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Sample records for isobaric vapor-liquid equilibrium

  1. Isobaric vapor-liquid equilibrium for ethanol + water + potassium nitrate

    SciTech Connect

    Vercher, E.; Pena, M.P.; Martinez-Andreu, A.

    1996-01-01

    An increasing research interest in the determination of the salt effect in the vapor-liquid equilibrium of binary systems has developed over the last few decades due to the importance of distillation with salts in the separation of close boiling and azeotropic mixtures. Isobaric vapor-liquid equilibrium for ethanol (1) + water (2) + potassium nitrate (3) at various concentrations of salt and with ethanol mole fractions from 0 to 0.642 has been measured at 100.0 kPa. The results were correlated by assuming that the salt was in ionic form and it was associated only with the water.

  2. Isobaric vapor-liquid equilibrium for ethanol + water + sodium nitrate

    SciTech Connect

    Pena, M.P.; Vercher, E.; Martinez-Andreu, A.

    1996-09-01

    The salt effect on the vapor-liquid equilibrium of mixed solvents provides a potential technique of extractive distillation, in which a dissolved salt, rather than a liquid additive, is used as the separating agent. This salt distillation process has been used in the purification of close-boiling, azeotropic, and other systems which are difficult to separate. The isobaric vapor-liquid equilibrium for ethanol (1) + water (2) + sodium nitrate (3) at various concentrations of salt and with ethanol mole fractions from 0 to 0.774 has been measured at 100.0 kPa. The results were correlated by assuming that the salt was in ionic form and it was associated only with the water.

  3. Isobaric vapor-liquid equilibrium data for the ethanol-water-strontium bromide system

    SciTech Connect

    Vercher, E.; Pena, M.P.; Martinez-Andreu, A. . Dept. de Ingenieria Quimica)

    1994-04-01

    Isobaric experimental data of vapor-liquid equilibrium for the ethanol-water-strontium bromide system at different mole fractions of strontium bromide have been measured at 100.6 kPa. Data were correlated by Jaques and Furter's method. Thermodynamic consistency was checked by Herington's method with satisfactory results.

  4. Isobaric vapor-liquid equilibrium for methyldichlorosilane-dimethyldichlorosilane-benzene system*

    PubMed Central

    Qiu, Zu-min; Xie, Xin-liang; Yu, Shu-xian; Chen, Wen-you; Xie, Feng-xia; Liu, Juan

    2005-01-01

    The elucidation of vapor-liquid equilibrium (VLE) of the halogenated silane was necessary for the production of silicon derivatives, especially for methylvinyldichlorosilane, due to the lack of the relevant reports. Isobaric VLE for the system methyldichlorosilane-dimethyldichlorosilane-benzene and isobaric VLE of the three binary systems were measured with a new pump-ebulliometer at the pressure of 101.325 kPa. These binary compositions of the equilibrium vapor were calculated according to the Q function of molar excess Gibbs energy by the indirect method and the resulted VLE data agreed well with the thermodynamic consistency. Moreover, the experimental data were correlated with the Wilson, NRTL, Margules and van Laar equations by means of the least-squares fit, the acquired optimal interaction parameters were fitted to experimental vapor-liquid equilibrium data for binary systems. The binary parameters of Wilson equation were also used to calculate the bubble point temperature and the vapor phase composition for the ternary mixtures without any additional adjustment. The predicted vapor-liquid equilibrium for the ternary system was in a good agreement with the experimental results. The VLE of binary and multilateral systems provided essential theory for the production of the halogenated silane. PMID:16187419

  5. Isobaric vapor-liquid equilibrium for ethanol + water + copper(II) chloride

    SciTech Connect

    Vercher, E.; Pena, M.P.; Martinez-Andreu, A.

    1995-05-01

    The extractive distillation in which an electrolyte is employed as the extractive agent is an important alternative to the conventional methods for separating mixtures involving azeotropes. Isobaric vapor-liquid equilibrium for ethanol (1) + water(2) + copper(II) chloride (3) at different mole fractions of copper(II) chloride has been measured at 100.0 kPa. The results in the range where the mole fraction of salt in the liquid phase was less than 0.146 times the mole fraction of water were correlated by assuming that the salt was in ionic form and it was associated only with the water. Thermodynamic consistency was checked according to Herington`s method with satisfactory results.

  6. Isobaric vapor-liquid equilibrium of the systems cumene + benzyl alcohol and phenol + benzyl alcohol at 10 kPa

    SciTech Connect

    Resa, J.M.; Quintana, T.; Cepeda, E. . Dept. Ingenieria Quimica)

    1994-01-01

    Isobaric vapor-liquid equilibrium data are reported for the binary systems cumene + benzyl alcohol and phenol + benzyl alcohol at 10 kPa. The activity coefficient data were tested for thermodynamic consistency by the methods of Herington, Black, and Van Ness and correlated with the Wilson equation. None of the systems show an azeotrope.

  7. Isobaric vapor-liquid equilibrium for methyldichlorosilane-methyltrichlorosilane-dimethyldichlorosilane system*

    PubMed Central

    Qiu, Zu-min; Xie, Xin-liang; Luo, Mei; Xie, Feng-xia

    2005-01-01

    This paper describes measurement of vapor-liquid equilibrium (VLE) data of methyldichlorosilane-methyltrichloro silane-dimethyldichlorosilane system and that of the three binary systems at 101.325 kPa with a new pump-ebulliometer. The equilibrium composition of the vapor phase was calculated from pTx by indirect method. The model parameters of the liquid activity coefficient of the Wilson, NRTL, Margules and van Laar equations was corrected by the least square method. The ternary system VLE data were predicted by the Wilson equation, with the calculated boiling points showing good agreement with the experimental data. PMID:15909344

  8. A "User-Friendly" Program for Vapor-Liquid Equilibrium.

    ERIC Educational Resources Information Center

    Da Silva, Francisco A.; And Others

    1991-01-01

    Described is a computer software package suitable for teaching and research in the area of multicomponent vapor-liquid equilibrium. This program, which has a complete database, can accomplish phase-equilibrium calculations using various models and graph the results. (KR)

  9. Isobaric vapor-liquid equilibria for binary and ternary systems composed of water, 1-propanol, and 2-propanol at 100 kPa

    SciTech Connect

    Gabaldon, C.; Marzal, P.; Monton, J.B.; Rodrigo, M.A.

    1996-11-01

    Isobaric vapor-liquid equilibria data were obtained for the 2-propanol + 1-propanol binary system and the water + 1-propanol + 2-propanol ternary system at 100 kPa. The data were found to be thermodynamically consistent according to the Van Ness-Byer-Gibbs method for the binary system and according to the McDermott-Ellis method for the ternary one. The binary system is well represented by assuming ideal behavior. The binary interaction parameters obtained from this and previous work are used to predict the vapor-liquid equilibrium for the ternary system using the UNIQUAC, NRTL, and Wilson models. The ternary system is well predicted from binary data.

  10. Isobaric vapor-liquid equilibria in the binary system hexane + 2-propanol

    SciTech Connect

    Wisniak, J.; Akunis, A.

    1995-07-01

    New vapor-liquid equilibrium data have been obtained for the binary system hexane + 2-propanol at 94.4 kPa to compare with previously reported data assumed to be thermodynamically inconsistent. The system exhibits large positive deviations from ideal behavior and an azeotrope that boils at 332.92 K and contains 73.3 mol% hexane. The activity coefficients and boiling point of the solution were correlated with its composition by the Redlich-Kister, Wilson, UNIFAC, UNIQUAC, and Wisniak-Tamir models.

  11. Recommended Vapor-Liquid Equilibrium Data. Part 1: Binary n-Alkanol-n-Alkane Systems

    NASA Astrophysics Data System (ADS)

    Gral, Marian; Oracz, Pawe?; Skrzecz, Adam; Bok, Andrzej; Ma̧czy?ski, Andrzej

    2002-09-01

    The recommended vapor-liquid equilibrium (VLE) data for 39 binary n-alcohol-n-alkane systems have been obtained after critical evaluation of all data (490 data sets) reported in the open literature up to the middle of 2001. The evaluation procedure consisted in combining the thermodynamic consistency tests, data correlation, comparison with enthalpy of mixing data, and comparison of VLE data for various mixtures. The data were correlated with equations based on the local compositions concept as well as with the equation of state appended with a chemical term (EoSC) proposed by Gral. The recommended data are presented in the form of individual pages containing tables of data, figures, and auxiliary information. Each page corresponds to one system and contains three isotherms (spaced by at least 15 K) and one isobar (preferably at 101.32 kPa). Experimental gaps were completed with the predicted data.

  12. Isobaric vapor-liquid equilibria of the water + 1-propanol system at 30, 60, and 100 kPa

    SciTech Connect

    Gabaldon, C.; Marzal, P.; Monton, J.B.; Rodrigo, M.A.

    1996-09-01

    Isobaric vapor-liquid equilibria for the water + 1-propanol system are reported at 30, 60, and 100 kPa. The results were found to be thermodynamically consistent according to Van Ness-Byer-Gibbs, Kojima, and Wisniak methods. The system shows a minimum boiling azeotrope, and the azeotropic composition is scarcely shifted with pressure. Results were compared with literature values. The data were correlated with Margules, Van Laar, Wilson, NRTL, and UNIQUAC liquid-phase activity coefficient models.

  13. Isobaric vapor-liquid equilibria of the water + 2-propanol system at 30, 60, and 100 kPa

    SciTech Connect

    Marzal, P.; Monton, J.B.; Rodrigo, M.A.

    1996-05-01

    Distillation is perhaps the separation process most widely used in the chemical processing industry. The correct design of distillation columns requires the availability of accurate and, if possible, thermodynamically consistent vapor-liquid equilibria (VLE) data. The present work is part of a project studying the effect of pressure on the behavior of the azeotropic point in mixtures in which at least one component is an alcohol. Isobaric vapor-liquid equilibria were obtained for the water + 2-propanol system at 30, 60, and 100 kPa. The activity coefficients were found to be thermodynamically consistent by the methods of Van Ness-Byer-Gibbs, Kojima, and Wisniak. The data were correlated with five liquid phase activity coefficient models (Margules, Van Laar, Wilson, NRTL, and UNIQUAC).

  14. Isobaric vapor-liquid equilibria of tetrachloroethylene + 1-propanol and + 2-propanol at 20 and 100 kPa

    SciTech Connect

    Dejoz, A.; Gonzalez-Alfaro, V.; Miguel, P.J.; Vazquez, M.I.

    1996-11-01

    Isobaric vapor-liquid equilibria were obtained for tetrachloroethylene + 1-propanol and +2-propanol systems at 20 and 100 kPa using a dynamic still. The experimental error in temperature was {+-} 0.1 K, in pressure {+-} 0.01 kPa and {+-} 0.1 kPa for the experiments carried out at 20 and 100 kPa, respectively, and in liquid and vapor composition 0.001. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality. The data were well correlated with the Wilson equation.

  15. Recommended Vapor-Liquid Equilibrium Data. Part 2: Binary Alkanol-Alkane Systems

    NASA Astrophysics Data System (ADS)

    Gral, Marian; Oracz, Pawe?; Skrzecz, Adam; Bok, Andrzej; Ma̧czy?ski, Andrzej

    2003-12-01

    The recommended vapor-liquid equilibrium (VLE) data for 36 binary systems involving primary, secondary, and tertiary alcohols with n-alkanes and isoalkanes [with the exception of 1-alkanols-n-alkane systems, which were presented in Part 1 of this seriesJ. Phys. Chem. Ref. Data 31(3), 702 (2002)] have been obtained after critical evaluation of all data (744 data sets) reported in the open literature up to the middle of 2002. The evaluation procedure consisted in combining the thermodynamic consistency tests, data correlation, comparison with enthalpy of mixing data, and comparison of VLE data for various mixtures. The data were correlated with equations based on local compositions concept as well as with equation of state appended with chemical term (EoSC) proposed by Gral. The recommended data are presented in the form of sheets containing tables of data, figures and auxiliary information. Each sheet corresponds to one system and contains three isotherms (spaced by at least 15 K) and one isobar (preferably at 101.32 kPa). Experimental gaps were completed with the predicted data.

  16. Vapor-liquid equilibrium and density measurements of tetraalklylammonium bromide + propanol + water systems

    SciTech Connect

    Slusher, J.T.; Cummings, P.T.; Hu, Y.; Vega, C.A.; O`Connell, J.P.

    1995-07-01

    Isobaric vapor-liquid equilibrium (VLE) measurements at atmospheric pressure were made for 1.0--3.0 m tetrapropylammonium bromide (TPAB) and 3.0 m tetrabutylammonium bromide (TBAB) in mixtures of 2-propanol and water, and 3.0 m TPAB and 3.0 m TBAB in mixtures of 1-propanol and water. In addition, VLE measurements were made on 3.0 m TBAB in 2-propanol + water mixtures at 0.080 bar. The effects of the salt on the VLE in each system were assessed via relative volatilities. The effect of the solute was to salt-out at high alcohol concentrations and salt-in at low alcohol concentrations. A vibrating-tube decimeter was used to obtain solution densities at 25 C from 0.1 to 4 m TBAB or TPAB in the pure solvent and in aqueous 1-propanol and 2-propanol solutions. Variations of the apparent molar volumes with salt molality in the mixed solvent differed markedly from those of the alcohol-free binary, while subtle distinctions were seen among the various salt and alcohol molecular structures.

  17. Isobaric vapor-liquid equilibria in the systems methyl 1,1-dimethylethyl ether + hexane and + heptane

    SciTech Connect

    Wisniak, J.; Magen, E.; Shachar, M.; Zeroni, I.; Segura, H.; Reich, R.

    1997-03-01

    The vapor-liquid equilibrium at 94 kPa has been determined for the binary systems of methyl 1,1-dimethylethyl ether (MTBE) with hexane and with heptane. Both systems deviate slightly from ideal behavior, can be described as regular solutions, and do not present an azeotrope. The activity coefficients and boiling point of the solutions were correlated with its composition by the Redlich-Kister, Wohl, Wilson, UNIQUAC, NRTL, and Wisniak-Tamir equations.

  18. Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

    NASA Technical Reports Server (NTRS)

    Thompson, W. R.; Zollweg, John A.; Gabis, David H.

    1992-01-01

    A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

  19. Monte Carlo simulation of equilibrium reactions at modified vapor-liquid interfaces.

    PubMed

    Turner, C Heath

    2007-02-27

    The equilibrium conversion of a chemical reaction is known to be affected by its local environment. Various factors may alter reaction equilibria, including shifts in pressure or temperature, solvation, adsorption within porous materials, or the presence of an interface. Previously, reactive Monte Carlo simulations have been used to predict the equilibrium behavior of chemical reactions at vapor-liquid interfaces. Here, a route is tested for tuning the interfacial conversion of a Lennard-Jones dimerization reaction by adding surfactants to the vapor-liquid interface. Several temperatures are explored as well as several different surfactant models. Even with the addition of a small concentration of surfactants, the simulations predict significant shifts in the conversion at the interface. In general, the shifts in the conversion tend to be related to the values of the interfacial tension. PMID:17309206

  20. Isobaric vapor-liquid equilibria of trichloroethylene with 1-butanol and 2-butanol at 20 and 100 kPa

    SciTech Connect

    Dejoz, A.; Gonzalez-Alfaro, V.; Miguel, P.J.; Vazquez, M.I.

    1996-01-01

    Knowledge of vapor-liquid equilibria is of great importance to the development of chemical processing and the design of separation equipment. Vapor-liquid equilibria for trichloroethylene + 1-butanol, and +2-butanol are reported at 20 and 100 kPa. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality.

