ADS)

Kolyado, A. V.; Alenova, S. M.; Garkushin, I. K.

2018-05-01

Phase equilibria in a four-component system of pentanedioic, hexanedioic, nonanedioic, and decanedioic acids are studied via differential thermal analysis. The determined eutectic composition is pentanedioic acid, 48.1 wt %; hexanedioic acid, 10.0 wt %; nonanedioic acid, 25.7 wt %; and decanedioic acid, 16.2 wt %. The melting point of the eutectic mixture is 63.1°C.

Thermodynamic properties and interactions of salt hydrates used as phase change materials

NASA Astrophysics Data System (ADS)

Braunstein, J.

1982-12-01

The state-of-the-art of salt hydrates as phase change materials for low temperature thermal energy storage is reviewed with the objective of recommending research that would result in more practicable use of these materials. Areas for review included phase equilibria, nucleation behavior and melting kinetics of the commonly used hydrates.

Graphic Representation of Carbon Dioxide Equilibria in Biological Systems.

ERIC Educational Resources Information Center

Kindig, Neal B.; Filley, Giles F.

1983-01-01

The log C-pH diagram is a useful means of displaying quantitatively the many variables (including temperature) that determine acid-base equilibria in biological systems. Presents the diagram as extended to open/closed biological systems and derives a new water-ion balance method for determining equilibrium pH. (JN)

Predicting mixture phase equilibria and critical behavior using the SAFT-VRX approach.

PubMed

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.

Substituent Effects on Keto-Enol Equilibria Using NMR Spectroscopy

ERIC Educational Resources Information Center

Manbeck, Kimberly A.; Boaz, Nicholas C.; Bair, Nathaniel C.; Sanders, Allix M. S.; Marsh, Anderson L.

2011-01-01

In this extension to a classic physical chemistry experiment, students record the proton nuclear magnetic resonance spectra of the [beta]-diketones 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-chloro-2,4-pentanedione to investigate the effect of substituents on keto-enol tautomerization equilibria. From the integrated intensities of keto and…

Sapphirine-bearing granulites from the Tongbai orogen, China: Petrology, phase equilibria, zircon U-Pb geochronology and implications for Paleozoic ultrahigh temperature metamorphism

NASA Astrophysics Data System (ADS)

Xiang, Hua; Zhong, Zeng-Qiu; Li, Ye; Qi, Min; Zhou, Han-Wen; Zhang, Li; Zhang, Ze-Ming; Santosh, M.

2014-11-01

We report here for the first time the occurrence of sapphirine-bearing granulites within the Qinling Group of the Qinling-Tongbai orogen and provide robust evidence for extreme crustal metamorphism at ultrahigh-temperature (UHT) conditions. We document the UHT indicator of sapphirine and spinel in a mafic granulite consisting of orthopyroxene, biotite, plagioclase, amphibole and rutile/ilmenite. The ferromagnesian minerals in the sapphirine-bearing granulite have high XMg [Mg/(Mg + Fe)] (orthopyroxene XMg = 0.84-0.95; biotite XMg = 0.81; amphibole XMg = 0.87-0.96). The phase equilibria modeling demonstrates that the early spinel-bearing assemblage is stable at 923-950 °C and 6.7-8.9 kbar, and the peak assemblage of Opx + Pl + Spr/Spl + Amp + Bt + Ilm (+ melt) defines a field at 922-947 °C and 8.4-10.2 kbar. Rutiles have variable Zr concentrations but mostly cluster at ca. 1,500 and 3400 ppm. Zr-in-rutile geothermometry yielded high temperatures of up to 890-940 °C. Zircon U-Pb dating of the granulite constrains the timing of the immediate post-peak and retrograde metamorphic stages as 429 ± 7 Ma and 412 ± 4 Ma, respectively. The UHT metamorphism, together with extensive occurrence of coeval magmatic suites suggests that the Tongbai orogen experienced a Paleozoic Andean-type orogeny probably derived from mid-oceanic ridge subduction of the Qinling Ocean.

Isothermal vapor-liquid equilibria for the systems 1-chloro-1,1-difluoroethane + hydrogen fluoride, 1,1-dichloro-1-fluoroethane + hydrogen fluoride, and chlorodifluoromethane + hydrogen fluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Y.W.; Lee, Y.Y.

1997-03-01

Isothermal vapor-liquid equilibria for the three binary systems (1-chloro-1,1-difluoroethane + hydrogen fluoride, 1,1-dichloro-1-fluoroethane + hydrogen fluoride, and chlorodifluoromethane + 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. All of the systems form minimum boiling heterogeneous azeotropes.

Fluorite solubility equilibria in selected geothermal waters

USGS Publications Warehouse

Nordstrom, D. Kirk; 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.

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.

Geostrophic tripolar vortices in a two-layer fluid: Linear stability and nonlinear evolution of equilibria

NASA Astrophysics Data System (ADS)

Reinaud, J. N.; Sokolovskiy, M. A.; Carton, X.

2017-03-01

We investigate equilibrium solutions for tripolar vortices in a two-layer quasi-geostrophic flow. Two of the vortices are like-signed and lie in one layer. An opposite-signed vortex lies in the other layer. The families of equilibria can be spanned by the distance (called separation) between the two like-signed vortices. Two equilibrium configurations are possible when the opposite-signed vortex lies between the two other vortices. In the first configuration (called ordinary roundabout), the opposite signed vortex is equidistant to the two other vortices. In the second configuration (eccentric roundabouts), the distances are unequal. We determine the equilibria numerically and describe their characteristics for various internal deformation radii. The two branches of equilibria can co-exist and intersect for small deformation radii. Then, the eccentric roundabouts are stable while unstable ordinary roundabouts can be found. Indeed, ordinary roundabouts exist at smaller separations than eccentric roundabouts do, thus inducing stronger vortex interactions. However, for larger deformation radii, eccentric roundabouts can also be unstable. Then, the two branches of equilibria do not cross. The branch of eccentric roundabouts only exists for large separations. Near the end of the branch of eccentric roundabouts (at the smallest separation), one of the like-signed vortices exhibits a sharp inner corner where instabilities can be triggered. Finally, we investigate the nonlinear evolution of a few selected cases of tripoles.

Strategic trade between two regions with partial local consumer protection - General setup and nash equilibria

NASA Astrophysics Data System (ADS)

Iordanov, Iordan V.; Vassilev, Andrey A.

2017-12-01

We construct a model of the trade relations between two regions for the case when the trading entities (consumers) compete for a scarce good and there is an element of strategic interdependence in the trading process. Additionally, local consumers enjoy partial protection in the form of guaranteed access to a part of the locally-supplied quantity of the good. The model is formulated for the general asymmetric case, where the two regions differ in terms of parameters such as income, size of the local market supply, degree of protection and transportation costs. For this general model we establish the existence of Nash equilibria and obtain their form as a function of the model parameters, producing a typology of the equilibria. This is a required step in order to rigorously study various types of price dynamics for the model.

High-pressure sapphire cell for phase equilibria measurements of CO2/organic/water systems.

PubMed

Pollet, Pamela; Ethier, Amy L; Senter, James C; Eckert, Charles A; Liotta, Charles L

2014-01-24

The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. Specifically, the sapphire cell enables visual data collection from multiple loadings to solve a set of material balances to precisely determine phase composition. Ternary phase diagrams can then be established to determine the proportion of each component in each phase at a given condition. In principle, any ternary system can be studied although ternary systems (gas-liquid-liquid) are the specific examples discussed herein. For instance, the ternary THF-Water-CO2 system was studied at 25 and 40 °C and is described herein. Of key importance, this technique does not require sampling. Circumventing the possible disturbance of the system equilibrium upon sampling, inherent measurement errors, and technical difficulties of physically sampling under pressure is a significant benefit of this technique. Perhaps as important, the sapphire cell also enables the direct visual observation of the phase behavior. In fact, as the CO2 pressure is increased, the homogeneous THF-Water solution phase splits at about 2 MPa. With this technique, it was possible to easily and clearly observe the cloud point and determine the composition of the newly formed phases as a function of pressure. The data acquired with the sapphire cell technique can be used for many applications. In our case, we measured swelling and composition for tunable solvents, like gas-expanded liquids, gas-expanded ionic liquids and Organic Aqueous Tunable Systems (OATS)(1-4). For the latest system, OATS, the high-pressure sapphire cell enabled the study of (1) phase behavior as a function of pressure and temperature, (2) composition of each phase (gas-liquid-liquid) as a function of pressure and temperature and (3) catalyst partitioning in the two liquid phases as a function of pressure and composition. Finally, the sapphire cell is an especially effective tool to gather

Surface currents on the plasma-vacuum interface in MHD equilibria

NASA Astrophysics Data System (ADS)

Hanson, James D.

2016-10-01

The VMEC non-axisymmetric MHD equilibrium code can compute free-boundary equilibria. Since VMEC assumes that magnetic fields within the plasma form closed and nested flux surfaces, the plasma-vacuum interface is a flux surface, and the total magnetic field there has no normal component. VMEC imposes this condition of zero normal field using the potential formulation of Merkel, and solves a Neumann problem for the magnetic potential in the exterior region. This boundary condition necessarily admits the possibility of a surface current on the plasma-vacuum interface. While this current may be small in MHD equilibrium, this current may be readily computed in terms of a magnetic potential in both the interior and exterior regions. Examples of the surface current for VMEC equilibria will be shown. This material is based upon work supported by Auburn University and the U.S. Department of Energy, Office of Science, Office of Fusion Energy Sciences under Award Number DE-FG02-03ER54692.

Estimating Values of H2O-ACTIVITIES in the Mantle Using Amphibole Equilibria

NASA Astrophysics Data System (ADS)

Lamb, W. M.; Hunt, L. E.

2017-12-01

Determining values of H2O activity (aH2O) for mantle rocks will yield a better understanding of those mantle processes that are controlled, in part, by the availability of H2O (e.g., melting and deformation). The H contents of the upper mantle can be estimated from amount of H contained in nominally anhydrous minerals (NAMs). However, for many common NAMs, the relation between aH2O and H content is not well known, and certain NAMs may be prone to retrograde H loss. The activities of H2O and other fluids species (e.g., CO2) may be estimated using mineral equilibria. Equilibria involving amphibole can, for example, be used to estimate values of aH2O and hydrogen fugacity (ƒH2). Spinel equilibria can be applied to estimate values of oxygen fugacity (ƒO2) that, when combined with ƒH2, will provide a second estimate of aH2O. We have characterized mineral chemistries in 11 amphibole-bearing peridotite xenoliths from the southwestern U.S.A. The compositions of co-existing pyroxenes ± garnet yield P-T conditions of ≈ 1.1 GPa, and 880 to 980˚C, and application of dehydration equilibria yields values of aH2O ranging from 0.04 to 0.19. The compositions of coexisting spinel + olivine + opx yield DlogƒO2(FMQ) of -0.2 to +0.9. Values of ƒH2, estimated using amphibole dehydrogenation equilibria (6 to 91 bars) were combined with values of ƒO2 to estimate aH2O in nine samples (≈ 0.02 to 0.12). The difference between these two values of aH2O, estimated using dehydration equilibria versus ƒH2 + ƒO2, is generally < 0.1, suggesting that the amphiboles experienced little or no retrograde H-loss. All samples equilibrated at low values of aH2O, and these values may be used to predict NAM H-contents. For example, according to Gaetani et al. (2014, Cont. Min. Pet., p. 965), the concentration of H in olivine is a function of P, T, the fugacities of H2O and O2, and olivine composition. Their relation yields relatively low predicted H-contents of 10 to 28 wt. ppm for olivine in

Phase equilibria and formation of vesicles of dioleoylphosphatidylcholine in glycerol/water mixtures.

PubMed

Johansson, L B; Kalman, B; Wikander, G; Fransson, A; Fontell, K; Bergenståhl, B; Lindblom, G

1993-07-04

The lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) forms a lamellar liquid crystalline phase (L alpha) in arbitrary mixtures of glycerol and water. The phase has been characterized by means of X-ray diffraction, 31P-NMR spectroscopy and differential scanning calorimetry (DSC). In the L alpha state, and for DOPC concentrations greater than 50% (w/w), the thickness of the lipid bilayer decreases, while the area of the polar head group increases with increasing glycerol concentration. The phase transition from gel to L alpha state occurs in the range of 240 to 260 K. Contrary to a previous (McDaniel, R.V., McIntosh, T.J. and Simon, S.A. (1983) Biochim. Biophys. Acta 731, 97) study of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) we find that in the gel state, the thickness of the DOPC lipid bilayer is greater than that in the L alpha state. This suggests that in the gel state, the lipid acyl chains of DOPC are in extended configuration. The lamellar phase reaches its maximum swelling at about 50% (w/w) of DOPC. At lower DOPC concentrations a two-phase system is formed where the lamellar phase exists in equilibrium with excess of solvent. Unilamellar vesicles can be prepared from a diluted suspension of the lamellar phase either by using the sonicator or extruder technique. We show this by means of 31P-NMR, EPR and fluorescence spectroscopy. The mean radius of the vesicles, prepared by a sonicator, has been determined at different glycerol/water mixtures. It is found to decrease continuously from 100 A at 100% water to a minimum of 75 A at about 50% water in the solvent mixture. By further decreasing the water content in the solution, the radius rapidly increases, and a mean radius of 450 A is estimated at a water content of 10%. The rotational relaxation times of a fluorescent probe and two EPR spin probes, solubilized in DOPC vesicles, have been measured at different glycerol/water mixtures. It is found that the rotational rates are always much slower in

Analysis of the expected density of internal equilibria in random evolutionary multi-player multi-strategy games.

PubMed

Duong, Manh Hong; Han, The Anh

2016-12-01

In this paper, we study the distribution and behaviour of internal equilibria in a d-player n-strategy random evolutionary game where the game payoff matrix is generated from normal distributions. The study of this paper reveals and exploits interesting connections between evolutionary game theory and random polynomial theory. The main contributions of the paper are some qualitative and quantitative results on the expected density, [Formula: see text], and the expected number, E(n, d), of (stable) internal equilibria. Firstly, we show that in multi-player two-strategy games, they behave asymptotically as [Formula: see text] as d is sufficiently large. Secondly, we prove that they are monotone functions of d. We also make a conjecture for games with more than two strategies. Thirdly, we provide numerical simulations for our analytical results and to support the conjecture. As consequences of our analysis, some qualitative and quantitative results on the distribution of zeros of a random Bernstein polynomial are also obtained.

Finding Bounded Rational Equilibria. Part 2; Alternative Lagrangians and Uncountable Move Spaces

NASA Technical Reports Server (NTRS)

Wolpert, David H.

2004-01-01

A long-running difficulty with conventional game theory has been how to modify it to accommodate the bounded rationality characterizing all real-world players. A recurring issue in statistical physics is how best to approximate joint probability distributions with decoupled (and therefore far more tractable) distributions. It has recently been shown that the same information theoretic mathematical structure, known as Probability Collectives (PC) underlies both issues. This relationship between statistical physics and game theory allows techniques and insights &om the one field to be applied to the other. In particular, PC provides a formal model-independent definition of the degree of rationality of a player and of bounded rationality equilibria. This pair of papers extends previous work on PC by introducing new computational approaches to effectively find bounded rationality equilibria of common-interest (team) games.

Oscillations and Multiple Equilibria in Microvascular Blood Flow.

PubMed

Karst, Nathaniel J; Storey, Brian D; Geddes, John B

2015-07-01

We investigate the existence of oscillatory dynamics and multiple steady-state flow rates in a network with a simple topology and in vivo microvascular blood flow constitutive laws. Unlike many previous analytic studies, we employ the most biologically relevant models of the physical properties of whole blood. Through a combination of analytic and numeric techniques, we predict in a series of two-parameter bifurcation diagrams a range of dynamical behaviors, including multiple equilibria flow configurations, simple oscillations in volumetric flow rate, and multiple coexistent limit cycles at physically realizable parameters. We show that complexity in network topology is not necessary for complex behaviors to arise and that nonlinear rheology, in particular the plasma skimming effect, is sufficient to support oscillatory dynamics similar to those observed in vivo.

Efficiency reduction and pseudo-convergence in replica exchange sampling of peptide folding unfolding equilibria

NASA Astrophysics Data System (ADS)

Denschlag, Robert; Lingenheil, Martin; Tavan, Paul

2008-06-01

Replica exchange (RE) molecular dynamics (MD) simulations are frequently applied to sample the folding-unfolding equilibria of β-hairpin peptides in solution, because efficiency gains are expected from this technique. Using a three-state Markov model featuring key aspects of β-hairpin folding we show that RE simulations can be less efficient than conventional techniques. Furthermore we demonstrate that one is easily seduced to erroneously assign convergence to the RE sampling, because RE ensembles can rapidly reach long-lived stationary states. We conclude that typical REMD simulations covering a few tens of nanoseconds are by far too short for sufficient sampling of β-hairpin folding-unfolding equilibria.

Hermite Polynomials and the Inverse Problem for Collisionless Equilibria

NASA Astrophysics Data System (ADS)

Allanson, O.; Neukirch, T.; Troscheit, S.; Wilson, F.

2017-12-01

It is long established that Hermite polynomial expansions in either velocity or momentum space can elegantly encode the non-Maxwellian velocity-space structure of a collisionless plasma distribution function (DF). In particular, Hermite polynomials in the canonical momenta naturally arise in the consideration of the 'inverse problem in collisionless equilibria' (IPCE): "for a given macroscopic/fluid equilibrium, what are the self-consistent Vlasov-Maxwell equilibrium DFs?". This question is of particular interest for the equilibrium and stability properties of a given macroscopic configuration, e.g. a current sheet. It can be relatively straightforward to construct a formal solution to IPCE by a Hermite expansion method, but several important questions remain regarding the use of this method. We present recent work that considers the necessary conditions of non-negativity, convergence, and the existence of all moments of an equilibrium DF solution found for IPCE. We also establish meaningful analogies between the equations that link the microscopic and macrosopic descriptions of the Vlasov-Maxwell equilibrium, and those that solve the initial value problem for the heat equation. In the language of the heat equation, IPCE poses the pressure tensor as the 'present' heat distribution over an infinite domain, and the non-Maxwellian features of the DF as the 'past' distribution. We find sufficient conditions for the convergence of the Hermite series representation of the DF, and prove that the non-negativity of the DF can be dependent on the magnetisation of the plasma. For DFs that decay at least as quickly as exp(-v^2/4), we show non-negativity is guaranteed for at least a finite range of magnetisation values, as parameterised by the ratio of the Larmor radius to the gradient length scale. 1. O. Allanson, T. Neukirch, S. Troscheit & F. Wilson: From one-dimensional fields to Vlasov equilibria: theory and application of Hermite polynomials, Journal of Plasma Physics, 82

Surface currents on the plasma-vacuum interface in MHD equilibria

NASA Astrophysics Data System (ADS)

Hanson, James

2017-10-01

The VMEC non-axisymmetric MHD equilibrium code can compute free-boundary equilibria. Since VMEC assumes that magnetic fields within the plasma form closed and nested flux surfaces, the plasma-vacuum interface is a flux surface, and the total magnetic field there has no normal component. VMEC imposes this condition of zero normal field using the potential formulation of Merkel, and solves a Neumann problem for the magnetic potential in the exterior region. This boundary condition necessarily admits the possibility of a surface current on the interface. While this surface current may be small in MHD equilibrium, it is readily computed in terms of the magnetic potentials in both the interior and exterior regions, evaluated on the surface. If only the external magnetic potential is known (as in VMEC), then the surface current can be computed from the discontinuity of the tangential field across the interface. Examples of the surface current for VMEC equilibria will be shown for a zero-pressure stellarator equilibrium. Field-line following of the vacuum magnetic field shows magnetic islands within the plasma region.

Floating liquid phase in sedimenting colloid-polymer mixtures.

PubMed

Schmidt, Matthias; Dijkstra, Marjolein; Hansen, Jean-Pierre

2004-08-20

Density functional theory and computer simulation are used to investigate sedimentation equilibria of colloid-polymer mixtures within the Asakura-Oosawa-Vrij model of hard sphere colloids and ideal polymers. When the ratio of buoyant masses of the two species is comparable to the ratio of differences in density of the coexisting bulk (colloid) gas and liquid phases, a stable "floating liquid" phase is found, i.e., a thin layer of liquid sandwiched between upper and lower gas phases. The full phase diagram of the mixture under gravity shows coexistence of this floating liquid phase with a single gas phase or a phase involving liquid-gas equilibrium; the phase coexistence lines meet at a triple point. This scenario remains valid for general asymmetric binary mixtures undergoing bulk phase separation.

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

PubMed

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

2017-10-19

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

Collisionless current sheet equilibria

NASA Astrophysics Data System (ADS)

Neukirch, T.; Wilson, F.; Allanson, O.

2018-01-01

Current sheets are important for the structure and dynamics of many plasma systems. In space and astrophysical plasmas they play a crucial role in activity processes, for example by facilitating the release of magnetic energy via processes such as magnetic reconnection. In this contribution we will focus on collisionless plasma systems. A sensible first step in any investigation of physical processes involving current sheets is to find appropriate equilibrium solutions. The theory of collisionless plasma equilibria is well established, but over the past few years there has been a renewed interest in finding equilibrium distribution functions for collisionless current sheets with particular properties, for example for cases where the current density is parallel to the magnetic field (force-free current sheets). This interest is due to a combination of scientific curiosity and potential applications to space and astrophysical plasmas. In this paper we will give an overview of some of the recent developments, discuss their potential applications and address a number of open questions.

Multiple equilibria, bifurcations and selection scenarios in cosymmetric problem of thermal convection in porous medium

NASA Astrophysics Data System (ADS)

Govorukhin, Vasily N.; Shevchenko, Igor V.

2017-12-01

We study convection in a two-dimensional container of porous material saturated with fluid and heated from below. This problem belongs to the class of dynamical systems with nontrivial cosymmetry. The cosymmetry gives rise to a hidden parameter in the system and continuous families of infinitely many equilibria, and leads to non-trivial bifurcations. In this article we present our numerical studies that demonstrate nonlinear phenomena resulting from the existence of cosymmetry. We give a comprehensive picture of different bifurcations which occur in cosymmetric dynamical systems and in the convection problem. It includes internal and external (as an invariant set) bifurcations of one-parameter families of equilibria, as well as bifurcations leading to periodic, quasiperiodic and chaotic behaviour. The existence of infinite number of stable steady-state regimes begs the important question as to which of them can realize in physical experiments. In this paper, this question (known as the selection problem) is studied in detail. In particular, we show that the selection scenarios strongly depend on the initial temperature distribution of the fluid. The calculations are carried out by the global cosymmetry-preserving Galerkin method, and numerical methods used to analyse cosymmetric systems are also described.

Ca-Rich Carbonate Melts: A Regular-Solution Model, with Applications to Carbonatite Magma + Vapor Equilibria and Carbonate Lavas on Venus

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

1995-01-01

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The

First-principles Monte Carlo simulations of reaction equilibria in compressed vapors

DOE PAGES

Fetisov, Evgenii O.; Kuo, I-Feng William; Knight, Chris; ...

2016-06-13

Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gasmore » equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO 2 and N 2O in mole fractions approaching 1%, whereas N 3 and O 3 are not observed. Lastly, the equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data.« less

First-principles Monte Carlo simulations of reaction equilibria in compressed vapors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fetisov, Evgenii O.; Kuo, I-Feng William; Knight, Chris

Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gasmore » equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO 2 and N 2O in mole fractions approaching 1%, whereas N 3 and O 3 are not observed. Lastly, the equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data.« less

First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors

PubMed Central

2016-01-01

Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gas equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO2 and N2O in mole fractions approaching 1%, whereas N3 and O3 are not observed. The equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data. PMID:27413785

Phase Diagram of Quaternary System NaBr-KBr-CaBr2-H2O at 323 K

NASA Astrophysics Data System (ADS)

Cui, Rui-Zhi; Wang, Wei; Yang, Lei; Sang, Shi-Hua

2018-03-01

The phase equilibria in the system NaBr-KBr-CaBr2-H2O at 323 K were studied using the isothermal dissolution equilibrium method. Using the experimental solubilities of salts data, phase diagram was constructed. The phase diagram have two invariant points, five univariant curves, and four crystallization fields. The equilibrium solid phases in the system are NaBr, NaBr · 2H2O, KBr, and CaBr2 · 4H2O. The solubilities of salts in the system at 323 K were calculated by Pitzer's equation. There is shown that the calculated solubilities agree well with experimental data.

Isobaric vapor-liquid equilibria for binary systems α-phenylethylamine + toluene and α-phenylethylamine + cyclohexane at 100 kPa

NASA Astrophysics Data System (ADS)

Wu, Xiaoru; Gao, Yingyu; Ban, Chunlan; Huang, Qiang

2016-09-01

In this paper the results of the vapor-liquid equilibria study at 100 kPa are presented for two binary systems: α-phenylethylamine(1) + toluene (2) and (α-phenylethylamine(1) + cyclohexane(2)). The binary VLE data of the two systems were correlated by the Wilson, NRTL, and UNIQUAC models. For each binary system the deviations between the results of the correlations and the experimental data have been calculated. For the both binary systems the average relative deviations in temperature for the three models were lower than 0.99%. The average absolute deviations in vapour phase composition (mole fractions) and in temperature T were lower than 0.0271 and 1.93 K, respectively. Thermodynamic consistency has been tested for all vapor-liquid equilibrium data by the Herrington method. The values calculated by Wilson and NRTL equations satisfied the thermodynamics consistency test for the both two systems, while the values calculated by UNIQUAC equation didn't.

On the manifestation of coexisting nontrivial equilibria leading to potential well escapes in an inhomogeneous floating body

NASA Astrophysics Data System (ADS)

Sequeira, Dane; Wang, Xue-She; Mann, B. P.

2018-02-01

This paper examines the bifurcation and stability behavior of inhomogeneous floating bodies, specifically a rectangular prism with asymmetric mass distribution. A nonlinear model is developed to determine the stability of the upright and tilted equilibrium positions as a function of the vertical position of the center of mass within the prism. These equilibria positions are defined by an angle of rotation and a vertical position where rotational motion is restricted to a two dimensional plane. Numerical investigations are conducted using path-following continuation methods to determine equilibria solutions and evaluate stability. Bifurcation diagrams and basins of attraction that illustrate the stability of the equilibrium positions as a function of the vertical position of the center of mass within the prism are generated. These results reveal complex stability behavior with many coexisting solutions. Static experiments are conducted to validate equilibria orientations against numerical predictions with results showing good agreement. Dynamic experiments that examine potential well hopping behavior in a waveflume for various wave conditions are also conducted.

Equilibria, information and frustration in heterogeneous network games with conflicting preferences

NASA Astrophysics Data System (ADS)

Mazzoli, M.; Sánchez, A.

2017-11-01

Interactions between people are the basis on which the structure of our society arises as a complex system and, at the same time, are the starting point of any physical description of it. In the last few years, much theoretical research has addressed this issue by combining the physics of complex networks with a description of interactions in terms of evolutionary game theory. We here take this research a step further by introducing a most salient societal factor such as the individuals’ preferences, a characteristic that is key to understanding much of the social phenomenology these days. We consider a heterogeneous, agent-based model in which agents interact strategically with their neighbors, but their preferences and payoffs for the possible actions differ. We study how such a heterogeneous network behaves under evolutionary dynamics and different strategic interactions, namely coordination games and best shot games. With this model we study the emergence of the equilibria predicted analytically in random graphs under best response dynamics, and we extend this test to unexplored contexts like proportional imitation and scale free networks. We show that some theoretically predicted equilibria do not arise in simulations with incomplete information, and we demonstrate the importance of the graph topology and the payoff function parameters for some games. Finally, we discuss our results with the available experimental evidence on coordination games, showing that our model agrees better with the experiment than standard economic theories, and draw hints as to how to maximize social efficiency in situations of conflicting preferences.

Illite equilibria in solutions: III. A re-interpretation of the data of Sass et al. (1987)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aja, S.U.

1991-11-01

In a recent solubility study of Goose Lake and Beavers Bend illite, SASS et al. (1987) inferred the existence of three components of natural illites (K{sub 0.24}/O{sub 10}(OH){sub 2}), (K{sub 0.67}/O{sub 10}(OH){sub 2}), and (K{sub 0.90}/O{sub 10}(OH){sub 2}) which were interpreted to be smectite, illite, and K-mica, respectively. They also speculated that illite-smectite equilibrium is metastable under diagenetic conditions except between 90 and 110C where it is stabilized by an ordering transition. A re-interpretation of the data of SASS et al. (1987) indicates that the solubility-controlling phases have the following K atoms per half cell: 0.29, 0.52, 0.69, 0.084, andmore » 1.0. Furthermore, solution equilibration investigations of kaolinite-microcline mixtures have shown that these two minerals do not coexist stably. Thus, the question of an ordering transition whose main effect is to stabilize illite-smectite equilibria relative to kaolinite-microcline assemblage does not arise.« less

Liquid-liquid equilibria for hydrogen fluoride + 1,1-dichloro-1-fluoroethane + 1-chloro-1,1-difluoroethane at {minus}20 and 20 C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Y.W.; Lee, Y.Y.

1995-03-01

1,1-Dichloro-1-fluoroethane is presently under consideration as a replacement for trichlorofluoromethane, which is widely used as a foam blowing agent. 1-Chloro-1,1-difluoroethane is the major raw material for the production of poly(vinylidene fluoride). These two materials are normally manufactured by the fluorination of 1,1,1-trichloroethane or vinylidene chloride with hydrogen fluoride. A phase separator is normally used to retrieve hydrogen fluoride from the product stream. To design the phase separator, liquid-liquid equilibrium data are required. Liquid-liquid equilibria for the ternary system (hydrogen fluoride + 1,1-dichloro-1-fluoroethane + 1-chloro-1,1-difluoroethane) have been measured at {minus}20 and 20 C. The results are correlated with the NRTL model,more » and the relevant parameters are presented.« less

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

NASA Astrophysics Data System (ADS)

Yang, Chao

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

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

NASA Astrophysics Data System (ADS)

Skotnicka, Agnieszka; Czeleń, Przemysław; Gawinecki, Ryszard

2017-04-01

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

The topological phase diagram of cimetidine: A case of overall monotropy.

PubMed

Céolin, R; Rietveld, I B

2017-03-01

Cimetidine is a histamine H 2 -receptor antagonist used against peptic ulcers. It is known to exhibit crystalline polymorphism. Forms A and D melt within 0.35 degrees from each other and the enthalpies of fusion are similar as well. The present paper demonstrates how to construct a pressure-temperature phase diagram with only calorimetric and volumetric data available. The phase diagram provides the stability domains and the phase equilibria for the phases A, D, the liquid and the vapor. Cimetidine is overall monotropic with form D the only stable solid phase. Copyright © 2016 Académie Nationale de Pharmacie. Published by Elsevier Masson SAS. All rights reserved.

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

NASA Astrophysics Data System (ADS)

Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

2015-01-01

The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

Existence of equilibria in quantum Bertrand-Edgeworth duopoly game

NASA Astrophysics Data System (ADS)

Sekiguchi, Yohei; Sakahara, Kiri; Sato, Takashi

2012-12-01

Both classical and quantum version of two models of price competition in duopoly market, the one is realistic and the other is idealized, are investigated. The pure strategy Nash equilibria of the realistic model exists under stricter condition than that of the idealized one in the classical form game. This is the problem known as Edgeworth paradox in economics. In the quantum form game, however, the former converges to the latter as the measure of entanglement goes to infinity.

A novel grid multiwing chaotic system with only non-hyperbolic equilibria

NASA Astrophysics Data System (ADS)

Zhang, Sen; Zeng, Yicheng; Li, Zhijun; Wang, Mengjiao; Xiong, Le

2018-05-01

The structure of the chaotic attractor of a system is mainly determined by the nonlinear functions in system equations. By using a new saw-tooth wave function and a new stair function, a novel complex grid multiwing chaotic system which belongs to non-Shil'nikov chaotic system with non-hyperbolic equilibrium points is proposed in this paper. It is particularly interesting that the complex grid multiwing attractors are generated by increasing the number of non-hyperbolic equilibrium points, which are different from the traditional methods of realising multiwing attractors by adding the index-2 saddle-focus equilibrium points in double-wing chaotic systems. The basic dynamical properties of the new system, such as dissipativity, phase portraits, the stability of the equilibria, the time-domain waveform, power spectrum, bifurcation diagram, Lyapunov exponents, and so on, are investigated by theoretical analysis and numerical simulations. Furthermore, the corresponding electronic circuit is designed and simulated on the Multisim platform. The Multisim simulation results and the hardware experimental results are in good agreement with the numerical simulations of the same system on Matlab platform, which verify the feasibility of this new grid multiwing chaotic system.

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

NASA Astrophysics Data System (ADS)

Narayanan, Vineed; Venkatarathnam, G.

2018-03-01

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

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.

Phase equilibria modelling and zircon dating for Precambrian metapelites from Xinghuadukou Group in Lvlin Forest of Erguna Massif, NE China

NASA Astrophysics Data System (ADS)

Xu, Jiulei; Zheng, Changqing; Tajcmanova, Lucie; Zhong, Xin; Xu, Xuechun; Han, Xiaomeng; Wang, Zhaoyuan

2017-04-01

Xinghuadukou Group, the basement metamorphic complex of Erguna Massif in NE China, is considered to be Mesoproterozoic with Sm-Nd age of 1157±32 Ma. However, the new zircon data from these metamorphic supracrustal rocks in Lvlin Forest show that they formed in Neoproterozoic with the age of 800 Ma. Old zircon age with 2.5 Ga, 2.0 Ga and 1.8 Ga, indicate that the Erguna Massif had an affinity to both Columbia and Rodinia continents. Furthermore, we also present 500 Ma metamorphic age in micashists and 500 Ma age of adjacent granitoids that might have thermally influenced its surrounding. No detailed studies have been undertaken on the metamorphic evolution of the Xinghuadukou Complex. The typical paragneissic mineral assemblage of garnet sillimanite mica schist is Grt+Sil+Bt+Mus+Qtz±Kfs. (Zhou et al., 2011) proposed that the Xinghuadukou Complex appears to have undergone similar granulite facies metamorphic conditions based on the similarity of mineral assemblages to the Mashan Complex in the Jiamusi Massif, NE China. However, the new phase equilibria modelling result shows that these rocks are high amphibolite facies product with 650℃. We can easily find K-feldspar formed by partial melting due to the consuming of muscovite. Also the remaining muscovite is directly connected with a fluid channel in thin sections which indicate that the remaining muscovite formed from retrograde with the existence of fluid. The zoned garnet has low MgO and high CaO content in rims and high MgO and low CaO content in core. It seems that this garnet has high pressure and low temperature (HP-LT) in rims and low pressure and high temperature (LP-HT) in core which would point to an anti-clockwise metamorphic evolution. Zhou, J.B., Wilde, S.A., Zhang, X.Z., Zhao, G.C., Liu, F.L., Qiao, D.W., Ren, S.M. and Liu, J.H., 2011b. A> 1300km late Pan-African metamorphic belt in NE China: new evidence from the Xing'an block and its tectonic implications. Tectonophysics, 509(3): 280-292.