  1. Condensation coefficient of methanol vapor near vapor-liquid equilibrium states

    NASA Astrophysics Data System (ADS)

    Fujikawa, S.; Yano, T.; Ichijo, M.; Iwanami, K.

    This paper is concerned with the nonequilibrium condensation from a vapor to a liquid phase on the plate endwall of a shock tube behind a reflected shock wave. The growth of a liquid film on the endwall is measured by an optical interferometer using a laser beam. The experiment is carefully conducted on the precisely designed apparatus, and thereby the condensation coefficient of methanol vapor is determined in a wide range of vapor-liquid conditions from near to far from equilibrium states. The result shows that the condensation coefficient increases with the increase of the ratio of number densities of vapor and saturated vapor at the interface.

  2. Isobaric vapor-liquid equilibria of ethylbenzene + m-xylene and ethylbenzene + o-xylene systems at 6. 66 and 26. 66 kPa

    SciTech Connect

    Monton, J.B.; Llopis, F.J. . Dept. de Ingenieria Quimica)

    1994-01-01

    Vapor-liquid equilibrium data were obtained for systems of ethylbenzene with m- and o-xylenes at 6.66 and 26.66 kPa. The activity coefficients were found to be thermodynamically consistent. They were equally well correlated with the Margules, Van Laar, Wilson, NRTL, and UNIQUAC equations. The parameters of these equations are given.

  3. A new vapor-liquid equilibrium apparatus for hydrogen fluoride containing systems

    SciTech Connect

    Jongcheon Lee; Hwayong Kim; Jong Sung Lim; Jae-Duck Kim; Youn Yong Lee

    1996-12-31

    A new circulating type apparatus has been constructed to obtain reliable equilibrium PTxy data for hydrogen fluoride (HF) containing system. Equilibrium cell with Pyrex windows protected by Teflon PFA sheets to prevent the corrosion was used. Isothermal vapor-liquid equilibrium data for the 1,1-difluoroethane (HFC-152a) + HF system at 288.23 and 298.35 K were obtained, and compared with PTx measurement results. Experimental data were correlated using Lencka and Anderko equation of state for HF with the Wong-Sandler mixing rule as well as the van der Waals one fluid mixing rule. The Wong-Sandler mixing rule gives better results. 5 refs., 3 figs.

  4. Monte Carlo simulation of equilibrium reactions at vapor-liquid interfaces.

    PubMed

    Turner, C Heath

    2005-12-15

    Chemical reactions are known to behave differently, depending upon their local environment. While the interactions with neighboring molecules may alter both the kinetics of chemical reactions and the overall equilibrium conversion, we have performed simulations of the latter. The particular environment that we address is the vapor-liquid interface, since only a few, limited studies have explored the influence of an interface on equilibrium reaction behavior. Simple dimerization reactions are modeled, as well as more complex multicomponent reactions, using the reactive Monte Carlo (RxMC) simulation technique. We find that the conversion of a reaction can be markedly different at an interface as compared to the bulk vapor and liquid phases, and these trends are analyzed with respect to specific intermolecular interactions. In conjunction, we calculate the surface tension of the reacting fluids at the interface, which is found to have unusual scaling behavior, with respect to the system temperature. PMID:16375335

  5. Vapor-liquid equilibrium in the ternary system hexane + 1-chlorobutane + 2-propanol and its binaries

    SciTech Connect

    Wisniak, J.; Akunis, A.

    1995-09-01

    Vapor-liquid equilibrium at 94.4 kPa has been determined for the ternary system hexane + 1-chlorobutane + 2-propanol and the binary systems hexane + 1-chlorobutane and 1-chlorobutane + 2-propanol. The binary system hexane + 1-chlorobutane exhibits moderate deviations from ideality and an azeotrope that contains 97.5 mol % hexane and boils at 339.25 K. The binary system 1-chlorobutane + 2-propanol presents strong deviations from ideality and an azeotrope that contains 62.8 mol % 1-chlorobutane and boils at 341.60 K. The equilibrium data were correlated by the Redlich-Kister, Wilson, UNIQUAC, UNIFAC, and Wisniak-Tamir equations, and the appropriate parameters are reported. The activity coefficients of the ternary system are predicted from those of the pertinent binary systems very well by the Wilson equation and not so well by the Redlich-Kister equation. A ternary azeotrope is not present.

  6. Isobaric vapor-liquid equilibria for binary systems composed of octane, decane, and dodecane at 20 kPa

    SciTech Connect

    Dejoz, A.; Gonzalez-Alfaro, V.; Miguel, P.J.; Vazquez, M.I.

    1996-01-01

    The most common operation in the chemical industry is the separation of liquid mixtures through distillation. Efficient design of distillation equipment requires quantitative knowledge of vapor-liquid equilibria (VLE) in binary or multicomponent mixtures. Vapor-liquid equilibria were measured for binary systems of octane + decane, decane + dodecane, and octane + dodecane at 20.00 kPa using a recirculating still. The results are thermodynamically consistent according to the point-to-point consistency test, and deviation from ideal behavior is small for all systems.

  7. Vapor-Liquid Equilibrium Measurements of the Binary R32+R125 Refrigerant Mixture

    NASA Astrophysics Data System (ADS)

    Higashi, Yukihiro; Miyake, Takeshi; Fujii, Ken-Ichi

    Vapor-liquid equilibrium (VLE) data of the binary R32+R125 refrigerant mixture including R410A (50mass% R32 + 50mass% R125) were obtained by the circulation-type experimental apparatus with a liquid-bath thermostat. VLE measurements were carried out in the temperatures between 263.15 K and 318.15 K and in the pressures between 505 kPa and 2724 kPa. The experimental uncertainties of temperature, pressure, and composition measurements were estimated to be within 3 mK, 0.1 %, and 0.4 %, respectively. The present data were compared with reported experimental data against the REFPROP 6.01 as well as REFPROP 7.0 calculation results.

  8. Densities and isobaric vapor-liquid equilibria for the mixtures formed by four butyl esters and 1-butanol

    SciTech Connect

    Gonzalez, E.; Ortega, J.

    1996-01-01

    Densities of 298.15 K and the vapor-liquid equilibria for 1-butanol + butyl methanoate, + butyl ethanoate, + butyl propanoate, and + butyl butanoate have been measured at 101.32 kPa in small capacity ebulliometer. All results were found to be thermodynamically consistent with a point-to-point test. The mixtures containing butyl methanoate and butyl ethanoate show azeotropes at T = 379.14 K, x = 0.871 and T = 389.64 K, x = 0.222, respectively. Different group-contribution methods were applied to these mixtures.

  9. Dependence of the vapor-liquid equilibrium on the attractive intermolecular forces

    NASA Astrophysics Data System (ADS)

    Cuadros, F.; Okrasinski, W.; Sanfeld, A.

    1996-04-01

    By means of fitting computer simulation data of 3D Lennard-Jones fluids, we present very simple analytical equations for the pressure and chemical potential as functions of the temperature and density. The standard thermodynamic requirement of liquid-vapor equilibrium, i.e., at a given temperature, the pressure and chemical potential in the gas phase are equal to the corresponding values in the liquid phase, leads to the determination of the vapor-liquid coexistence curve. By then using the Weeks-Chandler-Andersen separation of the intermolecular potential, we were able to determine the differing location of the coexistence curve in the phase plane as the intensity of the attractive forces is changed. This curve varies linearly with respect to the perturbative parameter of the Weeks-Chandler-Andersen theory. These results could be very useful in the study of vapour pressure curves of fluids composed of noninert moleculesionic fluids, ferrofluids, polar fluids, etc.which have a different intensity of the attractive intermolecular forces relative to the repulsive forces than the relation between the two forces given by the Lennard-Jones model. Finally, the variation in the location of the critical point with respect to differing intensities of the attractive forces is also dealt with.

  10. Isobaric vapor-liquid equilibria of 1-butanol + N,N-dimethylformamide and 1-pentanol + N,N-dimethylformamide systems at 50.00 and 100.00 kPa

    SciTech Connect

    Marzal, P.; Gabaldon, C.; Seco, A.; Monton, J.B.

    1995-05-01

    The experimental determinations of vapor-liquid equilibria (VLE) are indispensable for the design of separation processes such as distillation columns, extractive distillation, and selection of solvents. Isobaric vapor-liquid equilibria were obtained for the 1-butanol + N,N-dimethylformamide and 1-pentanol + N,N-dimethylformamide systems at 50.00 and 100.00 kPa. The activity coefficients were found to be thermodynamically consistent. The data were correlated with five liquid phase activity coefficient models (Margules, Van Laar, Wilson, NRTL, and UNIQUAC). Experimental vapor pressures of N,N-dimethylformamide are also included.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  12. Collection of VLE data for acid gas---alkanolamine systems using fourier transform infrared spectroscopy. [Vapor-liquid equilibrium

    SciTech Connect

    Bullin, J.A.; Frazier, R.E.

    1992-01-01

    The industrial standard process for the purification of natural gas is to remove acid gases, mainly hydrogen sulfide and carbon dioxide, by the absorption and reaction of these gases with alkanolamines. Inadequate data for vapor--liquid equilibrium (VLE) hinder the industry from converting operations to more energy efficient amine mixtures and conserving energy. Some energy reductions have been realized in the past decade by applying such amine systems as hindered'' amines, methyldiethanolamine (MDEA), and MDEA based amine mixtures. However, the lack of reliable and accurate fundamental VLE data impedes the commercial application of these more efficient alkanolamine systems. The first project objective is to improve the accuracy of vapor--liquid equilibrium measurements at low hydrogen sulfide concentrations. The second project objective is to measure the VLE for amine mixtures. By improving the accuracy of the VLE measurements on MDEA and mixtures with other amines, energy saving can be quickly and confidently implemented in the many existing absorption units already in use. If about 25% of the existing 95.3 billion SCFD gas purification capacity is converted to these new amine systems, the energy savings are estimated to be about 3 [times] 10[sup 14] BTU/yr.

  13. Vapor-liquid equilibrium and critical asymmetry of square well and short square well chain fluids.

    PubMed

    Li, Liyan; Sun, Fangfang; Chen, Zhitong; Wang, Long; Cai, Jun

    2014-08-01

    The critical behavior of square well fluids with variable interaction ranges and of short square well chain fluids have been investigated by grand canonical ensemble Monte Carlo simulations. The critical temperatures and densities were estimated by a finite-size scaling analysis with the help of histogram reweighting technique. The vapor-liquid coexistence curve in the near-critical region was determined using hyper-parallel tempering Monte Carlo simulations. The simulation results for coexistence diameters show that the contribution of |t|(1-?) to the coexistence diameter dominates the singular behavior in all systems investigated. The contribution of |t|(2?) to the coexistence diameter is larger for the system with a smaller interaction range ?. While for short square well chain fluids, longer the chain length, larger the contribution of |t|(2?). The molecular configuration greatly influences the critical asymmetry: a short soft chain fluid shows weaker critical asymmetry than a stiff chain fluid with same chain length. PMID:25106611

  14. Isobaric vapor-liquid equilibria of p-xylene + o-xylene and m-xylene + o-xylene systems at 6. 66 and 26. 66 kPa

    SciTech Connect

    Llopis, F.J.; Monton, J.B. . Dept. de Ingenieria Quimica)

    1994-01-01

    Vapor-liquid equilibrium data were obtained for systems of o-xylene with p- and m-xylenes at 6.66 and 26.66 kPa. The activity coefficients were found to be thermodynamically consistent. They were equally well correlated with the Margules, Van Laar, Wilson, NRTL, and UNIQUAC equations. The parameters of these equations are given.

  15. Vapor-Liquid Equilibrium in the Mixture Butan-2-one C4H8O + C5H12O Pentan-1-ol (EVLM1241, LB5627_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Butan-2-one C4H8O + C5H12O Pentan-1-ol (EVLM1241, LB5627_E)' providing data from direct measurement of temperature at variable mole fraction in vapor phase and constant pressure.

  16. Vapor-Liquid Equilibrium in the Mixture Butan-2-one C4H8O + C5H12O Pentan-1-ol (EVLM1211, LB5624_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Butan-2-one C4H8O + C5H12O Pentan-1-ol (EVLM1211, LB5624_E)' providing data from direct measurement of temperature at variable mole fraction in liquid phase and constant pressure.

  17. Vapor-Liquid Equilibrium in the Mixture Butan-2-one C4H8O + C5H10O2 Isopropyl ethanoate (EVLM1231, LB5697_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Butan-2-one C4H8O + C5H10O2 Isopropyl ethanoate (EVLM1231, LB5697_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  18. Vapor-Liquid Equilibrium in the Mixture Ethanol C2H6O + C4H8O Butan-2-one (EVLM1231, LB5731_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Ethanol C2H6O + C4H8O Butan-2-one (EVLM1231, LB5731_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  19. Vapor-Liquid Equilibrium in the Mixture Methanol CH4O + C6H14O2 1-Propoxypropan-2-ol (EVLM1231, LB5714_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Methanol CH4O + C6H14O2 1-Propoxypropan-2-ol (EVLM1231, LB5714_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  20. Vapor-Liquid Equilibrium in the Mixture Methanol CH4O + C6H13N Cyclohexylamine (EVLM1231, LB5616_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Methanol CH4O + C6H13N Cyclohexylamine (EVLM1231, LB5616_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  1. Vapor-liquid equilibria in binary systems containing ethanol with hexamethyldisiloxane and dimethyl sulfoxide

    SciTech Connect

    Kaczmarek, B.; Radecki, A. )

    1989-04-01

    Results of the experimental determination of isobaric vapor-liquid equilibrium data for the binary systems hexamethylidisiloxane (HMDS) with ethanol and ethanol with dimethyl sulfoxide (DMSO) are reported. This work is a continuation of studies on phase equilibria in binary systems.

  2. On the vapor-liquid equilibrium of attractive chain fluids with variable degree of molecular flexibility

    NASA Astrophysics Data System (ADS)

    van Westen, Thijs; Vlugt, Thijs J. H.; Gross, Joachim

    2015-06-01

    We study the isotropic (vapor and liquid) phase behavior of attractive chain fluids. Special emphasis is placed on the role of molecular flexibility, which is studied by means of a rod-coil model. Two new equations of state (EoSs) are developed for square-well- (SW) and Lennard-Jones (LJ) chain fluids. The EoSs are developed by applying the perturbation theory of Barker and Henderson (BH) to a reference fluid of hard chain molecules. The novelty of the approach is based on (1) the use of a recently developed hard-chain reference EoS that explicitly incorporates the effects of molecular flexibility, (2) the use of recent molecular simulation data for the radial distribution function of hard-chain fluids, and (3) a newly developed effective segment size, which effectively accounts for the soft repulsion between segments of LJ chains. It is shown that the effective segment size needs to be temperature-, density-, and chain-length dependent. To obtain a simplified analytical EoS, the perturbation terms are fitted by polynomials in density (SW and LJ), chain length (SW and LJ), and temperature (only for LJ). It is shown that the equations of state result in an accurate description of molecular simulation data for vapor-liquid equilibria (VLE) and isotherms of fully flexible SW- and LJ chain fluids and their mixtures. To evaluate the performance of the equations of state in describing the effects of molecular flexibility on VLE, we present new Monte Carlo simulation results for the VLE of rigid linear- and partially flexible SW- and LJ chain fluids. For SW chains, the developed EoS is in a good agreement with simulation results. For increased rigidity of the chains, both theory and simulations predict an increase of the VL density difference and a slight increase of the VL critical temperature. For LJ chains, the EoS proves incapable of reproducing part of these trends.

  3. On the vapor-liquid equilibrium of attractive chain fluids with variable degree of molecular flexibility.

    PubMed

    van Westen, Thijs; Vlugt, Thijs J H; Gross, Joachim

    2015-06-14

    We study the isotropic (vapor and liquid) phase behavior of attractive chain fluids. Special emphasis is placed on the role of molecular flexibility, which is studied by means of a rod-coil model. Two new equations of state (EoSs) are developed for square-well- (SW) and Lennard-Jones (LJ) chain fluids. The EoSs are developed by applying the perturbation theory of Barker and Henderson (BH) to a reference fluid of hard chain molecules. The novelty of the approach is based on (1) the use of a recently developed hard-chain reference EoS that explicitly incorporates the effects of molecular flexibility, (2) the use of recent molecular simulation data for the radial distribution function of hard-chain fluids, and (3) a newly developed effective segment size, which effectively accounts for the soft repulsion between segments of LJ chains. It is shown that the effective segment size needs to be temperature-, density-, and chain-length dependent. To obtain a simplified analytical EoS, the perturbation terms are fitted by polynomials in density (SW and LJ), chain length (SW and LJ), and temperature (only for LJ). It is shown that the equations of state result in an accurate description of molecular simulation data for vapor-liquid equilibria (VLE) and isotherms of fully flexible SW- and LJ chain fluids and their mixtures. To evaluate the performance of the equations of state in describing the effects of molecular flexibility on VLE, we present new Monte Carlo simulation results for the VLE of rigid linear- and partially flexible SW- and LJ chain fluids. For SW chains, the developed EoS is in a good agreement with simulation results. For increased rigidity of the chains, both theory and simulations predict an increase of the VL density difference and a slight increase of the VL critical temperature. For LJ chains, the EoS proves incapable of reproducing part of these trends. PMID:26071717

  4. The influence of equilibrium chemical reactions on vapor-liquid phase diagrams

    SciTech Connect

    Barbosa, D.; Doherty, M.F.

    1986-01-01

    Phase diagrams for simultaneous chemical reaction and phase equilibrium are presented for ideal and non-ideal systems. It is shown that reactive-azeotropes can occur for ideal mixtures. The conditions for formation of reactive-azeotropes in constant volatility systems are derived. These conditions show that for such systems reactive-azeotropes can occur only when the volatiles of the reactants are either all higher or all lower than the volatilities of the products.

  5. Precise reduction of vapor/liquid equilibrium data by molecularly-based expressions: An alternative to the series expansion approach

    SciTech Connect

    Nass, K.K.; Abbott, M.M.

    1986-09-01

    Current techniques for predicting vapor/liquid equilibrium (VLE) require an accurate data base for evaluation of the predictive parameters. The data base in turn depends not only on accurate experimental measurements but also on the precise reduction of the raw data. Popular empirical expressions such as the Redlich-Kister equation contain adequate flexibility for precise data reduction but the parameters lack physical significance, making direct extension to multicomponent systems difficult. As an alternative to the series expansion approach, the authors propose a set of molecularly-inspired expressions for the excess Gibbs energy that are physico-chemically meaningful, but also sufficiently flexible for precise reduction of data. Modeling efforts based on chemical theory are coupled with expressions from a choice of physical models to yield a ''smart'' correlative scheme capable of representing a variety of mixture behavior. Results from fitting (P,x) data for an assortment of binary systems are discussed, as well as some of the problems that can arise during the reduction procedure.

  6. Determination of vapor-liquid equilibrium data and decontamination factors needed for the development of evaporator technology for use in volume reduction of radioactive waste streams

    SciTech Connect

    Betts, S.E.

    1993-10-01

    A program is currently in progress at Argonne National Laboratory to evaluate and develop evaporator technology for concentrating radioactive waste streams. By concentrating radioactive waste streams, disposal costs can be significantly reduced. To effectively reduce the volume of waste, the evaporator must achieve high decontamination factors so that the distillate is sufficiently free of radioactive material. One technology that shows a great deal of potential for this application is being developed by LICON, Inc. In this program, Argonne plans to apply LICON`s evaporator designs to the processing of radioactive solutions. Concepts that need to be incorporated into the design of the evaporator include, criticality safety, remote operation and maintenance, and materials of construction. To design an effective process for concentrating waste streams, both solubility and vapor-liquid equilibrium data are needed. The key issue, however, is the high decontamination factors that have been demonstrated by this equipment. Two major contributions were made to this project. First, a literature survey was completed to obtain available solubility and vapor-liquid equilibrium data. Some vapor-liquid data necessary for the project but not available in the literature was obtained experimentally. Second, the decontamination factor for the evaporator was determined using neutron activation analysis (NAA).

  7. Isothermal vapor--liquid equilibrium data for binary systems at high pressures; Carbon dioxide-methanol, carbon dioxide-ethanol, carbon dioxide--1-propanol, methane--ethanol, methane--1-propanol, ethane--ethanol, and ethane--1-propanol systems

    SciTech Connect

    Suzuki, K.; Sue, H. ); Itou, M.; Smith, R.L.; Inomata, H.; Aria, K.; Saito, S. )

    1990-01-01

    This paper reports an experiment conducted on isothermal vapor-liquid equilibrium data for binary systems at high pressure. Carbon dioxide-methanol, carbon dioxide-ethanol, carbon dioxide-1-propanol, methane-ethanol, methane-1-propanol, ethane-ethanol, and ethane-1-propanol were measured by a new static phase equilibrium apparatus at 313.4 and 333,4 K.

  8. Determination of vapor-liquid equilibrium data in microfluidic segmented flows at elevated pressures using Raman spectroscopy.

    PubMed

    Luther, Sebastian K; Stehle, Simon; Weihs, Kristian; Will, Stefan; Braeuer, Andreas

    2015-08-18

    A fast, noninvasive, and efficient analytical measurement strategy for the characterization of vapor-liquid equilibria (VLE) is presented, which is based on phase (state of matter) selective Raman spectroscopy in multiphase flows inside microcapillay systems (MCS). Isothermal VLE data were measured in binary and ternary mixtures composed of acetone, water, carbon dioxide or nitrogen at elevated pressures up to 10 MPa and temperatures up to 333 K. For validation, the obtained data were compared with literature data and reference measurements in a high-pressure variable volume cell. Additionally, the mixtures were investigated at temperatures and pressures where no data is available in literature to extend the high-pressure VLE database. PMID:26171990

  9. Vapor-Liquid Equilibrium in the Mixture 1-Chloropropane C3H7Cl + C4H8O2 1,4-Dioxane (EVLM1231, LB5713_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1-Chloropropane C3H7Cl + C4H8O2 1,4-Dioxane (EVLM1231, LB5713_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  10. Vapor-Liquid Equilibrium in the Mixture Butan-1-ol C4H10O + C6H12O 4-Methylpentan-2-one (EVLM1231, LB5720_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Butan-1-ol C4H10O + C6H12O 4-Methylpentan-2-one (EVLM1231, LB5720_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  11. Vapor-Liquid Equilibrium in the Mixture Butan-2-ol C4H10O + C6H14O2 1-Propoxypropan-2-ol (EVLM1231, LB5716_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Butan-2-ol C4H10O + C6H14O2 1-Propoxypropan-2-ol (EVLM1231, LB5716_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  12. Vapor-Liquid Equilibrium in the Mixture Butan-2-ol C4H10O + C6H12O 4-Methylpentan-2-one (EVLM1231, LB5719_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Butan-2-ol C4H10O + C6H12O 4-Methylpentan-2-one (EVLM1231, LB5719_E)' providing data from direct measurement of temperature and mole fraction in vapor phase at variable mole fraction in liquid phase and constant pressure.

  13. Vapor-Liquid Equilibrium in the Mixture 1,1,1-Trichloroethane C2H3Cl3 + C6H10O Cyclohexanone (EVLM1111, LB5638_E)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Brnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1,1,1-Trichloroethane C2H3Cl3 + C6H10O Cyclohexanone (EVLM1111, LB5638_E)' providing data from direct measurement of pressure at variable mole fraction in liquid phase and constant temperature.

  14. Vapor-liquid equilibrium of the Mg(NO/sub 3/)/sub 2/-HNO/sub 3/-H/sub 2/O system

    SciTech Connect

    Thompson, B.E.; Derby, J.J.; Stalzer, E.H.

    1983-06-01

    The vapor-liquid equilibrium of the Mg(NO/sub 3/)/sub 2/-HNO/sub 3/-H/sub 2/O system in concentrations of 0 to 70 wt % Mg(NO/sub 3/)/sub 2/ and 0 to 75 wt % HNO/sub 3/ at atmospheric pressure was correlated by two approaches. One was based on a dissociation equilibrium expression in which the activities of the reacting species (HNO/sub 3/, NO/sub 3//sup -/, and H/sup +/) were approximated with mole fractions. The activity coefficients of the undissociated HNO/sub 3/ and H/sub 2/O were correlated as functions of the concentrations of magnesium nitrate and nitric acid by second-order polynomials. The average absolute difference between predicted and experimental values was 8% for the mole fraction of acid in the vapor and 8/sup 0/K for the bubble-point temperature. The second approach was to correlate the mean ionic rational activity coefficient of water with a form of the excess Gibbs energy composed of two terms. One term, a function of the ionic strength, accounts for the coulombic (ionic) interactions; the other term accounts for the non-coulombic (molecular) interactions. The average absolute difference between predicted and experimental values was 9% for the mole fraction of acid in the vapor, and 10/sup 0/K for the bubble-point temperature.

  15. Vapor-liquid equilibria of 1-propanol or 2-propanol with 2,2,4-trimethylpentane at 101. 3 kPa

    SciTech Connect

    Hiaki, Toshihiko; Takahashi, Kenji; Tsuji, Tomoya; Hongo, Masaru . Coll. of Industrial Technology); Kojima, Kazuo . Coll. of Science and Technology)

    1994-07-01

    Isobaric vapor-liquid equilibria were measured for 1-propanol or 2-propanol with 2,2,4-trimethylpentane at 101.3 kPa in an equilibrium still with circulation of both the vapor and liquid phases. The results were best correlated with the Wilson equation. The equilibrium composition of the samples was determined using a Shimadzu gas chromatography. The accuracy of liquid, x[sub i], and vapor, y[sub i], mole fractions was estimated as [+-] 0.002.

  16. Vapor-liquid equilibria for the binary systems of 1-butanol with some halohydrocarbons at 40.0 and 101.3 kPa

    SciTech Connect

    Artigas, H.; Lafuente, C.; Cea, P.; Royo, F.M.; Urieta, J.S.

    1997-01-01

    Isobaric vapor-liquid equilibrium measurements at 40.0 and 101.3 kPa are reported for 1-butanol + chlorocyclohexane, + chlorobenzene, + bromocyclohexane, + bromobenzene. Some of the studied systems show minimum temperature azeotropes. The experimental data were tested for thermodynamic consistency and satisfactorily correlated with the Margules, Van Laar, Wilson, NRTL, and UNIQUAC equations. Predictions with the UNIFAC method and ASOG method were also obtained.

  17. Vapor-liquid equilibrium data for the propane/-, n-butane/-, isobutane/-, and propylene/isopropyl fluoride systems at 30 and 50 /sup 0/C

    SciTech Connect

    Parrish, W.R.; Sitton, D.M.

    1982-07-01

    This paper presents vapor-liquid equillibrium data at 30 and 50 /sup 0/C for the binary systems of isopropyl fluoride + propane, propylene, isobutane, and n-butane. The isopropyl fluoride/butane systems exhibit positive azeotropes. The computed, equimolar Gibbs free energy for the propylene system is roughly one-half that of the three alliphatic systems.

  18. Isobaric Molecular Dynamics Version of the Generalized Replica Exchange Method (gREM): Liquid-Vapor Equilibrium.

    PubMed

    Ma?olepsza, Edyta; Secor, Maxim; Keyes, Tom

    2015-10-22

    A prescription for sampling isobaric generalized ensembles with molecular dynamics is presented and applied to the generalized replica exchange method (gREM), which was designed to simulate first-order phase transitions. The properties of the isobaric gREM ensemble are discussed, and a study is presented for the liquid-vapor equilibrium of the guest molecules given for gas hydrate formation with the mW water model. Phase diagrams, critical parameters, and a law of corresponding states are obtained. PMID:26398582

  19. Vapor-liquid equilibria of coal-derived liquids; 3: Binary systems with tetralin at 200 mmHg

    SciTech Connect

    Blanco, B.; Beltran, S.; Cabezas, J.L. . Dept. of Chemical Engineering); Coca, J. . Dept. of Chemical Engineering)

    1994-01-01

    Isobaric vapor-liquid equilibrium data are reported for binary systems of tetralin with p-xylene, [gamma]-picoline, piperidine, and pyridine; all systems were measured at 26.66 kPa (200 mmHg) with a recirculation still. Liquid-phase activity coefficients were correlated using the Van Laar, Wilson, NRTL, and UNIQUAC equations. Vapor-phase nonidealities were found negligible under the experimental conditions of this work, and deviations of the liquid phase from the ideal behavior, as described by Raoult's law, were found to be slightly positive for all the systems.

  20. Determination of equilibrium pitch of cholesteric phases by isobaric-isothermal Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Memmer, R.

    2001-05-01

    In canonical Monte Carlo simulations of chiral liquid crystals, generally cholesteric phases with nonequilibrium pitch were formed under periodic boundary conditions. In order to overcome system-size effects the phase diagram of chiral calamitic liquid crystals, described here by the chiral Gay-Berne fluid, was now studied by simulations in the isothermal-isobaric ensemble (NpT). In the temperature-chirality parameter plane a rich polymorphism could be proven. In the cholesteric phase the ability of the simulation box to change the dimensions during the simulations enabled the determination of the equilibrium pitch in dependence on the chirality parameter describing the strength of the chiral interaction. Additionally, in dependence on temperature first-order phase transitions characterized by phase transition enthalpy, entropy and relative volume change have been observed. On heating a cholesteric phase (N*), for the first time by computer simulation of a many-particle system based on model intermolecular interactions a temperature-driven phase transition to a blue phase could be proven, a characteristic feature of many experimental and theoretical phase diagrams of chiral liquid crystals. Additionally, on cooling a cholesteric system a phase with a helical superstructure and smectic layers formed perpendicular to the helical axis, both characteristics of a twist grain boundary (TGB) phase, has been observed. This clear evidence shows that a chiral interaction proportional to the first pseudoscalar term of the expansion in rotational invariants is able to yield the observed phase sequence TGB-like phase, cholesteric phase, blue phase, and isotropic phase in dependence on one scalar parameter given here by the temperature, only.

  1. Vapor-liquid equilibrium and polarization behavior of the GCP water model: Gaussian charge-on-spring versus dipole self-consistent field approaches to induced polarization.

    PubMed

    Chialvo, Ariel A; Moucka, Filip; Vlcek, Lukas; Nezbeda, Ivo

    2015-04-16

    We developed the Gaussian charge-on-spring (GCOS) version of the original self-consistent field implementation of the Gaussian Charge Polarizable water model and test its accuracy to represent the polarization behavior of the original model involving smeared charges and induced dipole moments. For that purpose we adapted the recently proposed multiple-particle-move (MPM) within the Gibbs and isochoric-isothermal ensembles Monte Carlo methods for the efficient simulation of polarizable fluids. We assessed the accuracy of the GCOS representation by a direct comparison of the resulting vapor-liquid phase envelope, microstructure, and relevant microscopic descriptors of water polarization along the orthobaric curve against the corresponding quantities from the actual GCP water model. PMID:25803267

  2. Densities and vapor-liquid equilibria in binary mixtures formed by propyl methanoate + ethanol, + propan-1-ol, and + butan-1-ol at 160.0 kPa

    SciTech Connect

    Falcon, J.; Ortega, J.; Gonzalez, E.