Electrochemical measurements and thermodynamic calculations of redox equilibria in pallasite meteorites - Implications for the eucrite parent body

NASA Technical Reports Server (NTRS)

Righter, Kevin; Arculus, Richard J.; Paslick, Cassi; Delano, John W.

1990-01-01

The intrinsic oxygen fugacity (IOF) of olivine separates from the Salta, Springwater, and Eagle Station pallasites was measured between 850 and 1150 C using oxygen-specific solid zirconia electrolytes at 100,000 Pa. Thermodynamic calculations of redox equilibria involving equalibrium pallasite assemblages are in good agreement with the experimental results and provide a lower limit to pallasite redox stability; others involving disequilibrium assemblages, suggest that pallasites experienced localized, late-stage oxidation and reduction effects. Consideration of the redox buffer metal-olivine-orthopyroxene utilizing calculated Eucrite Parent Body (EPB) mantle phase compositions indicates that small redox gradients may have existed in the EPB. Such gradients may have produced strong compositional variation within the EPB. In addition, there is apparently significant redox heterogeneity in the source area of Eagle Station Trio pallasites and Bocaiuva iron meteorites.

Nature of phase transitions in crystalline and amorphous GeTe-Sb2Te3 phase change materials.

PubMed

Kalkan, B; Sen, S; Clark, S M

2011-09-28

The thermodynamic nature of phase stabilities and transformations are investigated in crystalline and amorphous Ge(1)Sb(2)Te(4) (GST124) phase change materials as a function of pressure and temperature using high-resolution synchrotron x-ray diffraction in a diamond anvil cell. The phase transformation sequences upon compression, for cubic and hexagonal GST124 phases are found to be: cubic → amorphous → orthorhombic → bcc and hexagonal → orthorhombic → bcc. The Clapeyron slopes for melting of the hexagonal and bcc phases are negative and positive, respectively, resulting in a pressure dependent minimum in the liquidus. When taken together, the phase equilibria relations are consistent with the presence of polyamorphism in this system with the as-deposited amorphous GST phase being the low entropy low-density amorphous phase and the laser melt-quenched and high-pressure amorphized GST being the high entropy high-density amorphous phase. The metastable phase boundary between these two polyamorphic phases is expected to have a negative Clapeyron slope. © 2011 American Institute of Physics

Critical point analysis of phase envelope diagram

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soetikno, Darmadi; Siagian, Ucok W. R.; Kusdiantara, Rudy, E-mail: rkusdiantara@s.itb.ac.id

2014-03-24

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

Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capobianco, Ryan; Gruszkiewicz, Miroslaw; Wesolowski, David J

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 densitiesmore » 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.« less

Free-Boundary 3D Equilibria and Resistive Wall Instabilities with Extended-MHD

NASA Astrophysics Data System (ADS)

Ferraro, N. M.

2015-11-01

The interaction of the plasma with external currents, either imposed or induced, is a critical element of a wide range of important tokamak phenomena, including resistive wall mode (RWM) stability and feedback control, island penetration and locking, and disruptions. A model of these currents may be included within the domain of extended-MHD codes in a way that preserves the self-consistency, scalability, and implicitness of their numerical methods. Such a model of the resistive wall and non-axisymmetric coils is demonstrated using the M3D-C1 code for a variety of applications, including RWMs, perturbed non-axisymmetric equilibria, and a vertical displacement event (VDE) disruption. The calculated free-boundary equilibria, which include Spitzer resistivity, rotation, and two-fluid effects, are compared to external magnetic and internal thermal measurements for several DIII-D discharges. In calculations of the perturbed equilibria in ELM suppressed discharges, the tearing response at the top of the pedestal is found to correlate with the onset of ELM suppression. Nonlinear VDE calculations, initialized using a vertically unstable DIII-D equilibrium, resolve in both space and time the currents induced in the wall and on the plasma surface, and also the currents flowing between the plasma and the wall. The relative magnitude of these contributions and the total impulse to the wall depend on the resistive wall time, although the maximum axisymmetric force on the wall over the course of the VDE is found to be essentially independent of the wall conductivity. This research was supported by US DOE contracts DE-FG02-95ER54309, DE-FC02-04ER54698 and DE-AC52-07NA27344.

Medium-β free-boundary equilibria of a quasi-isodynamic stellarator

NASA Astrophysics Data System (ADS)

Mikhailov, M. I.; Drevlak, M.; Nührenberg, J.; Shafranov, V. D.

2012-06-01

Free-boundary MHD equilibria with magnetic surfaces in the vacuum region surrounding the plasma [E. Strumberger, Nucl. Fusion 37, 19 (1997); M. Drevlak, D. Monticello, and A. Reiman, Nucl. Fusion 45, 731 (2005)] are obtained for a quasi-isodynamic stellarator [A. A. Subbotin, M. I. Mikhailov, V. D. Shafranov et al., Nucl. Fusion 46, 921 (2006); M. I. Mikhailov, J. Nuhrenberg, and V. D. Shafranov, Plasma Phys. Rep. 35, 529 (2009)].

Medium-{beta} free-boundary equilibria of a quasi-isodynamic stellarator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mikhailov, M. I.; Drevlak, M.; Nuehrenberg, J.

Free-boundary MHD equilibria with magnetic surfaces in the vacuum region surrounding the plasma [E. Strumberger, Nucl. Fusion 37, 19 (1997); M. Drevlak, D. Monticello, and A. Reiman, Nucl. Fusion 45, 731 (2005)] are obtained for a quasi-isodynamic stellarator [A. A. Subbotin, M. I. Mikhailov, V. D. Shafranov et al., Nucl. Fusion 46, 921 (2006); M. I. Mikhailov, J. Nuhrenberg, and V. D. Shafranov, Plasma Phys. Rep. 35, 529 (2009)].

Acid-base equilibria inside amine-functionalized mesoporous silica.

PubMed

Yamaguchi, Akira; Namekawa, Manato; Kamijo, Toshio; Itoh, Tetsuji; Teramae, Norio

2011-04-15

Acid-base equilibria and effective proton concentration inside a silica mesopore modified with a trimethyl ammonium (TMAP) layer were studied by steady-state fluorescence experiments. The mesoporous silica with a dense TMAP layer (1.4 molecules/nm(2)) was prepared by a post grafting of N-trimethoxysilylpropyl-N,N,N-trimethylammonium at surfactant-templated mesoporous silica (diameter of silica framework =3.1 nm). The resulting TMAP-modified mesoporous silica strongly adsorbed of anionic fluorescence indicator dyes (8-hydroxypyrene-1,3,6-trisulfonate (pyranine), 8-aminopyrene-1,3,6-trisulfonate (APTS), 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid disulfuric acid (TPPS), 2-naphthol-3,6-disulfonate (2NT)) and fluorescence excitation spectra of these dyes within TMAP-modified mesoporous silica were measured by varying the solution pH. The fluorescence experiments revealed that the acid-base equilibrium reactions of all pH indicator dyes within the TMAP-modified silica mesopore were quite different from those in bulk water. From the analysis of the acid-base equilibrium of pyranine, the following relationships between solution pH (pH(bulk)) and the effective proton concentration inside the pore (pH(pore)) were obtained: (1) shift of pH(pore) was 1.8 (ΔpH(pore)=1.8) for the pH(bulk) change from 2.1 to 9.1 (ΔpH(bulk)=7.0); (2) pH(pore) was not simply proportional to pH(bulk); (3) the inside of the TMAP-modified silica mesopore was suggested to be in a weak acidic or neutral condition when pH(bulk) was changed from 2.0 to 9.1. Since these relationships between pH(bulk) and pH(pore) could explain the acid-base equilibria of other pH indicator dyes (APTS, TPPS, 2NT), these relationships were inferred to describe the effective proton concentration inside the TMAP-modified silica mesopore. © 2011 American Chemical Society

A new problem in mathematical physics associated with the problem of coherent phase transformation

NASA Astrophysics Data System (ADS)

Grinfeld, M. A.

1985-06-01

The description of heterogeneous coherent phase equilibria in an elastic single component system is shown to lead, in the approximation of small intrinsic deformation, to a new problem in mathematical physics with an unknown bound. The low order terms of the resulting system of equilibrium equations coincide with the equations of the classical linear theory of elasticity (generally speaking, anisotropic); however, the problem remains strongly nonlinear overall, inasmuch as it contains an unknown bound and a boundary condition on it which is quadratic with respect to translation. The formulas obtained are used to find certain explicit solutions to the boundary problems. As an example, the problem of heterogeneous equilibria in an infinite rectangular isotropic beam with free faces and constant loading on the surfaces x squared = const can be examined. A modeling problem for the asymptote of small intrinsic deformation during coherent phase transformation is presented as a scalar analog of the vector problem considered initially.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Dynamics of a neutral delay equation for an insect population with long larval and short adult phases

NASA Astrophysics Data System (ADS)

Gourley, Stephen A.; Kuang, Yang

We present a global study on the stability of the equilibria in a nonlinear autonomous neutral delay differential population model formulated by Bocharov and Hadeler. This model may be suitable for describing the intriguing dynamics of an insect population with long larval and short adult phases such as the periodical cicada. We circumvent the usual difficulties associated with the study of the stability of a nonlinear neutral delay differential model by transforming it to an appropriate non-neutral nonautonomous delay differential equation with unbounded delay. In the case that no juveniles give birth, we establish the positivity and boundedness of solutions by ad hoc methods and global stability of the extinction and positive equilibria by the method of iteration. We also show that if the time adjusted instantaneous birth rate at the time of maturation is greater than 1, then the population will grow without bound, regardless of the population death process.

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

PubMed

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

2016-01-28

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

Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review.

PubMed

Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao

2017-11-02

Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

Acquisition and evaluation of thermodynamic data for morenosite-retgersite equilibria at 0.1 MPa

USGS Publications Warehouse

Chou, I.-Ming; Seal, R.R.

2003-01-01

Metal-sulfate salts in mine drainage environments commonly occur as solid solutions containing Fe, Cu, Mg, Zn, Al, Mn, Ni, Co, Cd, and other elements. Thermodynamic data for some of the end-member salts containing Fe, Cu, Zn, and Mg have been collected and evaluated previously, and the present study extends to the system containing Ni. Morenosite (NiSO4-7H2O)-retgersite (NiSO4-6H2O) equilibria were determined along five humidity buffer curves at 0.1 MPa and between 5 and 22??C. Reversals along these humidity-buffer curves yield In K = 17.58-6303.35/T, where K is the equilibrium constant, and T is temperature in K. The derived standard Gibbs free energy of reaction is 8.84 kJ/mol, which agrees very well with the values of 8.90, 8.83, and 8.85 kJ/mol based on the vapor pressure measurements of Schumb (1923), Bonnell and Burridge (1935), and Stout et al. (1966). respectively. This value also agrees reasonably well with the values of 8.65 and 9.56 kJ/mol calculated from the data compiled by Wagman et al. (1982) and DeKock (1982), respectively. The temperature-humidity relationships defined by this study for dehydration equilibria between morenosite and retgersite explain the more common occurrence of retgersite relative to morenosite in nature.

Large Uncertainty in Estimating pCO2 From Carbonate Equilibria in Lakes

NASA Astrophysics Data System (ADS)

Golub, Malgorzata; Desai, Ankur R.; McKinley, Galen A.; Remucal, Christina K.; Stanley, Emily H.

2017-11-01

Most estimates of carbon dioxide (CO2) evasion from freshwaters rely on calculating partial pressure of aquatic CO2 (pCO2) from two out of three CO2-related parameters using carbonate equilibria. However, the pCO2 uncertainty has not been systematically evaluated across multiple lake types and equilibria. We quantified random errors in pH, dissolved inorganic carbon, alkalinity, and temperature from the North Temperate Lakes Long-Term Ecological Research site in four lake groups across a broad gradient of chemical composition. These errors were propagated onto pCO2 calculated from three carbonate equilibria, and for overlapping observations, compared against uncertainties in directly measured pCO2. The empirical random errors in CO2-related parameters were mostly below 2% of their median values. Resulting random pCO2 errors ranged from ±3.7% to ±31.5% of the median depending on alkalinity group and choice of input parameter pairs. Temperature uncertainty had a negligible effect on pCO2. When compared with direct pCO2 measurements, all parameter combinations produced biased pCO2 estimates with less than one third of total uncertainty explained by random pCO2 errors, indicating that systematic uncertainty dominates over random error. Multidecadal trend of pCO2 was difficult to reconstruct from uncertain historical observations of CO2-related parameters. Given poor precision and accuracy of pCO2 estimates derived from virtually any combination of two CO2-related parameters, we recommend direct pCO2 measurements where possible. To achieve consistently robust estimates of CO2 emissions from freshwater components of terrestrial carbon balances, future efforts should focus on improving accuracy and precision of CO2-related parameters (including direct pCO2) measurements and associated pCO2 calculations.

A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach

USGS Publications Warehouse

Mehta, A.P.; Makogon, T.Y.; Burruss, R.C.; Wendlandt, R.F.; Sloan, E.D.

1996-01-01

A composite phase diagram is presented for Structure H (sH) clathrate hydrates. In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

Development of Simulation Methods in the Gibbs Ensemble to Predict Polymer-Solvent Phase Equilibria

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas; Jayaraman, Arthi

Solvent vapor annealing (SVA) of polymer thin films is a promising method for post-deposition polymer film morphology control. The large number of important parameters relevant to SVA (polymer, solvent, and substrate chemistries, incoming film condition, annealing and solvent evaporation conditions) makes systematic experimental study of SVA a time-consuming endeavor, motivating the application of simulation and theory to the SVA system to provide both mechanistic insight and scans of this wide parameter space. However, to rigorously treat the phase equilibrium between polymer film and solvent vapor while still probing the dynamics of SVA, new simulation methods must be developed. In this presentation, we compare two methods to study polymer-solvent phase equilibrium-Gibbs Ensemble Molecular Dynamics (GEMD) and Hybrid Monte Carlo/Molecular Dynamics (Hybrid MC/MD). Liquid-vapor equilibrium results are presented for the Lennard Jones fluid and for coarse-grained polymer-solvent systems relevant to SVA. We found that the Hybrid MC/MD method is more stable and consistent than GEMD, but GEMD has significant advantages in computational efficiency. We propose that Hybrid MC/MD simulations be used for unfamiliar systems in certain choice conditions, followed by much faster GEMD simulations to map out the remainder of the phase window.

Phase behavior of CO/sub 2/ - Appalachian oil systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Monger, T.G.; Khakoo, A.

1981-01-01

The phase behavior of carbon dioxide with two Appalachian crude oils was examined at temperatures below and above the CO/sub 2/ critical temperature. Overall the observed phase equilibria emulate that reported for Western crude oil systems at low reservoir temperatures, but several contrasts in phase behavior are also apparent. Phase behavior of differences are interpreted in light of carbon-13 nuclear magnetic resonance spectroscopy measurements which show that the Appalachian crudes have significantly higher paraffinic and lower aromatic contents than those typically observed for Western crudes. Data analyses suggest that CO/sub 2/ preferentially condenses into a high paraffin oil, whereas hydrocarbonmore » extraction by a CO/sub 2/ -rich phase is the predominant mechanism for crude oils with significant aromatic content. 24 refs.« less

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins.

PubMed

Pesavento, Maria; Sturini, Michela; D'Agostino, Girolamo; Biesuz, Raffaela

2010-02-19

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs-Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition. Copyright 2009. Published by Elsevier B.V.

Multidimensional equilibria and their stability in copolymer-solvent mixtures

NASA Astrophysics Data System (ADS)

Glasner, Karl; Orizaga, Saulo

2018-06-01

This paper discusses localized equilibria which arise in copolymer-solvent mixtures. A free boundary problem associated with the sharp-interface limit of a density functional model is used to identify both lamellar and concentric domain patterns composed of a finite number of layers. Stability of these morphologies is studied through explicit linearization of the free boundary evolution. For the multilayered lamellar configuration, transverse instability is observed for sufficiently small dimensionless interfacial energies. Additionally, a crossover between small and large wavelength instabilities is observed depending on whether solvent-polymer or monomer-monomer interfacial energy is dominant. Concentric domain patterns resembling multilayered micelles and vesicles exhibit bifurcations wherein they only exist for sufficiently small dimensionless interfacial energies. The bifurcation of large radii vesicle solutions is studied analytically, and a crossover from a supercritical case with only one solution branch to a subcritical case with two is observed. Linearized stability of these configurations shows that azimuthal perturbation may lead to instabilities as interfacial energy is decreased.

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.

Nonlinear Magnetic Dynamics and The Switching Phase Diagrams in Spintronic Devices

NASA Astrophysics Data System (ADS)

Yan, Shu

Spin-transfer torque induced magnetic switching, by which the spin-polarized current transfers its magnetic moment to the ferromagnetic layer and changes its magnetization, holds great promise towards faster and smaller magnetic bits in data-storage applications due to the lower power consumption and better scalability. We propose an analytic approach which can be used to calculate the switching phase diagram of a nanomagnetic system in the presence of both magnetic field and spin-transfer torque in an exact fashion. This method is applied to the study of switching conditions for the uniaxial, single domain magnetic layers in different spin-transfer devices. In a spin valve with spin polarization collinear with the easy axis, we get a modified Stoner-Wohlfarth astroid which represents many of the features that have been found in experiment. It also shows a self-crossing boundary and demonstrates a region with three stable equilibria. We demonstrate that the region of stable equilibria with energy near the maximum can be reached only through a narrow bottleneck in the field space, which sets a stringent requirement for magnetic field alignment in the experiments. Switching diagrams are then calculated for the setups with magnetic field not perfectly aligned with the easy axis. In a ferromagnet-heavy-metal bilayer device with strong spin Hall effect, the in plane current becomes spin-polarized and transfers its magnetic moment to the ferromagnetic layer by diffusion. The three-dimensional asymmetric phase diagram is calculated. In the case that the external field is confined in the vertical plane defined by the direction of the current and the easy axis, the spin-transfer torque shifts the conventional in-plane (IP) equilibria within the same plane, and also creates two out-of-plane (OOP) equilibria, one of which can be stable. The threshold switching currents for IP switching and OOP switching are discussed. We also address the magnetic switching processes. Damping

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.

A Chain of Modeling Tools For Gas and Aqueous Phase Chemstry

NASA Astrophysics Data System (ADS)

Audiffren, N.; Djouad, R.; Sportisse, B.

Atmospheric chemistry is characterized by the use of large set of chemical species and reactions. Handling with the set of data required for the definition of the model is a quite difficult task. We prsent in this short article a preprocessor for diphasic models (gas phase and aqueous phase in cloud droplets) named SPACK. The main interest of SPACK is the automatic generation of lumped species related to fast equilibria. We also developped a linear tangent model using the automatic differentiation tool named ODYSSEE in order to perform a sensitivity analysis of an atmospheric multi- phase mechanism based on RADM2 kinetic scheme.Local sensitivity coefficients are computed for two different scenarii. We focus in this study on the sensitivity of the ozone,NOx,HOx, system with respect to some aqueous phase reactions and we inves- tigate the influence of the reduction in the photolysis rates in the area below the cloud region.

GPU.proton.DOCK: Genuine Protein Ultrafast proton equilibria consistent DOCKing.

PubMed

Kantardjiev, Alexander A

2011-07-01

GPU.proton.DOCK (Genuine Protein Ultrafast proton equilibria consistent DOCKing) is a state of the art service for in silico prediction of protein-protein interactions via rigorous and ultrafast docking code. It is unique in providing stringent account of electrostatic interactions self-consistency and proton equilibria mutual effects of docking partners. GPU.proton.DOCK is the first server offering such a crucial supplement to protein docking algorithms--a step toward more reliable and high accuracy docking results. The code (especially the Fast Fourier Transform bottleneck and electrostatic fields computation) is parallelized to run on a GPU supercomputer. The high performance will be of use for large-scale structural bioinformatics and systems biology projects, thus bridging physics of the interactions with analysis of molecular networks. We propose workflows for exploring in silico charge mutagenesis effects. Special emphasis is given to the interface-intuitive and user-friendly. The input is comprised of the atomic coordinate files in PDB format. The advanced user is provided with a special input section for addition of non-polypeptide charges, extra ionogenic groups with intrinsic pK(a) values or fixed ions. The output is comprised of docked complexes in PDB format as well as interactive visualization in a molecular viewer. GPU.proton.DOCK server can be accessed at http://gpudock.orgchm.bas.bg/.

Multi-rotor internal rotations and conformational equilibria in oxiraneethanol and assignment of its vibrational spectra

NASA Astrophysics Data System (ADS)

Badawi, Hassan M.; Ali, Shaikh A.

2009-09-01

The complex internal rotations and conformational equilibria in oxiraneethanol were investigated at the DFT-B3LYP/6-311G** level of theory. Four minima were predicted in the CCOH potential energy scans of the molecule to have relative energies of about 2 kcal/mol or less and all were calculated to have real frequencies upon full optimization of structural parameters and the calculation of the Gibb's free-energies at the DFT level of calculation. At the DFT-B3LYP, the MP2 and the MP4(SDQ) levels of theory, the G1gg1 conformation, predicted to be the lowest energy conformation for oxiraneethanol, was in excellent agreement with the rotational microwave study. The equilibrium mixture was calculated to be about 47% G1gg1, 32% Cg1g, 15% Gg1t and 6% G1g1g at the B3LYP/6-311G** level of theory at 298.15 K. Solvent study corroborated the presence of the high energy Cg1g form in the liquid phase of oxiraneethanol. The vibrational frequencies of oxiraneethanol in its two stable forms were computed at the B3LYP level and vibrational assignments were made for the two lowest energy G1gg1 and Cg1g forms on the basis of calculated and experimental data of the molecule.

Competition and equilibria in electricity markets based on two-settlement system: A conjectural variation approach

NASA Astrophysics Data System (ADS)

Watts, David

This dissertation studies electricity markets based on two-settlement systems and applies the concept of conjectural variation (CV) as a tool for representing different levels of competitiveness in the market. Some recent theoretical works are addressed to support the use of CV as a solution concept. A notion of consistency is introduced to make the level of competitiveness of the market endogenous, and allows finding consistent CV equilibria and the corresponding conditions for existence of equilibria. First, a case is studied in which firms hold exogenous levels of forward commitments. Then, backward induction and sub-game perfection are used to solve sequentially for the spot and forward market equilibrium. This allows analyzing how firms take positions in the forward market, based on considering their later impact on the spot market. It is concluded that positions taken in the forward market depend largely on firms expectations about the competitiveness of both the spot and the forward market. Forward markets are welfare enhancing even if they are not as competitive as the associated spot market as long as they are not too oligopolistie. The above formulation is used to model a dynamic scenario to analyze market stability, linking this research to Dr. Alvarado's earlier research on market stability. This brings about interesting trade offs between market power and market stability.

Scaling-law equilibria for calcium in canopy-type models of the solar chromosphere

NASA Technical Reports Server (NTRS)

Jones, H. P.

1982-01-01

Scaling laws for resonance line formation are used to obtain approximate excitation and ionization equilibria for a three-level model of singly ionized calcium. The method has been developed for and is applied to the study of magnetograph response in the 8542 A infrared triplet line to magnetostatic canopies which schematically model diffuse, nearly horizontal fields in the low solar chromosphere. For this application, the method is shown to be efficient and semi-quantitative, and the results indicate the type and range of effects on calcium-line radiation which result from reduced gas pressure inside the magnetic regions.

Modelling and stability analysis of switching impulsive power systems with multiple equilibria

NASA Astrophysics Data System (ADS)

Zhu, Liying; Qiu, Jianbin; Chadli, Mohammed

2017-12-01

This paper tries to model power systems accompanied with a series of faults in the form of switched impulsive Hamiltonian systems (SIHSs) with multiple equilibria (ME) and unstable subsystems (US), and then analyze long-term stability issues of the power systems from the viewpoint of mathematics. According to the complex phenomena of switching actions of stages and generators, impulses of state, and existence of multiple equilibria, this paper first introduces an SIHS with ME and US to formulate a switching impulsive power system composed of an active generator, a standby generator, and an infinite load. Then, based on special system structures, a unique compact region containing all ME is determined, and novel stability concepts of region stability (RS), asymptotic region stability (ARS), and exponential region stability (ERS) are defined for such SIHS with respect to the region. Third, based on the introduced stability concepts, this paper proposes a necessary and sufficient condition of RS and ARS and a sufficient condition of ERS for the power system with respect to the region via the maximum energy function method. Finally, numerical simulations are carried out for a power system to show the effectiveness and practicality of the obained novel results.

Pyroxene-melt equilibria. [for lunar maria basalts

NASA Technical Reports Server (NTRS)

Nielsen, R. L.; Drake, M. J.

1979-01-01

A thermodynamic analysis of pyroxene-melt equilibria is performed through use of a literature survey of analyses of high-Ca pyroxene and coexisting silicate melt pairs and analyses of low-Ca pyroxene silicate melt pairs. Reference is made to a modified version of a model developed by Bottinga and Weill (1972) which more successfully accounts for variations in melt composition than does a model which considers the melt to be composed of simple oxides which mix ideally. By using a variety of pyroxene melt relations, several pyroxene-melt and low-Ca pyroxene-high-Ca pyroxene geothermometers are developed which have internally consistant precisions of approximately + or - 20 C. Finally, it is noted that these equations may have application in modeling the evolution of mineral compositions during differentiation of basaltic magmas.

Phase equilibria of a low S and C lunar core: Implications for an early lunar dynamo and physical state of the current core

NASA Astrophysics Data System (ADS)

Righter, K.; Go, B. M.; Pando, K. A.; Danielson, L.; Ross, D. K.; Rahman, Z.; Keller, L. P.

2017-04-01

Multiple lines of geochemical and geophysical evidence suggest the Moon has a small metallic core, yet the composition of the core is poorly constrained. The physical state of the core (now or in the past) depends on detailed knowledge of its composition, and unfortunately, there is little available data on relevant multicomponent systems (i.e., Fe-Ni-S-C) at lunar interior conditions. In particular, there is a dearth of phase equilibrium data to elucidate whether a specific core composition could help to explain an early lunar geodynamo and magnetic field intensities, or current solid inner core/liquid outer core states. We utilize geochemical information to estimate the Ni, S and C contents of the lunar core, and then carry out phase equilibria experiments on several possible core compositions at the pressure and temperature conditions relevant to the lunar interior. The first composition is 0.5 wt% S and 0.375 wt% C, based on S and C contents of Apollo glasses. A second composition contains 1 wt% each of S and C, and assumes that the lunar mantle experienced degassing of up to 50% of its S and C. Finally a third composition contains C as the dominant light element. Phase equilibrium experiments were completed at 1, 3 and 5 GPa, using piston cylinder and multi-anvil techniques. The first composition has a liquidus near 1550 °C and solidus near 1250 °C. The second composition has a narrower liquidus and solidus temperatures of 1400 and 1270 °C, respectively, while the third composition is molten down to 1150 °C. As the composition crystallizes, the residual liquid becomes enriched in S and C, but S enrichment is greater due to the incorporation of C (but not S) into solid metallic FeNi. Comparison of these results to thermal models for the Moon allow an evaluation of which composition is consistent with the geophysical data of an early dynamo and a currently solid inner and liquid outer core. Composition 1 has a high enough liquidus to start crystallizing

Phase equilibria computations of multicomponent mixtures at specified internal energy and volume

NASA Astrophysics Data System (ADS)

Myint, Philip C.; Nichols, Albert L., III; Springer, H. Keo

2017-06-01

Hydrodynamic simulation codes for high-energy density science applications often use internal energy and volume as their working variables. As a result, the codes must determine the thermodynamic state that corresponds to the specified energy and volume by finding the global maximum in entropy. This task is referred to as the isoenergetic-isochoric flash. Solving it for multicomponent mixtures is difficult because one must find not only the temperature and pressure consistent with the energy and volume, but also the number of phases present and the composition of the phases. The few studies on isoenergetic-isochoric flash that currently exist all require the evaluation of many derivatives that can be tedious to implement. We present an alternative approach that is based on a derivative-free method: particle swarm optimization. The global entropy maximum is found by running several instances of particle swarm optimization over different sets of randomly selected points in the search space. For verification, we compare the predicted temperature and pressure to results from the related, but simpler problem of isothermal-isobaric flash. All of our examples involve the equation of state we have recently developed for multiphase mixtures of the energetic materials HMX, RDX, and TNT. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Foraging swarms as Nash equilibria of dynamic games.

PubMed

Özgüler, Arif Bülent; Yildiz, Aykut

2014-06-01

The question of whether foraging swarms can form as a result of a noncooperative game played by individuals is shown here to have an affirmative answer. A dynamic game played by N agents in 1-D motion is introduced and models, for instance, a foraging ant colony. Each agent controls its velocity to minimize its total work done in a finite time interval. The game is shown to have a unique Nash equilibrium under two different foraging location specifications, and both equilibria display many features of a foraging swarm behavior observed in biological swarms. Explicit expressions are derived for pairwise distances between individuals of the swarm, swarm size, and swarm center location during foraging.

Determination of melanterite-rozenite and chalcanthite-bonattite equilibria by humidity measurements at 0.1 MPa

USGS Publications Warehouse

Chou, I.-Ming; Seal, R.R.; Hemingway, B.S.

2002-01-01

Melanterite (FeSO4??7H2O)-rozenite (FeSO4??4H2O) and chalcanthite (CuSO4??5H2O)-bonattite (CuSO4??3H2O) equilibria were determined by humidity measurements at 0.1 MPa. Two methods were used; one is the gas-flow-cell method (between 21 and 98 ??C), and the other is the humidity-buffer method (between 21 and 70 ??C). The first method has a larger temperature uncertainty even though it is more efficient. With the aid of humidity buffers, which correspond to a series of saturated binary salt solutions, the second method yields reliable results as demonstrated by very tight reversals along each humidity buffer. These results are consistent with those obtained by the first method, and also with the solubility data reported in the literature. Thermodynamic analysis of these data yields values of 29.231 ?? 0.025 and 22.593 ?? 0.040 kJ/mol for standard Gibbs free energy of reaction at 298.15 K and 0.1 MPa for melanterite-rozenite and chalcanthite-bonattite equilibria, respectively. The methods used in this study hold great potential for unraveling the thermodynamic properties of sulfate salts involved in dehydration reactions at near ambient conditions.

Equilibria of the symmetric collinear restricted four-body problem with radiation pressure

NASA Astrophysics Data System (ADS)

Arribas, M.; Abad, A.; Elipe, A.; Palacios, M.

2016-02-01

In this paper, a restricted four-body problem with radiation pressure is considered. The three primaries are supposed in a collinear central configuration where both masses and both radiation forces of peripheral bodies are equal. After an adequate formulation, the problem is reduced to a tri-parametric one. A complete analysis of the position of equilibria and their stability in the space of parameters is performed.

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)

Equilibria of a Two-Person Non-Zerosum Noisy Game of Timing,

DTIC Science & Technology

1981-01-01

AD-A097 158 YALE UNIV NEW HAVEN CT COWLES FOUNDATION FOR RESEARC -ETC F/B 12/1 EQUILIBRIA OF A TWO-PERSON ON-ZEROSUN OISY GAME OF TIMING, CUb .JAN al...pubUo zeleale Distribution Unlimited. 1. Introduction Two toothpaste manufacturers are competing for a larger share of the dentifrice market . Each is...successfully capturing a share of the market , if its product hits the stores first. (This is assuming that the toothpaste is being technologically

Phase diagrams for lead-free solder alloys

NASA Astrophysics Data System (ADS)

Kattner, Ursula R.

2002-12-01

The need for new, improved solder alloys and a better understanding of reactions during the soldering process grows steadily as the need for smaller and more reliable electronic products increases. Information obtained from phase equilibria data and thermodynamic calculations has proven to be an important tool in the design and understanding of new lead-free solder alloys. A wide range of candidate alloys can be rapidly evaluated for proper freezing ranges, susceptibility to contamination effects, and reactions with substrate materials before the expensive process of preparing and testing candidate alloys is initiated.

The phase diagram of hydrogen in ultra thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jisrawi, N.M.; Ruckman, M.W.; Reisfeld, G.

This paper, we discuss changes in the phase diagram of hydrogen in both bilayer (i.e. 200-2000 {Angstrom} Nb/100 {Angstrom} Pd on glass) and multilayer configurations. Comparison of x-ray diffraction, electrical resistivity and volumetric measurements of the films before and after hydrogen charging indicate that the phase equilibria between a correlated (high concentration) and a dilute phase of hydrogen in Nb is not sensitive to the number of layers in the films. On the other hand, the experimental methods show different behavior for 200 {Angstrom} thick Nb films and thicker (>400 {Angstrom}) Nb layers. The diffraction results also show that, whilemore » charging with hydrogen, the Nb layers mainly expand along the surface normal of the films, while the Pd layers expand in all directions equally, and transform to the bulk {alpha} phase.« less

Thermodynamic characteristics of the protolytic equilibria of tetramethylenediamine- N,N,N', N'-tetraacetic acid

NASA Astrophysics Data System (ADS)

Gridchin, S. N.; Nikol'skii, V. M.

2014-04-01

The stepwise dissociation constants of tetramethylenediamine- N,N,N', N'-tetraacetic acid (H4L) are determined by means of potentiometry at 298.15 K and ionic strength values of 0.1, 0.5, and 1.0 (KNO3). The heat effects of the dissociation of the betaine groups of the complexone are measured by direct calorimetry. The standard thermodynamic characteristics of the protolytic equilibria of H4L are calculated via combined use of the results from thermochemical and potentiometric studies performed under identical experimental conditions. Our results are compared with the corresponding data on relative compounds.

Experimental Investigation of Gas/Slag/Matte/Spinel Equilibria in the Cu-Fe-O-S-Si System at 1473 K (1200 °C) and P(SO2) = 0.25 atm

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Fallah-Mehrjardi, Ata; Hayes, Peter C.; Jak, Evgueni

2018-04-01

New experimental data were obtained on the gas/slag/matte/spinel equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C) and P(SO2) = 0.25 atm covering Cu concentrations in matte between 42 and 78 wt pct Cu. Accurate measurements were obtained using high-temperature equilibration and the rapid quenching technique, followed by electron-probe X-ray microanalysis of equilibrium phase compositions. The use of spinel substrates made to support the samples ensures equilibrium with this primary phase solid, eliminates crucible contamination, and facilitates direct gas-condensed phase equilibrium and high quenching rates. Particular attention was given to the confirmation of the achievement of equilibrium. The results quantify the relationship between Cu in matte and oxygen partial pressure, sulfur in matte, oxygen in matte, Fe/SiO2 at slag liquidus, sulfur in slag, and dissolved copper in slag.

PARALLEL ASSAY OF OXYGEN EQUILIBRIA OF HEMOGLOBIN

PubMed Central

Lilly, Laura E.; Blinebry, Sara K.; Viscardi, Chelsea M.; Perez, Luis; Bonaventura, Joe; McMahon, Tim J.