    1996-07-01

    Densities and excess volumes were determined at 298.15 K for propyl methanoate + ethanol, + propan-1-ol, and + butan-1-ol. The results of those quantities were then correlated to get the concentrations of vapor-liquid equilibrium obtained isobarically at 160 kPa for the same mixtures. Two mixtures show azeotropes: for propyl methanoate (1) + ethanol (2), x{sub 1} = 0.443 at T = 358.7 K; and for propyl methanoate (1) + propan-1-ol (2), x{sub 1} = 0.762 at T = 368.2 K. The mixtures are thermodynamically consistent, and the predictions made using several group-contribution models are satisfactory.

  3. 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

  4. 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…

  5. Semi-empirical correlation for binary interaction parameters of the PengRobinson equation of state with the van der Waals mixing rules for the prediction of high-pressure vaporliquid equilibrium

    PubMed Central

    Fateen, Seif-Eddeen K.; Khalil, Menna M.; Elnabawy, Ahmed O.

    2012-01-01

    PengRobinson equation of state is widely used with the classical van der Waals mixing rules to predict vapor liquid equilibria for systems containing hydrocarbons and related compounds. This model requires good values of the binary interaction parameter kij. In this work, we developed a semi-empirical correlation for kij partly based on the HuronVidal mixing rules. We obtained values for the adjustable parameters of the developed formula for over 60 binary systems and over 10 categories of components. The predictions of the new equation system were slightly better than the constant-kij model in most cases, except for 10 systems whose predictions were considerably improved with the new correlation. PMID:25685411

  6. Boundary conditions on the vapor liquid interface at strong condensation

    NASA Astrophysics Data System (ADS)

    Kryukov, A. P.; Levashov, V. Yu.

    2015-08-01

    The problem of the formulation of boundary conditions on the vapor-liquid interface is considered. The different approaches to this problem and their difficulties are discussed. Usually, a quasi-equilibrium scheme is used. At sufficiently large deviations from thermodynamic equilibrium, a molecular kinetics approach should be used for the description of the vapor flow at condensation. The formulation of the boundary conditions at the vapor liquid interface to solve the Boltzmann kinetic equation for the distribution of molecules by velocity is a sophisticated problem. It appears that molecular dynamics simulation (MDS) can be used to provide this solution at the interface. The specific problems occur in the realization of MDS on large time and space scales. Some of these problems, and a hierarchy of continuum, kinetic and molecular dynamic time scales, are discussed in the paper. A description of strong condensation at the kinetic level is presented for the steady one-dimensional problem. A formula is provided for the calculation of the limiting condensation coefficient. It is shown that as the condensation coefficient approaches the limiting value, the vapor pressure rises significantly. The results of the corresponding calculations for the Mach number and temperature at different vapor flows are demonstrated. As a result of the application of the molecular kinetics method and molecular dynamics simulation to the problem of the determination of argon condensation coefficients in the range of temperatures of vapor and liquid ratio 1.0-4.0, it is concluded that the condensation coefficient is close to unity.

  7. Vapor-liquid phase separator permeability results

    NASA Technical Reports Server (NTRS)

    Yuan, S. W. K.; Frederking, T. H. K.

    1981-01-01

    Continued studies are described in the area of vapor-liquid phase separator work with emphasis on permeabilities of porous sintered plugs (stainless steel, nominal pore size 2 micrometer). The temperature dependence of the permeability has been evaluated in classical fluid using He-4 gas at atmospheric pressure and in He-2 on the basis of a modified, thermosmotic permeability of the normal fluid.

  8. Isothermal vapor-liquid equilibria for 2-methyl-2-butanol + 2-methyl-1-butanol + 1-pentanol

    SciTech Connect

    Aucejo, A.; Burguet, M.C.; Monton, J.B.; Munoz, R.; Sanchotello, M.; Vazquez, M.I. . Dept. de Ingenieria Quimica)

    1994-07-01

    Vapor-liquid equilibria (VLE) for 2-methyl-2-butanol + 2-methyl-1-butanol and 2-methyl-2-butanol + 2-methyl-1-butanol + 1-pentanol have been measured at 373.15 K. The binary VLE results have been correlated by different liquid-phase activity coefficient models. The binary interaction parameters obtained from Wilson, NRTL, and UNIQUAC models in this and a previously study are used to predict the VLE data for the ternary system. Vapor-liquid equilibrium (VLE) data are necessary for the design of distillation processes.

  9. Vapor-liquid phase separator studies

    NASA Technical Reports Server (NTRS)

    Yuan, S. W. K.; Hepler, W. A.; Frederking, T. H. K.

    1985-01-01

    A study of porous plug use for vapor-liquid phase seperation in spaceborne cryogenic systems was conducted. The three main topics addressed were: (1) the usefulness of porous media in designs that call for variable areas and flow rates; (2) the possibility of prediction of main parameters of porous plugs for a given material; and (3) prediction of all parameters of the plug, including secondary parameters.

  10. Vapor-liquid-solid growth of <110> silicon nanowire arrays

    NASA Astrophysics Data System (ADS)

    Eichfeld, Sarah M.; Hainey, Mel F.; Shen, Haoting; Kendrick, Chito E.; Fucinato, Emily A.; Yim, Joanne; Black, Marcie R.; Redwing, Joan M.

    2013-09-01

    The epitaxial growth of <110> silicon nanowires on (110) Si substrates by the vapor-liquid-solid growth process was investigated using SiCl4 as the source gas. A high percentage of <110> nanowires was obtained at high temperatures and reduced SiCl4 partial pressures. Transmission electron microscopy characterization of the <110> Si nanowires revealed symmetric V-shaped {111} facets at the tip and large {111} facets on the sidewalls of the nanowires. The symmetric {111} tip faceting was explained as arising from low catalyst supersaturation during growth which is expected to occur given the near-equilibrium nature of the SiCl4 process. The predominance of {111} facets obtained under these conditions promotes the growth of <110> SiNWs.

  11. [Vapor-liquid equilibria for multicomponent organic solvents].

    PubMed

    Ishidao, Toru; Ishimatsu, Sumiyo; Hori, Hajime

    2004-09-01

    Most organic solvents used in the workplace are mixed solvents consisting of several components. It is therefore very important to know the equilibrated vapor concentrations in order to control the work environment. In this study, the vapor-liquid equilibrium for multicomponent organic solvents is estimated by introducing the activity coefficients, which are calculated with the UNIFAC (Universal Quasichemical Functional Group Activity Coefficient) model. For two-component solvents, that is, the toluene-methanol and o-xylene-methanol systems, the calculated values of the vapor fraction and the equilibrated vapor concentrations are in good agreement with the reference ones. For three- or four-component solvents that are used as thinners, the calculated values are also generally in good agreement with the reference ones. PMID:15471281

  12. Design of a high-pressure ebulliometer, with vapor-liquid equilibrium results for the systems CHF2 Cl + CF3 CH3 and CF3 CH2 F + CH2F2

    NASA Astrophysics Data System (ADS)

    Weber, L. A.; Silva, A. M.

    1996-07-01

    We describe the design and operation of a new high-pressure metal ebulliometer which can operate at pressures to at least 3 MPa in the range 220 400 K. Infinite-dilution activity coefficients are presented for the system CHF2Cl + CF3-CH, at 275 K and for the system CF3-CH2F + CH2F2, at 260, 230, and 300 K. The Wilson activity coellicient model and a virial coefficient model are applied to these systems, and the phase equilibrium conditions are calculated. The results are shown to agree well with predicted and with published measured values. The excess enthalpy is calculated and compared with results from a Peng Robinson equation of state. Vapor densities on the dew curves are given.

  13. Vapor-Liquid Equilibria for Some Concentrated Aqueous PolymerSolutions

    SciTech Connect

    Striolo, Alberto; Prausnitz, John M.

    1999-07-01

    Vapor-liquid-equilibrium data were obtained for binary aqueous solutions of six water-soluble linear polymers in the range 70-95 C. A classical gravimetric sorption method was used to measure the amount of solvent absorbed as a function of vapor-phase water pressure. Polymers studied were polyvinylpyrrolidone, polyethyleneoxide, polyvinylalcohol, hydroxyethylcellulose, polyethylenimine, polymethylvinylether. The experimental data were reduced with Hino's lattice model that distinguished the interactions due to London dispersion forces and those due to hydrogen bonding.

  14. Vapor-liquid equilibria for the mixtures ether + 2-butanol and + propyl acetate at 101. 3 kPa

    SciTech Connect

    Benito, G.G.; Carton, A.; Uruena, M.A. . Dept. of Chemical Engineering)

    1994-04-01

    Vapor-liquid equilibrium data at 101.3 kPa pressure for the systems 2-butanol + dibutyl ether, 2-butanol + tetrahydrofuran, propyl acetate + dibutyl ether, and propyl acetate + tetrahydrofuran are reported. The experimental data were well correlated by different thermodynamic equations. The experimental data have also been compared with those predicted by the UNIFAC group contribution method.

  15. Influence of bond flexibility on the vapor-liquid phase equilibria of water.

    PubMed

    Raabe, Gabriele; Sadus, Richard J

    2007-01-28

    The authors performed Gibbs ensemble simulations on the vapor-liquid equilibrium of water to investigate the influence of incorporating intramolecular degrees of freedom in the simple point charge (SPC) water model. Results for vapor pressures, saturation densities, heats of vaporization, and the critical point for two different flexible models are compared with data for the corresponding rigid SPC and SPC/E models. They found that the introduction of internal vibrations, and also their parametrization, has an observable effect on the prediction of the vapor-liquid coexistence curve. The flexible SPC/Fw model, although optimized to describe bulk diffusion and dielectric constants at ambient conditions, gives the best prediction of saturation densities and the critical point of the examined models. PMID:17286493

  16. The calculation of vapor-liquid coexistence curve of Morse fluid: application to iron.

    PubMed

    Apfelbaum, E M

    2011-05-21

    The vapor-liquid coexistence curve of Morse fluid was calculated within the integral equations approach. The critical point coordinates were estimated. The parameters of Morse potential, fitted for elastic constants in solid phase, were used here to apply the results of present calculations to the determination of iron binodal. The properties of copper and sodium were considered in an analogous way. The calculations of pair correlation functions and isobars at liquid phase have shown that only for sodium these potential parameters allow one to obtain agreement with the measurements data. For iron another parameters are necessary to get this agreement in liquid phase. However, they give rise to very low critical temperature and pressure with respect to the estimates of other authors. Consequently, one can suppose that Morse potential is possibly inapplicable to the calculation of high temperature properties of non-alkali metals in disordered phases. PMID:21599072

  17. Vapor-liquid equilibria of sulfur dioxide in polar organic solvents

    SciTech Connect

    Demyanovich, R.J.; Lynn, S.

    1987-03-01

    Vapor-liquid equilibrium data for SO/sub 2/ in eight polar organic solvents and three mixtures of organic solvents were investigated over the temperature range 30-95/sup 0/C and over a concentration range of 0.02-0.16 weight fraction of SO/sub 2/. The solvents investigated were N, N-dimethylaniline (DMA); quinoline; the dimethyl ethers of diethylene glycol, triethylene glycol, and tetraethylene glycol; the monomethyl ether of diethylene glycol (DGM); tetramethylene sulfone; and tributyl phosphate. The mixed solvents investigated were various mixtures of DMA and DGM. The data were correlated by using the UNIQUAC, NRTL, Wilson, and Henry's law phase-equilibrium models.

  18. A theory of a curved vapor-liquid separation boundary: The lattice gas model

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.

    2010-02-01

    Molecular theory of curved vapor-liquid interphase boundaries was considered in terms of the lattice gas model. The theory uses the quasi-thermodynamic concept of curved layers of a separation boundary with a large radius. The transition from a rectangular lattice to such layers is performed by the introduction of a variable number of the nearest neighbors. The problems (1) of the transition from distributed molecular models to layer models reflecting macroscopic symmetry of the interphase boundary and (2) of a minimum linear size of the surface region to which thermodynamic approaches are applicable were considered. Equations for the quasi-equilibrium distribution of molecules at the vapor-liquid boundary in a metastable system were constructed in the quasi-chemical approximation taking into account direct correlations between the nearest interacting molecules. A metastable state is maintained by a pressure jump described by the macro-scopic Laplace equation on a separation surface inside the interphase region. Equations for local mean pressure values and normal and tangential pressure tensor components inside the interphase region were constructed. These equations were used to obtain microscopic difference mechanical equilibrium equations for curved boundaries of spherical and cylindrical drops in the metastable state. The relation between the micro-scopic difference mechanical equilibrium equations and similar differential equations and the macroscopic Laplace equation, which described pressure jump in a metastable system, was considered. Various definitions of surface tension are discussed.

  19. The effect of sulfur on vapor liquid fractionation of metals in hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Borisova, Anastassia Yu.; Harrichoury, Jean-Claude

    2008-02-01

    Despite the growing evidence that the vapor phase, formed through magma degassing and ore fluid boiling, can selectively concentrate and transport metals, the effects of major volatile components like sulfur, chlorine or carbon dioxide on the metal vapor-liquid fractionation and vapor-phase transport under magmatic-hydrothermal conditions remain poorly known. We performed systematic experiments to investigate the effect of sulfur ligands on metal vapor-liquid partitioning in model H 2O-S-NaCl-KCl-NaOH systems at temperatures from 350 to 500 C. Results show that at acidic-to-neutral conditions, vapor-liquid equilibrium distribution coefficients, Km = mvapor / mliquid, where m is the mass concentration of the metal in corresponding phase, of metalloids (As, Sb) and base metals (Zn, Fe, Pb, Ag) are in the range 0.1-1.0 and 0.001-0.1, respectively, and are not significantly affected by the presence of geologically common sulfur concentrations, up to 1-3 wt.% S. In contrast, the partitioning of Cu, Au, and Pt into the vapor increases by a factor of 100 in comparison to the S-free water-salt system, yielding Km values of 0.5-1.0, 1-10, and 10-20, respectively, due to formation of volatile neutral complexes with H 2S and, possibly, SO 2. In neutral-to-basic systems, Zn, Pb, Fe and Ag show 10-100-fold increase of their partition coefficients, whereas Cu, Au and Pt exhibit Km values of up to several orders of magnitude lower, compared to acidic conditions at similar temperature, pressure and sulfur contents. These vapor-liquid distribution patterns result from combined effects of i) formation of volatile species with reduced sulfur ligands in the vapor phase, ii) changes in the metal speciation in the coexisting liquid phase as a function of pH, and iii) solute-solvent interactions in both phases. Our data explain the vapor-liquid fractionation trends for many metals as inferred in coexisting brine and vapor inclusions from magmatic-hydrothermal deposits, and provide a first experimental evidence for the dramatic increase of the mobility of Cu, Au and Pt in sulfur-enriched acidic magmatic-hydrothermal vapors, consistent with geological models of Au Cu ores formation and distribution in porphyry-epithermal settings.

  20. Combination downflow-upflow vapor-liquid separator

    DOEpatents

    Kidwell, John H. (Uniontown, OH); Prueter, William P. (Alliance, OH); Eaton, Andrew M. (Alliance, OH)

    1987-03-10

    An improved vapor-liquid separator having a vertically disposed conduit for flow of a mixture. A first, second and third plurality of curved arms penetrate and extend within the conduit. A cylindrical member is radially spaced from the conduit forming an annulus therewith and having perforations and a retaining lip at its upper end.

  1. Silicon nanowire synthesis by a vapor-liquid-solid approach

    NASA Technical Reports Server (NTRS)

    Mao, Aaron; Ng, H. T.; Nguyen, Pho; McNeil, Melanie; Meyyappan, M.