2013-01-01

Methods to systematically analyze in parallel the function of multiple protein or cell samples in vivo or ex vivo (i.e. functional proteomics) in a controlled gaseous environment have thus far been limited. Here we describe an apparatus and procedure that enables, for the first time, parallel assay of oxygen equilibria in multiple samples. Using this apparatus, numerous simultaneous oxygen equilibrium curves (OECs) can be obtained under truly identical conditions from blood cell samples or purified hemoglobins (Hbs). We suggest that the ability to obtain these parallel datasets under identical conditions can be of immense value, both to biomedical researchers and clinicians who wish to monitor blood health, and to physiologists studying non-human organisms and the effects of climate change on these organisms. Parallel monitoring techniques are essential in order to better understand the functions of critical cellular proteins. The procedure can be applied to human studies, wherein an OEC can be analyzed in light of an individual’s entire genome. Here, we analyzed intraerythrocytic Hb, a protein that operates at the organism’s environmental interface and then comes into close contact with virtually all of the organism’s cells. The apparatus is theoretically scalable, and establishes a functional proteomic screen that can be correlated with genomic information on the same individuals. This new method is expected to accelerate our general understanding of protein function, an increasingly challenging objective as advances in proteomic and genomic throughput outpace the ability to study proteins’ functional properties. PMID:23827235

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

PubMed

Sutter, Eli; Sutter, Peter

2008-02-01

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

Benzoic Acid and Chlorobenzoic Acids: Thermodynamic Study of the Pure Compounds and Binary Mixtures With Water.

PubMed

Reschke, Thomas; Zherikova, Kseniya V; Verevkin, Sergey P; Held, Christoph

2016-03-01

Benzoic acid is a model compound for drug substances in pharmaceutical research. Process design requires information about thermodynamic phase behavior of benzoic acid and its mixtures with water and organic solvents. This work addresses phase equilibria that determine stability and solubility. In this work, Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) was used to model the phase behavior of aqueous and organic solutions containing benzoic acid and chlorobenzoic acids. Absolute vapor pressures of benzoic acid and 2-, 3-, and 4-chlorobenzoic acid from literature and from our own measurements were used to determine pure-component PC-SAFT parameters. Two binary interaction parameters between water and/or benzoic acid were used to model vapor-liquid and liquid-liquid equilibria of water and/or benzoic acid between 280 and 413 K. The PC-SAFT parameters and 1 binary interaction parameter were used to model aqueous solubility of the chlorobenzoic acids. Additionally, solubility of benzoic acid in organic solvents was predicted without using binary parameters. All results showed that pure-component parameters for benzoic acid and for the chlorobenzoic acids allowed for satisfying modeling phase equilibria. The modeling approach established in this work is a further step to screen solubility and to predict the whole phase region of mixtures containing pharmaceuticals. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

REVIEWS OF TOPICAL PROBLEMS: Order-disorder transformations and phase equilibria in strongly nonstoichiometric compounds

NASA Astrophysics Data System (ADS)

Gusev, Aleksandr I.

2000-01-01

Data on order-disorder phase transformations in strongly nonstoichiometric carbides and nitrides MXy (X=C, N) of Group IV and V transition metals at temperatures below 1300-1400 K are reviewed. The order-parameter functional method as applied to atomic and vacancy ordering in strongly nonstoichiometric MXy compounds and to phase equilibrium calculations for M-X systems is discussed. Phase diagram calculations for the Ti-C, Zr-C, Hf-C, V-C, Nb-C, Ta-C, Ti-N, and Ti-B-C systems (with the inclusion of the ordering of nonstoichiometric carbides and nitrides) and those for pseudobinary carbide M(1)C-M(2)C systems are presented. Heat capacity, electrical resistivity and magnetic susceptibility changes at reversible order-disorder phase transformations in nonstoichiometric carbides are considered.

The properties of clusters in the gas phase. IV - Complexes of H2O and HNOx clustering on NOx/-/

NASA Technical Reports Server (NTRS)

Lee, N.; Castleman, A. W., Jr.; Keesee, R. G.

1980-01-01

Thermodynamic quantities for the gas-phase clustering equilibria of NO2(-) and NO3(-) were determined with high-pressure mass spectrometry. A comparison of values of the free energy of hydration derived from the data shows good agreement with formerly reported values at 296 K. New data for larger NO2(-) and NO3(-) hydrates as well as NO2(-)(HNO2)n were obtained in this study. To aid in understanding the bonding and stability of the hydrates of nitrite and nitrate ions, CNDO/2 calculations were performed, and the results are discussed. A correlation between the aqueous-phase total hydration enthalpy of a single ion and its gas-phase hydration enthalpy was obtained. Atmospheric implications of the data are also briefly discussed.

The Spectral Web of stationary plasma equilibria. II. Internal modes

NASA Astrophysics Data System (ADS)

Goedbloed, J. P.

2018-03-01

The new method of the Spectral Web to calculate the spectrum of waves and instabilities of plasma equilibria with sizeable flows, developed in the preceding Paper I [Goedbloed, Phys. Plasmas 25, 032109 (2018)], is applied to a collection of classical magnetohydrodynamic instabilities operating in cylindrical plasmas with shear flow or rotation. After a review of the basic concepts of the complementary energy giving the solution path and the conjugate path, which together constitute the Spectral Web, the cylindrical model is presented and the spectral equations are derived. The first example concerns the internal kink instabilities of a cylindrical force-free magnetic field of constant α subjected to a parabolic shear flow profile. The old stability diagram and the associated growth rate calculations for static equilibria are replaced by a new intricate stability diagram and associated complex growth rates for the stationary model. The power of the Spectral Web method is demonstrated by showing that the two associated paths in the complex ω-plane nearly automatically guide to the new class of global Alfvén instabilities of the force-free configuration that would have been very hard to predict by other methods. The second example concerns the Rayleigh-Taylor instability of a rotating theta-pinch. The old literature is revisited and shown to suffer from inconsistencies that are remedied. The most global n = 1 instability and a cluster sequence of more local but much more unstable n =2 ,3 ,…∞ modes are located on separate solution paths in the hydrodynamic (HD) version of the instability, whereas they merge in the MHD version. The Spectral Web offers visual demonstration of the central position the HD flow continuum and of the MHD Alfvén and slow magneto-sonic continua in the respective spectra by connecting the discrete modes in the complex plane by physically meaningful curves towards the continua. The third example concerns the magneto-rotational instability

Intermediate phases in some rare earth-ruthenium systems

NASA Technical Reports Server (NTRS)

Sharifrazi, P.; Raman, A.; Mohanty, R. C.

1984-01-01

The phase equilibria and crystal structures of intermediate phases were investigated in eight representative RE-Ru systems using powder X-ray diffraction and metallographic techniques. The Fe3C, Mn5C2 and Er5Ru3 structures occur in all but the Ce-Ru systems. Phases analogous to Er5Ru3 possess an unknown crystal structure similar to Er5Rh3(I). MgCu2 and MgZn2 type Laves phases are encountered in the light rare earth and heavy rare earth systems, respectively, and RERu2 phases, where RE = Nd and Sm, possess both the Laves phase structures. An intermediate phase, NdRu, with an unknown structure, occurs only in the Nd-Ru system. A bcc structure with 40 atoms per unit cell is encountered in the phases Er3Ru2 and Y3Ru2. The behavior of cerium in Ce-Ru alloys is unique in that four unidentified structures, not encountered in other RE-Ru systems, have been encountered. Also a phase designated as Ce3Ru is found with the Th7Fe3 type structure.

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

First-principles calculations, experimental study, and thermodynamic modeling of the Al-Co-Cr system.

PubMed

Liu, Xuan L; Gheno, Thomas; Lindahl, Bonnie B; Lindwall, Greta; Gleeson, Brian; Liu, Zi-Kui

2015-01-01

The phase relations and thermodynamic properties of the condensed Al-Co-Cr ternary alloy system are investigated using first-principles calculations based on density functional theory (DFT) and phase-equilibria experiments that led to X-ray diffraction (XRD) and electron probe micro-analysis (EPMA) measurements. A thermodynamic description is developed by means of the calculations of phase diagrams (CALPHAD) method using experimental and computational data from the present work and the literature. Emphasis is placed on modeling the bcc-A2, B2, fcc-γ, and tetragonal-σ phases in the temperature range of 1173 to 1623 K. Liquid, bcc-A2 and fcc-γ phases are modeled using substitutional solution descriptions. First-principles special quasirandom structures (SQS) calculations predict a large bcc-A2 (disordered)/B2 (ordered) miscibility gap, in agreement with experiments. A partitioning model is then used for the A2/B2 phase to effectively describe the order-disorder transitions. The critically assessed thermodynamic description describes all phase equilibria data well. A2/B2 transitions are also shown to agree well with previous experimental findings.

High pressure study of water-salt systems, phase equilibria, partitioning, thermodynic properties and implication for large icy worlds hydrospheres.

NASA Astrophysics Data System (ADS)

Journaux, B.; Brown, J. M.; Abramson, E.; Petitgirard, S.; Pakhomova, A.; Boffa Ballaran, T.; Collings, I.

2017-12-01

Water salt systems are predicted to be present in deep hydrosphere inside water-rich planetary bodies, following water/rock chemical interaction during early differentiation stages or later hydrothermal activity. Unfortunately the current knowledge of the thermodynamic and physical properties of aqueous salt mixtures at high pressure and high temperature is still insufficient to allow realistic modeling of the chemical or dynamic of thick planetary hydrospheres. Recent experimental results have shown that the presence of solutes, and more particularly salts, in equilibrium with high pressure ices have large effects on the stability fields, buoyancy and chemistry of all the phases present at these extreme conditions. Effects currently being investigated by our research group also covers ice melting curve depressions that depend on the salt species and incorporation of solutes inside the crystallographic lattice of high pressure ices. Both of these could have very important implication at the planetary scale, enabling thicker/deeper liquid oceans, and allowing chemical transportation through the high pressure ice layer in large icy worlds. We will present the latest results obtained in-situ using diamond anvil cell, coupled with Synchrotron X-Ray diffraction, Raman Spectroscopy and optical observations, allowing to probe the crystallographic structure, equations of state, partitioning and phase boundary of high pressure ice VI and VII in equilibrium with Na-Mg-SO4-Cl ionic species at high pressures (1-10 GPa). The difference in melting behavior depending on the dissolved salt species was characterized, suggesting differences in ionic speciation at liquidus conditions. The solidus P-T conditions were also measured as well as an increase of lattice volumes interpreted as an outcome of ionic incorporation in HP ice during incongruent crystallization. The measured phase diagrams, lattice volumes and important salt incorporations suggest a more complex picture of the

Phase Equilibria of ``Cu2O''-``FeO''-CaO-MgO-Al2O3 Slags at PO2 of 10-8.5 atm in Equilibrium with Metallic Copper for a Copper Slag Cleaning Production

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.

Recent advances in the study of the UO2-PuO2 phase diagram at high temperatures

NASA Astrophysics Data System (ADS)

Böhler, R.; Welland, M. J.; Prieur, D.; Cakir, P.; Vitova, T.; Pruessmann, T.; Pidchenko, I.; Hennig, C.; Guéneau, C.; Konings, R. J. M.; Manara, D.

2014-05-01

Recently, novel container-less laser heating experimental data have been published on the melting behaviour of pure PuO2 and PuO2-rich compositions in the uranium dioxide-plutonium dioxide system. Such data showed that previous data obtained by more traditional furnace heating techniques were affected by extensive interaction between the sample and its containment. It is therefore paramount to check whether data so far used by nuclear engineers for the uranium-rich side of the pseudo-binary dioxide system can be confirmed or not. In the present work, new data are presented both in the UO2-rich part of the phase diagram, most interesting for the uranium-plutonium dioxide based nuclear fuel safety, and in the PuO2 side. The new results confirm earlier furnace heating data in the uranium-dioxide rich part of the phase diagram, and more recent laser-heating data in the plutonium-dioxide side of the system. As a consequence, it is also confirmed that a minimum melting point must exist in the UO2-PuO2 system, at a composition between x(PuO2) = 0.4 and x(PuO2) = 0.7 and 2900 K ⩽ T ⩽ 3000 K. Taking into account that, especially at high temperature, oxygen chemistry has an effect on the reported phase boundary uncertainties, the current results should be projected in the ternary U-Pu-O system. This aspect has been extensively studied here by X-ray diffraction and X-ray absorption spectroscopy. The current results suggest that uncertainty bands related to oxygen behaviour in the equilibria between condensed phases and gas should not significantly affect the qualitative trend of the current solid-liquid phase boundaries.

Axisymmetric plasma equilibria in a Kerr metric

NASA Astrophysics Data System (ADS)

Elsässer, Klaus

2001-10-01

Plasma equilibria near a rotating black hole are considered within the multifluid description. An isothermal two-component plasma with electrons and positrons or ions is determined by four structure functions and the boundary conditions. These structure functions are the Bernoulli function and the toroidal canonical momentum per mass for each species. The quasi-neutrality assumption (no charge density, no toroidal current) allows to solve Maxwell's equations analytically for any axisymmetric stationary metric, and to reduce the fluid equations to one single scalar equation for the stream function \\chi of the positrons or ions, respectively. The basic smallness parameter is the ratio of the skin depth of electrons to the scale length of the metric and fluid quantities, and, in the case of an electron-ion plasma, the mass ratio m_e/m_i. The \\chi-equation can be solved by standard methods, and simple solutions for a Kerr geometry are available; they show characteristic flow patterns, depending on the structure functions and the boundary conditions.

Calculation of {alpha}/{gamma} equilibria in SA508 grade 3 steels for intercritical heat treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, B.J.; Kim, H.D.; Hong, J.H.

1998-05-01

An attempt has been made to suggest an optimum temperature for intercritical heat treatment of an SA508 grade 3 steel for nuclear pressure vessels, based on thermodynamic calculation of the {alpha}/{gamma} phase equilibria. A thermodynamic database constructed for the Fe-Mn-Ni-Mo-Cr-Si-V-Al-C-N ten-component system and an empirical criterion that the amount of reformed austenite should be around 40 pct were used for thermodynamic calculation and derivation of the optimum heat-treatment temperature, respectively. The calculated optimum temperature, 720 C, was in good agreement with an experimentally determined temperature of 725 C obtained through an independent experimental investigation of the same steel. The agreementmore » between the calculated and measured fraction of reformed austenite during the intercritical heat treatment was also confirmed. Based on the agreement between calculation and experiment, it could be concluded that thermodynamic calculations can be successfully applied to the materials and/or process design as an additive tool to the already established technology, and that the currently constructed thermodynamic database for steel systems shows an accuracy that makes such applications possible.« less

Role of a continuous MHD dynamo in the formation of 3D equilibria in fusion plasmas

NASA Astrophysics Data System (ADS)

Piovesan, P.; Bonfiglio, D.; Cianciosa, M.; Luce, T. C.; Taylor, N. Z.; Terranova, D.; Turco, F.; Wilcox, R. S.; Wingen, A.; Cappello, S.; Chrystal, C.; Escande, D. F.; Holcomb, C. T.; Marrelli, L.; Paz-Soldan, C.; Piron, L.; Predebon, I.; Zaniol, B.; DIII-D, The; RFX-Mod Teams

2017-07-01

Stationary 3D equilibria can form in fusion plasmas via saturation of magnetohydrodynamic (MHD) instabilities or stimulated by external 3D fields. In these cases the current profile is anomalously broad due to magnetic flux pumping produced by the MHD modes. Flux pumping plays an important role in hybrid tokamak plasmas, maintaining the minimum safety factor above unity and thus removing sawteeth. It also enables steady-state hybrid operation, by redistributing non-inductive current driven near the center by electron cyclotron waves. A validated flux pumping model is not yet available, but it would be necessary to extrapolate hybrid operation to future devices. In this work flux pumping physics is investigated for helical core equilibria stimulated by external 3D fields in DIII-D hybrid plasmas. We show that flux pumping can be produced in a continuous way by an MHD dynamo emf. The same effect maintains helical equilibria in reversed-field pinch (RFP) plasmas. The effective MHD dynamo loop voltage is calculated for experimental 3D equilibrium reconstructions, by balancing Ohm’s law over helical flux surfaces, and is consistent with the expected current redistribution. Similar results are also obtained with more sophisticated nonlinear MHD simulations. The same modelling approach is applied to helical RFP states forming spontaneously in RFX-mod as the plasma current is raised above 0.8-1 MA. This comparison allows to identify the underlying physics common to tokamak and RFP: a helical core displacement modulates parallel current density along flux tubes, which requires a helical electrostatic potential to build up, giving rise to a helical MHD dynamo flow.

Role of a continuous MHD dynamo in the formation of 3D equilibria in fusion plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piovesan, P.; Bonfiglio, D.; Cianciosa, M.

Stationary 3D equilibria can form in fusion plasmas via saturation of magnetohydrodynamic (MHD) instabilities or stimulated by external 3D fields. In these cases the current profile is anomalously broad due to magnetic flux pumping produced by the MHD modes. Flux pumping plays an important role in hybrid tokamak plasmas, maintaining the minimum safety factor above unity and thus removing sawteeth. It also enables steady-state hybrid operation, by redistributing non-inductive current driven near the center by electron cyclotron waves. A validated flux pumping model is not yet available, but it would be necessary to extrapolate hybrid operation to future devices. Inmore » this work flux pumping physics is investigated for helical core equilibria stimulated by external 3D fields in DIII-D hybrid plasmas. We show that flux pumping can be produced in a continuous way by an MHD dynamo emf. The same effect maintains helical equilibria in reversed-field pinch (RFP) plasmas. The effective MHD dynamo loop voltage is calculated for experimental 3D equilibrium reconstructions, by balancing Ohm’s law over helical flux surfaces, and is consistent with the expected current redistribution. Similar results are also obtained with more sophisticated nonlinear MHD simulations. The same modelling approach is applied to helical RFP states forming spontaneously in RFX-mod as the plasma current is raised above 0.8–1 MA. This comparison allows to identify the underlying physics common to tokamak and RFP: a helical core displacement modulates parallel current density along flux tubes, which requires a helical electrostatic potential to build up, giving rise to a helical MHD dynamo flow.« less

Role of a continuous MHD dynamo in the formation of 3D equilibria in fusion plasmas

DOE PAGES

Piovesan, P.; Bonfiglio, D.; Cianciosa, M.; ...

2017-04-28

Stationary 3D equilibria can form in fusion plasmas via saturation of magnetohydrodynamic (MHD) instabilities or stimulated by external 3D fields. In these cases the current profile is anomalously broad due to magnetic flux pumping produced by the MHD modes. Flux pumping plays an important role in hybrid tokamak plasmas, maintaining the minimum safety factor above unity and thus removing sawteeth. It also enables steady-state hybrid operation, by redistributing non-inductive current driven near the center by electron cyclotron waves. A validated flux pumping model is not yet available, but it would be necessary to extrapolate hybrid operation to future devices. Inmore » this work flux pumping physics is investigated for helical core equilibria stimulated by external 3D fields in DIII-D hybrid plasmas. We show that flux pumping can be produced in a continuous way by an MHD dynamo emf. The same effect maintains helical equilibria in reversed-field pinch (RFP) plasmas. The effective MHD dynamo loop voltage is calculated for experimental 3D equilibrium reconstructions, by balancing Ohm’s law over helical flux surfaces, and is consistent with the expected current redistribution. Similar results are also obtained with more sophisticated nonlinear MHD simulations. The same modelling approach is applied to helical RFP states forming spontaneously in RFX-mod as the plasma current is raised above 0.8–1 MA. This comparison allows to identify the underlying physics common to tokamak and RFP: a helical core displacement modulates parallel current density along flux tubes, which requires a helical electrostatic potential to build up, giving rise to a helical MHD dynamo flow.« less

Free energy and phase equilibria for the restricted primitive model of ionic fluids from Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Orkoulas, Gerassimos; Panagiotopoulos, Athanassios Z.

1994-07-01

In this work, we investigate the liquid-vapor phase transition of the restricted primitive model of ionic fluids. We show that at the low temperatures where the phase transition occurs, the system cannot be studied by conventional molecular simulation methods because convergence to equilibrium is slow. To accelerate convergence, we propose cluster Monte Carlo moves capable of moving more than one particle at a time. We then address the issue of charged particle transfers in grand canonical and Gibbs ensemble Monte Carlo simulations, for which we propose a biased particle insertion/destruction scheme capable of sampling short interparticle distances. We compute the chemical potential for the restricted primitive model as a function of temperature and density from grand canonical Monte Carlo simulations and the phase envelope from Gibbs Monte Carlo simulations. Our calculated phase coexistence curve is in agreement with recent results of Caillol obtained on the four-dimensional hypersphere and our own earlier Gibbs ensemble simulations with single-ion transfers, with the exception of the critical temperature, which is lower in the current calculations. Our best estimates for the critical parameters are T*c=0.053, ρ*c=0.025. We conclude with possible future applications of the biased techniques developed here for phase equilibrium calculations for ionic fluids.

Petrologic and geophysical study of the source of long wavelength crustal magnetic anomalies

NASA Technical Reports Server (NTRS)

Marsch, B.; Schlinger, C. M.

1983-01-01

The magnetic mineralogy and magnetic signature of banded ion formations, diagenetic (unmetamorphosed) and low grade banded iron formations, high-grade mineralogy, and phase equilibria of magnetite inorogenic magmers are discussed.

Navigable networks as Nash equilibria of navigation games.

PubMed

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

2015-07-03

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

Experimental Investigation of Gas/Slag/Matte/Tridymite Equilibria in the Cu-Fe-O-S-Si System in Controlled Gas Atmospheres: Experimental Results at 1473 K (1200 °C) and P(SO2) = 0.25 atm

NASA Astrophysics Data System (ADS)

Fallah-Mehrjardi, Ata; Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

2017-12-01

Experimental studies were undertaken to determine the gas/slag/matte/tridymite equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C), P(SO2) = 0.25 atm, and a range of P(O2)'s. The experimental methodology involved high-temperature equilibration using a substrate support technique in controlled gas atmospheres (CO/CO2/SO2/Ar), rapid quenching of equilibrium phases, followed by direct measurement of the chemical compositions of the phases with Electron Probe X-ray Microanalysis (EPMA). The experimental data for slag and matte were presented as a function of copper concentration in matte (matte grade). The data provided are essential for the evaluation of the effect of oxygen potential under controlled atmosphere on the matte grade, liquidus composition of slag and chemically dissolved copper in slag. The new data provide important accurate and reliable quantitative foundation for improvement of the thermodynamic databases for copper-containing systems.

Toward the accurate first-principles prediction of ionization equilibria in proteins.

PubMed

Khandogin, Jana; Brooks, Charles L

2006-08-08

The calculation of pK(a) values for ionizable sites in proteins has been traditionally based on numerical solutions of the Poisson-Boltzmann equation carried out using a high-resolution protein structure. In this paper, we present a method based on continuous constant pH molecular dynamics (CPHMD) simulations, which allows the first-principles description of protein ionization equilibria. Our method utilizes an improved generalized Born implicit solvent model with an approximate Debye-Hückel screening function to account for salt effects and the replica-exchange (REX) protocol for enhanced conformational and protonation state sampling. The accuracy and robustness of the present method are demonstrated by 1 ns REX-CPHMD titration simulations of 10 proteins, which exhibit anomalously large pK(a) shifts for the carboxylate and histidine side chains. The experimental pK(a) values of these proteins are reliably reproduced with a root-mean-square error ranging from 0.6 unit for proteins containing few buried ionizable side chains to 1.0 unit or slightly higher for proteins containing ionizable side chains deeply buried in the core and experiencing strong charge-charge interactions. This unprecedented level of agreement with experimental benchmarks for the de novo calculation of pK(a) values suggests that the CPHMD method is maturing into a practical tool for the quantitative prediction of protein ionization equilibria, and this, in turn, opens a door to atomistic simulations of a wide variety of pH-coupled conformational phenomena in biological macromolecules such as protein folding or misfolding, aggregation, ligand binding, membrane interaction, and catalysis.

An internally consistent set of thermodynamic data for twentyone CaO-Al2O3-SiO2- H2O phases by linear parametric programming

NASA Astrophysics Data System (ADS)

Halbach, Heiner; Chatterjee, Niranjan D.

1984-11-01

The technique of linear parametric programming has been applied to derive sets of internally consistent thermodynamic data for 21 condensed phases of the quaternary system CaO-Al2O3-SiO2-H2O (CASH) (Table 4). This was achieved by simultaneously processing: a) calorimetric data for 16 of these phases (Table 1), and b) experimental phase equilibria reversal brackets for 27 reactions (Table 3) involving these phases. Calculation of equilibrium P-T curves of several arbitrarily picked reactions employing the preferred set of internally consistent thermodynamic data from Table 4 shows that the input brackets are invariably satisfied by the calculations (Fig. 2a). By contrast, the same equilibria calculated on the basis of a set of thermodynamic data derived by applying statistical methods to a large body of comparable input data (Haas et al. 1981; Hemingway et al. 1982) do not necessarily agree with the experimental reversal brackets. Prediction of some experimentally investigated phase relations not included into the linear programming input database also appears to be remarkably successful. Indications are, therefore, that the thermodynamic data listed in Table 4 may be used with confidence to predict geologic phase relations in the CASH system with considerable accuracy. For such calculated phase diagrams and their petrological implications, the reader's attention is drawn to the paper by Chatterjee et al. (1984).

CFD analysis of laboratory scale phase equilibrium cell operation

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

CFD analysis of laboratory scale phase equilibrium cell operation.

PubMed

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

2017-10-01

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

On the composition dependence of faceting behaviour of primary phases during solidification

NASA Astrophysics Data System (ADS)

Saroch, Mamta; Dubey, K. S.; Ramachandrarao, P.

1993-02-01

The entropy of solution of the primary aluminium-rich phase in the aluminium-tin melts has been evaluated as a function of temperature using available thermodynamic and phase equilibria data with a view to understand the faceting behaviour of this phase. It was noticed that the range of compositions in which alloys of aluminium and tin yield a faceted primary phase is correlated with the domain of compositions over which the entropy of solution shows a strong temperature dependence. It is demonstrated that both a high value of the entropy of solution and a strong temperature dependence of it are essential for providing faceting. A strong temperature dependence of the entropy of solution is in turn a consequence of negligible liquidus slope and existence of retrograde solubility. The AgBi and AgPb systems have similar features.

Micropollutant and sludge characterization for modeling sorption equilibria.

PubMed

Barret, Maialen; Carrère, Hélène; Latrille, Eric; Wisniewski, Christelle; Patureau, Dominique

2010-02-01

The sorption of hydrophobic micropollutants in sludge is one of the major mechanisms which drive their fate within wastewater treatment systems. The objective of this study was to investigate the influence of both sludge and micropollutant characteristics on the equilibria of sorption to particles and to dissolved and colloidal matter (DCM). For this purpose, the equilibrium constants were measured for 13 polycyclic aromatic hydrocarbons, 5 polychlorobiphenyls and the nonylphenol, and five different sludge types encountered in treatment systems: a primary sludge, a secondary sludge, the same secondary sludge after thermal treatment, after anaerobic digestion, and after both treatments. After thermal treatment, no more sorption to DCM was observed. Anaerobic biological treatment was shown to enhance micropollutants sorption to particles and to DCM of one logarithmic unit, due to matter transformation. Partial least-squares linear regressions of sorption data as a function of micropollutant and sludge properties revealed that sludge physical and chemical characteristics were more influential than micropollutant characteristics. Two models were provided to predict the sorption of such micropollutants in any sludge. To our knowledge, this is the first time that a three-compartment approach is used to accurately model micropollutant sorption in sludge and to understand the driving mechanisms.

Navigable networks as Nash equilibria of navigation games

PubMed Central

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

2015-01-01

Common sense suggests that networks are not random mazes of purposeless connections, but that these connections are organized so that networks can perform their functions well. One function common to many networks is targeted transport or navigation. Here, using game theory, we show that minimalistic networks designed to maximize the navigation efficiency at minimal cost share basic structural properties with real networks. These idealistic networks are Nash equilibria of a network construction game whose purpose is to find an optimal trade-off between the network cost and navigability. We show that these skeletons are present in the Internet, metabolic, English word, US airport, Hungarian road networks, and in a structural network of the human brain. The knowledge of these skeletons allows one to identify the minimal number of edges, by altering which one can efficiently improve or paralyse navigation in the network. PMID:26138277

Phase Equilibria and Thermodynamic Descriptions of Ag-Ge and Ag-Ge-Ni Systems

NASA Astrophysics Data System (ADS)

Rajkumar, V. B.; Chen, Sinn-Wen

2018-07-01

Gibbs energy modeling of Ag-Ge and Ag-Ge-Ni systems was done using the calculation of the phase diagram method with associated data from this work and relevant literature information. In the Ag-Ge system, the solidus temperatures of Ag-rich alloys are measured using differential thermal analysis, and the energy of mixing for the FCC_A1 phase is calculated using the special quasi-random structures technique. The isothermal sections of the Ag-Ge-Ni system at 1023 K and 673 K are also experimentally determined. These data and findings in the relevant literature are used to model the Gibbs energy of the Ag-Ge and Ag-Ge- Ni systems. A reaction scheme and a liquidus projection of the Ag-Ge-Ni system are determined.

Applications of ionic liquids in biphasic separation: Aqueous biphasic systems and liquid-liquid equilibria.

PubMed

Shukla, Shashi Kant; Pandey, Shubha; Pandey, Siddharth

2018-07-20

Ionic liquids (ILs) have been receiving much attention in many fields of analytical chemistry because of their various interesting properties which distinguish them from volatile organic compounds. They offer both directional and non-directional forces towards a solute molecule and therefore act as excellent solvents for a wide range of polar and non-polar compounds. Because of the presence of various possible interactions, ILs easily undergo biphasic separation with water and other less polar/non-polar organic solvents. Their ability to create biphasic splitting makes them a promising candidate for liquid-liquid separation processes, such as aqueous biphasic systems and liquid-liquid equilibria. Various aspects of ILs in these separation methods are discussed in view of the origin of physical forces responsible for the biphasic interactions, the effect of structural components, temperature, pressure, pH and additives. The specific advantages of using ILs in aqueous biphasic systems and liquid-liquid equilibria in binary and ternary systems are discussed with a view to defining their future role in separation processes by giving major emphasis on developing non-toxic ILs with physical and solution properties tailored to the needs of specific sample preparation techniques. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Unifying dynamical and structural stability of equilibria.

PubMed

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.

Approximation of Nash equilibria and the network community structure detection problem

PubMed Central

2017-01-01

Game theory based methods designed to solve the problem of community structure detection in complex networks have emerged in recent years as an alternative to classical and optimization based approaches. The Mixed Nash Extremal Optimization uses a generative relation for the characterization of Nash equilibria to identify the community structure of a network by converting the problem into a non-cooperative game. This paper proposes a method to enhance this algorithm by reducing the number of payoff function evaluations. Numerical experiments performed on synthetic and real-world networks show that this approach is efficient, with results better or just as good as other state-of-the-art methods. PMID:28467496

Effect of organic matter on CO(2) hydrate phase equilibrium in phyllosilicate suspensions.

PubMed

Park, Taehyung; Kyung, Daeseung; Lee, Woojin

2014-06-17

In this study, we examined various CO2 hydrate phase equilibria under diverse, heterogeneous conditions, to provide basic knowledge for successful ocean CO2 sequestration in offshore marine sediments. We investigated the effect of geochemical factors on CO2 hydrate phase equilibrium. The three-phase (liquid-hydrate-vapor) equilibrium of CO2 hydrate in the presence of (i) organic matter (glycine, glucose, and urea), (ii) phyllosilicates [illite, kaolinite, and Na-montmorillonite (Na-MMT)], and (iii) mixtures of them was measured in the ranges of 274.5-277.0 K and 14-22 bar. Organic matter inhibited the phase equilibrium of CO2 hydrate by association with water molecules. The inhibition effect decreased in the order: urea < glycine < glucose. Illite and kaolinite (unexpandable clays) barely affected the CO2 hydrate phase equilibrium, while Na-MMT (expandable clay) affected the phase equilibrium because of its interlayer cations. The CO2 hydrate equilibrium conditions, in the illite and kaolinite suspensions with organic matter, were very similar to those in the aqueous organic matter solutions. However, the equilibrium condition in the Na-MMT suspension with organic matter changed because of reduction of its inhibition effect by intercalated organic matter associated with cations in the Na-MMT interlayer.

Low temperature geothermal systems in carbonate-evaporitic rocks: Mineral equilibria assumptions and geothermometrical calculations. Insights from the Arnedillo thermal waters (Spain).

PubMed

Blasco, Mónica; Gimeno, María J; Auqué, Luis F

2018-02-15

Geothermometrical calculations in low-medium temperature geothermal systems hosted in carbonate-evaporitic rocks are complicated because 1) some of the classical chemical geothermometers are, usually, inadequate (since they were developed for higher temperature systems with different mineral-water equilibria at depth) and 2) the chemical geothermometers calibrated for these systems (based on the Ca and Mg or SO 4 and F contents) are not free of problems either. The case study of the Arnedillo thermal system, a carbonate-evaporitic system of low temperature, will be used to deal with these problems through the combination of several geothermometrical techniques (chemical and isotopic geothermometers and geochemical modelling). The reservoir temperature of the Arnedillo geothermal system has been established to be in the range of 87±13°C being the waters in equilibrium with respect to calcite, dolomite, anhydrite, quartz, albite, K-feldspar and other aluminosilicates. Anhydrite and quartz equilibria are highly reliable to stablish the reservoir temperature. Additionally, the anhydrite equilibrium explains the coherent results obtained with the δ 18 O anhydrite - water geothermometer. The equilibrium with respect to feldspars and other aluminosilicates is unusual in carbonate-evaporitic systems and it is probably related to the presence of detrital material in the aquifer. The identification of the expected equilibria with calcite and dolomite presents an interesting problem associated to dolomite. Variable order degrees of dolomite can be found in natural systems and this fact affects the associated equilibrium temperature in the geothermometrical modelling and also the results from the Ca-Mg geothermometer. To avoid this uncertainty, the order degree of the dolomite present in the Arnedillo reservoir has been determined and the results indicate 18.4% of ordered dolomite and 81.6% of disordered dolomite. Overall, the results suggest that this multi

Axisymmetric Plasma Equilibria in General Relativity

NASA Astrophysics Data System (ADS)

Elsässer, Klaus

Axisymmetric plasma equilibria near a rotating black hole are considered within the multifluid description. An isothermal two-component plasma with electrons and positrons or ions is determined by four structure functions and the boundary conditions. These structure functions are the Bernoulli function and the toroidal canonical momentum per mass for each species; they remain arbitrary if no gain and loss processes are considered, in close analogy to the free flux functions in ideal magnetohydrodynamics. Several simplifying assumptions allow the reduction of the basic equations to one single scalar equation for the stream function χ of positrons or ions, respectively, playing the rôle of the Grad/Shafranov equation in magnetohydrodynamics; in particular, Maxwell's equations can be solved analytically for a quasineutral plasma when both the charge density and the toroidal electric current density are negligible (in contrast to the Tokamak situation). The basic smallness parameter is the ratio of the skin depth of electrons to the scale length of the metric and fluid quantities, and, in the case of an electron-ion plasma, the mass ratio me/mi. The χ-equation can be solved by standard methods, and simple solutions for a Kerr geometry are available; they show characteristic flow patterns, depending on the structure functions and the boundary conditions.