    2005-01-01

    Synthesis of silicon nanowires is studied by using a vapor-liquid-solid growth technique. Silicon tetrachloride reduction with hydrogen in the gas phase is used with gold serving as catalyst to facilitate growth. Only a narrow set of conditions of SiCl4 concentration and temperature yield straight nanowires. High concentrations and temperatures generally result in particulates, catalyst coverage and deactivation, and coatinglike materials.

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

    SciTech Connect

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

    2004-10-20

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

  3. Molecular model for carbon dioxide optimized to vapor-liquid equilibria.

    PubMed

    Merker, Thorsten; Engin, Cemal; Vrabec, Jadran; Hasse, Hans

    2010-06-21

    A molecular model for carbon dioxide is presented, and the parameters of the Lennard-Jones sites, the bond length, and the quadrupole moment are optimized to experimental vapor-liquid equilibrium data. The resulting molecular model shows mean unsigned deviations to the experiment over the whole temperature range from triple point to critical point of 0.4% in saturated liquid density, 1.8% in vapor pressure, and 8.1% in enthalpy of vaporization. The molecular model is assessed by comparing predicted thermophysical properties with experimental data and a reference equation of state for a large part of the fluid region. The average deviations for density and residual enthalpy are 4.5% and 1.7%, respectively. The model is also capable to predict the radial distribution function, the second virial coefficient, and transport properties, the average deviations of the latter are 12%. PMID:20572726

  4. Vapors-liquid phase separator. [infrared telescope heat sink

    NASA Technical Reports Server (NTRS)

    Frederking, T. H. K.; Brown, G. S.; Chuang, C.; Kamioka, Y.; Kim, Y. I.; Lee, J. M.; Yuan, S. W. K.

    1980-01-01

    The use of porous plugs, mostly with in the form of passive devices with constant area were considered as vapor-liquid phase separators for helium 2 storage vessels under reduced gravity. The incorporation of components with variable cross sectional area as a method of flow rate modification was also investigated. A particular device which uses a shutter-type system for area variation was designed and constructed. This system successfully permitted flor rate changes of up to plus or minus 60% from its mean value.

  5. Nanopillar growth mode by vapor-liquid-solid epitaxy

    NASA Astrophysics Data System (ADS)

    Taraci, J. L.; Dailey, J. W.; Clement, T.; Smith, David J.; Drucker, Jeff; Picraux, S. T.

    2004-06-01

    We report epitaxial growth of Ge nanopillars (NPs ) on Si(100) by vapor-liquid-solid (VLS) growth from digermane. This growth morphology is characterized by short, low-aspect-ratio pillars and is markedly different from the long, narrow nanowires (NWs ) previously reported for VLS growth. The NP growth mode occurs at low digermane pressures. It is attributed to surface-diffusion-induced lateral growth in combination with an insufficient Ge concentration gradient in the AuGe eutectic to catalyze NW growth. High resolution electron microscopy confirms that the NPs are epitaxial with the Si (100) substrate and are fully relaxed and strain free.

  6. Integrated vapor-liquid-solid silicon mass sensors (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Bryce, Brian A.; Gorman, Jason J.; Keylyuk, Sergiy; Davydov, Albert

    2015-08-01

    We present the results and progress of research to create a multiplex chemical sensor based on Au catalyzed vapor-liquid-solid (VLS) silicon nanowires deployed as resonant mass sensors. Each element of this sensor has a single VLS wire grown in close proximity to a Si photodiode. Together they create a Fabry-Prot interferometer that allows for the sensitive detection of the beam's resonant motion. Small changes in mass on the cantilever that occur as a result of chemical absorption on the functionalized Au surface shift the resonant frequency. Our integrated approach will allow large reductions in system complexity for this sensor class.

  7. Vapor-liquid equilibria in the systems of toluene/aniline, aniline/naphthalene, and naphthalene/quinoline

    SciTech Connect

    Lee, C.H.; Mohamed, R.S.; Holder, G.D. )

    1992-04-01

    This paper reports on vapor-liquid equilibria for the aniline/naphthalene, toluene/aniline, and naphthalene/quinoline systems that have been determined at 0-1500 kPa and 490-623 K by using a static equilibrium cell. The data can be accurately correlated with the modified Peng-Robinson equation of state by using density-dependent mixing rules. The binary interaction parameters and correction factors for the equation of state are reported at each isotherm. The presence of coal-derived solids in these binary systems did not influence any of the binary bubble pressures.

  8. Magnetotail dynamics under isobaric constraints

    NASA Technical Reports Server (NTRS)

    Birn, Joachim; Schindler, Karl; Janicke, Lutz; Hesse, Michael

    1994-01-01

    Using linear theory and nonlinear MHD simulations, we investigate the resistive and ideal MHD stability of two-dimensional plasma configurations under the isobaric constraint dP/dt = 0, which in ideal MHD is equivalent to conserving the pressure function P = P(A), where A denotes the magnetic flux. This constraint is satisfied for incompressible modes, such as Alfven waves, and for systems undergoing energy losses. The linear stability analysis leads to a Schroedinger equation, which can be investigated by standard quantum mechanics procedures. We present an application to a typical stretched magnetotail configuration. For a one-dimensional sheet equilibrium characteristic properties of tearing instability are rediscovered. However, the maximum growth rate scales with the 1/7 power of the resistivity, which implies much faster growth than for the standard tearing mode (assuming that the resistivity is small). The same basic eigen-mode is found also for weakly two-dimensional equilibria, even in the ideal MHD limit. In this case the growth rate scales with the 1/4 power of the normal magnetic field. The results of the linear stability analysis are confirmed qualitatively by nonlinear dynamic MHD simulations. These results suggest the interesting possibility that substorm onset, or the thinning in the late growth phase, is caused by the release of a thermodynamic constraint without the (immediate) necessity of releasing the ideal MHD constraint. In the nonlinear regime the resistive and ideal developments differ in that the ideal mode does not lead to neutral line formation without the further release of the ideal MHD constraint; instead a thin current sheet forms. The isobaric constraint is critically discussed. Under perhaps more realistic adiabatic conditions the ideal mode appears to be stable but could be driven by external perturbations and thus generate the thin current sheet in the late growth phase, before a nonideal instability sets in.

  9. Vapor-Liquid Equilibria of Imidazolium Ionic Liquids with Cyano Containing Anions with Water and Ethanol.

    PubMed

    Khan, Imran; Batista, Marta L S; Carvalho, Pedro J; Santos, Luís M N B F; Gomes, José R B; Coutinho, João A P

    2015-08-13

    Isobaric vapor-liquid equilibria of 1-butyl-3-methylimidazolium thiocyanate ([C4C1im][SCN]), 1-butyl-3-methylimidazolium dicyanamide ([C4C1im][N(CN)2]), 1-butyl-3-methylimidazolium tricyanomethanide ([C4C1im][C(CN)3]), and 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1im][B(CN)4]), with water and ethanol were measured over the whole concentration range at 0.1, 0.07, and 0.05 MPa. Activity coefficients were estimated from the boiling temperatures of the binary systems, and the data were used to evaluate the ability of COSMO-RS for describing these molecular systems. Aiming at further understanding the molecular interactions on these systems, molecular dynamics (MD) simulations were performed. On the basis of the interpretation of the radial and spatial distribution functions along with coordination numbers obtained through MD simulations, the effect of the increase of CN-groups in the IL anion in its capability to establish hydrogen bonds with water and ethanol was evaluated. The results obtained suggest that, for both water and ethanol systems, the anion [N(CN)2](-) presents the higher ability to establish favorable interactions due to its charge, and that the ability of the anions to interact with the solvent, decreases with further increasing of the number of cyano groups in the anion. The ordering of the partial charges in the nitrogen atoms from the CN-groups in the anions agrees with the ordering obtained for VLE and activity coefficient data. PMID:26168205

  10. On the isobaric thermal expansivity of liquids

    NASA Astrophysics Data System (ADS)

    Troncoso, Jacobo; Navia, Paloma; Roman, Luis; Bessieres, David; Lafitte, Thomas

    2011-03-01

    The temperature and pressure dependence of isobaric thermal expansivity, ?p, in liquids is discussed in this paper. Reported literature data allow general trends in this property that are consistent with experimental evidence to be established. Thus, a negative pressure dependence is to be expected except around the critical point. On the other hand, ?p exhibits broad regions of negative and positive temperature dependence in the (T, p) plane depending on the nature of the particular liquid. These trends are rationalized here in terms of various molecular-based equations of state. The analysis of the Lennard-Jones, hard sphere square well and restricted primitive model equations allows understanding the differences in the ?p behavior between liquids of diverse chemical nature (polar, nonpolar, and ionic): broader regions of negative temperature and positive pressure dependencies are obtained for liquids characterized by larger ranges of the interparticle potential. Also, using the statistical associating fluid theory (SAFT) allowed the behavior of more complex systems (basically, those potentially involving chain and association effects) to be described. The effect of chain length is rather simple: increasing it is apparently equivalent to raise the interaction range. By contrast, association presents a quite complex effect on ?p, which comes from a balance between the dispersive and associative parts of the interaction potential. Thus, if SAFT parameters are adjusted to obtain low association ability, ?p is affected by each mechanism at clearly separate regions, one at low temperature, due to association, and the other to dispersive forces, which has its origin in fluctuations related with vapor-liquid transition.

  11. New mode of vapor-liquid-solid nanowire growth.

    PubMed

    Dubrovskii, V G; Cirlin, G E; Sibirev, N V; Jabeen, F; Harmand, J C; Werner, P

    2011-03-01

    We report on the new mode of the vapor-liquid-solid nanowire growth with a droplet wetting the sidewalls and surrounding the nanowire rather than resting on its top. It is shown theoretically that such an unusual configuration happens when the growth is catalyzed by a lower surface energy metal. A model of a nonspherical elongated droplet shape in the wetting case is developed. Theoretical predictions are compared to the experimental data on the Ga-catalyzed growth of GaAs nanowires by molecular beam epitaxy. In particular, it is demonstrated that the experimentally observed droplet shape is indeed nonspherical. The new VLS mode has a major impact on the crystal structure of GaAs nanowires, helping to avoid the uncontrolled zinc blende-wurtzite polytylism under optimized growth conditions. Since the triple phase line nucleation is suppressed on surface energetic grounds, all nanowires acquire pure zinc blende phase along the entire length, as demonstrated by the structural studies of our GaAs nanowires. PMID:21344916

  12. Transient-pressure analysis in geothermal steam reservoirs with an immobile vaporizing liquid phase

    USGS Publications Warehouse

    Moench, A.F.; Atkinson, P.G.

    1978-01-01

    A finite-difference model for the radial horizontal flow of steam through a porous medium is used to evaluate transient-pressure behavior in the presence of an immobile vaporizing or condensing liquid phase. Graphs of pressure drawdown and buildup in terms of dimensionless pressure and time are obtained for a well discharging steam at a constant mass flow rate for a specified time. The assumptions are made that the steam is in local thermal equilibrium with the reservoir rocks, that temperature changes are due only to phase change, and that effects of vapor-pressure lowering are negligible. Computations show that when a vaporizing liquid phase is present the pressure drawdown exhibits behavior similar to that observed in noncondensable gas reservoirs, but delayed in time. A theoretical analysis allows for the computation of this delay and demonstrates that it is independent of flow geometry. The response that occurs upon pressure buildup is markedly different from that in a noncondensable gas system. This result may provide a diagnostic tool for establishing the existence of phase-change phenomena within a reservoir. ?? 1979.

  13. Riemannian geometry study of vapor-liquid phase equilibria and supercritical behavior of the Lennard-Jones fluid.

    PubMed

    May, Helge-Otmar; Mausbach, Peter

    2012-03-01

    The behavior of thermodynamic response functions and the thermodynamic scalar curvature in the supercritical region have been studied for a Lennard-Jones fluid based on a revised modified Benedict-Webb-Rubin equation of state. Response function extrema are sometimes used to estimate the Widom line, which is characterized by the maxima of the correlation lengths. We calculated the Widom line for the Lennard-Jones fluid without using any response function extrema. Since the volume of the correlation length is proportional to the Riemannian thermodynamic scalar curvature, the locus of the Widom line follows the slope of maximum curvature. We show that the slope of the Widom line follows the slope of the isobaric heat capacity maximum only in the close vicinity of the critical point and that, therefore, the use of response function extrema in this context is problematic. Furthermore, we constructed the vapor-liquid coexistence line for the Lennard-Jones fluid using the fact that the correlation length, and therefore the thermodynamic scalar curvature, must be equal in the two coexisting phases. We compared the resulting phase envelope with those from simulation data where multiple histogram reweighting was used and found striking agreement between the two methods. PMID:22587083

  14. Isobaric groundwater well

    DOEpatents

    Hubbell, Joel M. (Idaho Falls, ID); Sisson, James B. (Idaho Falls, ID)

    1999-01-01

    A method of measuring a parameter in a well, under isobaric conditions, including such parameters as hydraulic gradient, pressure, water level, soil moisture content and/or aquifer properties the method as presented comprising providing a casing having first and second opposite ends, and a length between the ends, the casing supporting a transducer having a reference port; placing the casing lengthwise into the well, second end first, with the reference port vented above the water table in the well; and sealing the first end. A system is presented for measuring a parameter in a well, the system comprising a casing having first and second opposite ends, and a length between the ends and being configured to be placed lengthwise into a well second end first; a transducer, the transducer having a reference port, the reference port being vented in the well above the water table, the casing being screened across and above the water table; and a sealing member sealing the first end. In one embodiment, the transducer is a tensiometer transducer and in other described embodiments, another type transducer is used in addition to a tensiometer.

  15. High-pressure vapor-liquid equilibria in the propane-1-propanol system

    SciTech Connect

    Muehlbauer, A.L.; Raal, J.D. )

    1993-04-01

    High-pressure isothermal vapor liquid equilibrium data were measured for the propane-1-propanol system at 81.6, 105.2, and 120.1 C in a static equilibrium cell with liquid-phase sampling by a piston-driven sampling rod and homogenizing the sample with a static jet mixer. The vapor phase was sampled by releasing it into an evacuated manifold, and the gas chromatograph was calibrated with a new variable volumetric device. Satisfactory modeling was achieved with the combined method using the UNIQUAC equation with equations of sate: the group contribution EOS, Peng-Robinson EOS, or the two-parameter Virial EOS. Differences between the measured and calculated vapor-phase mole fractions, however, were significant for the lower pressure regions of the 81.6 and 120.1 C isotherms. UNIQUAC parameters, hitherto unavailable, with fairly strong temperature dependence in the 81.6 to 120.1 C range are proposed for the system. The covariance matrix indicated a significant correlation among the parameters. The classical mixing rule interaction parameters required for the original Peng-Robinson EOS in the combined method were obtained using the direct method and were temperature-independent for the isotherms for which the propane was supercritical. The possibility of propane/1-propanol immiscibility was theoretically examined according to the criteria of Baker et al. The plots of Gibbs energy of mixing vs. phase mole fractions did not indicate liquid-phase splitting, but the inferences are EOS-dependent and must await visual confirmation. The authors earlier vapor-phase thermodynamic consistency test indicated the data for all three data sets not to be inconsistent.