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.

Phase equilibria modeling in igneous petrology: use of COMAGMAT model for simulating fractionation of ferro-basaltic magmas and the genesis of high-alumina basalt

NASA Astrophysics Data System (ADS)

Ariskin, Alexei A.

1999-05-01

A new version of COMAGMAT-3.5 model designed for computer simulations of equilibrium and fractional crystallization of basaltic magmas at low to high pressures is presented. The most important modifications of COMAGMAT include an ability to calculate more accurately the crystallization of magnetite and ilmenite, allowing the user to study numerically the effect of oxygen fugacity on basalt magma fractionation trends. Methodological principles of the use of COMAGMAT were discussed based on its thermodynamical and empirical basis, including specific details of the model calibration. Using COMAGMAT-3.5 a set of phase equilibria calculations (called Geochemical Thermometry) has been conducted for six cumulative rocks from the Marginal Border Series of the Skaergaard intrusion. As a result, initial magma temperature (1165±10°C) and trapped melt composition proposed to be parental magma to the Skaergaard intrusion were determined. Computer simulations of perfect fractionation of this composition as well as another proposed parent produced petrochemical trends opposite to those followed from natural observations. This is interpreted as evidence for an initial Skaergaard magma containing a large amount of olivine and plagioclase crystals (about 40-45%), so that the proposed and calculated parents are related through the melt trapped in the crystal-liquid mixture. This promotes the conclusion that the Skaergaard magma fractionation process was intermediate between equilibrium and fractional crystallization. In this case the classic Wager's trend should be considered an exception rather than a rule for the differentiation of ferro-basaltic magmas. A polybaric version of COMAGMAT has been applied for the genetic interpretation of a volcanic suite from the Klyuchevskoi volcano, Kamchatka, Russia. To identify petrological processes responsible for the observed suite ranging from high-magnesia to high-alumina basalts, we used the model to simulate the Klyuchevskoi suite

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

PubMed

Rickaby, R E M

2015-03-13

Life and the chemical environment are united in an inescapable feedback cycle. The periodic table of the elements essential for life has transformed over Earth's history, but, as today, evolved in tune with the elements available in abundance in the environment. The most revolutionary time in life's history was the advent and proliferation of oxygenic photosynthesis which forced the environment towards a greater degree of oxidation. Consideration of three inorganic chemical equilibria throughout this gradual oxygenation prescribes a phased release of trace metals to the environment, which appear to have coevolved with employment of these new chemicals by life. Evolution towards complexity was chemically constrained, and changes in availability of notably Fe, Zn and Cu paced the systematic development of complex organisms. Evolving life repeatedly catalysed its own chemical challenges via the unwitting release of new and initially toxic chemicals. Ultimately, the harnessing of these allowed life to advance to greater complexity, though the mechanism responsible for translating novel chemistry to heritable use remains elusive. Whether a chemical acts as a poison or a nutrient lies both in the dose and in its environmental history. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Complexation equilibria and spectrophotometric determination of iron(III) with 1-amino-4-hydroxyanthraquinone.

PubMed

Abu-Bakr, M S; Sedaira, H; Hashem, E Y

1994-10-01

The complex equilibria of iron(III) with 1-amino-4-hydroxyanthraquinone (AMHA) were studied spectrophotometrically in 40% (v/v) ethanol and an ionic strength of 0.1M (NaClO(4)). The complexation reactions were demonstrated and characterized using graphical logarithmic analysis of the absorbance-pH graphs. A simple, rapid, selective and sensitive method for the spectrophotometric determination of trace amounts of Fe(III) is developed based on the formation of Fe(AMHA) complex at pH 2.5 (lambda(max) = 640 nm, epsilon approximately = 2.1 x 10(4) L. mol(-1) . cm(-1)) in the presence of a large number of foreign ions. Interferences caused by palladium(II) was masked by the addition of cyanide ions. The method has been applied to the determination of iron in some synthetic samples and polymetallic iron ores.

Constructing Integrable Full-pressure Full-current Free-boundary Stellarator Magnetohydrodynamic Equilibria

NASA Astrophysics Data System (ADS)

Hudson, S. R.; Monticello, D. A.; Reiman, A. H.; Strickler, D. J.; Hirshman, S. P.

2003-06-01

For the (non-axisymmetric) stellarator class of plasma confinement devices to be feasible candidates for fusion power stations it is essential that, to a good approximation, the magnetic field lines lie on nested flux surfaces; however, the inherent lack of a continuous symmetry implies that magnetic islands are guaranteed to exist. Magnetic islands break the smooth topology of nested flux surfaces and chaotic field lines result when magnetic islands overlap. An analogous case occurs with 11/2-dimension Hamiltonian systems where resonant perturbations cause singularities in the transformation to action-angle coordinates and destroy integrability. The suppression of magnetic islands is a critical issue for stellarator design, particularly for small aspect ratio devices. Techniques for `healing' vacuum fields and fixed-boundary plasma equilibria have been developed, but what is ultimately required is a procedure for designing stellarators such that the self-consistent plasma equilibrium currents and the coil currents combine to produce an integrable magnetic field, and such a procedure is presented here for the first time. Magnetic islands in free-boundary full-pressure full-current stellarator magnetohydrodynamic equilibria are suppressed using a procedure based on the Princeton Iterative Equilibrium Solver [A.H.Reiman & H.S.Greenside, Comp. Phys. Comm., 43:157, 1986.] which iterates the equilibrium equations to obtain the plasma equilibrium. At each iteration, changes to a Fourier representation of the coil geometry are made to cancel resonant fields produced by the plasma. As the iterations continue, the coil geometry and the plasma simultaneously converge to an equilibrium in which the island content is negligible. The method is applied to a candidate plasma and coil design for the National Compact Stellarator eXperiment [G.H.Neilson et.al., Phys. Plas., 7:1911, 2000.].

A Locust Phase Change Model with Multiple Switching States and Random Perturbation

NASA Astrophysics Data System (ADS)

Xiang, Changcheng; Tang, Sanyi; Cheke, Robert A.; Qin, Wenjie

2016-12-01

Insects such as locusts and some moths can transform from a solitarious phase when they remain in loose populations and a gregarious phase, when they may swarm. Therefore, the key to effective management of outbreaks of species such as the desert locust Schistocercagregaria is early detection of when they are in the threshold state between the two phases, followed by timely control of their hopper stages before they fledge because the control of flying adult swarms is costly and often ineffective. Definitions of gregarization thresholds should assist preventive control measures and avoid treatment of areas that might not lead to gregarization. In order to better understand the effects of the threshold density which represents the gregarization threshold on the outbreak of a locust population, we developed a model of a discrete switching system. The proposed model allows us to address: (1) How frequently switching occurs from solitarious to gregarious phases and vice versa; (2) When do stable switching transients occur, the existence of which indicate that solutions with larger amplitudes can switch to a stable attractor with a value less than the switching threshold density?; and (3) How does random perturbation influence the switching pattern? Our results show that both subsystems have refuge equilibrium points, outbreak equilibrium points and bistable equilibria. Further, the outbreak equilibrium points and bistable equilibria can coexist for a wide range of parameters and can switch from one to another. This type of switching is sensitive to the intrinsic growth rate and the initial values of the locust population, and may result in locust population outbreaks and phase switching once a small perturbation occurs. Moreover, the simulation results indicate that the switching transient patterns become identical after some generations, suggesting that the evolving process of the perturbation system is not related to the initial value after some fixed number of

Phase Equilibria of Stored Chemical Energy Reactants.

DTIC Science & Technology

1984-07-25

aluminate-lithium ferrate system. Detection of a Li1 Al4/7Fe 3/704 compound: C. R. Acad. Sci., Ser. C, V. 273, No. 15, p. 888-90. McNicol, B. D. and Pott...thermodynamic properties of lithium ferrate (LiO.5Fe2 .504) and lithium aluminate (LiO 5Al 2 504) from 5 to 545 K: J. Chem. Thermodyn., V. 7, No. 7, p. 693- 2...1977, Study of low-temperature hydrothermal crystallization in lithium oxide-silicon dioxide-water, potassium oxide-silicon dioxide-water, and

Acid/base equilibria in clusters and their role in proton exchange membranes: Computational insight

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glezakou, Vanda A; Dupuis, Michel; Mundy, Christopher J

2007-10-24

We describe molecular orbital theory and ab initio molecular dynamics studies of acid/base equilibria of clusters AH:(H 2O) n↔A -:H +(H 2O) n in low hydration regime (n = 1-4), where AH is a model of perfluorinated sulfonic acids, RSO 3H (R = CF 3CF 2), encountered in polymeric electrolyte membranes of fuel cells. Free energy calculations on the neutral and ion pair structures for n = 3 indicate that the two configurations are close in energy and are accessible in the fluctuation dynamics of proton transport. For n = 1,2 the only relevant configuration is the neutral form. Thismore » was verified through ab initio metadynamics simulations. These findings suggest that bases are directly involved in the proton transport at low hydration levels. In addition, the gas phase proton affinity of the model sulfonic acid RSO 3H was found to be comparable to the proton affinity of water. Thus, protonated acids can also play a role in proton transport under low hydration conditions and under high concentration of protons. This work was supported by the Division of Chemical Science, Office of Basic Energy Sciences, US Department of Energy (DOE under Contract DE-AC05-76RL)1830. Computations were performed on computers of the Molecular Interactions and Transformations (MI&T) group and MSCF facility of EMSL, sponsored by US DOE and OBER located at PNNL. This work was benefited from resource of the National Energy Research Scientific Computing Centre, supported by the Office of Science of the US DOE, under Contract No. DE-AC03-76SF00098.« less

Nash points, Ky Fan inequality and equilibria of abstract economies in Max-Plus and -convexity

NASA Astrophysics Data System (ADS)

Briec, Walter; Horvath, Charles

2008-05-01

-convexity was introduced in [W. Briec, C. Horvath, -convexity, Optimization 53 (2004) 103-127]. Separation and Hahn-Banach like theorems can be found in [G. Adilov, A.M. Rubinov, -convex sets and functions, Numer. Funct. Anal. Optim. 27 (2006) 237-257] and [W. Briec, C.D. Horvath, A. Rubinov, Separation in -convexity, Pacific J. Optim. 1 (2005) 13-30]. We show here that all the basic results related to fixed point theorems are available in -convexity. Ky Fan inequality, existence of Nash equilibria and existence of equilibria for abstract economies are established in the framework of -convexity. Monotone analysis, or analysis on Maslov semimodules [V.N. Kolokoltsov, V.P. Maslov, Idempotent Analysis and Its Applications, Math. Appl., volE 401, Kluwer Academic, 1997; V.P. Litvinov, V.P. Maslov, G.B. Shpitz, Idempotent functional analysis: An algebraic approach, Math. Notes 69 (2001) 696-729; V.P. Maslov, S.N. Samborski (Eds.), Idempotent Analysis, Advances in Soviet Mathematics, Amer. Math. Soc., Providence, RI, 1992], is the natural framework for these results. From this point of view Max-Plus convexity and -convexity are isomorphic Maslov semimodules structures over isomorphic semirings. Therefore all the results of this paper hold in the context of Max-Plus convexity.

Theoretical Aspects of Differential Scanning Calorimetry as a Tool for the Studies of Equilibrium Thermodynamics in Pharmaceutical Solid Phase Transitions.

PubMed

Faroongsarng, Damrongsak

2016-06-01

Although differential scanning calorimetry (DSC) is a non-equilibrium technique, it has been used to gain energetic information that involves phase equilibria. DSC has been widely used to characterize the equilibrium melting parameters of small organic pharmaceutical compounds. An understanding of how DSC measures an equilibrium event could make for a better interpretation of the results. The aim of this mini-review was to provide a theoretical insight into the DSC measurement to obtain the equilibrium thermodynamics of a phase transition especially the melting process. It was demonstrated that the heat quantity obtained from the DSC thermogram (ΔH) was related to the thermodynamic enthalpy of the phase transition (ΔH (P) ) via: ΔH = ΔH (P) /(1 + K (- 1)) where K was the equilibrium constant. In melting, the solid and liquefied phases presumably coexist resulting in a null Gibbs free energy that produces an infinitely larger K. Thus, ΔH could be interpreted as ΔH (P). Issues of DSC investigations on melting behavior of crystalline solids including polymorphism, degradation impurity due to heating in situ, and eutectic melting were discussed. In addition, DSC has been a tool for determination of the impurity based on an ideal solution of the melt that is one of the official methods used to establish the reference standard.

Hidden attractors in dynamical models of phase-locked loop circuits: Limitations of simulation in MATLAB and SPICE

NASA Astrophysics Data System (ADS)

Kuznetsov, N. V.; Leonov, G. A.; Yuldashev, M. V.; Yuldashev, R. V.

2017-10-01

During recent years it has been shown that hidden oscillations, whose basin of attraction does not overlap with small neighborhoods of equilibria, may significantly complicate simulation of dynamical models, lead to unreliable results and wrong conclusions, and cause serious damage in drilling systems, aircrafts control systems, electromechanical systems, and other applications. This article provides a survey of various phase-locked loop based circuits (used in satellite navigation systems, optical, and digital communication), where such difficulties take place in MATLAB and SPICE. Considered examples can be used for testing other phase-locked loop based circuits and simulation tools, and motivate the development and application of rigorous analytical methods for the global analysis of phase-locked loop based circuits.

Theory and discretization of ideal magnetohydrodynamic equilibria with fractal pressure profiles

NASA Astrophysics Data System (ADS)

Kraus, B. F.; Hudson, S. R.

2017-09-01

In three-dimensional ideal magnetohydrodynamics, closed flux surfaces cannot maintain both rational rotational-transform and pressure gradients, as these features together produce unphysical, infinite currents. A proposed set of equilibria nullifies these currents by flattening the pressure on sufficiently wide intervals around each rational surface. Such rational surfaces exist at every scale, which characterizes the pressure profile as self-similar and thus fractal. The pressure profile is approximated numerically by considering a finite number of rational regions and analyzed mathematically by classifying the irrational numbers that support gradients into subsets. Applying these results to a given rotational-transform profile in cylindrical geometry, we find magnetic field and current density profiles compatible with the fractal pressure.

Data Science Innovations That Streamline Development, Documentation, Reproducibility, and Dissemination of Models in Computational Thermodynamics: An Application of Image Processing Techniques for Rapid Computation, Parameterization and Modeling of Phase Diagrams

NASA Astrophysics Data System (ADS)

Ghiorso, M. S.

2014-12-01

Computational thermodynamics (CT) represents a collection of numerical techniques that are used to calculate quantitative results from thermodynamic theory. In the Earth sciences, CT is most often applied to estimate the equilibrium properties of solutions, to calculate phase equilibria from models of the thermodynamic properties of materials, and to approximate irreversible reaction pathways by modeling these as a series of local equilibrium steps. The thermodynamic models that underlie CT calculations relate the energy of a phase to temperature, pressure and composition. These relationships are not intuitive and they are seldom well constrained by experimental data; often, intuition must be applied to generate a robust model that satisfies the expectations of use. As a consequence of this situation, the models and databases the support CT applications in geochemistry and petrology are tedious to maintain as new data and observations arise. What is required to make the process more streamlined and responsive is a computational framework that permits the rapid generation of observable outcomes from the underlying data/model collections, and importantly, the ability to update and re-parameterize the constitutive models through direct manipulation of those outcomes. CT procedures that take models/data to the experiential reference frame of phase equilibria involve function minimization, gradient evaluation, the calculation of implicit lines, curves and surfaces, contour extraction, and other related geometrical measures. All these procedures are the mainstay of image processing analysis. Since the commercial escalation of video game technology, open source image processing libraries have emerged (e.g., VTK) that permit real time manipulation and analysis of images. These tools find immediate application to CT calculations of phase equilibria by permitting rapid calculation and real time feedback between model outcome and the underlying model parameters.

In situ high temperature X-Ray diffraction study of the phase equilibria in the UO2-PuO2-Pu2O3 system

NASA Astrophysics Data System (ADS)

Belin, Renaud C.; Strach, Michal; Truphémus, Thibaut; Guéneau, Christine; Richaud, Jean-Christophe; Rogez, Jacques

2015-10-01

The region of the U-Pu-O phase diagram delimited by the compounds UO2-PuO2-Pu2O3 is known to exhibit a miscibility gap at low temperature. Consequently, MOX fuels with a composition entering this region could decompose into two fluorite phases and thus exhibit chemical heterogeneities. The experimental data on this domain found in the literature are scarce and usually provided using DTA that is not suitable for the investigation of such decomposition phenomena. In the present work, new experimental data, i.e. crystallographic phases, lattice parameters, phase fractions and temperature of phase separation, were measured in the composition range 0.14 < Pu/(U + Pu) < 0.62 and 1.85 < O/(U + Pu) < 2 from 298 to 1750 K using a novel in situ high temperature X-ray diffraction apparatus. A very good agreement is found between the temperature of phase separation determined from our results and using the thermodynamic model of the U-Pu-O system based on the CALPHAD method. Also, the combined use of thermodynamic calculations and XRD results refinement proved helpful in the determination of the O/M ratio of the samples during cooling. The methodology used in the current work might be useful to investigate other oxides systems exhibiting a miscibility gap.

Kinetic study of radiation-reaction-limited particle acceleration during the relaxation of unstable force-free equilibria

DOE PAGES

Yuan, Yajie; Nalewajko, Krzysztof; Zrake, Jonathan; ...

2016-09-07

Many powerful and variable gamma-ray sources, including pulsar wind nebulae, active galactic nuclei and gamma-ray bursts, seem capable of accelerating particles to gamma-ray emitting energies efficiently over very short timescales. These are likely due to the rapid dissipation of electromagnetic energy in a highly magnetized, relativistic plasma. In order to understand the generic features of such processes, we have investigated simple models based on the relaxation of unstable force-free magnetostatic equilibria. In this work, we make the connection between the corresponding plasma dynamics and the expected radiation signal, using 2D particle-in-cell simulations that self-consistently include synchrotron radiation reactions. We focusmore » on the lowest order unstable force-free equilibrium in a 2D periodic box. We find that rapid variability, with modest apparent radiation efficiency as perceived by a fixed observer, can be produced during the evolution of the instability. The "flares" are accompanied by an increased polarization degree in the high energy band, with rapid variation in the polarization angle. Furthermore, the separation between the acceleration sites and the synchrotron radiation sites for the highest energy particles facilitates acceleration beyond the synchrotron radiation reaction limit. We also discuss the dynamical consequences of the radiation reaction, and some astrophysical applications of this model. Our current simulations with numerically tractable parameters are not yet able to reproduce the most dramatic gamma-ray flares, e.g., from the Crab Nebula. As a result, higher magnetization studies are promising and will be carried out in the future.« less

KINETIC STUDY OF RADIATION-REACTION-LIMITED PARTICLE ACCELERATION DURING THE RELAXATION OF UNSTABLE FORCE-FREE EQUILIBRIA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Yajie; Nalewajko, Krzysztof; Zrake, Jonathan

2016-09-10

Many powerful and variable gamma-ray sources, including pulsar wind nebulae, active galactic nuclei and gamma-ray bursts, seem capable of accelerating particles to gamma-ray emitting energies efficiently over very short timescales. These are likely due to the rapid dissipation of electromagnetic energy in a highly magnetized, relativistic plasma. In order to understand the generic features of such processes, we have investigated simple models based on the relaxation of unstable force-free magnetostatic equilibria. In this work, we make the connection between the corresponding plasma dynamics and the expected radiation signal, using 2D particle-in-cell simulations that self-consistently include synchrotron radiation reactions. We focusmore » on the lowest order unstable force-free equilibrium in a 2D periodic box. We find that rapid variability, with modest apparent radiation efficiency as perceived by a fixed observer, can be produced during the evolution of the instability. The “flares” are accompanied by an increased polarization degree in the high energy band, with rapid variation in the polarization angle. Furthermore, the separation between the acceleration sites and the synchrotron radiation sites for the highest energy particles facilitates acceleration beyond the synchrotron radiation reaction limit. We also discuss the dynamical consequences of the radiation reaction, and some astrophysical applications of this model. Our current simulations with numerically tractable parameters are not yet able to reproduce the most dramatic gamma-ray flares, e.g., from the Crab Nebula. Higher magnetization studies are promising and will be carried out in the future.« less

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.

Liquidus Diagram of the Ba-Y-Cu-O System in the Vicinity of the Ba2YCu3O6+x Phase Field

PubMed Central

Wong-Ng, Winnie; Cook, Lawrence P.

1998-01-01

This paper describes the melting equilibria in the vicinity of the high Tc phase Ba2YCu3O6+x, including evidence for two Ba-Y-Cu-O immiscible liquids. Melting equilibria have been investigated in purified air using a combination of differential thermal analysis (DTA), thermogravimetric analysis (TGA), powder x-ray diffraction (XRD), MgO wick entrapment of liquid for analysis, scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDS), and hydrogen reduction for determination of copper oxidation state. For relatively barium-rich compositions, it was necessary to prepare the starting materials under controlled atmosphere conditions using BaO. A liquidus diagram was derived from quantitative data for the melts involved in various melting reactions. In general the 1/2(Y2O3) contents of the melts participating in these equilibria were low (mole fraction <4 %). The primary phase field of Ba2YCu3O6+x occurs at a mole fraction of <2.0 % 1/2Y2O3 and lies very close along the BaO-CuOx edge, extending from a mole fraction of ≈43 % CuO to a mole fraction of ≈76 % CuO. It is divided by a liquid miscibility gap and extends on either side about this gap. The topological sequence of melting reactions associated with the liquidus is presented as a function of temperature. Implications for the growth of Ba2YCu3O6+x crystals are discussed. PMID:28009382

Crystal Chemistry of Three-component White Dwarfs and Neutron Star Crusts: Phase Stability, Phase Stratification, and Physical Properties

NASA Astrophysics Data System (ADS)

Engstrom, T. A.; Yoder, N. C.; Crespi, V. H.

2016-02-01

A systematic search for multicomponent crystal structures is carried out for five different ternary systems of nuclei in a polarizable background of electrons, representative of accreted neutron star crusts and some white dwarfs. Candidate structures are “bred” by a genetic algorithm and optimized at constant pressure under the assumption of linear response (Thomas-Fermi) charge screening. Subsequent phase equilibria calculations reveal eight distinct crystal structures in the T = 0 bulk phase diagrams, five of which are complicated multinary structures not previously predicted in the context of compact object astrophysics. Frequent instances of geometrically similar but compositionally distinct phases give insight into structural preferences of systems with pairwise Yukawa interactions, including and extending to the regime of low-density colloidal suspensions made in a laboratory. As an application of these main results, we self-consistently couple the phase stability problem to the equations for a self-gravitating, hydrostatically stable white dwarf, with fixed overall composition. To our knowledge, this is the first attempt to incorporate complex multinary phases into the equilibrium phase-layering diagram and mass-radius-composition dependence, both of which are reported for He-C-O and C-O-Ne white dwarfs. Finite thickness interfacial phases (“interphases”) show up at the boundaries between single-component body-centered cubic (bcc) crystalline regions, some of which have lower lattice symmetry than cubic. A second application—quasi-static settling of heavy nuclei in white dwarfs—builds on our equilibrium phase-layering method. Tests of this nonequilibrium method reveal extra phases that play the role of transient host phases for the settling species.

PIES free boundary stellarator equilibria with improved initial conditions

NASA Astrophysics Data System (ADS)

Drevlak, M.; Monticello, D.; Reiman, A.

2005-07-01

The MFBE procedure developed by Strumberger (1997 Nucl. Fusion 37 19) is used to provide an improved starting point for free boundary equilibrium computations in the case of W7-X (Nührenberg and Zille 1986 Phys. Lett. A 114 129) using the Princeton iterative equilibrium solver (PIES) code (Reiman and Greenside 1986 Comput. Phys. Commun. 43 157). Transferring the consistent field found by the variational moments equilibrium code (VMEC) (Hirshmann and Whitson 1983 Phys. Fluids 26 3553) to an extended coordinate system using the VMORPH code, a safe margin between plasma boundary and PIES domain is established. The new EXTENDER_P code implements a generalization of the virtual casing principle, which allows field extension both for VMEC and PIES equilibria. This facilitates analysis of the 5/5 islands of the W7-X standard case without including them in the original PIES computation.

Phase relations in the system NaCl-KCl-H2O. III: Solubilities of halite in vapor-saturated liquids above 445°C and redetermination of phase equilibrium properties in the system NaCl-H2O to 1000°C and 1500 bars

USGS Publications Warehouse

Chou, I.-Ming

1987-01-01

Through use of these new halite solubility data and the data from synthetic fluid inclusions [formed by healing fractures in inclusion-free Brazilian quartz in the presence of two coexisting, immiscible NaCl-H2O fluids at various temperatures and pressures (Bodnar et al., 1985)], phase equilibria in the system NaCl-H2O have been redetermined to 1000°C and 1500 bars.

The Co-Sb-Ga System: Isoplethal Section and Thermodynamic Modeling

NASA Astrophysics Data System (ADS)

Gierlotka, Wojciech; Chen, Sinn-wen; Chen, Wei-an; Chang, Jui-shen; Snyder, G. Jeffrey; Tang, Yinglu

2015-04-01

The Co-Sb-Ga ternary system is an important thermoelectric material system, and its phase equilibria are in need of further understanding. The CoSb3-GaSb isoplethal section is experimentally determined in this study. Phase equilibria of the ternary Co-Sb-Ga system are assessed, and the system's thermodynamic models are developed. In addition to the terminal phases and liquid phase, there are six binary intermediate phases and a ternary Co3Sb2Ga4 phase. The Ga solution in the CoSb3 compound is described by a dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model. Phase diagrams are calculated using the developed thermodynamic models, and a reaction scheme is proposed based on the calculation results. The calculated results are in good agreement with the experimentally determined phase diagrams, including the CoSb3-GaSb isoplethal section, the liquidus projection, and an isothermal section at 923 K (650 °C). The dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model gives good descriptions of both phase equilibria and thermoelectric properties of the CoSb3 phase with Ga doping.

Thermodynamic foundations of applications of ab initio methods for determination of the adsorbate equilibria: hydrogen at the GaN(0001) surface.

PubMed

Kempisty, Pawel; Strąk, Paweł; Sakowski, Konrad; Kangawa, Yoshihiro; Krukowski, Stanisław

2017-11-08

Thermodynamic foundations of ab initio modeling of vapor-solid and vapor-surface equilibria are introduced. The chemical potential change is divided into enthalpy and entropy terms. The enthalpy path passes through vapor-solid transition at zero temperature. The entropy path avoids the singular point at zero temperature passing a solid-vapor transition under normal conditions, where evaporation entropy is employed. In addition, the thermal changes are calculated. The chemical potential difference contribution of the following terms: vaporization enthalpy, vaporization entropy, the temperature-entropy related change, the thermal enthalpy change and mechanical pressure is obtained. The latter term is negligibly small for the pressure typical for epitaxy. The thermal enthalpy change is two orders smaller than the first three terms which have to be taken into account explicitly. The configurational vaporization entropy change is derived for adsorption processes. The same formulation is derived for vapor-surface equilibria using hydrogen at the GaN(0001) surface as an example. The critical factor is the dependence of the enthalpy of evaporation (desorption energy) on the pinning of the Fermi level bringing a drastic change of the value from 2.24 eV to -2.38 eV. In addition it is shown that entropic contributions considerable change the hydrogen equilibrium pressure over the GaN(0001) surface by several orders of magnitude. Thus a complete and exact formulation of vapor-solid and vapor-surface equilibria is presented.

Phase equilibria in the UO 2-PuO 2 system under a temperature gradient

NASA Astrophysics Data System (ADS)

Kleykamp, Heiko

2001-04-01

The phase behaviour of U 0.80Pu 0.20O 1.95 was investigated under a steady-state temperature gradient between the solidus and liquidus by a short-time power-to-melt irradiation experiment. The radial U, Pu, Am and O profiles in the fuel pin after redistribution were measured by X-ray microanalysis. During irradiation, an inner fuel melt forms which is separated from the outer solid only by one concentric liquid-solid-phase boundary. The UO 2 concentration increases to 85% and the PuO 2 concentration decreases to 15% on the solid side of the interface. Opposite gradients occur on the liquid side of the interface. The concentration discontinuity is a consequence of the necessary equality of the chemical potentials of UO 2 and PuO 2 on both sides of the phase boundary which corresponds to a 2750°C isotherm. The radial oxygen profile results in an O/(U + Pu) ratio of 2.00 at the fuel surface and 1.92 at the central void of the fuel. The redistribution is caused by the thermal diffusion of oxygen vacancies in the lattice along the temperature gradient. This process is quantified by the heat of transport Q*v which ranges between -10 kJ/mol at the central void and about -230 kJ/mol near the fuel surface.

The Existence and Stability Analysis of the Equilibria in Dengue Disease Infection Model

NASA Astrophysics Data System (ADS)

Anggriani, N.; Supriatna, A. K.; Soewono, E.

2015-06-01

In this paper we formulate an SIR (Susceptible - Infective - Recovered) model of Dengue fever transmission with constant recruitment. We found a threshold parameter K0, known as the Basic Reproduction Number (BRN). This model has two equilibria, disease-free equilibrium and endemic equilibrium. By constructing suitable Lyapunov function, we show that the disease- free equilibrium is globally asymptotic stable whenever BRN is less than one and when it is greater than one, the endemic equilibrium is globally asymptotic stable. Numerical result shows the dynamic of each compartment together with effect of multiple bio-agent intervention as a control to the dengue transmission.

Theory and discretization of ideal magnetohydrodynamic equilibria with fractal pressure profiles

DOE PAGES

Kraus, B. F.; Hudson, S. R.

2017-09-29

In three-dimensional ideal magnetohydrodynamics, closed flux surfaces cannot maintain both rational rotational-transform and pressure gradients, as these features together produce unphysical, infinite currents. A proposed set of equilibria nullifies these currents by flattening the pressure on sufficiently wide intervals around each rational surface. Such rational surfaces exist at every scale, which characterizes the pressure profile as self-similar and thus fractal. The pressure profile is approximated numerically by considering a finite number of rational regions and analyzed mathematically by classifying the irrational numbers that support gradients into subsets. As a result, applying these results to a given rotational-transform profile in cylindricalmore » geometry, we find magnetic field and current density profiles compatible with the fractal pressure.« less

Theory and discretization of ideal magnetohydrodynamic equilibria with fractal pressure profiles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kraus, B. F.; Hudson, S. R.

In three-dimensional ideal magnetohydrodynamics, closed flux surfaces cannot maintain both rational rotational-transform and pressure gradients, as these features together produce unphysical, infinite currents. A proposed set of equilibria nullifies these currents by flattening the pressure on sufficiently wide intervals around each rational surface. Such rational surfaces exist at every scale, which characterizes the pressure profile as self-similar and thus fractal. The pressure profile is approximated numerically by considering a finite number of rational regions and analyzed mathematically by classifying the irrational numbers that support gradients into subsets. As a result, applying these results to a given rotational-transform profile in cylindricalmore » geometry, we find magnetic field and current density profiles compatible with the fractal pressure.« less

Surprising Impact of Remote Groups on the Folding-Unfolding and Dimer-Chain Equilibria of Bifunctionl H-Bonding Unimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Rui; Cheng, Shuang; Baker, Erin Shammel

2016-01-28

Oligoamide 1, consisting of two H-bonding units linked by a trimethylene linker, was previously found to form a very stable, folded dimer. In this work, replacing the side chains and end groups of 1 led to derivatives that show the surprising impact of end groups on the folding and dimer-chain equilibria of the resultant molecules.

Schaeffler-Type Phase Diagram of Ti-Based Alloys

NASA Astrophysics Data System (ADS)

Ishida, K.

2017-10-01

The α(hcp)/β(bcc) phase equilibria of Ti-based multi-component alloys can be described by a Schaeffler-type diagram, where Al and Mo equivalents (Aleq and Moeq) are used. Aleq is thermodynamically defined by the ratio of partial molar free energy changes transfer of one mole of each α forming element and Al from a dilute solution of α to β phases, while Moeq is also deduced by similar thermodynamic quantities of β forming element and Mo. Aleq and Moeq for 40 alloying elements are estimated from the thermodynamic parameters assessed by Kaufman and Murray. It is shown that three types of Ti alloys, i.e., α and near α, α+β, and β alloys, can be exactly classified using Aleq and Moeq. The Ms and β transus temperatures can also be predicted by Aleq and Moeq. The proposed Aleq and Moeq are very useful for alloy design, heat treatment, and microstructural evolution of Ti-based alloys.

CRYSTAL CHEMISTRY OF THREE-COMPONENT WHITE DWARFS AND NEUTRON STAR CRUSTS: PHASE STABILITY, PHASE STRATIFICATION, AND PHYSICAL PROPERTIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engstrom, T. A.; Yoder, N. C.; Crespi, V. H., E-mail: tae146@psu.edu, E-mail: ncy5007@psu.edu, E-mail: vhc2@psu.edu

A systematic search for multicomponent crystal structures is carried out for five different ternary systems of nuclei in a polarizable background of electrons, representative of accreted neutron star crusts and some white dwarfs. Candidate structures are “bred” by a genetic algorithm and optimized at constant pressure under the assumption of linear response (Thomas–Fermi) charge screening. Subsequent phase equilibria calculations reveal eight distinct crystal structures in the T = 0 bulk phase diagrams, five of which are complicated multinary structures not previously predicted in the context of compact object astrophysics. Frequent instances of geometrically similar but compositionally distinct phases give insight into structural preferencesmore » of systems with pairwise Yukawa interactions, including and extending to the regime of low-density colloidal suspensions made in a laboratory. As an application of these main results, we self-consistently couple the phase stability problem to the equations for a self-gravitating, hydrostatically stable white dwarf, with fixed overall composition. To our knowledge, this is the first attempt to incorporate complex multinary phases into the equilibrium phase-layering diagram and mass–radius-composition dependence, both of which are reported for He–C–O and C–O–Ne white dwarfs. Finite thickness interfacial phases (“interphases”) show up at the boundaries between single-component body-centered cubic (bcc) crystalline regions, some of which have lower lattice symmetry than cubic. A second application—quasi-static settling of heavy nuclei in white dwarfs—builds on our equilibrium phase-layering method. Tests of this nonequilibrium method reveal extra phases that play the role of transient host phases for the settling species.« less

Multiple Equilibria Associated with Response of the ITCZ to Seasonal SST Forcing

NASA Technical Reports Server (NTRS)

Chao, Winston C.