  16. A three-dimensional phase field model for nanowire growth by the vapor-liquid-solid mechanism

    NASA Astrophysics Data System (ADS)

    Wang, Yanming; Ryu, Seunghwa; McIntyre, Paul C.; Cai, Wei

    2014-07-01

    We present a three-dimensional multi-phase field model for catalyzed nanowire (NW) growth by the vapor-liquid-solid (VLS) mechanism. The equation of motion contains both a Ginzburg-Landau term for deposition and a diffusion (Cahn-Hilliard) term for interface relaxation without deposition. Direct deposition from vapor to solid, which competes with NW crystal growth through the molten catalyst droplet, is suppressed by assigning a very small kinetic coefficient at the solid-vapor interface. The thermodynamic self-consistency of the model is demonstrated by its ability to reproduce the equilibrium contact angles at the VLS junction. The incorporation of orientation dependent gradient energy leads to faceting of the solid-liquid and solid-vapor interfaces. The model successfully captures the curved shape of the NW base and the Gibbs-Thomson effect on growth velocity.

  17. Turbulence and heat exchange in condensing vapor-liquid flow

    NASA Astrophysics Data System (ADS)

    Lakehal, Djamel; Fulgosi, Marco; Banerjee, Sanjoy; Yadigaroglu, George

    2008-06-01

    Turbulence and heat exchange during condensation of a vapor stream countercurrently flowing to a subcooled liquid stream in a slightly inclined channel has been investigated by direct numerical simulation (DNS). Condensation rates and imposed pressure gradients have been varied, and capillary-gravity waves have been allowed to develop at the (deformable) vapor-liquid interface. These simulations extend our previous DNS of turbulence and scalar exchange in stratified gas-liquid flows without condensation. The previous studies indicated that for conditions in which the gas-liquid interface remained continuous, i.e., did not "break," scalar exchange rates on both the gas and liquid sides were largely determined by sweeps which brought high momentum fluid from the bulk flow to the interface. As sweep frequencies were found to scale with interfacial friction velocities, scalar exchange coefficients could be parametrized with a surface renewal theory. The issue addressed in the current work is how these findings are altered by condensation which acts somewhat like suction through a wall on the vapor side and injection through a wall on the liquid side. Both suction and injection have been found to affect shear stresses, turbulence characteristics, and scalar exchange rates, and hence similar effects might be expected during condensation. The present simulations indicate that the turbulence characteristics in both phases are affected, with turbulence intensities and Reynolds stresses being enhanced on the vapor side and attenuated on the liquid side. For a given imposed pressure gradient, the interfacial shear stress decreases as a result of the interfacial momentum exchange due to condensation. Interfacial waves are also found to be damped by condensation and the streamwise vortical structures on the liquid side are attenuated. The frequencies of sweeps and ejections, however, do scale with the interfacial friction velocity, reduced due to condensation, as does the liquid-side heat transfer coefficient. The simulations indicate that the scaling relationship between the interfacial friction velocity and the liquid-side heat transfer coefficient is similar to that in the absence of condensation, although the interfacial friction velocity itself is different, being dependent on condensation rates. As condensation rates depend in turn on the liquid-side heat transfer, their prediction becomes a coupled problem. A procedure for determining condensation rates as a function of imposed pressure gradient and liquid subcooling is derived from the simulations.

  18. Nanophase diagram of binary eutectic Au-Ge nanoalloys for vapor-liquid-solid semiconductor nanowires growth

    PubMed Central

    Lu, Haiming; Meng, Xiangkang

    2015-01-01

    Although the vapor-liquid-solid growth of semiconductor nanowire is a non-equilibrium process, the equilibrium phase diagram of binary alloy provides important guidance on the growth conditions, such as the temperature and the equilibrium composition of the alloy. Given the small dimensions of the alloy seeds and the nanowires, the known phase diagram of bulk binary alloy cannot be expected to accurately predict the behavior of the nanowire growth. Here, we developed a unified model to describe the size- and dimensionality-dependent equilibrium phase diagram of Au-Ge binary eutectic nanoalloys based on the size-dependent cohesive energy model. It is found that the liquidus curves reduce and shift leftward with decreasing size and dimensionality. Moreover, the effects of size and dimensionality on the eutectic composition are small and negligible when both components in binary eutectic alloys have the same dimensionality. However, when two components have different dimensionality (e.g. Au nanoparticle-Ge nanowire usually used in the semiconductor nanowires growth), the eutectic composition reduces with decreasing size. PMID:26053237

  19. Delta isobars in neutron stars

    NASA Astrophysics Data System (ADS)

    Pagliara, Giuseppe; Drago, Alessandro; Lavagno, Andrea; Pigato, Daniele

    2015-05-01

    The appearance of delta isobars in beta-stable matter is regulated by the behavior of the symmetry energy at densities larger than saturation density. We show that by taking into account recent constraints on the density derivative of the symmetry energy and the theoretical and experimental results on the excitations of delta isobars in nuclei, delta isobars are necessary ingredients for the equations of state used for studying neutron stars. We analyze the effect of the appearance of deltas on the structure of neutron stars: as in the case of hyperons, matter containing delta is too soft for allowing the existence of 2M⊙ neutron stars. Quark stars on the other hand, could reach very massive configurations and they could form from a process of conversion of hadronic stars in which an initial seed of strangeness appears through hyperons.

  20. Molecular gas dynamics applied to phase change processes at a vapor-liquid interface: shock-tube experiment and MGD computation for methanol

    NASA Astrophysics Data System (ADS)

    Fujikawa, S.; Yano, T.; Kobayashi, K.; Iwanami, K.; Ichijo, M.

    This paper deals with a molecular gas-dynamics method applied to the accurate determination of the condensation coefficient of methanol vapor. The method consisted of an experiment using a shock tube and computations using a molecular gas-dynamics equation. The experiments were performed in such situations where the shift from a vapor-liquid equilibrium state to a nonequilibrium one is realized by a shock wave in a scale of molecular mean free time of vapor molecules. The temporal evolution in thickness of a liquid film formed on the shock-tube endwall behind a reflected shock wave is measured by an optical interferometer. By comparing the measured liquid-film thickness with numerical solutions for a polyatomic version of the Gaussian-BGK model of the Boltzmann equation, the condensation coefficient of methanol vapor is accurately determined in vapor-liquid nonequilibrium states. As a result, it is clear that the condensation coefficient is just unity very near to an equilibrium state, but is smaller far from the equilibrium state.

  1. EXPERIMENTAL MEASUREMENT AND MODELING OF THE VAPOR-LIQUID EQUILIBRIUM OF CARBON DIOXIDE + CHLOROFORM. (R826734)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  2. Choice of basis mixtures for the prediction of vapor-liquid equilibria using the UNIFAC model

    SciTech Connect

    Kushner, T.M.; Fainburg, G.D.; Vitman, T.A.; Serafimov, L.A.

    1988-07-01

    A link was established between the accurate prediction of vapor-liquid equilibria and azeotropes using the UNIFAC group model and the choice of the basis information. The component activity coefficients are plotted as functions of composition for all the sets of data in each binary system. The activity coefficients at infinite dilution are determined as graphical extrapolations of these plots. The plot for the butanol-hydrocarbon system is shown. It is shown that azeotrope parameters can be used as the basis information to predict vapor-liquid equilibria for several sets of systems.

  3. Vapor-liquid equilibria for systems of 1-butanol with 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, and 3-methyl-2-butanol at 30 and 100 kPa

    SciTech Connect

    Aucejo, A.; Burguet, M.C.; Monton, J.B.; Munoz, R.; Sanchotello, M.; Vazquez, M.I. . Dept. de Ingenieria Quimica)

    1994-04-01

    Vapor-liquid equilibrium data were measured for binary systems of 1-butanol with 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, and 3-methyl-2-butanol at 30 and 100 kPa. The experimental data obtained in this work are thermodynamically consistent according to a point-to-point consistency test, and deviation from ideal behavior is small in all cases. They can be equally well correlated with the Margules, Van Laar, Wilson, NRTL, and UNIQUAC equations.

  4. Naturally occurring vapor-liquid-solid (VLS) Whisker growth of germanium sulfide

    USGS Publications Warehouse

    Finkelman, R.B.; Larson, R.R.; Dwornik, E.J.

    1974-01-01

    The first naturally occurring terrestrial example of vapor-liquid-solid (VLS) growth has been observed in condensates from gases released by burning coal in culm banks. Scanning electron microscopy, X-ray diffraction, and energy dispersive analysis indicate that the crystals consist of elongated rods (??? 100 ??m) of germanium sulfide capped by bulbs depleted in germanium. ?? 1974.

  5. Influence of solid-state characteristics on critical parameters of vapor-liquid phase transition

    NASA Astrophysics Data System (ADS)

    Khomkin, A. L.; Shumikhin, A. S.

    2015-11-01

    New method for calculation of critical point parameters and binodal of vapor-liquid (dielectric-metal) phase transition is suggested. Method is based on the hypothesis that cohesion, which determines the main properties of solid state, determines also the properties in vicinity of critical point. Comparison with known experimental data for rare gases and mercury shows satisfactory agreement with our calculations.

  6. Ternary vapor-liquid equilibria of 2-propanol + cyclohexane + toluene at 318.15 K

    SciTech Connect

    Nagata, Isamu; Tamura, Kazuhiro; Ksiazczak, A.

    1996-11-01

    Isothermal vapor-liquid equilibria of 2-propanol + cyclohexane + toluene were measured using a modified Boublik still at 318.15 K. The experimental results are compared with those calculated using the UNIQUAC associated-solution model with only binary parameters.

  7. Vapor liquid equilibria on the ternary lithium fluoride-sodium fluoride-beryllium fluoride system

    NASA Astrophysics Data System (ADS)

    Fukuda, Grant Takeshi

    Molten mixtures of LiF, NaF, and BeF2 (FLiNaBe) have been proposed as a liquid first wall for selected fusion reactor designs. Because currently envisaged reactor technologies for igniting and/or sustaining a, fusion reaction require vacuum conditions, the volatility of these liquids is an issue for concern. Many physical properties of the ternary LiF-NaF-BeF 2 (FLiNaBe) system have already been studied as part of the molten salt reactor program, but the vapor pressure has not been measured. A study of the vapor liquid equilibrium of FLiNaBe by Thermogravimetric Analysis (TGA) and Knudsen Cell Mass Spectrometry (KCMS) is presented. The ternary system is treated as a pseudo-binary system by fixing the ratio of LiF:NaF and varying the amount of BeF2. Measurements have been performed over a composition range of 0.3--0.8 mole fraction BeF2 and from 875--975K. Experimental data, are correlated in terms of the BeF 2 activity coefficient. Measurements were also carried out on the binary systems LiF-BeF2 and NaF-BeF2. Measured values of the BeF2 activity coefficient in the binary LiF-BeF2 and NaF-BeF2 systems compare satisfactorily with previous results published in the research literature. The vapor phase of FLiNaBe was found to consist of primarily the species BeF2, LiBeF3, and NaBeF 3 over the temperature and composition range studied. Mixtures of BeF2-containing fluoride salts are highly non-ideal; the BeF2 activity coefficient exhibits both positive and negative deviations from ideality over the composition range studied. An associated solution model with 3 adjustable parameters is used to fit the BeF2 activity coefficient data of the LiF-BeF2 and NaF-BeF2 systems. The parameters obtained from fitting binary data are then used to fit the ternary system. The extension of the model to the ternary system results in a single additional parameter that can only be determined from fitting ternary data. Overall the agreement between the model and experimental data is within ˜30% and the model can be used to predict the vapor pressure over a wide composition range.

  8. Phase equilibrium measurements on nine binary mixtures

    SciTech Connect

    Wilding, W.V.; Giles, N.F.; Wilson, L.C.

    1996-11-01

    Phase equilibrium measurements have been performed on nine binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following systems at two temperatures each: (aminoethyl)piperazine + diethylenetriamine; 2-butoxyethyl acetate + 2-butoxyethanol; 2-methyl-2-propanol + 2-methylbutane; 2-methyl-2-propanol + 2-methyl-2-butene; methacrylonitrile + methanol; 1-chloro-1,1-difluoroethane + hydrogen chloride; 2-(hexyloxy)ethanol + ethylene glycol; butane + ammonia; propionaldehyde + butane. Equilibrium vapor and liquid phase compositions were derived form the PTx data using the Soave equation of state to represent the vapor phase and the Wilson or the NRTL activity coefficient model to represent the liquid phase. A large immiscibility region exists in the butane + ammonia system at 0 C. Therefore, separate vapor-liquid-liquid equilibrium measurements were performed on this system to more precisely determine the miscibility limits and the composition of the vapor phase in equilibrium with the two liquid phases.

  9. Universal adsorption at the vapor-liquid interface near the consolute point

    NASA Technical Reports Server (NTRS)

    Schmidt, James W.

    1990-01-01

    The ellipticity of the vapor-liquid interface above mixtures of methylcyclohexane (C7H14) and perfluoromethylcyclohexane (C7F14) has been measured near the consolute point T(c) = 318.6 K. The data are consistent with a model of the interface that combines a short-ranged density-vs height profile in the vapor phase with a much longer-ranged composition-versus-height profile in the liquid. The value of the free parameter produced by fitting the model to the data is consistent with results from two other simple mixtures and a mixture of a polymer and solvent. This experiment combines precision ellipsometry of the vapor-liquid interface with in situ measurements of refractive indices of the liquid phases, and it precisely locates the consolute point.

  10. Thermal Lattice Boltzmann Simulations for Vapor-Liquid Two-Phase Flows in Two Dimensions

    NASA Astrophysics Data System (ADS)

    Wei, Yikun; Qian, Yuehong

    2011-11-01

    A lattice Boltzmann model with double distribution functions is developed to simulate thermal vapor-liquid two-phase flows. In this model, the so-called mesoscopic inter-particle pseudo-potential for the single component multi-phase lattice Boltzmann model is used to simulate the fluid dynamics and the internal energy field is simulated by using a energy distribution function. Theoretical results for large-scale dynamics including the internal energy equation can be derived and numerical results for the coexistence curve of vapor-liquid systems are in good agreement with the theoretical predictions. It is shown from numerical simulations that the model has the ability to mimic phase transitions, bubbly flows and slugging flows. This research is support in part by the grant of Education Ministry of China IRT0844 and the grant of Shanghai CST 11XD1402300.

  11. Measurements of the vapor-liquid coexistence curve and the critical locus for several refrigerant mixtures

    SciTech Connect

    Higashi, Y.; Uematsu, M.; Watanabe, K.; Hanley, H.J.M.; Cezairliyan, A.

    1986-01-01

    Measurements of the vapor-liquid coexistence curve in the critical region for the systems of binary refrigerant mixture, i.e., Refrigerant 22 + Refrigerant 114 and Refrigerant 13B1 + Refrigerant 114, have been made by visual observation of the meniscus at the vapor-liquid interface within an optical cell. The experimental uncertainty of the temperature, density, and mass fraction is estimated within 15 mK, 0.5%, and 0.05%, respectively. The critical locus for these mixtures has been determined taking into consideration the disappearing meniscus level and the intensity of the critical opalescence. In accordance with the previous results of the Refrigerant 12 + Refrigerant 22 system, the coexistence curve for binary refrigerant mixtures is discussed. The composition dependence of the critical parameters for refrigerant mixtures is also discussed and compared with that of several predictive methods.

  12. Preferred orientations of laterally grown silicon films over amorphous substrates using the vapor-liquid-solid technique

    NASA Astrophysics Data System (ADS)

    LeBoeuf, J. L.; Brodusch, N.; Gauvin, R.; Quitoriano, N. J.

    2014-12-01

    A novel method has been optimized so that adhesion layers are no longer needed to reliably deposit patterned gold structures on amorphous substrates. Using this technique allows for the fabrication of amorphous oxide templates known as micro-crucibles, which confine a vapor-liquid-solid (VLS) catalyst of nominally pure gold to a specific geometry. Within these confined templates of amorphous materials, faceted silicon crystals have been grown laterally. The novel deposition technique, which enables the nominally pure gold catalyst, involves the undercutting of an initial chromium adhesion layer. Using electron backscatter diffraction it was found that silicon nucleated in these micro-crucibles were 30% single crystals, 45% potentially twinned crystals and 25% polycrystals for the experimental conditions used. Single, potentially twinned, and polycrystals all had an aversion to growth with the {1 0 0} surface parallel to the amorphous substrate. Closer analysis of grain boundaries of potentially twinned and polycrystalline samples revealed that the overwhelming majority of them were of the 60 ?3 coherent twin boundary type. The large amount of coherent twin boundaries present in the grown, two-dimensional silicon crystals suggest that lateral VLS growth occurs very close to thermodynamic equilibrium. It is suggested that free energy fluctuations during growth or cooling, and impurities were the causes for this twinning.

  13. Vapor-liquid equilibria and salt apparent molar volumes of the water + 2-propanol + tetrabutylammonium bromide system

    SciTech Connect

    Slusher, J.T.; Decker, K.J.; Liu, H.; Cummings, P.T. . Dept. of Chemical Engineering); Vega, C.A. . Dept. of Chemistry); O'Connell, J.P. . Chemical Engineering)

    1994-07-01

    Vapor-liquid equilibrium and density measurements have been performed on 1.00--5.89 m tetrabutylammonium bromide (TBAB) in mixtures of 2-propanol and water. The VLE experiments were performed using a modified Othmer still at ambient pressure. The effect of salt on the relative volatility of 2-propanol was evaluated at molalities of 1.00, 1.79, and 5.89 over the full range of solvent composition. At each salt molality, as the alcohol concentration increased, salting-in and then salting-out behavior of the alcohol was observed. The azeotrope was shifted but apparently not eliminated for the salt concentrations studied. Density measurements at 25, 40, and 55 C were taken using a vibrating tube densimeter at four salt molalities over the full range of solvent composition. As salt molality increased, the apparent molar volume of TBAB exhibits a minimum between 1 to 2 m TBAB in pure water, it is slightly larger and monotonically increased in pure 2-propanol, and it is larger yet, with a maximum at lower 2-propanol amounts, in the ternary mixture.

  14. Sintered plug flow modulation of a vapor-liquid phase separator for a helium II vessel

    NASA Technical Reports Server (NTRS)

    Frederking, T. H. K.; Chuang, C.; Kamioka, Y.; Lee, J. M.; Yuan, S. W. K.

    1984-01-01

    Presented is a system for modulation of a superfluid (helium II) flow in a vapor-liquid phase separator, for use in cryogenic storage tanks in future space missions. The system consists of a semicircular mechanically operated shutter, downstream of the separator plug, rotated at 0.1 rpm to control the operational surface area of the separator. The mass flow rate was varied from 10 to 22 mg/s. Pressure gradients across the plug are also discussed.

  15. Isothermal vapor-liquid equilibria for methanol + ethanol + water, methanol + water, and ethanol + water

    SciTech Connect

    Kurihara, Kiyofumi; Takeda, Kouichi; Kojima, Kazuo; Minoura, Tsuyoshi

    1995-05-01

    Isothermal vapor-liquid equilibria were measured for the ternary system methanol + ethanol + water and its constituent binary systems of methanol + water and ethanol + water at 323.15, 328.15, and 333.15 K. The apparatus that was used made it possible to control the measured temperature and total pressure by computer. The experimental binary data were correlated by the NRTL equation. The ternary system was predicted using the binary NRTL parameters with good accuracy.

  16. On the Electronic Nature of the Surface Potential at the Vapor-Liquid Interface of Water

    SciTech Connect

    Kathmann, S M; Kuo, I; Mundy, C J

    2008-02-05

    The surface potential at the vapor-liquid interface of water is relevant to many areas of chemical physics. Measurement of the surface potential has been experimentally attempted many times, yet there has been little agreement as to its magnitude and sign (-1.1 to +0.5 mV). We present the first computation of the surface potential of water using ab initio molecular dynamics. We find that the surface potential {chi} = -18 mV with a maximum interfacial electric field = 8.9 x 10{sup 7} V/m. A comparison is made between our quantum mechanical results and those from previous molecular simulations. We find that explicit treatment of the electronic density makes a dramatic contribution to the electric properties of the vapor-liquid interface of water. The E-field can alter interfacial reactivity and transport while the surface potential can be used to determine the 'chemical' contribution to the real and electrochemical potentials for ionic transport through the vapor-liquid interface.

  17. Isothermal vapor-liquid equilibria for the binary systems of chlorine with difluoromethane, chlorodifluoromethane, and dichlorodifluoromethane at 10 C

    SciTech Connect

    Kang, Y.W.; Cho, S.Y.; Nah, I.W.

    1998-07-01

    Isothermal vapor-liquid equilibria for difluoromethane + chlorine, chlorodifluoromethane + chlorine, and dichlorodifluoromethane + chlorine have been measured. The experimental data are correlated with the Peng-Robinson equation of state, and the relevant parameters are presented. All of the binary systems form minimum boiling homogeneous azeotropes at the experimental conditions. The correlation of the vapor-liquid equilibria was found to be in good agreement with the experimental data.

  18. Isothermal vapor-liquid equilibria for the 2-propanol + water system containing poly(ethylene glycol) at 298.15 K

    SciTech Connect

    Tsuji, T.; Hasegawa, K.; Hiaki, T.; Hongo, M.

    1996-09-01

    Isothermal vapor-liquid equilibrium measurements were performed for the 2-propanol + water system containing poly(ethylene glycol) (PEG) at 298.15 K by a flow type apparatus. Three different PEGs whose molecular weights are 200, 1000, and 20,000 were employed, and their mass fractions in the liquid phase were up to 0.35. The volatility of water was reduced by the addition of PEG, and the azeotropic point of the 2-propanol + water system was changed to a higher mole fraction of 2-propanol. Activity coefficients of solvent were calculated by assuming the monodispersity of PEG. It was found that the activity coefficients of water were selectively decreased by the addition of PEG. These phenomena did not depend on the molecular weight of PEG.

  19. A nucleation-growth model of nanowires produced by the vapor-liquid-solid process

    NASA Astrophysics Data System (ADS)

    Li, Na; Li, Wenxuan; Liu, Lijun; Tan, Teh Y.

    2013-08-01

    Within the framework of the vapor-liquid-solid process of Si nanowire growth, an expression describing the Si nanowire growth rate is derived and fitted to multiple experimental data sets with excellent agreement. The derivation is based on the two-dimensional island nucleation-growth process which appeared to have been first mentioned by Givargizov and Chernov [Sov. Phys. Crystallog. 18, 89 (1973)]. This nucleation-growth process is in principle different from the conventional diffusion limited or reaction barrier limited processes.

  20. Effect of molecular flexibility of Lennard-Jones chains on vapor-liquid interfacial properties

    NASA Astrophysics Data System (ADS)

    Blas, F. J.; Bravo, A. I. Moreno-Ventas; Algaba, J.; Martnez-Ruiz, F. J.; MacDowell, L. G.

    2014-03-01

    We have determined the interfacial properties of short fully flexible chains formed from tangentially bonded Lennard-Jones monomeric units from direct simulation of the vapor-liquid interface. The results obtained are compared with those corresponding to rigid-linear chains formed from the same chain length, previously determined in the literature [F. J. Blas, A. I. M.-V. Bravo, J. M. Mguez, M. M. Pieiro, and L. G. MacDowell, J. Chem. Phys. 137, 084706 (2012)]. The full long-range tails of the potential are accounted for by means of an improved version of the inhomogeneous long-range corrections of Jane?ek [J. Phys. Chem. B 129, 6264 (2006)] proposed recently by MacDowell and Blas [J. Chem. Phys. 131, 074705 (2008)] valid for spherical as well as for rigid and flexible molecular systems. Three different model systems comprising of 3, 5, and 6 monomers per molecule are considered. The simulations are performed in the canonical ensemble, and the vapor-liquid interfacial tension is evaluated using the test-area method. In addition to the surface tension, we also obtained density profiles, coexistence densities, critical temperature and density, and interfacial thickness as functions of temperature, paying particular attention to the effect of the chain length and rigidity on these properties. According to our results, the main effect of increasing the chain length (at fixed temperature) is to sharpen the vapor-liquid interface and to increase the width of the biphasic coexistence region. As a result, the interfacial thickness decreases and the surface tension increases as the molecular chains get longer. Comparison between predictions for fully flexible and rigid-linear chains, formed by the same number of monomeric units, indicates that the main effects of increasing the flexibility, i.e., passing from a rigid-linear to a fully flexible chain, are: (a) to decrease the difference between the liquid and vapor densities; (b) to decrease the critical temperature and to increase the critical density; (c) to smooth the density profiles along the interfacial region; (d) to increase the interfacial thickness; and (e) to decrease the vapor-liquid surface tension.

  1. VLS /vapor-liquid-solid/ - Newly discovered growth mechanism on the lunar surface.

    NASA Technical Reports Server (NTRS)

    Carter, J. L.

    1973-01-01

    A probable vapor-liquid-solid (VLS) type of growth has been discovered for the first time in nature on the surface of lunar rock 15015. Scanning electron microprobe and energy dispersive x-ray data indicate that the growth occurs as metallic iron stalks from about 0.015 to 0.15 micrometer in diameter, with bulbous tips consisting of a mixture of iron and sulfur and measuring from about 0.03 to 0.2 micrometer in diameter. The stalk length is two to ten times the bulb diameter.

  2. Isothermal vapor-liquid equilibria for benzene + cyclohexane + 1-propanol and for three constituent binary systems

    SciTech Connect

    Kurihara, Kiyofumi; Uchiyama, Masanori; Kojima, Kazuo

    1997-01-01

    Isothermal vapor-liquid equilibria were measured for the ternary system of benzene + cyclohexane + 1-propanol and its constituent binary systems of benzene + cyclohexane, cyclohexane + 1-propanol, and benzene + 1-propanol at 323.15 and 333.15 K, using the apparatus proposed in a previous study. The experimental binary data were correlated using the NRTL equation. The ternary system was predicted using the binary NRTL parameters. The average absolute percent deviations between the predicted and experimental ternary total pressures are 0.5% at 323.15 K and 0.4% at 333.15 K.

  3. Unseeded growth of germanium nanowires by vapor-liquid-solid mechanism

    NASA Astrophysics Data System (ADS)

    Zaitseva, N.; Harper, J.; Gerion, D.; Saw, C.

    2005-01-01

    Single-crystal germanium nanowires have been synthesized in the temperature range 380-430 C without the use of any metal catalysts. Tetraethylgermane was used as a precursor in combination with different organic solvents to produce nanowires with controlled diameter ranging from 5 nm to 700 nm. The growth direction of nanowires is along <011> direction. The method is based on the vapor-liquid-solid mechanism, with the classical liquid-metal catalyst replaced by droplets of high-boiling-point hydrocarbons.

  4. Low-temperature, vapor-liquid-solid, laterally grown silicon films using alloyed catalysts

    NASA Astrophysics Data System (ADS)

    LeBoeuf, Jerome L.; Brodusch, Nicolas; Gauvin, Raynald; Quitoriano, Nathaniel J.

    2014-12-01

    Using amorphous oxide templates known as micro-crucibles which confine a vapor-liquid-solid catalyst to a specific geometry, two-dimensional silicon thin-films of a single orientation have been grown laterally over an amorphous substrate and defects within crystals have been necked out. The vapor-liquid-solid catalysts consisted nominally of 99% gold with 1% titanium, chromium, or aluminum, and each alloy affected the processing of micro-crucibles and growth within them significantly. It was found that chromium additions inhibited the catalytic effect of the gold catalysts, titanium changed the morphology of the catalyst during processing and aluminum stabilized a potential third phase in the gold-silicon system upon cooling. Two mechanisms for growing undesired nanowires were identified both of which hindered the VLS film growth, fast silane cracking rates and poor gold etching, which left gold nanoparticles near the gold-vapor interface. To reduce the silane cracking rates, growth was done at a lower temperature while an engineered heat and deposition profile helped to reduce NWs caused by the second mechanism. Through experimenting with catalyst compositions, the fundamental mechanisms which produce concentration gradients across the gold-silicon alloy within a given micro-crucible have been proposed. Using the postulated mechanisms, micro-crucibles were designed which promote high-quality, single crystal growth of semiconductors.

  5. Nimbus 7 SMMR derived seasonal variations in the water vapor, liquid water, and surface winds over the global oceans

    NASA Technical Reports Server (NTRS)

    Prabhakara, C.; Short, D. A.

    1984-01-01

    A study based on monthly mean maps of atmospheric water vapor, liquid water, and surface wind derived from Nimbus-7 SMMR over the oceans for 13 months, is examined. A discussion of the retrieval technique used to derive the parameters is presented. The seasonal changes in the strength and position of several of the parameter features are revealed by the December 1978 and June 1979 maps. Zonal averages of the water vapor, liquid water, and surface wind for December and June are compared with information derived from conventional measurements and the results are presented in graphs.

  6. Vapor-Liquid-Solid Etch of Semiconductor Surface Channels by Running Gold Nanodroplets.

    PubMed

    Nikoobakht, Babak; Herzing, Andrew; Muramoto, Shin; Tersoff, Jerry

    2015-12-01

    We show that Au nanoparticles spontaneously move across the (001) surface of InP, InAs, and GaP when heated in the presence of water vapor. As they move, the particles etch crystallographically aligned grooves into the surface. We show that this process is a negative analogue of the vapor-liquid-solid (VLS) growth of semiconductor nanowires: the semiconductor dissolves into the catalyst and reacts with water vapor at the catalyst surface to create volatile oxides, depleting the dissolved cations and anions and thus sustaining the dissolution process. This VLS etching process provides a new tool for directed assembly of structures with sublithographic dimensions, as small as a few nanometers in diameter. Au particles above 100 nm in size do not exhibit this process but remain stationary, with oxide accumulating around the particles. PMID:26599639

  7. Physical model of the vapor-liquid (insulator-metal) transition in an exciton gas

    NASA Astrophysics Data System (ADS)

    Khomkin, A. L.; Shumikhin, A. S.

    2015-04-01

    We propose a simple physical model describing the transition of an exciton gas to a conducting exciton liquid. The transition occurs due to cohesive coupling of excitons in the vicinity of the critical point, which is associated with transformation of the exciton ground state to the conduction band and the emergence of conduction electrons. We calculate the cohesion binding energy for the exciton gas and, using it, derive the equations of state, critical parameters, and binodal. The computational method is analogous to that used by us earlier [5] for predicting the vapor-liquid (insulator-metal) phase transition in atomic (hypothetical, free of molecules) hydrogen and alkali metal vapors. The similarity of the methods used for hydrogen and excitons makes it possible to clarify the physical nature of the transition in the exciton gas and to predict more confidently the existence of a new phase transition in atomic hydrogen.

  8. Vapor-liquid phase equilibria of water modelled by a Kim-Gordon potential

    SciTech Connect

    Maerzke, K A; McGrath, M J; Kuo, I W; Tabacchi, G; Siepmann, J I; Mundy, C J

    2009-03-16

    Gibbs ensemble Monte Carlo simulations were carried out to investigate the properties of a frozen-electron-density (or Kim-Gordon, KG) model of water along the vapor-liquid coexistence curve. Because of its theoretical basis, such a KG model provides for seamless coupling to Kohn-Sham density functional theory for use in mixed quantum mechanics/molecular mechanics (QM/MM) implementations. The Gibbs ensemble simulations indicate rather limited transferability of such a simple KG model to other state points. Specifically, a KG model that was parameterized by Barker and Sprik to the properties of liquid water at 300 K, yields saturated vapor pressures and a critical temperature that are significantly under- and over-estimated, respectively.