1998-01-01

Supported by numerical experiment results, the abrupt change of the location of the intertropical convergence zone (ITCZ), from the equatorial trough flow regime to the monsoon trough flow regime is interpreted as a subcritical instability. The existence of these multiple quasi-equilibria is due to the balance of two "forces" on the ITCZ: one toward the equator, due to the earth's rotation, has a nonlinear latitudinal dependence; and the other toward the latitude of the sea surface (or ground) temperature peak has a relatively linear latitudinal dependence. This work pivots on the finding that the ITCZ and Hadley circulation can still exist without the pole-to-equator gradient of radiative-convective equilibrium temperature.

Advanced methods for preparation and characterization of infrared detector materials. [crystallization and phase diagrams of Hg sub 1-x Cd sub x Te

NASA Technical Reports Server (NTRS)

Lehoczy, S. L.

1979-01-01

Crystal growth of Hg sub 1-x Cd sub x Te and density measurements of ingot slices are discussed. Radial compositional variations are evaluated from the results of infrared transmission edge mapping. The pseudo-binary HgTe-CdTe phase diagram is examined with reference to differential thermal analysis measurements. The phase equilibria calculations, based on the 'regular association solution' theory (R.A.S.) are explained and, using the obtained R.A.S. parameters, the activities of Hg, Cd, and Te vapors and their partial pressures over the pseudo-binary melt are calculated.

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.

The Mathematics of Aggregation, Interdependence, Organizations and Systems of Nash Equilibria (NE): A Replacement for Game Theory

DTIC Science & Technology

2011-06-01

there a free-market economist in the House?, American Journal of Economics and Sociology, 66(2): 309-334. Jasny, B. R., Zahn, L.M., & Marshall, E...1   The Mathematics of Aggregation, Interdependence, Organizations and Systems of Nash equilibria (NE): A replacement for Game Theory...level data to group, organization and systems levels, making it one of social science’s biggest challenges, if not the most important (Giles, 2011). For

Extremal equilibria for reaction-diffusion equations in bounded domains and applications

NASA Astrophysics Data System (ADS)

Rodríguez-Bernal, Aníbal; Vidal-López, Alejandro

We show the existence of two special equilibria, the extremal ones, for a wide class of reaction-diffusion equations in bounded domains with several boundary conditions, including non-linear ones. They give bounds for the asymptotic dynamics and so for the attractor. Some results on the existence and/or uniqueness of positive solutions are also obtained. As a consequence, several well-known results on the existence and/or uniqueness of solutions for elliptic equations are revisited in a unified way obtaining, in addition, information on the dynamics of the associated parabolic problem. Finally, we ilustrate the use of the general results by applying them to the case of logistic equations. In fact, we obtain a detailed picture of the positive dynamics depending on the parameters appearing in the equation.

Thermodynamic characteristics of the acid-base equilibria of ethylenediamine- N, N'-diglutaric acid in aqueous solutions using calorimetric data

NASA Astrophysics Data System (ADS)

Gridchin, S. N.; Nikol'skii, V. M.

2017-10-01

The enthalpies of reaction of betaine group neutralization of ethylenediamine- N, N'-diglutaric acid (H4L) at 298.15 K and at different values of ionic strength of 0.1, 0.5, 1.0 (KNO3) is measured by direct calorimetry. The standard thermodynamic characteristics of the protolytic equilibria of H4L are calculated.

Experimental Investigation and Thermodynamic Assessment of Phase Equilibria in the PLLA/Dioxane/Water Ternary System for Applications in the Biomedical Field.

PubMed

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

Phase equilibria and crystal structure of the complex oxides in the Sr Fe Co O system

NASA Astrophysics Data System (ADS)

Aksenova, T. V.; Gavrilova, L. Ya.; Cherepanov, V. A.

2008-06-01

Phase relations in the Sr-Fe-Co-O system have been investigated at 1100 °C in air by X-ray powder diffraction on quenched samples. Solid solutions of the form SrFe 1-xCo xO 3-δ (0⩽ x⩽0.7), Sr 3Fe 2-yCo yO 7-δ (0⩽ y⩽0.4) and Sr 4Fe 6-zCo zO 13±δ (0⩽ z⩽1.6) were prepared by solid-state reaction and by the sol-gel method. The structural parameters of single-phase samples were refined by the Rietveld profile method. The variation of the lattice parameters with composition has been determined for each solid solution and a cross-section of the phase diagram at 1100 °C in air for the entire Sr-Fe-Co-O system has been constructed.

Phase diagram of the Y–Y{sub 2}Se{sub 3} system, enthalpies of phase transformations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andreev, O.V.; Kharitontsev, V.B.; Polkovnikov, A.A., E-mail: a.a.polkovnikov@yandex.ru

A phase diagram for the Y–Y{sub 2}Se{sub 3} system has been constructed in which the YSe and Y{sub 2}Se{sub 3} phases melt congruently. The daltonide type YSe phase (ST Y{sub 0,75}Se, a=1.1393 nm, melting point=2380 K, H=2200 MPa) forms a double-sided solid solution from 49–50–53 at% Se. In the 50–53 at% Se range, the unit cell parameter increases to 1.1500 nm, the microhardness increases to 4100 MPa and electrical resistivity increases from 0.018 to 0.114 Ω m. These changes are caused by the dominating influx of newly formed structural cationic vacancies arising from the selenium anions that are surplus formore » the 1:1 Y:Se stoichiometry. The full-valence Y{sub 2}Se{sub 3} composition exists as a low-temperature modification of ε-Y{sub 2}Se{sub 3} (ST Sc{sub 2}S{sub 3}, a=1.145 nm, b=0.818 nm, c=2.438 nm, melting point=1780 K, ∆fusion enthalpy=4±0.4 J/g) and transforms into a modification of ξ-Y{sub 2}Se{sub 3} that does not undergo fixing by thermo-hardening. The eutectic melting point between the YSe and Y{sub 2}Se{sub 3} phases is 1625±5 K, with a eutectic composition that is assumed to be 57.5 at% Se and have an enthalpy of fusion of 43±4.3 J/g. The eutectic for the Y and YSe phases appears at a temperature of 1600 K and 5 at% Se. - Highlights: • Phase equilibria in the Y–Y{sub 2}Se{sub 3} system from 1000 K to melt were studies. • High-temperature polymorphic transition for Y{sub 2}Se{sub 3} were observed. • Singular points in solid solutions areas for YSe and Y{sub 2}Se{sub 3} were found.« less

Thermal analysis, phase equilibria, and superconducting properties in magnesium boride and carbon doped magnesium boride

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

On signals of phase transitions in salmon population dynamics

PubMed Central

Krkošek, Martin; Drake, John M.

2014-01-01

Critical slowing down (CSD) reflects the decline in resilience of equilibria near a bifurcation and may reveal early warning signals (EWS) of ecological phase transitions. We studied CSD in the recruitment dynamics of 120 stocks of three Pacific salmon (Oncorhynchus spp.) species in relation to critical transitions in fishery models. Pink salmon (Oncorhynchus gorbuscha) exhibited increased variability and autocorrelation in populations that had a growth parameter, r, close to zero, consistent with EWS of extinction. However, models and data for sockeye salmon (Oncorhynchus nerka) indicate that portfolio effects from heterogeneity in age-at-maturity may obscure EWS. Chum salmon (Oncorhynchus keta) show intermediate results. The data do not reveal EWS of Ricker-type bifurcations that cause oscillations and chaos at high r. These results not only provide empirical support for CSD in some ecological systems, but also indicate that portfolio effects of age structure may conceal EWS of some critical transitions. PMID:24759855

Optimized Unlike-Pair Interactions for Water-Carbon Dioxide Mixtures described by the SPC/E and EPM2 Models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlcek, Lukas; Chialvo, Ariel A; Cole, David

The unlike- pair interaction parameters for the SPC/E- EPM2 models have been optimized to reproduce the mutual solubility of water and carbon dioxide at the conditions of liquid- supercritical fluid phase equilibria. An efficient global optimization of the parameters is achieved through an implementation of the coupling parameter approach, adapted to phase equilibria calculations in the Gibbs ensemble, that explicitly corrects for the over- polarization of the SPC/E water molecule in the non- polar CO2 environments. The resulting H2O- CO2 force field reproduces accurately the available experimental solubilities at the two fluid phases in equilibria as well as the correspondingmore » species tracer diffusion coefficients.« less

High-beta analytic equilibria in circular, elliptical, and D-shaped large aspect ratio axisymmetric configurations with poloidal and toroidal flows

NASA Astrophysics Data System (ADS)

López, O. E.; Guazzotto, L.

2017-03-01

The Grad-Shafranov-Bernoulli system of equations is a single fluid magnetohydrodynamical description of axisymmetric equilibria with mass flows. Using a variational perturbative approach [E. Hameiri, Phys. Plasmas 20, 024504 (2013)], analytic approximations for high-beta equilibria in circular, elliptical, and D-shaped cross sections in the high aspect ratio approximation are found, which include finite toroidal and poloidal flows. Assuming a polynomial dependence of the free functions on the poloidal flux, the equilibrium problem is reduced to an inhomogeneous Helmholtz partial differential equation (PDE) subject to homogeneous Dirichlet conditions. An application of the Green's function method leads to a closed form for the circular solution and to a series solution in terms of Mathieu functions for the elliptical case, which is valid for arbitrary elongations. To extend the elliptical solution to a D-shaped domain, a boundary perturbation in terms of the triangularity is used. A comparison with the code FLOW [L. Guazzotto et al., Phys. Plasmas 11(2), 604-614 (2004)] is presented for relevant scenarios.

End-State Relative Equilibria in the Sphere-Restricted Full Three-Body Problem

NASA Astrophysics Data System (ADS)

Gabriel, Travis; Scheeres, Daniel J.

2015-05-01

The Sphere-Restricted Full Three-Body Problem studies the motion of three finite density spheres as they interact under surface and gravitational forces. When accounting for the dissipation of energy, full-body systems may achieve minimum energy states that are unatainable in the classic treatment of the N-Body Problem. This serves as a simple model for the mechanics of rubble pile asteroids, interacting grains in a protoplanetary disk, and potentially the interactions of planetary ring particles. Previous studies of this problem have been performed in the case where the three spheres are of equal size and mass, with all possible relative equilibria and their stability having been identified as a function of the total angular momentum of the system. These studies uncovered that at certain levels of angular momentum there exists more than one stable relative equilibrium state. Thus a question of interest is which of these states a dissipative system would preferentially settle in provided some domain of initial conditions, and whether this would be a function of the dissipation parameters. Using perfectly-rigid dynamics, three-equal-sphere systems are simulated in a purpose-written C-based code to uncover these details. Results from this study are relevant to the mechanics and dynamics in small solar system bodies where relative forces are not great enough to compromise the rigidity of the constituents.

High-temperature experimental and thermodynamic modelling research on the pyrometallurgical processing of copper

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Shishin, Denis; Decterov, Sergei A.; Hayes, Peter C.; Jak, Evgueni

2017-01-01

Uncertainty in the metal price and competition between producers mean that the daily operation of a smelter needs to target high recovery of valuable elements at low operating cost. Options for the improvement of the plant operation can be examined and decision making can be informed based on accurate information from laboratory experimentation coupled with predictions using advanced thermodynamic models. Integrated high-temperature experimental and thermodynamic modelling research on phase equilibria and thermodynamics of copper-containing systems have been undertaken at the Pyrometallurgy Innovation Centre (PYROSEARCH). The experimental phase equilibria studies involve high-temperature equilibration, rapid quenching and direct measurement of phase compositions using electron probe X-ray microanalysis (EPMA). The thermodynamic modelling deals with the development of accurate thermodynamic database built through critical evaluation of experimental data, selection of solution models, and optimization of models parameters. The database covers the Al-Ca-Cu-Fe-Mg-O-S-Si chemical system. The gas, slag, matte, liquid and solid metal phases, spinel solid solution as well as numerous solid oxide and sulphide phases are included. The database works within the FactSage software environment. Examples of phase equilibria data and thermodynamic models of selected systems, as well as possible implementation of the research outcomes to selected copper making processes are presented.

A generalized procedure for the prediction of multicomponent adsorption equilibria

DOE PAGES

Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas

2015-04-07

Prediction of multicomponent adsorption equilibria has been investigated for several decades. While there are theories available to predict the adsorption behavior of ideal mixtures, there are few purely predictive theories to account for nonidealities in real systems. Most models available for dealing with nonidealities contain interaction parameters that must be obtained through correlation with binary-mixture data. However, as the number of components in a system grows, the number of parameters needed to be obtained increases exponentially. Here, a generalized procedure is proposed, as an extension of the predictive real adsorbed solution theory, for determining the parameters of any activity model,more » for any number of components, without correlation. This procedure is then combined with the adsorbed solution theory to predict the adsorption behavior of mixtures. As this method can be applied to any isotherm model and any activity model, it is referred to as the generalized predictive adsorbed solution theory.« less

Group Contribution Methods for Phase Equilibrium Calculations.

PubMed

Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

2015-01-01

The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

Sulfamerazine: Understanding the Influence of Slip Planes in the Polymorphic Phase Transformation through X-Ray Crystallographic Studies and ab Initio Lattice Dynamics.

PubMed

Pallipurath, Anuradha R; Skelton, Jonathan M; Warren, Mark R; Kamali, Naghmeh; McArdle, Patrick; Erxleben, Andrea

2015-10-05

Understanding the polymorphism exhibited by organic active-pharmaceutical ingredients (APIs), in particular the relationships between crystal structure and the thermodynamics of polymorph stability, is vital for the production of more stable drugs and better therapeutics, and for the economics of the pharmaceutical industry in general. In this article, we report a detailed study of the structure-property relationships among the polymorphs of the model API, Sulfamerazine. Detailed experimental characterization using synchrotron radiation is complemented by computational modeling of the lattice dynamics and mechanical properties, in order to study the origin of differences in millability and to investigate the thermodynamics of the phase equilibria. Good agreement is observed between the simulated phonon spectra and mid-infrared and Raman spectra. The presence of slip planes, which are found to give rise to low-frequency lattice vibrations, explains the higher millability of Form I compared to Form II. Energy/volume curves for the three polymorphs, together with the temperature dependence of the thermodynamic free energy computed from the phonon frequencies, explains why Form II converts to Form I at high temperature, whereas Form III is a rare polymorph that is difficult to isolate. The combined experimental and theoretical approach employed here should be generally applicable to the study of other systems that exhibit polymorphism.

Modeling of multiple equilibria in the self-aggregation of di-n-decyldimethylammonium chloride/octaethylene glycol monododecyl ether/cyclodextrin ternary systems.

PubMed

Leclercq, Loïc; Lubart, Quentin; Aubry, Jean-Marie; Nardello-Rataj, Véronique

2013-05-28

The surface tension equations of binary surfactant mixtures (di-n-decyldimethylammonium chloride and octaethylene glycol monododecyl ether) are established by combining the Szyszkowski equation of surfactant solutions, the ideal or nonideal mixing theory, and the phase separation model. For surfactant mixtures, the surface tension at the air-water interface is calculated using nonideal theory due to synergism between the two adsorbed surfactant types. The incorporation of cyclodextrin complexation model to the surface tension equations gives a robust model for the description of the surface tension isotherms of binary, ternary, and more complex systems involving numerous inclusion complexes. The surface tension data obtained experimentally shows excellent agreement with the theoretical model below and above the formation of micelles. The strong synergistic effect observed between the two surfactants is disrupted by the presence of CDs, leading to ideal behavior of ternary systems. Indeed, depending on the nature of the cyclodextrin (i.e., α, β, or γ), which allows a tuning of the cavity size, the binding constants with the surfactants are modified as well as the surface properties due to strong modification of equilibria involved in the ternary mixture.

The eigenfrequency spectrum of linear magnetohydrodynamic perturbations in stationary equilibria: A variational principle

NASA Astrophysics Data System (ADS)

Andries, Jesse

2010-11-01

The frequencies of the normal modes of oscillation of linear magnetohydrodynamic perturbations of a stationary equilibrium are related to the stationary points of a quadratic functional over the Hilbert space of Lagrangian displacement vectors, which is subject to a constraint. In the absence of a background flow (or of a uniform flow), the relation reduces to the well-known Rayleigh-Ritz variational principle. In contrast to the existing variational principles for perturbations of stationary equilibria, the present treatment does neither impose additional symmetry restrictions on the equilibrium, nor does it involve the generalization to bilinear functionals instead of quadratic forms. This allows a more natural interpretation of the quadratic forms as energy functionals.

Application of solid-phase microextraction in the investigation of protein binding of pharmaceuticals.

PubMed

Theodoridis, Georgios

2006-01-18

Protein-drug interactions of seven common pharmaceuticals were studied using solid-phase microextraction (SPME). SPME can be used in such investigations on the condition that no analyte depletion occurs. In multi-compartment systems (e.g. a proteinaceous matrix) only the free portion of the analyte is able to partition into the SPME fiber. In addition if no sample depletion occurs, the bound drug-free drug equilibria are not disturbed. In the present study seven pharmaceuticals (quinine, quinidine, naproxen, ciprofloxacin, haloperidol, paclitaxel and nortriptyline) were assayed by SPME. For quantitative purposes SPME was validated first in the absence of proteins. Calibration curves were constructed for each drug by HPLC-fluorescence and HPLC-UV analysis. SPME was combined to HPLC off-line, desorption occurring in HPLC inserts filled with 200 microL methanol. Binding of each drug to human serum albumin was studied independently. Experimental results were in agreement with literature data and ultrafiltration experiments, indicating the feasibility of the method for such bioanalytical purposes.

Experimental investigation of the phase equilibria and thermodynamic assessment in the U-Ga and U-Al-Ga systems

NASA Astrophysics Data System (ADS)

Moussa, Chantal; Berche, Alexandre; Barbosa, José; Pasturel, Mathieu; Stepnik, Bertrand; Tougait, Olivier

2018-02-01

The phase relations in the binary U-Ga and ternary U-Al-Ga systems were established as an isopleth section and two isothermal sections at 900 K and 1150 K for the whole concentration range, respectively. They were experimentally determined by means of powder and single crystal XRD, SEM-EDS analyses on both as-cast and heat-treated samples and DTA measurements. Both systems were thermodynamically assessed using the Calphad method based on the available data, i.e. phase relations and thermodynamic properties. The new description of the U-Ga phase diagram improves the composition-temperature description for most of invariant reactions. The U-Al-Ga system is characterized by large ternary extensions of the binary phases and the absence of ternary intermediate phase at both 900 K and 1150 K. These experimental results are nicely reproduced by the Calphad assessment, allowing to extract the thermodynamic parameters further used to calculate the liquidus projection and the invariant reactions along with their temperature.

A liquidus phase diagram for the groundmass of EETA 79001A (Eg), a primitive Shergottite composition

NASA Technical Reports Server (NTRS)

Jones, J. H.; Jurewicz, A. J. G.; Le, L.

1992-01-01

Shergottites are members of the SNC meteorite suite, which may be samples of Mars. If so, the shergottite in our collection that most likely represents primitive liquid from the Martian mantle is EETA 79001. EETA 79001 has the Nd isotopic signature of a long-term depleted mantle, a relatively high Mg number, and a slightly olivine-normative composition. The authors have performed experiments on the composition of EETA 79001 for traces of Eg. Other topics discussed include: comparison of calculated phase equilibria; nature of the olivine-pyroxene boundary; and interstitial liquids.

Hyper-resistivity and electron thermal conductivity due to destroyed magnetic surfaces in axisymmetric plasma equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weening, R. H.

2012-06-15

In order to model the effects of small-scale current-driven magnetic fluctuations in a mean-field theoretical description of a large-scale plasma magnetic field B(x,t), a space and time dependent hyper-resistivity {Lambda}(x,t) can be incorporated into the Ohm's law for the parallel electric field E Dot-Operator B. Using Boozer coordinates, a theoretical method is presented that allows for a determination of the hyper-resistivity {Lambda}({psi}) functional dependence on the toroidal magnetic flux {psi} for arbitrary experimental steady-state Grad-Shafranov axisymmetric plasma equilibria, if values are given for the parallel plasma resistivity {eta}({psi}) and the local distribution of any auxiliary plasma current. Heat transport inmore » regions of plasma magnetic surfaces destroyed by resistive tearing modes can then be modeled by an electron thermal conductivity k{sub e}({psi})=({epsilon}{sub 0}{sup 2}m{sub e}/e{sup 2}){Lambda}({psi}), where e and m{sub e} are the electron charge and mass, respectively, while {epsilon}{sub 0} is the permittivity of free space. An important result obtained for axisymmetric plasma equilibria is that the {psi}{psi}-component of the metric tensor of Boozer coordinates is given by the relation g{sup {psi}{psi}}({psi}){identical_to}{nabla}{psi} Dot-Operator {nabla}{psi}=[{mu}{sub 0}G({psi})][{mu}{sub 0}I({psi})]/{iota}({psi}), with {mu}{sub 0} the permeability of free space, G({psi}) the poloidal current outside a magnetic surface, I({psi}) the toroidal current inside a magnetic surface, and {iota}({psi}) the rotational transform.« less

Isotropic–Nematic Phase Transitions in Gravitational Systems. II. Higher Order Multipoles

NASA Astrophysics Data System (ADS)

Takács, Ádám; Kocsis, Bence

2018-04-01

The gravitational interaction among bodies orbiting in a spherical potential leads to the rapid relaxation of the orbital planes’ distribution, a process called vector resonant relaxation. We examine the statistical equilibrium of this process for a system of bodies with similar semimajor axes and eccentricities. We extend the previous model of Roupas et al. by accounting for the multipole moments beyond the quadrupole, which dominate the interaction for radially overlapping orbits. Nevertheless, we find no qualitative differences between the behavior of the system with respect to the model restricted to the quadrupole interaction. The equilibrium distribution resembles a counterrotating disk at low temperature and a spherical structure at high temperature. The system exhibits a first-order phase transition between the disk and the spherical phase in the canonical ensemble if the total angular momentum is below a critical value. We find that the phase transition erases the high-order multipoles, i.e., small-scale structure in angular momentum space, most efficiently. The system admits a maximum entropy and a maximum energy, which lead to the existence of negative temperature equilibria.

Gibbs Energy Modeling of Digenite and Adjacent Solid-State Phases

NASA Astrophysics Data System (ADS)

Waldner, Peter

2017-08-01

All sulfur potential and phase diagram data available in the literature for solid-state equilibria related to digenite have been assessed. Thorough thermodynamic analysis at 1 bar total pressure has been performed. A three-sublattice approach has been developed to model the Gibbs energy of digenite as a function of composition and temperature using the compound energy formalism. The Gibbs energies of the adjacent solid-state phases covelitte and high-temperature chalcocite are also modeled treating both sulfides as stoichiometric compounds. The novel model for digenite offers new interpretation of experimental data, may contribute from a thermodynamic point of view to the elucidation of the role of copper species within the crystal structure and allows extrapolation to composition regimes richer in copper than stoichiometric digenite Cu2S. Preliminary predictions into the ternary Cu-Fe-S system at 1273 K (1000 °C) using the Gibbs energy model of digenite for calculating its iron solubility are promising.

Duality, phase structures, and dilemmas in symmetric quantum games

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ichikawa, Tsubasa; Tsutsui, Izumi

Symmetric quantum games for 2-player, 2-qubit strategies are analyzed in detail by using a scheme in which all pure states in the 2-qubit Hilbert space are utilized for strategies. We consider two different types of symmetric games exemplified by the familiar games, the Battle of the Sexes (BoS) and the Prisoners' Dilemma (PD). These two types of symmetric games are shown to be related by a duality map, which ensures that they share common phase structures with respect to the equilibria of the strategies. We find eight distinct phase structures possible for the symmetric games, which are determined by themore » classical payoff matrices from which the quantum games are defined. We also discuss the possibility of resolving the dilemmas in the classical BoS, PD, and the Stag Hunt (SH) game based on the phase structures obtained in the quantum games. It is observed that quantization cannot resolve the dilemma fully for the BoS, while it generically can for the PD and SH if appropriate correlations for the strategies of the players are provided.« less

Conformational equilibria of light-activated rhodopsin in nanodiscs

PubMed Central

Van Eps, Ned; Caro, Lydia N.; Morizumi, Takefumi; Kusnetzow, Ana Karin; Szczepek, Michal; Hofmann, Klaus Peter; Bayburt, Timothy H.; Sligar, Stephen G.; Ernst, Oliver P.; Hubbell, Wayne L.

2017-01-01

Conformational equilibria of G-protein–coupled receptors (GPCRs) are intimately involved in intracellular signaling. Here conformational substates of the GPCR rhodopsin are investigated in micelles of dodecyl maltoside (DDM) and in phospholipid nanodiscs by monitoring the spatial positions of transmembrane helices 6 and 7 at the cytoplasmic surface using site-directed spin labeling and double electron–electron resonance spectroscopy. The photoactivated receptor in DDM is dominated by one conformation with weak pH dependence. In nanodiscs, however, an ensemble of pH-dependent conformational substates is observed, even at pH 6.0 where the MIIbH+ form defined by proton uptake and optical spectroscopic methods is reported to be the sole species present in native disk membranes. In nanodiscs, the ensemble of substates in the photoactivated receptor spontaneously decays to that characteristic of the inactive state with a lifetime of ∼16 min at 20 °C. Importantly, transducin binding to the activated receptor selects a subset of the ensemble in which multiple substates are apparently retained. The results indicate that in a native-like lipid environment rhodopsin activation is not analogous to a simple binary switch between two defined conformations, but the activated receptor is in equilibrium between multiple conformers that in principle could recognize different binding partners. PMID:28373559

The Impact of Prophage on the Equilibria and Stability of Phage and Host

NASA Astrophysics Data System (ADS)

Yu, Pei; Nadeem, Alina; Wahl, Lindi M.

2017-06-01

In this paper, we present a bacteriophage model that includes prophage, that is, phage genomes that are incorporated into the host cell genome. The general model is described by an 18-dimensional system of ordinary differential equations. This study focuses on asymptotic behaviour of the model, and thus the system is reduced to a simple six-dimensional model, involving uninfected host cells, infected host cells and phage. We use dynamical system theory to explore the dynamic behaviour of the model, studying in particular the impact of prophage on the equilibria and stability of phage and host. We employ bifurcation and stability theory, centre manifold and normal form theory to show that the system has multiple equilibrium solutions which undergo a series of bifurcations, finally leading to oscillating motions. Numerical simulations are presented to illustrate and confirm the analytical predictions. The results of this study indicate that in some parameter regimes, the host cell population may drive the phage to extinction through diversification, that is, if multiple types of host emerge; this prediction holds even if the phage population is likewise diverse. This parameter regime is restricted, however, if infecting phage are able to recombine with prophage sequences in the host cell genome.

Pressure driven currents near magnetic islands in 3D MHD equilibria: Effects of pressure variation within flux surfaces and of symmetry

NASA Astrophysics Data System (ADS)

Reiman, Allan H.

2016-07-01

In toroidal, magnetically confined plasmas, the heat and particle transport is strongly anisotropic, with transport along the field lines sufficiently strong relative to cross-field transport that the equilibrium pressure can generally be regarded as constant on the flux surfaces in much of the plasma. The regions near small magnetic islands, and those near the X-lines of larger islands, are exceptions, having a significant variation of the pressure within the flux surfaces. It is shown here that the variation of the equilibrium pressure within the flux surfaces in those regions has significant consequences for the pressure driven currents. It is further shown that the consequences are strongly affected by the symmetry of the magnetic field if the field is invariant under combined reflection in the poloidal and toroidal angles. (This symmetry property is called "stellarator symmetry.") In non-stellarator-symmetric equilibria, the pressure-driven currents have logarithmic singularities at the X-lines. In stellarator-symmetric MHD equilibria, the singular components of the pressure-driven currents vanish. These equilibria are to be contrasted with equilibria having B ṡ∇p =0 , where the singular components of the pressure-driven currents vanish regardless of the symmetry. They are also to be contrasted with 3D MHD equilibrium solutions that are constrained to have simply nested flux surfaces, where the pressure-driven current goes like 1 /x near rational surfaces, where x is the distance from the rational surface, except in the case of quasi-symmetric flux surfaces. For the purpose of calculating the pressure-driven currents near magnetic islands, we work with a closed subset of the MHD equilibrium equations that involves only perpendicular force balance, and is decoupled from parallel force balance. It is not correct to use the parallel component of the conventional MHD force balance equation, B ṡ∇p =0 , near magnetic islands. Small but nonzero values of B �

Distributed phased array architecture study

NASA Technical Reports Server (NTRS)

Bourgeois, Brian

1987-01-01

Variations in amplifiers and phase shifters can cause degraded antenna performance, depending also on the environmental conditions and antenna array architecture. The implementation of distributed phased array hardware was studied with the aid of the DISTAR computer program as a simulation tool. This simulation provides guidance in hardware simulation. Both hard and soft failures of the amplifiers in the T/R modules are modeled. Hard failures are catastrophic: no power is transmitted to the antenna elements. Noncatastrophic or soft failures are modeled as a modified Gaussian distribution. The resulting amplitude characteristics then determine the array excitation coefficients. The phase characteristics take on a uniform distribution. Pattern characteristics such as antenna gain, half power beamwidth, mainbeam phase errors, sidelobe levels, and beam pointing errors were studied as functions of amplifier and phase shifter variations. General specifications for amplifier and phase shifter tolerances in various architecture configurations for C band and S band were determined.

Primary Phase Field of the Pb-Doped 2223 High-Tc Superconductor in the (Bi, Pb)-Sr-Ca-Cu-O System

PubMed Central

Wong-Ng, W.; Cook, L. P.; Kearsley, A.; Greenwood, W.

1999-01-01

Both liquidus and subsolidus phase equilibrium data are of central importance for applications of high temperature superconductors in the (Bi, Pb)-Sr-Ca-Cu-O system, including material synthesis, melt processing and single crystal growth. The subsolidus equilibria of the 110 K high-Tc Pb-doped 2223 ([Bi, Pb], Sr, Ca, Cu) phase and the location of the primary phase field (crystallization field) have been determined in this study. For the quantitative determination of liquidus data, a wicking technique was developed to capture the melt for quantitative microchemical analysis. A total of 29 five-phase volumes that include the 2223 phase as a component was obtained. The initial melt compositions of these volumes range from a mole fraction of 7.3 % to 28.0 % for Bi, 11.3 % to 27.8 % for Sr, 1.2 % to 19.4 % for Pb, 9.8 % to 30.8 % for Ca, and 17.1 % to 47.0 % for Cu. Based on these data, the crystallization field for the 2223 phase was constructed using the convex hull technique. A section of this “volume” was obtained by holding two components of the composition at the median value, allowing projection on the other three axes to show the extent of the field.

Multiphase, multicomponent phase behavior prediction

NASA Astrophysics Data System (ADS)

Dadmohammadi, Younas

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

Particle paths and phase plane for time-dependent similarity solutions of the one-dimensional Vlasov-Maxwell equations

NASA Technical Reports Server (NTRS)

Roberts, Dana Aaron; Abraham-Shrauner, Barbara

1987-01-01

The phase trajectories of particles in a plasma described by the one-dimensional Vlasov-Maxwell equations are determined qualitatively, analyzing exact general similarity solutions for the cases of temporally damped and growing (sinusoidal or localized) electric fields. The results of numerical integration in both untransformed and Lie-group point-transformed coordinates are presented in extensive graphs and characterized in detail. The implications of the present analysis for the stability of BGK equilibria are explored, and the existence of nonlinear solutions arbitrarily close to and significantly different from the BGK solutions is demonstrated.

Quasi-Equilibria of the Rotunno-Emanuel Tropical Cyclone Model

NASA Technical Reports Server (NTRS)

Chao, Winston C.; Chen, Baode

2003-01-01

Long-term integrations using the Rotunno-Emanuel (RE) model demonstrate that given sufficient elapsed time the weak initial vortex specified by R E can also lead to tropical cyclogenesis, albeit at a slower growth rate. Thus the RE notion of the finite-amplitude nature of tropical cyclogenesis is valid only if the period of examination is limited to the first eight days. These results also show that, if initial vortex as specified by RE is used, prior to cyclogenesis the model state does not resemble the observed pre-genesis disturbances in the sense that there is no precipitation in the center of the disturbance. Another experiment using the same model but with the initial vortex replaced by a disturbance with a different structure shows that a state resembling the observed pre-genesis disturbances can be simulated and this state can lead to spontaneous cyclogenesis, a rapid transition between two quasi-equilibria. This spontaneous cyclogenesis is associated with the generation of a new convective region at large radius and its subsequent contraction, which reminds one of the observed eye-wall replacement, but the distinction from the latter is obvious.

Experimental study of phase separation in dividing two phase flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qian Yong; Yang Zhilin; Xu Jijun

1996-12-31

Experimental study of phase separation of air-water two phase bubbly, slug flow in the horizontal T-junction is carried out. The influences of the inlet mass quality X1, mass extraction rate G3/G1, and fraction of extracted liquid QL3/QL1 on phase separation characteristics are analyzed. For the first time, the authors have found and defined pulsating run effect by the visual experiments, which show that under certain conditions, the down stream flow of the T-junction has strangely affected the phase redistribution of the junction, and firstly point out that the downstream geometric condition is very important to the study of phase separationmore » phenomenon of two-phase flow in a T-junction. This kind of phenomenon has many applications in the field of energy, power, petroleum and chemical industries, such as the loss of coolant accident (LOCA) caused by a small break in a horizontal coolant pipe in nuclear reactor, and the flip-flop effect in the natural gas transportation pipeline system, etc.« less

a Theoretical Study of Coherent Structures in Nonneutral Plasma Columns

NASA Astrophysics Data System (ADS)

Lund, Steven M.

A ubiquitous feature of experimental and computer simulation studies of magnetically confined pure electron plasmas in cylindrical confinement devices is the formation of nonaxisymmetric (partial/partial theta ne 0) rotating equilibria. In this dissertation, nonaxisymmetric rotating equilibria are investigated theoretically for strongly magnetized, low-density (omega_sp{pe} {2}/omega_sp{ce}{2 } << 1) pure electron plasmas confined in a two-dimensional cylindrical geometry. These dynamic equilibria are also called rotating coherent structures, and are stationary (time-independent) in a frame of reference rotating with angular velocity omega_ {r} = const. about the cylinder axis (r = 0). Radial confinement of the pure electron plasma is provided by a uniform axial magnetic field B_0 {bf e}_{z}, and a grounded, perfectly conducting, cylindrical wall is located at radius r = r_{w}. The analysis is based on a nonrelativistic, guiding-center model in the cold-fluid limit (the continuity and Poisson equations) that treats the electrons as a massless fluid (m_{e} to 0) with E times B flow velocity V _{e} = -(c/B_0)nablaphi times {bf e}_{z}. Within this model, general rotating equilibria with electron density (n_{e} equiv n_{R}(r,theta-omega _{r}t) and electrostatic potential phi equiv phi_{R }(r,theta-omega_{r}t) have the property that the electron density is functionally related to the streamfunction psi _{R} = -ephi_{R} + omega_{r}(eB_0/2c)r^2 by n_{R} = n_{R }(psi_{R}). The streamfunction psi_{R} satisfies the nonlinear equilibrium equation nabla ^2psi_{R} = -4pi e^2n _{R}(psi_{R}) + 2omega_{r}eB_0/c with psi_{R} = omega _{r}(eB_0/2c)r_sp{w }{2} equiv psi_{w } = const. on the cylindrical wall at r = r_{w}. A general methodology for the solution of this equilibrium system is presented and several properties of rotating equilibria are analyzed. Following this analysis, two classes of nonaxisymmetric equilibria are investigated. These two classes of equilibria can have

High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

NASA Astrophysics Data System (ADS)

Eric, R. Hurman; Ozok, Hakan

1994-01-01

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.

A phased approach to clinical testing: criteria for progressing from Phase I to Phase II to Phase III studies.

PubMed

André, F E; Foulkes, M A

1998-01-01

The overall intent of clinical testing is to establish, in a series of phased studies, the clinical tolerance and acceptable "safety" of the candidate vaccine, as well as the type, level and persistence of the immune response after its inoculation, to a representative target population, according to a convenient administration schedule. The final stages involve the direct or indirect demonstration of protective efficacy, if possible in the population(s) for which the vaccine is intended. In addition, consistency of production must be demonstrated. At all these stages, the amount of prior information from preclinical and other studies affects and informs the objectives and design of subsequent studies. Progression from one testing phase to the next is dependent upon attaining the pre-set objectives of each series of studies. The precise objectives to be met will be decided on a case-by-case basis. The earliest assessments in humans (Phase I) involve evaluation of short-term clinical tolerance as measured by local and general reactogenicity, and gross assessments of immunogenicity, in a small number of highly selected individuals in an idealised situation. The selection of "optimal" dose and schedule are the result of further dose-ranging investigations (Phase II), involving more volunteers, with longer, more detailed follow-up assessments. It is at this stage that the accumulated evidence on its immunogenicity profile should be sufficient to assess whether or not the vaccine is worthy of further development. The next level of investigation (Phase III) aims to measure with greater precision the vaccine protective efficacy in the intended target population(s) by comparison of infection and/or disease attack rates in vaccine and placebo recipients. In consistency studies different production lots, manufactured at commercial scale, are tested to demonstrate consistency of manufacture. Additional bridging studies to establish similarity of lots at different production

Optimization, Monotonicity and the Determination of Nash Equilibria — An Algorithmic Analysis

NASA Astrophysics Data System (ADS)

Lozovanu, D.; Pickl, S. W.; Weber, G.-W.

2004-08-01

This paper is concerned with the optimization of a nonlinear time-discrete model exploiting the special structure of the underlying cost game and the property of inverse matrices. The costs are interlinked by a system of linear inequalities. It is shown that, if the players cooperate, i.e., minimize the sum of all the costs, they achieve a Nash equilibrium. In order to determine Nash equilibria, the simplex method can be applied with respect to the dual problem. An introduction into the TEM model and its relationship to an economic Joint Implementation program is given. The equivalence problem is presented. The construction of the emission cost game and the allocation problem is explained. The assumption of inverse monotony for the matrices leads to a new result in the area of such allocation problems. A generalization of such problems is presented.

Experimental confirmation of stable, small-debye-length, pure-electron-plasma equilibria in a stellarator.

PubMed

Kremer, J P; Pedersen, T Sunn; Lefrancois, R G; Marksteiner, Q

2006-09-01

The creation of the first small-Debye length, low temperature pure electron plasmas in a stellarator is reported. A confinement time of 20 ms has been measured. The long confinement time implies the existence of macroscopically stable equilibria and that the single particle orbits are well confined despite the lack of quasisymmetry in the device, the Columbia non-neutral torus. This confirms the beneficial confinement effects of strong electric fields and the resulting rapid E x B rotation of the electrons. The particle confinement time is presently limited by the presence of bulk insulating materials in the plasma, rather than any intrinsic plasma transport processes. A nearly flat temperature profile is seen in the inner part of the plasma.

The effects of magnetic B(y) component on geomagnetic tail equilibria

NASA Technical Reports Server (NTRS)

Hilmer, Robert V.; Voigt, Gerd-Hannes

1987-01-01

A two-dimensional linear magnetohydrostatic model of the magnetotail is developed here in order to investigate the effects of a significant B(y) component on the configuration of magnetotail equilibria. It is concluded that the enhanced B(y) values must be an essential part of the quiet magnetotail and do not result from a simple intrusion of the IMF. The B(y) field consists of a constant background component plus a nonuniform field existing only in the plasma sheet, where it is dependent on the plasma paramater beta and the strength of the magnetic B(z) component. B(y) is strongest at the neutral sheet and decreases monotonically in the + or - z direction, reaching a constant tail lobe value at the plasma sheet boundaries. The presence of a significant positive B(y) component produces currents, including field-aligned currents, that flow through the equatorial plane and toward and away from earth in the northern and southern halves of the plasma sheet, respectively.

Alumina-Forming Austenitic Stainless Steels Strengthened by Laves Phase and MC Carbide Precipitates

NASA Astrophysics Data System (ADS)

Yamamoto, Y.; Brady, M. P.; Lu, Z. P.; Liu, C. T.; Takeyama, M.; Maziasz, P. J.; Pint, B. A.

2007-11-01

Creep strengthening of Al-modified austenitic stainless steels by MC carbides or Fe2Nb Laves phase was explored. Fe-20Cr-15Ni-(0-8)Al and Fe-15Cr-20Ni-5Al base alloys (at. pct) with small additions of Nb, Mo, W, Ti, V, C, and B were cast, thermally-processed, and aged. On exposure from 650 °C to 800 °C in air and in air with 10 pct water vapor, the alloys exhibited continuous protective Al2O3 scale formation at an Al level of only 5 at. pct (2.4 wt pct). Matrices of the Fe-20Cr-15Ni-5Al base alloys consisted of γ (fcc) + α (bcc) dual phase due to the strong α-Fe stabilizing effect of the Al addition and exhibited poor creep resistance. However, adjustment of composition to the Fe-15Cr-20Ni-5Al base resulted in alloys that were single-phase γ-Fe and still capable of alumina scale formation. Alloys that relied solely on Fe2Nb Laves phase precipitates for strengthening exhibited relatively low creep resistance, while alloys that also contained MC carbide precipitates exhibited creep resistance comparable to that of commercially available heat-resistant austenitic stainless steels. Phase equilibria studies indicated that NbC precipitates in combination with Fe2Nb were of limited benefit to creep resistance due to the solution limit of NbC within the γ-Fe matrix of the alloys studied. However, when combined with other MC-type strengtheners, such as V4C3 or TiC, higher levels of creep resistance were obtained.

Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound

PubMed Central

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

Silicate-Oxide Equilibria in the Wilson Lake Terrane, Labrador - Evidence for a Pre- Metamorphic Oxidizing Event

NASA Astrophysics Data System (ADS)

Korhonen, F. J.; Stout, J. H.

2006-05-01

The presence of Fe3+ and Ti in silicates and their presumed equilibration with Fe2+-Fe3+-Ti oxide minerals has long been recognized as an important factor in metamorphic phase equilibria. The Red Wine Mountains massif is a granulite facies unit in the Wilson Lake terrane of central Labrador, where this equilibration is especially important for estimating both temperature and fO2 during peak metamorphism. Peak assemblages are sapphirine + quartz, and orthopyroxene + sillimanite + quartz. The coexisting oxides, which are largely responsible for the pronounced aeromagnetic high of the massif, consist of nearly pure magnetite and an exsolved titanohematite. Estimates of fO2 based on magnetite + integrated titanohematite compositions are slightly below that defined by the pure magnetite-hematite buffer. This assemblage is also responsible for the magnetic signature of metagabbro and metanorite dikes, a fact which challenges the conventional wisdom that the high Fe3+ content of the host paragneisses was inherited from a highly oxidized ferruginous shale. We suggest here that prior to granulite facies metamorphism, an oxidizing hydrothermal event either coeval or following the emplacement of mafic dikes into the paragneiss host was responsible for the highly oxidized nature of the massif as a whole. Subsequent metamorphism then produced the observed assemblages. This scenario is supported by recent U-Pb zircon and monazite ages of ca. 1626 ± 10 Ma, which indicate that both metagabbro dikes and host paragneiss were metamorphosed at the same time. Dike emplacement and the oxidizing event must have preceded 1626 Ma. The implications of this pre-metamorphic oxidizing event is that Fe3+ becomes an inherent and fixed component in the chemical system during metamorphism. Phase relationships, preliminary thermodynamic modeling, and geothermobarometric constraints indicate that peak temperatures are lower than those previously determined for Fe3+-absent systems. More appropriate

Silicate and Carbonatite Melts in the Mantle: Adding CO2 to the pMELTS Thermodynamic Model of Silicate Phase Equilibria

NASA Astrophysics Data System (ADS)

Antoshechkina, P. M.; Shorttle, O.

2016-12-01

The current rhyolite-MELTS algorithm includes a mixed H2O-CO2 vapor phase, and a self-consistent speciation model for CO2 and CaCO3 in the silicate liquid (Ghiorso & Gualda 2012; 2015). Although intended primarily to model crustal differentiation and degassing, GG15 captures much of the experimentally-observed melting behavior of CO2-rich mafic lithologies, including generation of small-degree carbonatite melts, a miscibility gap between carbonatite and silicate liquids at low P and a smooth transition to a single carbonated-silicate melt at high P (e.g. Dasgupta et al. 2007). However, solid and liquid carbonate phases were not used in calibration of GG15, and it is suitable only for P < 3 GPa. We present a preliminary model, based on pMELTS (Ghiorso et al. 2002), for melting of nominally-anhydrous carbonated peridotite and pyroxenite. In Antoshechkina et al. (2015; and references therein) we developed a scheme for calibration of molar volumes that directly interfaces with a MySQL database, adapted from LEPR (Hirschmann et al. 2008). Here, we further extend our database, e.g. to include multiple carbonate phases, and combine the calibration scheme with the libalphaMELTS interface to the rhyolite-MELTS, pMELTS, and H2O-CO2 fluid thermodynamic models (see magmasource.caltech.edu/alphamelts). We use a Monte-Carlo type calibration approach to fit the observed phases and compositions, though stop short of a fully Bayesian formulation. The CO2-fluid experimental database has been updated to include more recent and higher P studies, adding approximately 40 pure fluid plus liquid constraints that conform to the selection criteria used in GG15. To further expand the database, we plan to use some or all of: solid carbonate-bearing experiments; coexisting silicate and carbonatite liquids; phase-present, and phase-absent constraints. As a first approximation, we include four carbonate phases: pure calcite and aragonite, and binary solutions for dolomite-ankerite and magnesite

Phase Transformations and Formation of Ultra-Fine Microstructure During Hydrogen Sintering and Phase Transformation (HSPT) Processing of Ti-6Al-4V

NASA Astrophysics Data System (ADS)

Sun, Pei; Fang, Zhigang Zak; Koopman, Mark; Xia, Yang; Paramore, James; Ravi Chandran, K. S.; Ren, Yang; Lu, Jun

2015-12-01

The hydrogen sintering and phase transformation (HSPT) process is a novel powder metallurgy method for producing Ti alloys, particularly the Ti-6Al-4V alloy, with ultra-fine microstructure in the as-sintered state. The ultra-fine microstructure is obtained as a direct result of the use of H2 gas during sintering. The refinement of the microstructure during HSPT is similar to that of thermal hydrogen processing (THP) of bulk Ti alloys. For both THP and HSPT of Ti-6Al-4V alloy, the mechanisms of the grain refinement depend on the phase equilibria and phase transformations in the presence of hydrogen, which are surprisingly still not well established to date and are still subjected to research and debate. In recent work by the present authors, a pseudo-binary phase diagram of (Ti-6Al-4V)-H has been determined by using in situ synchrotron XRD and TGA/DSC techniques. Aided by this phase diagram, the current paper focuses on the series of phase transformations during sintering and cooling of Ti-6Al-4V in a hydrogen atmosphere and the mechanisms for the formation of the ultra-fine microstructures obtained. Using experimental techniques, including in situ synchrotron XRD, SEM, EBSD, and TEM, the microstructural refinement was found to be the result of (1) the precipitation of ultra-fine α/α2 within coarse β grains during an isothermal hold at intermediate temperatures, and (2) the eutectoid transformation of β → α + δ at approximately 473 K (200 °C).

Experimental study and thermodynamic modeling of the Al–Co–Cr–Ni system

DOE PAGES

Gheno, Thomas; Liu, Xuan L.; Lindwall, Greta; ...

2015-09-21

In this study, a thermodynamic database for the Al–Co–Cr–Ni system is built via the Calphad method by extrapolating re-assessed ternary subsystems. A minimum number of quaternary parameters are included, which are optimized using experimental phase equilibrium data obtained by electron probe micro-analysis and x-ray diffraction analysis of NiCoCrAlY alloys spanning a wide compositional range, after annealing at 900 °C, 1100 °C and 1200 °C, and water quenching. These temperatures are relevant to oxidation and corrosion resistant MCrAlY coatings, where M corresponds to some combination of nickel and cobalt. Comparisons of calculated and measured phase compositions show excellent agreement for themore » β–γ equilibrium, and good agreement for three-phase β–γ–σ and β–γ–α equilibria. An extensive comparison with existing Ni-base databases (TCNI6, TTNI8, NIST) is presented in terms of phase compositions.« less

Phase transformations in cast duplex stainless steels

NASA Astrophysics Data System (ADS)

Kim, Yoon-Jun

Duplex stainless steels (DSS) constitute both ferrite and austenite as a matrix. Such a microstructure confers a high corrosion resistance with favorable mechanical properties. However, intermetallic phases such as sigma (sigma) and chi (chi) can also form during casting or high-temperature processing and can degrade the properties of the DSS. This research was initiated to develop time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams of two types of cast duplex stainless steels, CD3MN (Fe-22Cr-5Ni-Mo-N) and CD3MWCuN (Fe-25Cr-7Ni-Mo-W-Cu-N), in order to understand the time and temperature ranges for intermetallic phase formation. The alloys were heat treated isothermally or under controlled cooling conditions and then characterized using conventional metallographic methods that included tint etching, and also using electron microscopy (SEM, TEM) and wavelength dispersive spectroscopy (WDS). The kinetics of intermetallic-phase (sigma + chi) formation were analyzed using the Johnson-Mehl-Avrami (JMA) equation in the case of isothermal transformations and a modified form of this equation in the case of continuous cooling transformations. The rate of intermetallic-phase formation was found to be much faster in CD3MWCuN than CD3MN due mainly to differences in the major alloying contents such as Cr, Ni and Mo. To examine in more detail the effects of these elements of the phase stabilities, a series of eight steel castings was designed with the Cr, Ni and Mo contents systematically varied with respect to the nominal composition of CD3MN. The effects of varying the contents of alloying additions on the formation of intermetallic phases were also studied computationally using the commercial thermodynamic software package, Thermo-Calc. In general, a was stabilized with increasing Cr addition and chi by increasing Mo addition. However, a delicate balance among Ni and other minor elements such as N and Si also exists. Phase equilibria in

Mechanisms of devitrification of grain boundary glassy phases in Si3N4 materials

NASA Technical Reports Server (NTRS)

Hench, L. L.

1982-01-01

Changes in the grain boundary (g.b.) phases of Si3N4 are analyzed, the effects of composition and thermal history on devitrification of the g.b. phases are determined, devitrification of the g.b. phases of Si3N are related to mechanical behavior and oxidation sensitivity of the material. The phase relationships that occur within the grain boundaries of Si3N4 containing various densification aids are reviewed. Comparisons of the effects of MgO, Y2O3, CeO2, and Y2O3 + AL2O3 are made in terms of the phase equilibria of the Si3N4 + SiO2 + additive compositional system. Two new equilibrium phase diagrams for the Si3N4-SiO2 and Y2O3 and Si3N4-SiO2-Ce2O3 systems are preented. The effects of Y2O3 vs CeO2 densification aids on the fracture surfaces of Si3N4 are compared. Auger electron spectroscopy shows that both oxides are concentrated within the fracture surface. Scanning electron microscopy shows evidence that Si3N4 with CeO2 formed an intergranular structure of fine grained oxynitride reaction products, as predicted by phase quilibria, whereas the Y2O3 containing sample shows evidence of an intergranular glassy phase.

Relativistic Self-similar Equilibria and Non-axisymmetric Neutral Modes

NASA Astrophysics Data System (ADS)

Cai, Mike J.; Shu, F. H.

2002-05-01

We have constructed semi-analytic axisymmetric scale free solutions to Einstein field equations with perfect fluid matter source. These spacetimes are self-similar under the simultaneous transformation r'= ar and t'=a1-nt. We explored the two dimensional solution space parameterized by the rescaling index n and the isothermal sound speed γ 1/2. The isopycnic surfaces are in general toroids. As the equilibrium configuration rotates faster, an ergo region develops in the form of the exterior of a cone centered about the symmetry axis. The sequence of solution terminates when frame dragging becomes infinite and the ergo cone closes onto the axis. In the extreme flattening limit, we have also searched for non-axisymmetric neutral modes in a self-similar disk. Two separate sets of tracks are discovered in the solution space. One corresponds to the bifurcation points to non-axisymmetric equilibria, which is confined in the non-ergo solutions. The other track signals the onset of instability driven by gravitational radiation. These solutions are formally infinite in extent, and thus can not represent realistic astrophysical systems. However, if these properties do not alter qualitatively when the self-similar configurations are truncated, then these solutions may serve as initial data for dynamic collapse in super massive black hole formation.

Determination of 200 °C Isothermal Section of Al-Ag-Ga Phase Diagram by Microanalysis, X-ray Diffraction, Hardness and Electrical Conductivity Measurements

NASA Astrophysics Data System (ADS)

Premović, Milena; Tomović, Milica; Minić, Duško; Manasijević, Dragan; Živković, Dragana; Ćosović, Vladan; Grković, Vladan; Đorđević, Aleksandar

2017-04-01

Ternary Al-Ag-Ga system at 200 °C was experimentally and thermodynamically assessed. Isothermal section was extrapolated using optimized thermodynamic parameters for constitutive binary systems. Microstructure and phase composition of the selected alloy samples were analyzed using light microscopy, scanning electron microscopy combined with energy-dispersive spectrometry and x-ray powder diffraction technique. The obtained experimental results were found to be in a close agreement with the predicted phase equilibria. Hardness and electrical conductivity of the alloy samples from four vertical sections Al-Ag80Ga20, Al-Ag60Ga40, Ag-Al80Ga20 and Ag-Al60Ga40 of the ternary Al-Ag-Ga system at 200 °C were experimentally determined using Brinell method and eddy current measurements. Additionally, hardness of the individual phases present in the microstructure of the studied alloy samples was determined using Vickers microhardness test. Based on experimentally obtained results, isolines of Brinell hardness and electrical conductivity were calculated for the alloys from isothermal section of the ternary Al-Ag-Ga system at 200 °C.

Multiple Quasi-Equilibria of the ITCZ and the Origin of Monsoon Onset. Part 2; Rotational ITCZ Attractors

NASA Technical Reports Server (NTRS)

Chao, Winston C.; Chen, Baode; Einaudi, Franco (Technical Monitor)

2000-01-01

Chao's numerical and theoretical work on multiple quasi-equilibria of the intertropical convergence zone (ITCZ) and the origin of monsoon onset is extended to solve two additional puzzles. One is the highly nonlinear dependence on latitude of the "force" acting on the ITCZ due to earth's rotation, which makes the multiple quasi-equilibria of the ITCZ and monsoon onset possible. The other is the dramatic difference in such dependence when different cumulus parameterization schemes are used in a model. Such a difference can lead to a switch between a single ITCZ at the equator and a double ITCZ, when a different cumulus parameterization scheme is used. Sometimes one of the double ITCZ can diminish and only the other remain, but still this can mean different latitudinal locations for the single ITCZ. A single idea based on two off-equator attractors for the ITCZ, due to earth's rotation and symmetric with respect to the equator, and the dependence of the strength and size of these attractors on the cumulus parameterization scheme solves both puzzles. The origin of these rotational attractors, explained in Part I, is further discussed. The "force" acting on the ITCZ due to earth's rotation is the sum of the "forces" of the two attractors. Each attractor exerts on the ITCZ a "force" of simple shape in latitude; but the sum gives a shape highly varying in latitude. Also the strength and the domain of influence of each attractor vary, when change is made in the cumulus parameterization. This gives rise to the high sensitivity of the "force" shape to cumulus parameterization. Numerical results, of experiments using Goddard's GEOS general circulation model, supporting this idea are presented. It is also found that the model results are sensitive to changes outside of the cumulus parameterization. The significance of this study to El Nino forecast and to tropical forecast in general is discussed.

Centrifuge workers study. Phase II, completion report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wooten, H.D.

1994-09-01

Phase II of the Centrifuge Workers Study was a follow-up to the Phase I efforts. The Phase I results had indicated a higher risk than expected among centrifuge workers for developing bladder cancer when compared with the risk in the general population for developing this same type of cancer. However, no specific agent could be identified as the causative agent for these bladder cancers. As the Phase II Report states, Phase I had been limited to workers who had the greatest potential for exposure to substances used in the centrifuge process. Phase II was designed to expand the survey tomore » evaluate the health of all employees who had ever worked in Centrifuge Program Departments 1330-1339 but who had not been interviewed in Phase I. Employees in analytical laboratories and maintenance departments who provided support services for the Centrifuge Program were also included in Phase II. In December 1989, the Oak Ridge Associated Universities (ORAU), now known as Oak Ridge Institute for Science and Education (ORISE), was contracted to conduct a follow-up study (Phase II). Phase H of the Centrifuge Workers Study expanded the survey to include all former centrifuge workers who were not included in Phase I. ORISE was chosen because they had performed the Phase I tasks and summarized the corresponding survey data therefrom.« less

21 CFR 312.85 - Phase 4 studies.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 5 2010-04-01 2010-04-01 false Phase 4 studies. 312.85 Section 312.85 Food and...-debilitating Illnesses § 312.85 Phase 4 studies. Concurrent with marketing approval, FDA may seek agreement from the sponsor to conduct certain postmarketing (phase 4) studies to delineate additional information...

21 CFR 312.85 - Phase 4 studies.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 5 2011-04-01 2011-04-01 false Phase 4 studies. 312.85 Section 312.85 Food and...-debilitating Illnesses § 312.85 Phase 4 studies. Concurrent with marketing approval, FDA may seek agreement from the sponsor to conduct certain postmarketing (phase 4) studies to delineate additional information...

Metastable phase equilibria in co-deposited Ni(1-x)Zr(x) thin films

NASA Astrophysics Data System (ADS)

Rubin, J. B.; Schwarz, R. B.

We determine the glass forming range (GFR) of co-deposited Ni(1-x)Zr(x) (0 less than x less than 1) thin films by measuring their electrical resistance during in situ constant-heating-rate anneals. The measured GFR is continuous for 0.10 less than x less than 0.87. We calculate the GFR of Ni-Zr melts as a function of composition and cooling rate using homogeneous nucleation theory and a published CALPHAD-type thermodynamic modeling of the equilibrium phase diagram. Assuming that the main competition to the retention of the amorphous structure during the cooling of the liquid comes from the partitionless crystallization of the terminal solid solutions, we calculate that for dT/dt = 10(exp 12) K/s, the GFR extends to x = 0.05 and x = 0.96. Better agreement with the measured values is obtained assuming a lower effective cooling rate during the condensation of the films.

Conformity-driven agents support ordered phases in the spatial public goods game

NASA Astrophysics Data System (ADS)

Javarone, Marco Alberto; Antonioni, Alberto; Caravelli, Francesco

2016-05-01

We investigate the spatial Public Goods Game in the presence of fitness-driven and conformity-driven agents. This framework usually considers only the former type of agents, i.e., agents that tend to imitate the strategy of their fittest neighbors. However, whenever we study social systems, the evolution of a population might be affected also by social behaviors as conformism, stubbornness, altruism, and selfishness. Although the term evolution can assume different meanings depending on the considered domain, here it corresponds to the set of processes that lead a system towards an equilibrium or a steady state. We map fitness to the agents' payoff so that richer agents are those most imitated by fitness-driven agents, while conformity-driven agents tend to imitate the strategy assumed by the majority of their neighbors. Numerical simulations aim to identify the nature of the transition, on varying the amount of the relative density of conformity-driven agents in the population, and to study the nature of related equilibria. Remarkably, we find that conformism generally fosters ordered cooperative phases and may also lead to bistable behaviors.

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

PubMed Central

Domańska, Urszula

2010-01-01

A review of the relevant literature on 1-alkyl-1-methylpyrrolidinium-based ionic liquids has been presented. The phase diagrams for the binary systems of {1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [EMPYR][CF3SO3] + water, or + 1-butanol} and for the binary systems of {1-propyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [PMPYR][CF3SO3] + water, or + an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol)} have been determined at atmospheric pressure using a dynamic method. The influence of alcohol chain length was discussed for the [PMPYR][CF3SO3]. A systematic decrease in the solubility was observed with an increase of the alkyl chain length of an alcohol. (Solid + liquid) phase equilibria with complete miscibility in the liquid phase region were observed for the systems involving water and alcohols. The solubility of the ionic liquid increases as the alkyl chain length on the pyrrolidinium cation increases. The correlation of the experimental data has been carried out using the Wilson, UNIQUAC and the NRTL equations. The phase diagrams reported here have been compared to the systems published earlier with the 1-alkyl-1-methylpyrrolidinium-based ionic liquids. The influence of the cation and anion on the phase behaviour has been discussed. The basic thermal properties of pure ILs, i.e., melting temperature and the enthalpy of fusion, the solid-solid phase transition temperature and enthalpy have been measured using a differential scanning microcalorimetry technique. PMID:20480044

Hydration and conformational equilibria of simple hydrophobic and amphiphilic solutes.

PubMed Central

Ashbaugh, H S; Kaler, E W; Paulaitis, M E

1998-01-01

We consider whether the continuum model of hydration optimized to reproduce vacuum-to-water transfer free energies simultaneously describes the hydration free energy contributions to conformational equilibria of the same solutes in water. To this end, transfer and conformational free energies of idealized hydrophobic and amphiphilic solutes in water are calculated from explicit water simulations and compared to continuum model predictions. As benchmark hydrophobic solutes, we examine the hydration of linear alkanes from methane through hexane. Amphiphilic solutes were created by adding a charge of +/-1e to a terminal methyl group of butane. We find that phenomenological continuum parameters fit to transfer free energies are significantly different from those fit to conformational free energies of our model solutes. This difference is attributed to continuum model parameters that depend on solute conformation in water, and leads to effective values for the free energy/surface area coefficient and Born radii that best describe conformational equilibrium. In light of these results, we believe that continuum models of hydration optimized to fit transfer free energies do not accurately capture the balance between hydrophobic and electrostatic contributions that determines the solute conformational state in aqueous solution. PMID:9675177

Review of critical flow rate, propagation of pressure pulse, and sonic velocity in two-phase media

NASA Technical Reports Server (NTRS)

Hsu, Y.

1972-01-01

For single-phase media, the critical discharge velocity, the sonic velocity, and the pressure pulse propagation velocity can be expressed in the same form by assuming isentropic, equilibria processes. In two-phase mixtures, the same concept is not valid due to the existence of interfacial transports of momentum, heat, and mass. Thus, the three velocities should be treated differently and separately for each particular condition, taking into account the various transport processes involved under that condition. Various attempts are reviewed to predict the critical discharge rate or the propagation velocities by considering slip ratio (momentum change), evaporation (mass and heat transport), flow pattern, etc. Experimental data were compared with predictions based on various theorems. The importance is stressed of the time required to achieve equilibrium as compared with the time available during the process, for example, of passing a pressure pulse.

Calculating Pressure-Driven Current Near Magnetic Islands for 3D MHD Equilibria

NASA Astrophysics Data System (ADS)

Radhakrishnan, Dhanush; Reiman, Allan

2016-10-01

In general, 3D MHD equilibria in toroidal plasmas do not result in nested pressure surfaces. Instead, islands and chaotic regions appear in the equilibrium. Near small magnetic islands, the pressure varies within the flux surfaces, which has a significant effect on the pressure-driven current, introducing singularities. Previously, the MHD equilibrium current near a magnetic island was calculated, including the effect of ``stellarator symmetry,'' wherein the singular components of the pressure-driven current vanish [A. H. Reiman, Phys. Plasmas 23, 072502 (2016)]. Here we first solve for pressure in a cylindrical plasma from the heat diffusion equation, after adding a helical perturbation. We then numerically calculate the corresponding Pfirsch-Schluter current. At the small island limit, we compare the pressure-driven current with the previously calculated solution, and far from the island, we recover the solution for nested flux surfaces. Lastly, we compute the current for a toroidal plasma for symmetric and non-symmetric geometries.

Direct calculation of liquid-vapor phase equilibria from transition matrix Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Errington, Jeffrey R.

2003-06-01

An approach for directly determining the liquid-vapor phase equilibrium of a model system at any temperature along the coexistence line is described. The method relies on transition matrix Monte Carlo ideas developed by Fitzgerald, Picard, and Silver [Europhys. Lett. 46, 282 (1999)]. During a Monte Carlo simulation attempted transitions between states along the Markov chain are monitored as opposed to tracking the number of times the chain visits a given state as is done in conventional simulations. Data collection is highly efficient and very precise results are obtained. The method is implemented in both the grand canonical and isothermal-isobaric ensemble. The main result from a simulation conducted at a given temperature is a density probability distribution for a range of densities that includes both liquid and vapor states. Vapor pressures and coexisting densities are calculated in a straightforward manner from the probability distribution. The approach is demonstrated with the Lennard-Jones fluid. Coexistence properties are directly calculated at temperatures spanning from the triple point to the critical point.

Application of Molecular Interaction Volume Model for Phase Equilibrium of Sn-Based Binary System in Vacuum Distillation

NASA Astrophysics Data System (ADS)

Kong, Lingxin; Yang, Bin; Xu, Baoqiang; Li, Yifu

2014-09-01

Based on the molecular interaction volume model (MIVM), the activities of components of Sn-Sb, Sb-Bi, Sn-Zn, Sn-Cu, and Sn-Ag alloys were predicted. The predicted values are in good agreement with the experimental data, which indicate that the MIVM is of better stability and reliability due to its good physical basis. A significant advantage of the MIVM lies in its ability to predict the thermodynamic properties of liquid alloys using only two parameters. The phase equilibria of Sn-Sb and Sn-Bi alloys were calculated based on the properties of pure components and the activity coefficients, which indicates that Sn-Sb and Sn-Bi alloys can be separated thoroughly by vacuum distillation. This study extends previous investigations and provides an effective and convenient model on which to base refining simulations for Sn-based alloys.

Vapor-liquid equilibria for 1,1-difluoroethane + acetylene and 1,1-difluoroethane + 1,1-dichloroethane at 303.2 K and 323.2 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, J.S.; Lee, Y.W.; Kim, J.D.

1996-09-01

Isothermal vapor-liquid equilibria for 1,1-difluoroethane (HFC-152a) + acetylene and 1,1-difluoroethane + 1,1-dichloroethane (HCC-150a) were measured in a circulation type apparatus at 303.2 K and 323.2 K. The experimental data were correlated with the Peng-Robinson equation of state using the Wong and Sandler mixing rule, and the relevant parameters are presented.

Using phase II data for the analysis of phase III studies: An application in rare diseases.

PubMed

Wandel, Simon; Neuenschwander, Beat; Röver, Christian; Friede, Tim

2017-06-01

Clinical research and drug development in orphan diseases are challenging, since large-scale randomized studies are difficult to conduct. Formally synthesizing the evidence is therefore of great value, yet this is rarely done in the drug-approval process. Phase III designs that make better use of phase II data can facilitate drug development in orphan diseases. A Bayesian meta-analytic approach is used to inform the phase III study with phase II data. It is particularly attractive, since uncertainty of between-trial heterogeneity can be dealt with probabilistically, which is critical if the number of studies is small. Furthermore, it allows quantifying and discounting the phase II data through the predictive distribution relevant for phase III. A phase III design is proposed which uses the phase II data and considers approval based on a phase III interim analysis. The design is illustrated with a non-inferiority case study from a Food and Drug Administration approval in herpetic keratitis (an orphan disease). Design operating characteristics are compared to those of a traditional design, which ignores the phase II data. An analysis of the phase II data reveals good but insufficient evidence for non-inferiority, highlighting the need for a phase III study. For the phase III study supported by phase II data, the interim analysis is based on half of the patients. For this design, the meta-analytic interim results are conclusive and would justify approval. In contrast, based on the phase III data only, interim results are inconclusive and require further evidence. To accelerate drug development for orphan diseases, innovative study designs and appropriate methodology are needed. Taking advantage of randomized phase II data when analyzing phase III studies looks promising because the evidence from phase II supports informed decision-making. The implementation of the Bayesian design is straightforward with public software such as R.

Melting phase relations in the Fe-S and Fe-S-O systems at core conditions in small terrestrial bodies

NASA Astrophysics Data System (ADS)

Pommier, Anne; Laurenz, Vera; Davies, Christopher J.; Frost, Daniel J.

2018-05-01

We report an experimental investigation of phase equilibria in the Fe-S and Fe-S-O systems. Experiments were performed at high temperatures (1400-1850 °C) and high pressures (14 and 20 GPa) using a multi-anvil apparatus. The results of this study are used to understand the effect of sulfur and oxygen on core dynamics in small terrestrial bodies. We observe that the formation of solid FeO grains occurs at the Fe-S liquid - Fe solid interface at high temperature ( > 1400 °C at 20 GPa). Oxygen fugacities calculated for each O-bearing sample show that redox conditions vary from ΔIW = -0.65 to 0. Considering the relative density of each phase and existing evolutionary models of terrestrial cores, we apply our experimental results to the cores of Mars and Ganymede. We suggest that the presence of FeO in small terrestrial bodies tends to contribute to outer-core compositional stratification. Depending on the redox and thermal history of the planet, FeO may also help form a transitional redox zone at the core-mantle boundary.

Building fast well-balanced two-stage numerical schemes for a model of two-phase flows

NASA Astrophysics Data System (ADS)

Thanh, Mai Duc

2014-06-01

We present a set of well-balanced two-stage schemes for an isentropic model of two-phase flows arisen from the modeling of deflagration-to-detonation transition in granular materials. The first stage is to absorb the source term in nonconservative form into equilibria. Then in the second stage, these equilibria will be composed into a numerical flux formed by using a convex combination of the numerical flux of a stable Lax-Friedrichs-type scheme and the one of a higher-order Richtmyer-type scheme. Numerical schemes constructed in such a way are expected to get the interesting property: they are fast and stable. Tests show that the method works out until the parameter takes on the value CFL, and so any value of the parameter between zero and this value is expected to work as well. All the schemes in this family are shown to capture stationary waves and preserves the positivity of the volume fractions. The special values of the parameter 0,1/2,1/(1+CFL), and CFL in this family define the Lax-Friedrichs-type, FAST1, FAST2, and FAST3 schemes, respectively. These schemes are shown to give a desirable accuracy. The errors and the CPU time of these schemes and the Roe-type scheme are calculated and compared. The constructed schemes are shown to be well-balanced and faster than the Roe-type scheme.

On application of asymmetric Kan-like exact equilibria to the Earth magnetotail modeling

NASA Astrophysics Data System (ADS)

Korovinskiy, Daniil B.; Kubyshkina, Darya I.; Semenov, Vladimir S.; Kubyshkina, Marina V.; Erkaev, Nikolai V.; Kiehas, Stefan A.

2018-04-01

A specific class of solutions of the Vlasov-Maxwell equations, developed by means of generalization of the well-known Harris-Fadeev-Kan-Manankova family of exact two-dimensional equilibria, is studied. The examined model reproduces the current sheet bending and shifting in the vertical plane, arising from the Earth dipole tilting and the solar wind nonradial propagation. The generalized model allows magnetic configurations with equatorial magnetic fields decreasing in a tailward direction as slow as 1/x, contrary to the original Kan model (1/x3); magnetic configurations with a single X point are also available. The analytical solution is compared with the empirical T96 model in terms of the magnetic flux tube volume. It is found that parameters of the analytical model may be adjusted to fit a wide range of averaged magnetotail configurations. The best agreement between analytical and empirical models is obtained for the midtail at distances beyond 10-15 RE at high levels of magnetospheric activity. The essential model parameters (current sheet scale, current density) are compared to Cluster data of magnetotail crossings. The best match of parameters is found for single-peaked current sheets with medium values of number density, proton temperature and drift velocity.

Collision Index and Stability of Elliptic Relative Equilibria in Planar {n}-body Problem

NASA Astrophysics Data System (ADS)

Hu, Xijun; Ou, Yuwei

2016-12-01

It is well known that a planar central configuration of the {n}-body problem gives rise to solutions where each particle moves on a specific Keplerian orbit while the totality of the particles move on a homographic motion. When the eccentricity {e} of the Keplerian orbit belongs in {[0,1)}, following Meyer and Schmidt, we call such solutions elliptic relative equilibria (shortly, ERE). In order to study the linear stability of ERE in the near-collision case, namely when {1-e} is small enough, we introduce the collision index for planar central configurations. The collision index is a Maslov-type index for heteroclinic orbits and orbits parametrised by half-lines that, according to the definition given by Hu and Portaluri (An index theory for unbounded motions of Hamiltonian systems, Hu and Portaluri (2015, preprint)), we shall refer to as half-clinic orbits and whose definition in this context, is essentially based on a blow up technique in the case {e=1}. We get the fundamental properties of collision index and approximation theorems. As applications, we give some new hyperbolic criteria and prove that, generically, the ERE of minimal central configurations are hyperbolic in the near-collision case, and we give a detailed analysis of Euler collinear orbits in the near-collision case.

Phase equilibria of chlorofluorocarbon alternative refrigerant mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, B.G.; Park, J.Y.; Lim, J.S.

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%.

Experimental Determination of the Phase Diagram of the CaO-SiO2-5 pctMgO-10 pctAl2O3-TiO2 System

NASA Astrophysics Data System (ADS)

Shi, Junjie; Sun, Lifeng; Zhang, Bo; Liu, Xuqiang; Qiu, Jiyu; Wang, Zhaoyun; Jiang, Maofa

2016-02-01

Ti-bearing CaO-SiO2-MgO-Al2O3-TiO2 slags are important for the smelting of vanadium-titanium bearing magnetite. In the current study, the pseudo-melting temperatures were determined by the single-hot thermocouple technique for the specified content of 5 to 25 pct TiO2 in the CaO-SiO2-5 pctMgO-10 pctAl2O3-TiO2 phase diagram system. The 1573 K to 1773 K (1300 °C to 1500 °C) liquidus lines were first calculated based on the pseudo-melting temperatures according to thermodynamic equations in the specific primary crystal field. The phase equilibria at 1573 K (1300 °C) were determined experimentally using the high-temperature equilibrium and quench method followed by X-ray fluorescence, X-ray diffraction, scanning electron microscope, and energy dispersive X-ray spectroscope analysis; the liquid phase, melilite solid solution phase (C2MS2,C2AS)ss, and perovskite phase of CaO·TiO2 were found. Therefore, the phase diagram was constructed for the specified region of the CaO-SiO2-5 pctMgO-10 pctAl2O3-TiO2 system.

Melting and Vaporization of the 1223 Phase in the System (Tl-Pb-Ba-Sr-Ca-Cu-O)

PubMed Central

Cook, L. P.; Wong-Ng, W.; Paranthaman, P.

1996-01-01

The melting and vaporization of the 1223 [(Tl,Pb):(Ba,Sr):Ca:Cu] oxide phase in the system (Tl-Pb-Ba-Sr-Ca-Cu-O) have been investigated using a combination of dynamic methods (differential thermal analysis, thermogravimetry, effusion) and post-quenching characterization techniques (powder x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectrometry). Vaporization rates, thermal events, and melt compositions were followed as a function of thallia loss from a 1223 stoichiometry. Melting and vaporization equilibria of the 1223 phase are complex, with as many as seven phases participating simultaneously. At a total pressure of 0.1 MPa the 1223 phase was found to melt completely at (980 ± 5) °C in oxygen, at a thallia partial pressure (pTl2O) of (4.6 ± 0.5) kPa, where the quoted uncertainties are standard uncertainties, i.e., 1 estimated standard deviation. The melting reaction involves five other solids and a liquid, nominally as follows: 1223→1212+(Ca,Sr)2CuO3+(Sr,Ca)CuO2+BaPbO3+(Ca,Sr)O+Liquid Stoichiometries of the participating phases have been determined from microchemical analysis, and substantial elemental substitution on the 1212 and 1223 crystallographic sites is indicated. The 1223 phase occurs in equilibrium with liquids from its melting point down to at least 935 °C. The composition of the lowest melting liquid detected for the bulk compositions of this study has been measured using microchemical analysis. Applications to the processing of superconducting wires and tapes are discussed. PMID:27805086

Phase-field modeling of chemical control of polarization stability and switching dynamics in ferroelectric thin films

DOE PAGES

Cao, Ye; Kalinin, Sergei V.

2016-12-15

Phase-field simulation (PFS) has revolutionized the understanding of domain structure and switching behavior in ferroelectric thin films and ceramics. Generally, PFS is based on the solution of (a set of) Landau-Ginzburg-Devonshire equations for a defined order parameter field(s) under physical boundary conditions (BCs) of fixed potential or charge. While well matched to the interfaces in bulk materials and devices, these BCs are generally not applicable to free ferroelectric surfaces. Here, we developed a self-consistent phase-field model with BCs based on electrochemical equilibria. We chose Pb(Zr 0.2Ti 0.8)O 3 ultrathin film consisting of (001) oriented single tetragonal domain ( Pz) asmore » a model system and systematically studied the effects of oxygen partial pressure, temperature, and surface ions on the ferroelectric state and compared it with the case of complete screening. We have further explored the polarization switching induced by the oxygen partial pressure and observed pronounced size effect induced by chemical screening. Finally, our paper thus helps to understand the emergent phenomena in ferroelectric thin films brought about by the electrochemical ionic surface compensations.« less

Phase-field modeling of chemical control of polarization stability and switching dynamics in ferroelectric thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Ye; Kalinin, Sergei V.

Phase-field simulation (PFS) has revolutionized the understanding of domain structure and switching behavior in ferroelectric thin films and ceramics. Generally, PFS is based on the solution of (a set of) Landau-Ginzburg-Devonshire equations for a defined order parameter field(s) under physical boundary conditions (BCs) of fixed potential or charge. While well matched to the interfaces in bulk materials and devices, these BCs are generally not applicable to free ferroelectric surfaces. Here, we developed a self-consistent phase-field model with BCs based on electrochemical equilibria. We chose Pb(Zr 0.2Ti 0.8)O 3 ultrathin film consisting of (001) oriented single tetragonal domain ( Pz) asmore » a model system and systematically studied the effects of oxygen partial pressure, temperature, and surface ions on the ferroelectric state and compared it with the case of complete screening. We have further explored the polarization switching induced by the oxygen partial pressure and observed pronounced size effect induced by chemical screening. Finally, our paper thus helps to understand the emergent phenomena in ferroelectric thin films brought about by the electrochemical ionic surface compensations.« less

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

USGS Publications Warehouse

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

2008-01-01

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

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

USGS Publications Warehouse

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

2005-01-01

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

Experimental Liquidus Studies of the Pb-Cu-Si-O System in Equilibrium with Metallic Pb-Cu Alloys

NASA Astrophysics Data System (ADS)

Shevchenko, M.; Nicol, S.; Hayes, P. C.; Jak, E.

2018-03-01

Phase equilibria of the Pb-Cu-Si-O system have been investigated in the temperature range from 1073 K to 1673 K (800 °C to 1400 °C) for oxide liquid (slag) in equilibrium with solid Cu metal and/or liquid Pb-Cu alloy, and solid oxide phases: (a) quartz or tridymite (SiO2) and (b) cuprite (Cu2O). High-temperature equilibration on silica or copper substrates was performed, followed by quenching, and direct measurement of Pb, Cu, and Si concentrations in the liquid and solid phases using the electron probe X-ray microanalysis has been employed to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-"CuO0.5"-SiO2 plane for presentation purposes. The present study is the first-ever systematic investigation of this system to describe the slag liquidus temperatures in the silica and cuprite primary phase fields.

Tradeoffs in Chemical and Thermal Variations in the Post-perovskite Phase Transition: Mixed Phase Regions in the Deep Lower Mantle?

NASA Astrophysics Data System (ADS)

Giles, G. F.; Spera, F. J.; Yuen, D. A.

2005-12-01

The recent discovery of a phase-transition in Mg-rich perovskite (Pv) to a post-perovskite (pPv) phase at lower mantle depths and its relationship to D", lower mantle heterogeneity and iron content prompted an investigation of the relative importance of lower mantle (LM) compositional and temperature fluctuations in creating topographic undulations on mixed phase regions. Above the transition, Mg-rich Pv makes up ~70 percent by mass of the LM. Using results from experimental phase equilibria, first-principles computations and thermodynamic relations for Fe2+-Mg mixing in silicates, a preliminary thermodynamic model for the perovskite to post-perovskite phase transition in the divariant system MgSiO3-FeSiO3 is developed. Complexities associated with components Fe2O3 and Al2O3 and other phases (Ca-Pv, magnesiowustite) are neglected. The model predicts phase transition pressures are sensitive to the FeSiO3 content of perovskite (~-1.5 GPa per one mole percent FeSiO3). This leads to considerable topography along the top boundary of the mixed phase region. The Clapeyron slope for the Pv to pPv transition at XFeSiO3=0.1 is +11 MPa/K about 20% higher than for pure Mg-Pv. Increasing bulk concentration of iron elevates the mixed (two-phase) layer above the core-mantle boundary (CMB); increasing temperature acts to push the mixed layer deeper into the LM into the D" thermal boundary layer resting upon the (CMB). For various LM geotherms and CMB temperatures, a single mixed layer of thickness ~300 km lies within the bottom 40% of the lower mantle. For low iron contents (XFeSiO3 ~5 mole percent or less), two perched layers are found. This is the divariant analog to the univariant double-crosser. The hotter the mantle, the deeper the mixed phase layer; the more iron-rich the LM, the higher the mixed phase layer. In a hotter Hadean Earth with interior temperatures everywhere 200-500 K warmer pPv is not stable unless the LM bulk composition is Fe-enriched compared to the present

Phased array-fed antenna configuration study

NASA Technical Reports Server (NTRS)

Crosswell, W. F.; Ball, D. E.; Taylor, R. C.

1983-01-01

The scope of this contract entails a configuration study for a phased array fed transmit antenna operating in the frequency band of 17.7 to 20.2 GHz. This initial contract provides a basis for understanding the design limitations and advantages of advanced phased array and cluster feeds (both utilizing intergral MMIC modules) illuminating folded reflector optics (both near field and focused types). Design parametric analyses are performed utilizing as constraints the objective secondary performance requirements of the Advanced Communications Technology Satellite (Table 1.0). The output of the study provides design information which serves as a data base for future active phased array fed antenna studies such as detailed designs required to support the development of a ground tested breadboard. In general, this study is significant because it provides the antenna community with an understanding of the basic principles which govern near field phased scanned feed effects on secondary reflector system performance. Although several articles have been written on analysis procedures and results for these systems, the authors of this report have observed phenomenon of near field antenna systems not previously documented. Because the physical justification for the exhibited performance is provided herein, the findings of this study add a new dimension to the available knowledge of the subject matter.

Magnetic islands and singular currents at rational surfaces in three-dimensional magnetohydrodynamic equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loizu, J., E-mail: joaquim.loizu@ipp.mpg.de; Princeton Plasma Physics Laboratory, P.O. Box 451, Princeton New Jersey 08543; Hudson, S.

2015-02-15

Using the recently developed multiregion, relaxed MHD (MRxMHD) theory, which bridges the gap between Taylor's relaxation theory and ideal MHD, we provide a thorough analytical and numerical proof of the formation of singular currents at rational surfaces in non-axisymmetric ideal MHD equilibria. These include the force-free singular current density represented by a Dirac δ-function, which presumably prevents the formation of islands, and the Pfirsch-Schlüter 1/x singular current, which arises as a result of finite pressure gradient. An analytical model based on linearized MRxMHD is derived that can accurately (1) describe the formation of magnetic islands at resonant rational surfaces, (2)more » retrieve the ideal MHD limit where magnetic islands are shielded, and (3) compute the subsequent formation of singular currents. The analytical results are benchmarked against numerical simulations carried out with a fully nonlinear implementation of MRxMHD.« less

Estimating disease prevalence in two-phase studies.

PubMed

Alonzo, Todd A; Pepe, Margaret Sullivan; Lumley, Thomas

2003-04-01

Disease prevalence is ideally estimated using a 'gold standard' to ascertain true disease status on all subjects in a population of interest. In practice, however, the gold standard may be too costly or invasive to be applied to all subjects, in which case a two-phase design is often employed. Phase 1 data consisting of inexpensive and non-invasive screening tests on all study subjects are used to determine the subjects that receive the gold standard in the second phase. Naive estimates of prevalence in two-phase studies can be biased (verification bias). Imputation and re-weighting estimators are often used to avoid this bias. We contrast the forms and attributes of the various prevalence estimators. Distribution theory and simulation studies are used to investigate their bias and efficiency. We conclude that the semiparametric efficient approach is the preferred method for prevalence estimation in two-phase studies. It is more robust and comparable in its efficiency to imputation and other re-weighting estimators. It is also easy to implement. We use this approach to examine the prevalence of depression in adolescents with data from the Great Smoky Mountain Study.

Homeostatic equilibria between free thyroid hormones and pituitary thyrotropin are modulated by various influences including age, body mass index and treatment.

PubMed

Hoermann, Rudolf; Midgley, John E M; Giacobino, Adrienne; Eckl, Walter A; Wahl, Hans Günther; Dietrich, Johannes W; Larisch, Rolf

2014-12-01

We examined the interrelationships of pituitary thyrotropin (TSH) with circulating thyroid hormones to determine whether they were expressed either invariably or conditionally and distinctively related to influences such as levothyroxine (L-T4) treatment. This prospective study employing 1912 consecutive patients analyses the interacting equilibria of TSH and free triiodothyronine (FT3) and free thyroxine (FT4) in the circulation. The complex interrelations between FT3, FT4 and TSH were modulated by age, body mass, thyroid volume, antibody status and L-T4 treatment. By group comparison and confirmation by more individual TSH-related regression, FT3 levels were significantly lower in L-T4-treated vs untreated nonhypothyroid autoimmune thyroiditis (median 4·6 vs 4·9 pm, P < 0·001), despite lower TSH (1·49 vs 2·93 mU/l, P < 0·001) and higher FT4 levels (16·8 vs 13·8 pm, P < 0·001) in the treated group. Compared with disease-free controls, the FT3-TSH relationship was significantly displaced in treated patients with carcinoma, with median TSH of 0·21 vs 1·63 (P < 0·001) at a comparable FT3 of 5·0 pm in the groups. Disparities were reflected by calculated deiodinase activity and remained significant even after accounting for confounding influences in a multivariable model. TSH, FT4 and FT3 each have their individual, but also interlocking roles to play in defining the overall patterns of thyroidal expression, regulation and metabolic activity. Equilibria typical of the healthy state are not invariant, but profoundly altered, for example, by L-T4 treatment. Consequently, this suggests the revisitation of strategies for treatment optimization. © 2014 John Wiley & Sons Ltd.

Simulating Donnan equilibria based on the Nernst-Planck equation

NASA Astrophysics Data System (ADS)

Gimmi, Thomas; Alt-Epping, Peter

2018-07-01

Understanding ion transport through clays and clay membranes is important for many geochemical and environmental applications. Ion transport is affected by electrostatic forces exerted by charged clay surfaces. Anions are partly excluded from pore water near these surfaces, whereas cations are enriched. Such effects can be modeled by the Donnan approach. Here we introduce a new, comparatively simple way to represent Donnan equilibria in transport simulations. We include charged surfaces as immobile ions in the balance equation and calculate coupled transport of all components, including the immobile charges, with the Nernst-Planck equation. This results in an additional diffusion potential that influences ion transport, leading to Donnan ion distributions while maintaining local charge balance. The validity of our new approach was demonstrated by comparing Nernst-Planck simulations using the reactive transport code Flotran with analytical solutions available for simple Donnan systems. Attention has to be paid to the numerical evaluation of the electrochemical migration term in the Nernst-Planck equation to obtain correct results for asymmetric electrolytes. Sensitivity simulations demonstrate the influence of various Donnan model parameters on simulated anion accessible porosities. It is furthermore shown that the salt diffusion coefficient in a Donnan pore depends on local concentrations, in contrast to the aqueous salt diffusion coefficient. Our approach can be easily implemented into other transport codes. It is versatile and facilitates, for instance, assessing the implications of different activity models for the Donnan porosity.

Dynamical analysis of a cubic Liénard system with global parameters (II)

NASA Astrophysics Data System (ADS)

Chen, Hebai; Chen, Xingwu

2016-06-01

In this paper, we continue to study the global dynamics of a cubic Liénard system for global parameters in the case of three equilibria to follow (2015 Nonlinearity 28 3535-62), which deals with the case of two equilibria. We first analyse qualitative properties of all equilibria and judge the existences of limit cycles and homoclinic loops and their numbers. Then we obtain the bifurcation diagram and all phase portraits as our main results. Based on these results, in the case of three equilibria a positive answer to conjecture 3.2 of (1998 Nonlinearity 11 1505-19), which is about the existence of some function whose graph is exactly the surface of double limit cycles, is obtained. Moreover, a parameter region for the nonexistence of figure-eight loops is given theoretically to compensate for previous numerical results and is illustrated numerically. Supported by NSFC 11471228, 11572263, the Fundamental Research Funds for the Central Universities and Cultivation Foundation of Excellent Doctoral Dissertation of Southwest Jiaotong University (2015).

Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marin, T.; Shkrob, I.; Dietz, M.

2011-04-14

Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between differentmore » clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.« less

Vapor-liquid equilibria for 1,1,1,2-tetrafluoroethane + 1-chloro-1,2,2,2-tetrafluoroethane and 1-chloro-1,2,2,2-tetrafluoroethane + 1-chloro-1,1-difluoroethane systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.; Lee, J.; Kim, H.

1996-07-01

Isothermal vapor-liquid equilibria were determined for two binary mixtures of refrigerants with a circulation type apparatus. The 1,1,1,2-tetrafluoroethane (HFC-134a) + 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124) system was studied at 296.45, 302.25, and 307.25 K. The 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124) + 1-chloro-1,1-difluoroethane (HCFC-142b) system was studied at 298.15 and 312.15 K. At each temperature, the pressure and vapor and liquid compositions were measured. Results were correlated with the Peng-Robinson equation of state.

Ammonium Ion Binding to DNA G-Quadruplexes: Do Electrospray Mass Spectra Faithfully Reflect the Solution-Phase Species?

NASA Astrophysics Data System (ADS)

Balthasart, Françoise; Plavec, Janez; Gabelica, Valérie

2013-01-01

G-quadruplex nucleic acids can bind ammonium ions in solution, and these complexes can be detected by electrospray mass spectrometry (ESI-MS). However, because ammonium ions are volatile, the extent to which ESI-MS quantitatively could provide an accurate reflection of such solution-phase equilibria is unclear. Here we studied five G-quadruplexes having known solution-phase structure and ammonium ion binding constants: the bimolecular G-quadruplexes (dG4T4G4)2, (dG4T3G4)2, and (dG3T4G4)2, and the intramolecular G-quadruplexes dG4(T4G4)3 and dG2T2G2TGTG2T2G2 (thrombin binding aptamer). We found that not all mass spectrometers are equally suited to reflect the solution phase species. Ion activation can occur in the electrospray source, or in a high-pressure traveling wave ion mobility cell. When the softest instrumental conditions are used, ammonium ions bound between G-quartets, but also additional ammonium ions bound at specific sites outside the external G-quartets, can be observed. However, even specifically bound ammonium ions are in some instances too labile to be fully retained in the gas phase structures, and although the ammonium ion distribution observed by ESI-MS shows biases at specific stoichiometries, the relative abundances in solution are not always faithfully reflected. Ion mobility spectrometry results show that all inter-quartet ammonium ions are necessary to preserve the G-quadruplex fold in the gas phase. Ion mobility experiments, therefore, help assign the number of inner ammonium ions in the solution phase structure.[Figure not available: see fulltext.

Topology-dependent rationality and quantal response equilibria in structured populations

NASA Astrophysics Data System (ADS)

Roman, Sabin; Brede, Markus

2017-05-01

Given that the assumption of perfect rationality is rarely met in the real world, we explore a graded notion of rationality in socioecological systems of networked actors. We parametrize an actors' rationality via their place in a social network and quantify system rationality via the average Jensen-Shannon divergence between the games Nash and logit quantal response equilibria. Previous work has argued that scale-free topologies maximize a system's overall rationality in this setup. Here we show that while, for certain games, it is true that increasing degree heterogeneity of complex networks enhances rationality, rationality-optimal configurations are not scale-free. For the Prisoner's Dilemma and Stag Hunt games, we provide analytic arguments complemented by numerical optimization experiments to demonstrate that core-periphery networks composed of a few dominant hub nodes surrounded by a periphery of very low degree nodes give strikingly smaller overall deviations from rationality than scale-free networks. Similarly, for the Battle of the Sexes and the Matching Pennies games, we find that the optimal network structure is also a core-periphery graph but with a smaller difference in the average degrees of the core and the periphery. These results provide insight on the interplay between the topological structure of socioecological systems and their collective cognitive behavior, with potential applications to understanding wealth inequality and the structural features of the network of global corporate control.

Topology-dependent rationality and quantal response equilibria in structured populations.

PubMed

Roman, Sabin; Brede, Markus

2017-05-01

Given that the assumption of perfect rationality is rarely met in the real world, we explore a graded notion of rationality in socioecological systems of networked actors. We parametrize an actors' rationality via their place in a social network and quantify system rationality via the average Jensen-Shannon divergence between the games Nash and logit quantal response equilibria. Previous work has argued that scale-free topologies maximize a system's overall rationality in this setup. Here we show that while, for certain games, it is true that increasing degree heterogeneity of complex networks enhances rationality, rationality-optimal configurations are not scale-free. For the Prisoner's Dilemma and Stag Hunt games, we provide analytic arguments complemented by numerical optimization experiments to demonstrate that core-periphery networks composed of a few dominant hub nodes surrounded by a periphery of very low degree nodes give strikingly smaller overall deviations from rationality than scale-free networks. Similarly, for the Battle of the Sexes and the Matching Pennies games, we find that the optimal network structure is also a core-periphery graph but with a smaller difference in the average degrees of the core and the periphery. These results provide insight on the interplay between the topological structure of socioecological systems and their collective cognitive behavior, with potential applications to understanding wealth inequality and the structural features of the network of global corporate control.

Reactions between palladium and gallium arsenide: Bulk versus thin-film studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, J.; Hsieh, K.; Schulz, K.J.

1988-01-01

Reactions between Pd and GaAs have been studied using bulk-diffusion couples of Pd (approx.0.6 mm thick)/GaAs and thin-film Pd (50 and 160 nm)/GaAs samples. The sequence of phase formation at 600 /sup 0/C between bulk Pd and GaAs was established. Initial formation of the solution phase ..mu.. and the ternary phase T does not represent the stable configuration. The stable configuration is GaAs chemically bondepsilonchemically bondlambdachemically bond..gamma..chemically bond..nu..chemically bondPd and is termed the diffusion path between GaAs and Pd. The sequence of phase formation for the bulk-diffusion couples is similar at 500 /sup 0/C. Phase formation for the thin-film Pd/GaAsmore » specimens was studied at 180, 220, 250, 300, 350, 400, 450, 600, and 1000 /sup 0/C for various annealing times. The sequence of phase formation obtained from the thin-film experiments is rationalized readily from the known ternary phase equilibria of Ga--Pd--As and the results from the bulk-diffusion couples of Pd/GaAs. The thin-film results reported in the literature are likewise rationalized. The diffusion path concept provides a useful guide in understanding the phase formation in Pd--GaAs interface or any other M--GaAs interface. This information is important in designing a uniform, stable contact for the metallization of GaAs.« less

Entropy Production in Collisionless Systems. II. Arbitrary Phase-space Occupation Numbers

NASA Astrophysics Data System (ADS)

Barnes, Eric I.; Williams, Liliya L. R.

2012-04-01

We present an analysis of two thermodynamic techniques for determining equilibria of self-gravitating systems. One is the Lynden-Bell (LB) entropy maximization analysis that introduced violent relaxation. Since we do not use the Stirling approximation, which is invalid at small occupation numbers, our systems have finite mass, unlike LB's isothermal spheres. (Instead of Stirling, we utilize a very accurate smooth approximation for ln x!.) The second analysis extends entropy production extremization to self-gravitating systems, also without the use of the Stirling approximation. In addition to the LB statistical family characterized by the exclusion principle in phase space, and designed to treat collisionless systems, we also apply the two approaches to the Maxwell-Boltzmann (MB) families, which have no exclusion principle and hence represent collisional systems. We implicitly assume that all of the phase space is equally accessible. We derive entropy production expressions for both families and give the extremum conditions for entropy production. Surprisingly, our analysis indicates that extremizing entropy production rate results in systems that have maximum entropy, in both LB and MB statistics. In other words, both thermodynamic approaches lead to the same equilibrium structures.

Thermodynamic Studies of High Temperature Materials Via Knudsen Cell Mass Spectrometry

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Brady, Michael P.

1997-01-01

The Knudsen Cell technique is a classic technique from high temperature chemistry for studying condensed phase/vapor equilibria. It is based on a small enclosure, usually about 1 cm in diameter by 1 cm high, with an orifice of well-defined geometry. This forms a molecular beam which is analyzed with mass spectrometry. There are many applications to both fundamental and applied problems with high temperature materials. Specific measurements include vapor pressures and vapor compositions above solids, activities of alloy components, and fundamental gas/solid reactions. The basic system is shown. Our system can accommodate a wide range of samples, temperatures, and attachments, such as gas inlets. It is one of only about ten such systems world-wide.

[Critical phenomena, phase equilibria, and the temperature and structural optimum of homeostasis, as revealed by a model system water-biopolymer-electrolyte].

PubMed

Rozhkov, S P

2005-01-01

Equations of spinodal and two quasispinodals corresponding to critical and supercritical phase transitions leading to a rise of different dynamic structures of solution in the phase diagram of a model system water-biopolymer-electrolyte were obtained. The section of the phase diagram was considered where there exists the probability of quasi-equilibrium monomer-cluster and the principle of water-ion homeostasis is realized. Based on these results, a possible mechanism of origination of unspecific adaptation reactions of a biomolecular system at the stage of chemical evolution was suggested.

From micron to mountain-scale, using accessory phase petrochronology to quantify the rates of deformation in the Himalaya and beyond

NASA Astrophysics Data System (ADS)

Mottram, C. M.

2016-12-01

Mountains form where the Earth's plates collide; during this upheaval rocks are deformed by massive forces. The rates and timescales over which these deformational processes occur are determined from tiny accessory minerals that record geological time through radioactive decay. However, there remain major unresolved challenges in using chemical and microstructural markers to link the dates yielded from these accessory phases to specific deformation events and discerning the effects of deformation on the isotopic and elemental tracers in these phases. Here, the chemical signatures and deformation textures from micron-scale accessory phases are used to decode the record of mountain belt-scale deformational processes encrypted in the rocks. The Himalayan orogen is used as an ideal natural laboratory to understand the chemical processes that have modified the Earth's crust during orogenesis. Combined laser ablation split-stream U-Th-Pb and REE analysis of deformed monazite and titanite, along with Electron BackScatter Diffraction (EBSD) imaging and Pressure-Temperature (P-T) phase equilibria modelling are used to: (1) link accessory phase `age' to `metamorphic stage'; (2) to quantify the influence of deformation on monazite (re)crystallisation mechanisms and its subsequent effect on the crystallographic structure, ages and trace-element distribution in individual grains; and (3) understand how deformation is accommodated through different chemical and structural processes that operate at varying scales through time. This study highlights the importance of fully integrating the pressure-temperature-time-deformation history of multiple accessory phases to better interpret the deformational history of the cores of evolving mountain belts.

Effect of Binding Components in Complex Sample Matrices on Recovery in Direct Immersion Solid-Phase Microextraction: Friends or Foe?

PubMed

Alam, Md Nazmul; Pawliszyn, Janusz

2018-02-20

The development of matrix compatible coatings for solid-phase microextraction (SPME) has enabled direct extraction of analytes from complex sample matrices. The direct immersion (DI) mode of SPME when utilized in conjunction with such extraction phases facilitates extraction of a wide range of analytes from complex matrices without the incurrence of fouling or coating saturation. In this work, mathematical models and computational simulations were employed to investigate the effect of binding components present in complex samples on the recovery of small molecules varying in logP for extractions carried out using the direct immersion approach. The presented findings corroborate that the studied approach indeed enables the extraction of both polar and nonpolar analytes from complex matrices, provided a suitable sorbent is employed. Further results indicated that, in certain cases, the kinetics of extraction of a given analyte in its free form might be dependent on the desorption kinetics of their bound form from matrix components, which might lower total recoveries of analytes with high affinity for the matrix. However, the binding of analytes to matrix components also enables SPME to extract a balanced quantity of different logP analytes, facilitated by multiphase equilibria, with a single extraction device.

Theory of equilibria of elastic braids with applications to DNA supercoiling

NASA Astrophysics Data System (ADS)

van der Heijden, Gert; Starostin, Eugene

2014-03-01

Motivated by supercoiling of DNA and other filamentous structures, we formulate a new theory for equilibria of 2-braids, i.e., structures formed by two elastic rods winding around each other in continuous contact and subject to a local interstrand interaction. Unlike in previous work no assumption is made on the shape of the contact curve. Rather, this shape is solved for. The theory is developed in terms of a moving frame of directors attached to one of the strands with one of the directors pointing to the position of the other strand. The constant-distance constraint is automatically satisfied by the introduction of what we call braid strains. The price we pay is that the potential energy involves arclength derivatives of these strains, thus giving rise to a second-order variational problem. The Euler-Lagrange equations for this problem give balance equations for the overall braid force and moment referred to the moving frame as well as differential equations that can be interpreted as effective constitutive relations encoding the effect that the second strand has on the first as the braid deforms under the action of end loads. Both open braid and closed braid solutions (links and knots) are computed and current applications to DNA supercoiling are discussed. Research supported by EPSRC and HFSP.

Study Of Phase Separation In Glass

NASA Technical Reports Server (NTRS)

Neilson, George F.; Weinberg, Michael C.; Smith, Gary L.

1989-01-01

Report describes an experimental study of effect of hydroxide content on phase separation in soda/silica glasses. Ordinary and gel glasses melted at 1,565 degree C, and melts stirred periodically. "Wet" glasses produced by passing bubbles of N2 saturated with water through melts; "dry" glasses prepared in similar manner, except N2 dried before passage through melts. Analyses of compositions of glasses performed by atomic-absorption and index-of-refraction measurements. Authors conclude hydroxide speeds up phase separation, regardless of method (gel or ordinary) by which glass prepared. Eventually helps material scientists to find ways to control morphology of phase separation.

Biologically-controlled multiple equilibria of tidal landforms and the fate of the Venice lagoon

NASA Astrophysics Data System (ADS)

Marani, Marco; D'Alpaos, Andrea; Lanzoni, Stefano; Carniello, Luca; Rinaldo, Andrea

2007-06-01

Looking across a tidal landscape, can one foresee the signs of impending shifts among different geomorphological structures? This is a question of paramount importance considering the ecological, cultural and socio-economic relevance of tidal environments and their worldwide decline. In this Letter we argue affirmatively by introducing a model of the coupled tidal physical and biological processes. Multiple equilibria, and transitions among them, appear in the evolutionary dynamics of tidal landforms. Vegetation type, disturbances of the benthic biofilm, sediment availability and marine transgressions or regressions drive the bio-geomorphic evolution of the system. Our approach provides general quantitative routes to model the fate of tidal landforms, which we illustrate in the case of the Venice lagoon (Italy), for which a large body of empirical observations exists spanning at least five centuries. Such observations are reproduced by the model, which also predicts that salt marshes in the Venice lagoon may not survive climatic changes in the next century if IPCC's scenarios of high relative sea level rise occur.

Thermodynamic effects of calcium and iron oxides on crystal phase formation in synthetic gasifier slags containing from 0 to 27wt.% V 2O 3

DOE PAGES

Nakano, Jinichiro; Duchesne, Marc; Bennett, James; ...

2014-11-15

Thermodynamic phase equilibria in synthetic slags (Al 2O 3–CaO–FeO–SiO 2–V 2O 3) were investigated with 0–27 wt.% vanadium oxide corresponding to industrial coal–petroleum coke (petcoke) feedstock blends in a simulated gasifier environment. Samples encompassing coal–petcoke mixed slag compositions were equilibrated at 1500 °C in a 64 vol.% CO/36 vol.% CO 2 atmosphere (Po 2 ≈ 10 –8 atm at 1500 °C) for 72 h, followed by rapid water quench, then analyzed by inductively coupled plasma optical emission spectrometry, X-ray diffractometry, and scanning electron microscopy with wavelength dispersive spectroscopy. With increasing CaO content, FeO content, or both; the slag homogeneity regionmore » expanded and a composition range exhibiting crystals was reduced. The mullite (Al 6Si 2O 13) crystalline phase was not present in the slags above 9 wt.% FeO while the karelianite (V 2O 3) crystalline phase was always present in compositions studied if a sufficient amount of vanadium existed in the slag. Furthermore, based on the present experimental equilibrium evaluation, a set of isothermal phase diagrams showing effects of CaO and FeO on thermodynamic phase stabilities in the vanadium-bearing slags is proposed. Some uses of the diagrams for potential industrial practice are discussed.« less

Microelectrode voltammetry of multi-electron transfers complicated by coupled chemical equilibria: a general theory for the extended square scheme.

PubMed

Laborda, Eduardo; Gómez-Gil, José María; Molina, Angela

2017-06-28

A very general and simple theoretical solution is presented for the current-potential-time response of reversible multi-electron transfer processes complicated by homogeneous chemical equilibria (the so-called extended square scheme). The expressions presented here are applicable regardless of the number of electrons transferred and coupled chemical processes, and they are particularized for a wide variety of microelectrode geometries. The voltammetric response of very different systems presenting multi-electron transfers is considered for the most widely-used techniques (namely, cyclic voltammetry, square wave voltammetry, differential pulse voltammetry and steady state voltammetry), studying the influence of the microelectrode geometry and the number and thermodynamics of the (electro)chemical steps. Most appropriate techniques and procedures for the determination of the 'interaction' between successive transfers are discussed. Special attention is paid to those situations where homogeneous chemical processes, such as protonation, complexation or ion association, affect the electrochemical behaviour of the system by different stabilization of the oxidation states.

Analysis of phase II studies on targeted agents and subsequent phase III trials: what are the predictors for success?

PubMed

Chan, John K; Ueda, Stefanie M; Sugiyama, Valerie E; Stave, Christopher D; Shin, Jacob Y; Monk, Bradley J; Sikic, Branimir I; Osann, Kathryn; Kapp, Daniel S

2008-03-20

To identify the characteristics of phase II studies that predict for subsequent "positive" phase III trials (those that reached the proposed primary end points of study or those wherein the study drug was superior to the standard regimen investigating targeted agents in advanced tumors. We identified all phase III clinical trials of targeted therapies against advanced cancers published from 1985 to 2005. Characteristics of the preceding phase II studies were reviewed to identify predictive factors for success of the subsequent phase III trial. Data were analyzed using the chi(2) test and logistic regression models. Of 351 phase II studies, 167 (47.6%) subsequent phase III trials were positive and 184 (52.4%) negative. Phase II studies from multiple rather than single institutions were more likely to precede a successful trial (60.4% v 39.4%; P < .001). Positive phase II results were more likely to lead to a successful phase III trial (50.8% v 22.5%; P = .003). The percentage of successful trials from pharmaceutical companies was significantly higher compared with academic, cooperative groups, and research institutes (89.5% v 44.2%, 45.2%, and 46.3%, respectively; P = .002). On multivariate analysis, these factors and shorter time interval between publication of phase II results and III study publication were independent predictive factors for a positive phase III trial. In phase II studies of targeted agents, multiple- versus single-institution participation, positive phase II trial, pharmaceutical company-based trials, and shorter time period between publication of phase II to phase III trial were independent predictive factors of success in a phase III trial. Investigators should be cognizant of these factors in phase II studies before designing phase III trials.

Theory and computation of general force balance in non-axisymmetric tokamak equilibria

NASA Astrophysics Data System (ADS)

Park, Jong-Kyu; Logan, Nikolas; Wang, Zhirui; Kim, Kimin; Boozer, Allen; Liu, Yueqiang; Menard, Jonathan

2014-10-01

Non-axisymmetric equilibria in tokamaks can be effectively described by linearized force balance. In addition to the conventional isotropic pressure force, there are three important components that can strongly contribute to the force balance; rotational, anisotropic tensor pressure, and externally given forces, i.e. ∇ --> p + ρv-> . ∇ --> v-> + ∇ --> . <-->Π + f-> = j-> × B-> , especially in, but not limited to, high β and rotating plasmas. Within the assumption of nested flux surfaces, Maxwell equations and energy minimization lead to the modified-generalized Newcomb equation for radial displacements with simple algebraic relations for perpendicular and parallel displacements, including an inhomogeneous term if any of the forces are not explicitly dependent on displacements. The general perturbed equilibrium code (GPEC) solves this force balance consistent with energy and torque given by external perturbations. Local and global behaviors of solutions will be discussed when ∇ --> . <-->Π is solved by the semi-analytic code PENT and will be compared with MARS-K. Any first-principle transport code calculating ∇ --> . <-->Π or f-> , e.g. POCA, can also be incorporated without demanding iterations. This work was supported by DOE Contract DE-AC02-09CH11466.

Two Phase Detonation Studies Conducted in 1971

NASA Technical Reports Server (NTRS)

Nicholls, J. A.

1972-01-01

The research covered by this third annual progress report represents a continuation of our efforts devoted to the study of detonation waves in liquid-gas systems. The motivation for the work is associated with liquid propellant rocket motor combustion instability although certainly the studies are also applicable to internal combustion engines, jet propulsion engines, safety aspects of spilled liquid fuel, coal mine explosions, and weaponry. The research has been divided into 5 phases, although all of them are intimately related. For the most part these phases are briefly summarized and the reader is referred to other publications for a more complete treatment. The exception to this is where the material herein represents the only printed information available on the particular facet of the problem. Phase A has been primarily concerned with the breakup and ignition of fuel drops by shock waves. The experimental portion of this study as well as a theoretical treatment of the ignition behavior was completed in the past year. The research is now concentrating on the passage of a shock wave over a burning drop. Phase B has been devoted to the assessment of the approximate energy release pattern in two phase detonations insofar as they affect the significant overpressures observed.

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

PubMed

Spalding, B P; Spalding, I R

2001-01-15

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

Interpretation of open system petrogenetic processes: Phase equilibria constraints on magma evolution

NASA Astrophysics Data System (ADS)

Defant, Marc J.; Nielsen, Roger L.

1990-01-01

occurred. Most basaltic magmas cannot evolve to high silica compositions without magnetite fractionation. Small amounts of rhyolite assimilation (assimilation/fractionation < 0.1), however, can drive evolving basalts to more silica rich compositions. If mass balance models are used to interpret these synthetic AFC data, low residuals are obtained if magnetite is added to the crystallizing assemblage. This approach works even for cases where magnetite was not a fractionating phase. Thus, the mass balance results are mathematically correct, but are geologically irrelevant.

Vapor-liquid equilibria for difluoromethane + dichloromethane at 303.2 and 313.2 K and 1,1-difluoroethane + vinyl chloride at 303.2 and 323.2 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, J.S.; Lee, Y.W.; Lee, Y.Y.

1997-05-01

Isothermal vapor-liquid equilibria for difluoromethane (HFC-32) + dichloromethane at 303.2 K and 313.2 K and 1,1-difluoroethane (HFC-152a) + vinyl chloride at 303.2 K and 323.2 K were measured in a circulation-type apparatus. The experimental data were correlated with the Peng-Robinson equation of state using the Wong and Sandler mixing rule, and the relevant parameters are presented.

DNS study of speed of sound in two-phase flows with phase change

NASA Astrophysics Data System (ADS)

Fu, Kai; Deng, Xiaolong

2017-11-01

Heat transfer through pipe flow is important for the safety of thermal power plants. Normally it is considered incompressible. However, in some conditions compressibility effects could deteriorate the heat transfer efficiency and even result in pipe rupture, especially when there is obvious phase change, due to the much lower sound speed in liquid-gas mixture flows. Based on the stratified multiphase flow model (Chang and Liou, JCP 2007), we present a new approach to simulate the sound speed in 3-D compressible two-phase dispersed flows, in which each face is divided into gas-gas, gas-liquid, and liquid-liquid parts via reconstruction by volume fraction, and fluxes are calculated correspondingly. Applying it to well-distributed air-water bubbly flows, comparing with the experiment measurements in air water mixture (Karplus, JASA 1957), the effects of adiabaticity, viscosity, and isothermality are examined. Under viscous and isothermal condition, the simulation results match the experimental ones very well, showing the DNS study with current method is an effective way for the sound speed of complex two-phase dispersed flows. Including the two-phase Riemann solver with phase change (Fechter et al., JCP 2017), more complex problems can be numerically studied.

LST phase A design update study

NASA Technical Reports Server (NTRS)

1973-01-01

An update is presented of the Phase A study of the Large Space Telescope (LST), based on changes in guidelines and new data developed subsequent to the Phase A study. The study defines an LST concept based on the broad mission guidelines provided by the Office of Space Science (OSS), the scientific requirements developed by OSS with the scientific community, and an understanding of long range NASA planning current at the time the study was performed. A low cost design approach was followed. This resulted in the use of standard spacecraft hardware, the provision for maintenance at the black box level, growth potential in systems designs, and sharing of shuttle maintenance flights with other payloads (See N73-18449 through N73-18453)

Evaluation of mineral-aqueous chemical equilibria of felsic reservoirs with low-medium temperature: A comparative study in Yangbajing geothermal field and Guangdong geothermal fields

NASA Astrophysics Data System (ADS)

Li, Jiexiang; Sagoe, Gideon; Yang, Guang; Lu, Guoping

2018-02-01

Classical geothermometers are useful tools for estimating reservoir temperatures of geothermal systems. However, their application to low-medium temperature reservoirs is limited because large variations of temperatures calculated by different classical geothermometers are usually observed. In order to help choose the most appropriate classical geothermometer for calculating the temperatures of low-medium temperature reservoirs, this study evaluated the mineral-aqueous equilibria of typical low-medium temperature felsic reservoirs in the Yangbajing geothermal field and Guangdong geothermal fields. The findings of this study support that reservoirs in the Guangdong geothermal fields have no direct magma influence. Also, natural reservoirs may represent the intermediate steady state before reaching full equilibrium, which rarely occurs. For the low-medium temperature geothermal systems without the influence of magma, even with seawater intrusion, the process of minerals reaching mineral-aqueous equilibrium is sequential: chlorite and chalcedony are the first, then followed by K-feldspar, kaolinite and K-mica. Chlorite may reach equilibrium at varying activity values, and the equilibrium between K-feldspar and kaolinite or K-feldspar and K-mica can fix the contents of K and Al in the solutions. Although the SiO2 and Al attain equilibrium state, albite and laumontite remain unsaturated and thus may affect low-medium temperature calculations. In this study, the chalcedony geothermometer was found to be the most suitable geothermometer for low-medium temperature reservoirs. The results of K-Mg geothermometer may be useful to complement that of the chalcedony geothermometer in low-medium temperature reservoir systems. Na-K geothermometer will give unreliable results at low-medium temperatures; and Na-K-Ca will also be unsuitable to calculate reservoir temperatures lower than 180 °C, probably caused by the chemical imbalance of laumontite.

Spin State Equilibria of Asteroids due to YORP Effects

NASA Astrophysics Data System (ADS)

Golubov, Oleksiy; Scheeres, Daniel J.; Lipatova, Veronika

2016-05-01

Spins of small asteroids are controlled by the Yarkovsky--O'Keefe--Radzievskii--Paddack (YORP) effect. The normal version of this effect has two components: the axial component alters the rotation rate, while the obliquity component alters the obliquity. Under this model the rotation state of an asteroid can be described in a phase plane with the rotation rate along the polar radius and the obliquity as the polar angle. The YORP effect induces a phase flow in this plane, which determines the distribution of asteroid rotation rates and obliquities.We study the properties of this phase flow for several typical cases. Some phase flows have stable attractors, while in others all trajectories go to very small or large rotation rates. In the simplest case of zero thermal inertia approximate analytical solutions to dynamics equations are possible. Including thermal inertia and the Tangential YORP effect makes the possible evolutionary scenarios much more diverse. We study possible evolution paths and classify the most general trends. Also we discuss possible implications for the distribution of asteroid rotation rates and obliquities.A special emphasis is put on asteroid (25143) Itokawa, whose shape model is well determined, but who's measured YORP acceleration does not agree with the predictions of normal YORP. We show that Itokawa's rotational state can be explained by the presence of tangential YORP and that it may be in or close to a stable spin state equilibrium. The implications of such states will be discussed.

NHEXAS PHASE I MARYLAND STUDY

EPA Science Inventory

The National Human Exposure Assessment Survey (NHEXAS) is a federal interagency research effort coordinated by the Environmental Protection Agency (EPA), Office of Research and Development (ORD). Phase I consists of demonstration/scoping studies using probability-based sampling ...

Studying Suspended Sediment Mechanism with Two-Phase PIV

NASA Astrophysics Data System (ADS)

Matinpour, H.; Atkinson, J. F.; Bennett, S. J.; Guala, M.

2017-12-01

Suspended sediment transport affects soil erosion, agriculture and water resources quality. Turbulent diffusion is the most primary force to maintain sediments in suspension. Although extensive previous literature have been studying the interactions between turbulent motion and suspended sediment, mechanism of sediments in suspension is still poorly understood. In this study, we investigate suspension of sediments as two distinct phases: one phase of sediments and another phase of fluid with turbulent motions. We designed and deployed a state-of-the-art two-phase PIV measurement technique to discriminate these two phases and acquire velocities of each phase separately and simultaneously. The technique that we have developed is employing a computer-vision based method, which enables us to discriminate sediment particles from fluid tracer particles based on two thresholds, dissimilar particle sizes and different particle intensities. Results indicate that fluid turbulence decreases in the presence of suspended sediments. Obtaining only sediment phase consecutive images enable us to compute fluctuation sediment concentration. This result enlightens understanding of complex interaction between the fluctuation velocities and the fluctuation of associated mass and compares turbulent viscosity with turbulent eddy diffusivity experimentally.

Studies in Three Phase Gas-Liquid Fluidised Systems

NASA Astrophysics Data System (ADS)

Awofisayo, Joyce Ololade

1992-01-01

Available from UMI in association with The British Library. The work is a logical continuation of research started at Aston some years ago when studies were conducted on fermentations in bubble columns. The present work highlights typical design and operating problems that could arise in such systems as waste water, chemical, biochemical and petroleum operations involving three-phase, gas-liquid -solid fluidisation; such systems are in increasing use. It is believed that this is one of few studies concerned with "true" three-phase, gas-liquid-solid fluidised systems, and that this work will contribute significantly to closing some of the gaps in knowledge in this area. The research work was experimentally based and involved studies of the hydrodynamic parameters, phase holdups (gas and solid), particle mixing and segregation, and phase flow dynamics (flow regime and circulation patterns). The studies have focused particularly on the solid behaviour and the influence of properties of solids present on the above parameters in three-phase, gas-liquid-solid fluidised systems containing single particle components and those containing binary and ternary mixtures of particles. All particles were near spherical in shape and two particle sizes and total concentration levels were used. Experiments were carried out in two- and three-dimensional bubble columns. Quantitative results are presented in graphical form and are supported by qualitative results from visual studies which are also shown as schematic diagrams and in photographic form. Gas and solid holdup results are compared for air-water containing single, binary and ternary component particle mixtures. It should be noted that the criteria for selection of the materials used are very important if true three-phase fluidisation is to be achieved: this is very evident when comparing the results with those in the literature. The fluid flow and circulation patterns observed were assessed for validation of the generally

NHEXAS PHASE I ARIZONA STUDY

EPA Science Inventory

The National Human Exposure Assessment Survey (NHEXAS) is a federal interagency research effort coordinated by the Environmental Protection Agency (EPA), Office of Research and Development (ORD). The objective of the NHEXAS Phase I Arizona study was to determine the distribution...

Experimental Investigation of the 1073 K (800 °C) Isothermal Section of the Al-V-Zr Ternary System

NASA Astrophysics Data System (ADS)

Zhu, Yude; Ouyang, Xuemei; Yin, Fucheng; Zhao, Manxiu; Lou, Jia

2018-03-01

This work is focused on an experimental investigation of the phase equilibria of the Al-V-Zr system at 1073 K (800 °C). The phase equilibria were analyzed using scanning electron microscopy (SEM) coupled with energy-dispersive spectrometry and X-ray diffraction. The results confirmed the presence of twelve three-phase regions and one ternary compound, Τ, which contains 10.0 to 16.5 at. pct Zr, 52.8 to 55.2 at. pct Al, and 29.3 to 36.3 at. pct V. The T phase can be in equilibrium with Al8V5, Al3Zr, Al2Zr, and α-V. The T phase belongs to the tetragonal crystal system with confirmed lattice parameters of a = 0.658531 nm and c = 0.517334 nm. The Al2Zr phase region is extraordinarily large and can be in equilibrium with all the compounds in the Al-Zr and V-Zr systems, with the exception of the AlZr phase.

Overcoming ecologic bias using the two-phase study design.

PubMed

Wakefield, Jon; Haneuse, Sebastien J-P A

2008-04-15

Ecologic (aggregate) data are widely available and widely utilized in epidemiologic studies. However, ecologic bias, which arises because aggregate data cannot characterize within-group variability in exposure and confounder variables, can only be removed by supplementing ecologic data with individual-level data. Here the authors describe the two-phase study design as a framework for achieving this objective. In phase 1, outcomes are stratified by any combination of area, confounders, and error-prone (or discretized) versions of exposures of interest. Phase 2 data, sampled within each phase 1 stratum, provide accurate measures of exposure and possibly of additional confounders. The phase 1 aggregate-level data provide a high level of statistical power and a cross-classification by which individuals may be efficiently sampled in phase 2. The phase 2 individual-level data then provide a control for ecologic bias by characterizing the within-area variability in exposures and confounders. In this paper, the authors illustrate the two-phase study design by estimating the association between infant mortality and birth weight in several regions of North Carolina for 2000-2004, controlling for gender and race. This example shows that the two-phase design removes ecologic bias and produces gains in efficiency over the use of case-control data alone. The authors discuss the advantages and disadvantages of the approach.

Finite-beta equilibria for Wendelstein 7-X configurations using the Princeton Iterative Equilibrium Solver code

NASA Astrophysics Data System (ADS)

Arndt, S.; Merkel, P.; Monticello, D. A.; Reiman, A. H.

1999-04-01

Fixed- and free-boundary equilibria for Wendelstein 7-X (W7-X) [W. Lotz et al., Plasma Physics and Controlled Nuclear Fusion Research 1990 (Proc. 13th Int. Conf. Washington, DC, 1990), (International Atomic Energy Agency, Vienna, 1991), Vol. 2, p. 603] configurations are calculated using the Princeton Iterative Equilibrium Solver (PIES) [A. H. Reiman et al., Comput. Phys. Commun., 43, 157 (1986)] to deal with magnetic islands and stochastic regions. Usually, these W7-X configurations require a large number of iterations for PIES convergence. Here, two methods have been successfully tested in an attempt to decrease the number of iterations needed for convergence. First, periodic sequences of different blending parameters are used. Second, the initial guess is vastly improved by using results of the Variational Moments Equilibrium Code (VMEC) [S. P. Hirshmann et al., Phys. Fluids 26, 3553 (1983)]. Use of these two methods have allowed verification of the Hamada condition and tendency of "self-healing" of islands has been observed.

Phase relations in the system NaCl-KCl-H2O: IV. Differential thermal analysis of the sylvite liquidus in the KCl-H2O binary, the liquidus in the NaCl-KCl-H2O ternary, and the solidus in the NaCl-KCl binary to 2 kb pressure, and a summary of experimental data for thermodynamic-PTX analysis of solid-liquid equilibria at elevated P-T conditions

USGS Publications Warehouse

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.

Ab initio thermodynamics and seismic properties of MgSiO3 polymorphs at mantle transition zone conditions: the geodynamic role of non-olivine phases

NASA Astrophysics Data System (ADS)

Belmonte, Donato; Ottonello, Giulio Armando; Vetuschi Zuccolini, Marino

2014-05-01

MgSiO3 polymorphs with the garnet, pyroxene and ilmenite structure play a key role in controlling phase equilibria and seismic velocity gradients in the mantle transition zone (440-660 km). Despite the relative abundance of structural and thermoelastic informations, thermodynamic data are still poorly constrained and their extrapolation at high pressure and temperature conditions is affected by large uncertainties. In this work, ab initio calculations of the thermodynamic properties of MgSiO3 polymorphs stable at MTZ conditions (tetragonal majorite, Mj; akimotoite, Ak; HP-clinoenstatite, HPCEn) have been carried out with the hybrid B3LYP density functional method. The static and vibrational features of these minerals (equation of state, elastic constants, seismic velocities and anisotropy, IR and Raman spectra, mode Grüneisen parameters) have been fully characterized in a broad range of P-T conditions. The vibrational density of states (vDOS) have been reproduced in the framework of quasi-harmonic approximation through a full phonon dispersion calculation or, alternatively, a modified Kieffer's model splitting the acoustic and optic modes contribution to the thermodynamic functions. The calculated heat capacities are in good agreement with the relatively few calorimetric investigations made so far on these minerals in the low- to medium-T range. However, physical unsoundness may affect the high-temperature extrapolation of calorimetric results, so that the use in phase equilibria calculation deserves great care. The calculated Gibbs free energies allow to define phase transition boundaries in the MgSiO3 phase diagram and locate the majorite-akimotite-perovskite triple point at P = 21.09 ± 0.13 GPa and T = 2247 ± 31 K. The effect of partial structural disorder in majorite, assessed via an interchange enthalpy (ΔHint = 15 kJ/mol) and configurational entropy [Sconf = 1.9 J/(mol×K)] contribution, must be taken into account to accurately reproduce the Mj

Spectrophotometric studies on the complexation equilibria of Ni and Pb with 2-carboxy-2-hydroxy-5'-sulfo-formazylbenzene. Simultaneous determination of trace amounts of Ni and Pb.

PubMed

Hashem, Elham Y; Abu-Bakr, Mohamed S; Hussain, Sawsan M

2004-01-01

Spectrophotometric studies have been made to investigate the reaction of Nickel and Lead with 2-carboxy-2'-hydroxy-5'-sulfoformazyl-benzene (zincon) in 50%(v/v) ethanol-water at 25 degrees C and an ionic strength of 0.1 M NaClO4. A complete picture of the complexation equilibria in the pH range (4.2-12.0) for nickel and (1.9-11.5) for lead are presented. Simple, rapid, selective and sensitive methods for the spectro-photometric determination of nickel and lead has been developed based on the color reaction of their complexes with zincon. The methods allow the determination of 4.69 microg mL(-1) of nickel at pH = 6.3 (lambdamax = 665 nm) and 10.3 microg ml(-1) of lead at pH = 5.6 (lambdamax = 610 nm). The apparent molar absorptivities were epsilon = 1.3 x 10(4) L mol(-1) cm(-1) for nickel and epsilon = 0.6 x 10(4) L mol(-1) cm(-1) for lead. The interference of a large number of foreign ions and complexing agents has been studied. Thiosulphate, as masking agent allows the simultaneous determination of nickel and lead in the presence of high concentrations of copper. Ascorbic acid, sodium cyanide and or sodium fluoride provide the elimination of many other interferences. The methods have been applied successfully to the simultaneous determination of nickel and lead in an aluminium and non-ferrous alloy.

Intercomparison of cloud model simulations of Arctic mixed-phase boundary layer clouds observed during SHEBA/FIRE-ACE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morrison, H.; Zuidema, Paquita; Ackerman, Andrew

2011-06-16

An intercomparison of six cloud-resolving and large-eddy simulation models is presented. This case study is based on observations of a persistent mixed-phase boundary layer cloud gathered on 7 May, 1998 from the Surface Heat Budget of Arctic Ocean (SHEBA) and First ISCCP Regional Experiment - Arctic Cloud Experiment (FIRE-ACE). Ice nucleation is constrained in the simulations in a way that holds the ice crystal concentration approximately fixed, with two sets of sensitivity runs in addition to the baseline simulations utilizing different specified ice nucleus (IN) concentrations. All of the baseline and sensitivity simulations group into two distinct quasi-steady states associatedmore » with either persistent mixed-phase clouds or all-ice clouds after the first few hours of integration, implying the existence of multiple equilibria. These two states are associated with distinctly different microphysical, thermodynamic, and radiative characteristics. Most but not all of the models produce a persistent mixed-phase cloud qualitatively similar to observations using the baseline IN/crystal concentration, while small increases in the IN/crystal concentration generally lead to rapid glaciation and conversion to the all-ice state. Budget analysis indicates that larger ice deposition rates associated with increased IN/crystal concentrations have a limited direct impact on dissipation of liquid in these simulations. However, the impact of increased ice deposition is greatly enhanced by several interaction pathways that lead to an increased surface precipitation flux, weaker cloud top radiative cooling and cloud dynamics, and reduced vertical mixing, promoting rapid glaciation of the mixed-phase cloud for deposition rates in the cloud layer greater than about 1-2x10-5 g kg-1 s-1. These results indicate the critical importance of precipitation-radiative-dynamical interactions in simulating cloud phase, which have been neglected in previous fixed-dynamical parcel studies of

The stability analysis of magnetohydrodynamic equilibria - Comparing the thermodynamic approach with the energy principle

NASA Technical Reports Server (NTRS)

Brinkmann, R. P.

1989-01-01

This paper is a contribution to the stability analysis of current-carrying plasmas, i.e., plasma systems that are forced by external mchanisms to carry a nonrelaxing electrical current. Under restriction to translationally invariant configurations, the thermodynamic stability criterion for a multicomponent plasma is rederived within the framework of nonideal MHD. The chosen dynamics neglects scalar resistivity, but allows for other types of dissipation effects both in Ohm's law and in the equation of motion. In the second section of the paper, the thermodynamic stability criterion is compared with the ideal MHD based energy principle of Bernstein et al. With the help of Schwarz's inequality, it is shown that the former criterion is always more 'pessimistic' than the latter, i.e., that thermodynamic stability implies stability according to the MHD principle, but not vice versa. This reuslt confirms the physical plausible idea that dissipational effects tend to weaken the stability properties of current-carrying plasma equilibria by breaking the constraints of ideal MHD and allowing for possibly destabilizing effects such as magnetic field line reconfiguration.

Conformational equilibria of alkanes in aqueous solution: relationship to water structure near hydrophobic solutes.

PubMed Central

Ashbaugh, H S; Garde, S; Hummer, G; Kaler, E W; Paulaitis, M E

1999-01-01

Conformational free energies of butane, pentane, and hexane in water are calculated from molecular simulations with explicit waters and from a simple molecular theory in which the local hydration structure is estimated based on a proximity approximation. This proximity approximation uses only the two nearest carbon atoms on the alkane to predict the local water density at a given point in space. Conformational free energies of hydration are subsequently calculated using a free energy perturbation method. Quantitative agreement is found between the free energies obtained from simulations and theory. Moreover, free energy calculations using this proximity approximation are approximately four orders of magnitude faster than those based on explicit water simulations. Our results demonstrate the accuracy and utility of the proximity approximation for predicting water structure as the basis for a quantitative description of n-alkane conformational equilibria in water. In addition, the proximity approximation provides a molecular foundation for extending predictions of water structure and hydration thermodynamic properties of simple hydrophobic solutes to larger clusters or assemblies of hydrophobic solutes. PMID:10423414

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

NASA Astrophysics Data System (ADS)

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

2009-02-01

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

Determination of goslarite-bianchite equilibria by the humidity-buffer technique at 0.1 MPa

USGS Publications Warehouse

Chou, I.-Ming; Seal, R.R.

2005-01-01

Goslarite-bianchite equilibria were determined along four humidity-buffer curves at 0.1 MPa and between 27 and 36 ??C. Results, based on tight reversals along each humidity buffer, can be represented by ln K (??0.005)=19.643-7015.38/T, where K is the equilibrium constant and T is temperature in K. Our data are in excellent agreement with several previous vapor-pressure measurements and are consistent with the solubility data reported in the literature. Thermodynamic analysis of these data yields 9.634 (??0.056) kJ mol-1 for the standard Gibbs free energy of reaction, which is in good agreement with the value of 9.658 kJ mol-1 calculated from the thermodynamic data compiled and evaluated by Wagman et al. [Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H., Halow. I., Bailey, S.M., Churney, K.L., Nuttal, R.L., 1982. The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C1 and C2 organic substances in SI units. J. Phys. Chem. Ref. Data 11, Suppl. 2].

Statistical study of generalized nonlinear phase step estimation methods in phase-shifting interferometry.

PubMed

Langoju, Rajesh; Patil, Abhijit; Rastogi, Pramod

2007-11-20

Signal processing methods based on maximum-likelihood theory, discrete chirp Fourier transform, and spectral estimation methods have enabled accurate measurement of phase in phase-shifting interferometry in the presence of nonlinear response of the piezoelectric transducer to the applied voltage. We present the statistical study of these generalized nonlinear phase step estimation methods to identify the best method by deriving the Cramér-Rao bound. We also address important aspects of these methods for implementation in practical applications and compare the performance of the best-identified method with other bench marking algorithms in the presence of harmonics and noise.

Dynamical analysis of an orbiting three-rigid-body system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagnozzi, Daniele, E-mail: daniele.pagnozzi@strath.ac.uk, E-mail: james.biggs@strath.ac.uk; Biggs, James D., E-mail: daniele.pagnozzi@strath.ac.uk, E-mail: james.biggs@strath.ac.uk

2014-12-10

The development of multi-joint-spacecraft mission concepts calls for a deeper understanding of their nonlinear dynamics to inform and enhance system design. This paper presents a study of a three-finite-shape rigid-body system under the action of an ideal central gravitational field. The aim of this paper is to gain an insight into the natural dynamics of this system. The Hamiltonian dynamics is derived and used to identify relative attitude equilibria of the system with respect to the orbital reference frame. Then a numerical investigation of the behaviour far from the equilibria is provided using tools from modern dynamical systems theory suchmore » as energy methods, phase portraits and Poincarè maps. Results reveal a complex structure of the dynamics as well as the existence of connections between some of the equilibria. Stable equilibrium configurations appear to be surrounded by very narrow regions of regular and quasi-regular motions. Trajectories evolve on chaotic motions in the rest of the domain.« less

Theory of equilibria of elastic 2-braids with interstrand interaction

NASA Astrophysics Data System (ADS)

Starostin, E. L.; van der Heijden, G. H. M.

2014-03-01

Motivated by continuum models for DNA supercoiling we formulate a theory for equilibria of 2-braids, i.e., structures formed by two elastic rods winding around each other in continuous contact and subject to a local interstrand interaction. No assumption is made on the shape of the contact curve. The theory is developed in terms of a moving frame of directors attached to one of the strands. The other strand is tracked by including in this frame the normalised closest-approach chord connecting the two strands. The kinematic constant-distance constraint is formulated at strain level through the introduction of what we call braid strains. As a result the total potential energy involves arclength derivatives of these strains, thus giving rise to a second-order variational problem. The Euler-Lagrange equations for this problem give balance equations for the overall braid force and moment referred to the moving frame as well as differential equations that can be interpreted as effective constitutive relations encoding the effect that the second strand has on the first as the braid deforms under the action of end loads. Hard contact models are used to obtain the normal contact pressure between strands that has to be non-negative for a physically realisable solution without the need for external devices such as clamps or glue to keep the strands together. The theory is first illustrated by a number of problems that can be solved analytically and then applied to several new problems that have not hitherto been treated.

Containerless Processing Studies in the MSFC Electrostatic Levitator

NASA Technical Reports Server (NTRS)

Rogers, J. R.; SanSoucie, M. P.

2012-01-01

Levitation or containerless processing represents an important tool in materials research. Levitated specimens are free from contact with a container, which permits studies of deeply undercooled melts, and high-temperature, highly reactive materials. Containerless processing provides data for studies of thermophysical properties, phase equilibria, metastable state formation, microstructure formation, undercooling, and nucleation. Levitation techniques include: acoustic, aero-acoustic, electromagnetic, and electrostatic. In microgravity, levitation can be achieved with greatly reduced positioning forces. Microgravity also reduces the effects of buoyancy and sedimentation in melts. The European Space Agency (ESA) and the German Aerospace Center (DLR) jointly developed an electromagnetic levitator facility (MSL-EML) for containerless materials processing in space. The MSL-EML will be accommodated in the European Columbus Facility on the International Space Station (ISS). The electrostatic levitator (ESL) facility at the Marshall Space Flight Center provides support for the development of containerless processing studies for the ISS. The capabilities of the facility and recent results will be discussed.

Study of geometric phase using classical coupled oscillators

NASA Astrophysics Data System (ADS)

Bhattacharjee, Sharba; Dey, Biprateep; Mohapatra, Ashok K.

2018-05-01

We illustrate the geometric phase associated with the cyclic dynamics of a classical system of coupled oscillators. We use an analogy between a classical coupled oscillator and a two-state quantum mechanical system to represent the evolution of the oscillator on an equivalent Hilbert space, which may be represented as a trajectory on the surface of a sphere. The cyclic evolution of the system leads to a change in phase, which consists of a dynamic phase along with an additional phase shift dependent on the geometry of the evolution. A simple experiment suitable for advanced undergraduate students is designed to study the geometric phase incurred during cyclic evolution of a coupled oscillator.

Dark Matter Equilibria in Galaxies and Galaxy Systems

NASA Astrophysics Data System (ADS)

Lapi, A.; Cavaliere, A.

2009-02-01

In the dark matter (DM) halos embedding galaxies and galaxy systems the "entropy" K ≡ σ2/ρ2/3 (a quantity that combines the radial velocity dispersion σ with the density ρ) is found from intensive N-body simulations to follow a power-law run K vprop r α throughout the halos' bulk, with α around 1.25. Taking up from phenomenology just that α≈ const. applies, we cut through the rich analytic contents of the Jeans equation describing the self-gravitating equilibria of the DM; we specifically focus on computing and discussing a set of novel physical solutions that we name α-profiles, marked by the entropy slope α itself, and by the maximal gravitational pull κcrit(α) required for a viable equilibrium to hold. We then use an advanced semianalytic description for the cosmological buildup of halos to constrain the values of α to within the narrow range 1.25-1.29 from galaxies to galaxy systems; these correspond to halos' current masses in the range 1011-1015 M sun. Our range of α applies since the transition time that—both in our semianalytic description and in state-of-the-art numerical simulations—separates two development stages: an early violent collapse that comprises a few major mergers and enforces dynamical mixing, followed by smoother mass addition through slow accretion. In our range of α we provide a close fit for the relation κcrit(α), and discuss a related physical interpretation in terms of incomplete randomization of the infall kinetic energy through dynamical mixing. We also give an accurate analytic representation of the α-profiles with parameters derived from the Jeans equation; this provides straightforward precision fits to recent detailed data from gravitational lensing in and around massive galaxy clusters, and thus replaces the empirical Navarro-Frenk-White formula relieving the related problems of high concentration and old age. We finally stress how our findings and predictions as to α and κcrit contribute to

Multi-path transportation futures study: Results from Phase 1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, Phil; Singh, Margaret; Plotkin, Steve

2007-03-09

This PowerPoint briefing provides documentation and details for Phase 1 of the Multi-Path Transportation Futures Study, which compares alternative ways to make significant reductions in oil use and carbon emissions from U.S. light vehicles to 2050. Phase I, completed in 2006, was a scoping study, aimed at identifying key analytic issues and constructing a study design. The Phase 1 analysis included an evaluation of several pathways and scenarios; however, these analyses were limited in number and scope and were designed to be preliminary.