  9. Growth mechanisms of vapor-liquid-solid grown nanowires: A detailed analysis of irregular nanowire formation

    NASA Astrophysics Data System (ADS)

    Koto, Makoto

    2014-04-01

    Although vapor-liquid-solid (VLS) growth has become a standard method for producing nanowires, the underlying growth mechanisms have not been fully elucidated because VLS growth is affected by thermodynamic and geometrical factors that, to date, have mainly been considered separately. Based on the assumption that the irregular nanowire growth reflects the conditions of the eutectic droplet during nanowire growth, we aimed to elucidate the thermodynamic and geometrical aspects of the growth mechanisms by the measurement and analysis of irregular kinked and curved Si nanowires grown by Au-catalyzed VLS. The results suggest that kinked nanowires may be caused by higher supersaturation, whereas curved nanowires may be caused by lower supersaturation within the eutectic Au-Si droplet. The results of measuring and analyzing irregular nanowires confirmed that both thermodynamic and geometrical effects complexly influence nanowire growth kinetics, particularly the supersaturation of eutectic droplets, and the effects are more pronounced in larger diameter nanowires.

  10. Glancing angle deposition in a pulsed laser ablation/vapor-liquid-solid grow system

    NASA Astrophysics Data System (ADS)

    Marcu, A.; Stokker, F.; Zamani, R. R.; Lungu, C. P.

    2015-02-01

    A high speed repetition rate laser was used in an 'eclipse' system configuration for growing ZnO nanowires on Au patterned substrates, using vapor-liquid-solid (VLS) technique. Experimental results have shown that the nanowire length increase in the vicinity of catalyst free areas and the grown length distribution over the catalyst covered areas depend on the number of the laser pulses per train. The results suggest that the nanowire over-growth, attributed to the particle surface diffusion, is effective in the ZnO VLS growth within about 100 ?m distances. 'Glancing angle setup' obtained for a submillimeter mask-substrate distance could provide control over VLS growing (or actually over 'non-growing') locations by suppressing the nanowire grow in the center of the catalyst covered areas.

  11. Broad compositional tunability of indium tin oxide nanowires grown by the vapor-liquid-solid mechanism

    SciTech Connect

    Zervos, M. Giapintzakis, J.; Mihailescu, C. N.; Luculescu, C. R.; Florini, N.; Komninou, Ph.; Kioseoglou, J.; Othonos, A.

    2014-05-01

    Indium tin oxide nanowires were grown by the reaction of In and Sn with O{sub 2} at 800 °C via the vapor-liquid-solid mechanism on 1 nm Au/Si(001). We obtain Sn doped In{sub 2}O{sub 3} nanowires having a cubic bixbyite crystal structure by using In:Sn source weight ratios > 1:9 while below this we observe the emergence of tetragonal rutile SnO{sub 2} and suppression of In{sub 2}O{sub 3} permitting compositional and structural tuning from SnO{sub 2} to In{sub 2}O{sub 3} which is accompanied by a blue shift of the photoluminescence spectrum and increase in carrier lifetime attributed to a higher crystal quality and Fermi level position.

  12. Oscillatory Mass Transport in Vapor-Liquid-Solid Growth of Sapphire Nanowires

    SciTech Connect

    Oh, Sang Ho; Chisholm, Matthew F; Kauffmann, Yaron; Kaplan, Prof. Wayne D.; Luo, Weidong; Ruhle, M.; Scheu, Christina

    2010-01-01

    In vapor-liquid-solid (VLS) growth, the liquid phase plays a pivotal role in mediating mass transport from the vapor source to the growth front of a nanowire. Such transport often takes place through the liquid phase. However, we observed by in situ transmission electron microscopy a different behavior for self-catalytic VLS growth of sapphire nanowires. The growth occurs in a layer-by-layer fashion and is accomplished by interfacial diffusion of oxygen through the ordered liquid aluminum atoms. Oscillatory growth and dissolution reactions at the top rim of the nanowires occur and supply the oxygen required to grow a new (0006) sapphire layer. A periodic modulation of the VLS triple-junction configuration accompanies these oscillatory reactions.

  13. On the existence of vapor-liquid phase transition in dusty plasmas

    SciTech Connect

    Kundu, M.; Sen, A.; Ganesh, R.; Avinash, K.

    2014-10-15

    The phenomenon of phase transition in a dusty-plasma system (DPS) has attracted some attention in the past. Earlier Farouki and Hamaguchi [J. Chem. Phys. 101, 9876 (1994)] have demonstrated the existence of a liquid to solid transition in DPS where the dust particles interact through a Yukawa potential. However, the question of the existence of a vapor-liquid (VL) transition in such a system remains unanswered and relatively unexplored so far. We have investigated this problem by performing extensive molecular dynamics simulations which show that the VL transition does not have a critical curve in the pressure versus volume diagram for a large range of the Yukawa screening parameter κ and the Coulomb coupling parameter Γ. Thus, the VL phase transition is found to be super-critical, meaning that this transition is continuous in the dusty plasma model given by Farouki and Hamaguchi. We provide an approximate analytic explanation of this finding by means of a simple model calculation.

  14. Atomic characterization of Au clusters in vapor-liquid-solid grown silicon nanowires

    NASA Astrophysics Data System (ADS)

    Chen, Wanghua; Pareige, Philippe; Castro, Celia; Xu, Tao; Grandidier, Bruno; Stivenard, Didier; Roca i Cabarrocas, Pere

    2015-09-01

    By correlating atom probe tomography with other conventional microscope techniques (scanning electron microscope, scanning transmission electron microscope, and scanning tunneling microscopy), the distribution and composition of Au clusters in individual vapor-liquid-solid grown Si nanowires is investigated. Taking advantage of the characteristics of atom probe tomography, we have developed a sample preparation method by inclining the sample at certain angle to characterize the nanowire sidewall without using focused ion beam. With three-dimensional atomic scale reconstruction, we provide direct evidence of Au clusters tending to remain on the nanowire sidewall rather than being incorporated into the Si nanowires. Based on the composition measurement of Au clusters (28% 1%), we have demonstrated the supersaturation of Si atoms in Au clusters, which supports the hypothesis that Au clusters are formed simultaneously during nanowire growth rather than during the cooling process.

  15. Isothermal and isobaric desorption of carbon dioxide by purge

    SciTech Connect

    Sircar, S.; Golden, T.C.

    1995-08-01

    Adsorption and desorption constitute the two most basic steps in all pressure swing adsorption (PSA) processes for gas separation. The desorption steps are the primary energy-consuming steps in the PSA process. They also dictate the overall separation efficiency. Isothermal and isobaric desorption of carbon dioxide was experimentally evaluated by purging adsorbent columns saturated with pure carbon dioxide with pure hydrogen, nitrogen, and methane. Three different activated carbons and two zeolites were investigated as adsorbents. The effects of purge gas flow rate, system pressure and temperature, strength of carbon dioxide adsorption, and selectivity of adsorption between carbon dioxide and the purge gas on the desorption process were measured. Instantaneous local equilibrium between gas and adsorbed phases was established under the conditions of the experiments. An analytical mathematical model for isothermal and isobaric desorption of binary gas mixtures by purge was developed. It was demonstrated that the efficiency of desorption by purge can be increased by (1) lowering the desorption pressure, (2) increasing the adsorbent temperature, and (3) increasing the selectivity of adsorption of the purge gas over the desorbing component.

  16. Isothermal vapor-liquid equilibrium of 1,2-dibromoethane + tetrachlorolmethane at temperatures between 283. 15 and 323. 15 K

    SciTech Connect

    Perez, P.; Valero, J.; Gracia, M. . Dept. de Quimica Organica-Quimica Fisica)

    1994-10-01

    Vapor pressures of 1, 2-dibromoethane + tetrachlormethane, at 5 K interval between 283.15 and 323.15 K, were measured by a static method. Activity coefficients and excess molar Gibbs free energies G[sup E] were calculated by Barker's method. Reduction of the vapor pressure results is well represented by the Redlich-Kister, Wilson, and NRTL correlations.

  17. Application of artificial intelligence control to the vapor-liquid-solid silicon carbide whisker process

    SciTech Connect

    Shalek, P.D.; Parkinson, W.J.

    1989-01-01

    Silicon carbide whiskers have excellent mechanical and chemical properties, making them very desirable as a reinforcement for structural ceramic and other composite materials. Los Alamos has developed a laboratory-scale batch process for producing very high quality SiC whiskers by the vapor-liquid-solid (VLS) method which is an active candidate for technology transfer involving significant scale-up. The process, however, involves quite complex chemical/physical and parametric relationships and has not as yet lent itself successfully to modeling. An expert computer system was therefore developed to facilitate the transfer of this technology to industry. Optimum conditions were determined by relating the many process parameters to product results to establish a set of rules for running the process. These are incorporated in a two-phase expert system designed to guide inexperienced users. In Phase 1, an expert consultant program provides the user with information that enables him to set up the run. This information is incorporated into the rule base that makes up Phase 2 --- the control system. At present, the operator functions as the controller by responding to the decisions of the expert system; automation can be added later. 13 refs., 16 figs.

  18. 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.

  19. Directed synthesis of germanium oxide nanowires by vapor-liquid-solid oxidation.

    PubMed

    Gunji, M; Thombare, S V; Hu, S; McIntyre, P C

    2012-09-28

    We report on the directed synthesis of germanium oxide (GeO(x)) nanowires (NWs) by locally catalyzed thermal oxidation of aligned arrays of gold catalyst-tipped germanium NWs. During oxygen anneals conducted above the Au-Ge binary eutectic temperature (T > 361 C), one-dimensional oxidation of as-grown Ge NWs occurs by diffusion of Ge through the Au-Ge catalyst droplet, in the presence of an oxygen containing ambient. Elongated GeO(x) wires grow from the liquid catalyst tip, consuming the adjoining Ge NWs as they grow. The oxide NWs' diameter is dictated by the catalyst diameter and their alignment generally parallels that of the growth direction of the initial Ge NWs. Growth rate comparisons reveal a substantial oxidation rate enhancement in the presence of the Au catalyst. Statistical analysis of GeO(x) nanowire growth by ex situ transmission electron microscopy and scanning electron microscopy suggests a transition from an initial, diameter-dependent kinetic regime, to diameter-independent wire growth. This behavior suggests the existence of an incubation time for GeO(x) NW nucleation at the start of vapor-liquid-solid oxidation. PMID:22947505

  20. Identification of an Intrinsic Source of Doping Inhomogeneity in VaporLiquidSolid-Grown Nanowires

    SciTech Connect

    Connell, Justin G.; Yoon, KunHo; Perea, Daniel E.; Schwalbach, Edwin J.; Voorhees, Peter W.; Lauhon, Lincoln

    2013-01-09

    The vapor-liquid-solid (VLS) process of semiconductor nanowire growth is an attractive approach to low-dimensional materials and heterostructures because it provides a mechanism to modulate, in situ, nanowire composition and doping, but the ultimate limits on doping control are ultimately dictated by the growth process itself. Under widely used conditions for the chemical vapor deposition growth of Si and Ge nanowires from a Au catalyst droplet, we find that dopants incorporated from the liquid are not uniformly distributed. Specifically, atom probe tomographic analysis revealed up to 100-fold enhancements in dopant concentration near the VLS tri-junction in both B-doped Si and P-doped Ge nanowires. We hypothesize that radial and azimuthal inhomogeneities arise from a faceted liquid-solid interface present during nanowire growth, and we present a simple model to account for the distribution. As the same segregation behavior was observed in two distinct semiconductors with different dopants, the observed inhomogeneity is likely to be present in other VLS grown nanowires.

  1. Fabrication and performance evaluation of a high temperature co-fired ceramic vaporizing liquid microthruster

    NASA Astrophysics Data System (ADS)

    How Cheah, Kean; Low, Kay-Soon

    2015-01-01

    This paper presents the study of a microelectromechanical system (MEMS)-scaled microthruster using ceramic as the structural material. A vaporizing liquid microthruster (VLM) has been fabricated using the high temperature co-fired ceramic (HTCC) technology. The developed microthruster consists of five components, i.e. inlet, injector, vaporizing chamber, micronozzle and microheater, all integrated in a chip with a dimension of 30?mm 26?mm 8?mm. In the dry test, the newly developed microheater which is deposited on zirconia substrate consumes 21% less electrical power than those deposited on silicon substrate to achieve a temperature of 100?C. Heating temperature as high as 409.1?C can be achieved using just 5?W of electrical power. For simplicity and safety, a functional test of the VLM with water as propellant has been conducted in the laboratory. Full vaporization of water propellant feeding at different flow rates has been successfully demonstrated. A maximum thrust of 633.5?N at 1?l?s-1 propellant consumption rate was measured using a torsional thrust stand.

  2. Vapor-liquid phase equilibria of water modelled by a Kim-Gordon potential

    SciTech Connect

    Maerzke, Katie A.; McGrath, M. J.; Kuo, I-F W.; Tabacchi, Gloria; Siepmann, Joern I.; Mundy, Christopher J.

    2009-09-07

    Gibbs ensemble Monte Carlo simulations were carried out to investigate the properties of a frozen-electron-density (or Kim-Gordon, KG) model of water along the vapor-liquid coexistence curve. Because of its theoretical basis, such a KG model provides for seamless coupling to Kohn-Sham density functional theory for use in mixed quantum mechanics/molecular mechanics (QM/MM) implementations. The Gibbs ensemble simulations indicate rather limited transferability of such a simple KG model to other state points. Specifically, a KG model that was parameterized by Barker and Sprik to the properties of liquid water at 300 K, yields saturated vapor pressures and a critical temperature that are significantly under- and overestimated, respectively. We present a comprehensive density functional theory study to asses the accuracy of two popular exchange correlation functionals on the structure and density of liquid water at ambient conditions This work was supported by the US Department of Energy Office of Basic Energy Science Chemical Sciences Program. Battelle operates Pacific Northwest National Laboratory for the US Department of Energy.

  3. Spontaneous, Defect-Free Kinking via Capillary Instability during Vapor-Liquid-Solid Nanowire Growth.

    PubMed

    Li, Yanying; Wang, Yanming; Ryu, Seunghwa; Marshall, Ann F; Cai, Wei; McIntyre, Paul C

    2016-03-01

    Kinking, a common anomaly in nanowire (NW) vapor-liquid-solid (VLS) growth, represents a sudden change of the wire's axial growth orientation. This study focuses on defect-free kinking during germanium NW VLS growth, after nucleation on a Ge (111) single crystal substrate, using Au-Ge catalyst liquid droplets of defined size. Statistical analysis of the fraction of kinked NWs reveals the dependence of kinking probability on the wire diameter and the growth temperature. The morphologies of kinked Ge NWs studied by electron microscopy show two distinct, defect-free, kinking modes, whose underlying mechanisms are explained with the help of 3D multiphase field simulations. Type I kinking, in which the growth axis changes from vertical [111] to ⟨110⟩, was observed in Ge NWs with a nominal diameter of ∼20 nm. This size coincides with a critical diameter at which a spontaneous transition from ⟨111⟩ to ⟨110⟩ growth occurs in the phase field simulations. Larger diameter NWs only exhibit Type II kinking, in which the growth axis changes from vertical [111] directly to an inclined ⟨111⟩ axis during the initial stages of wire growth. This is caused by an error in sidewall facet development, which produces a shrinkage in the area of the (111) growth facet with increasing NW length, causing an instability of the Au-Ge liquid droplet at the tip of the NW. PMID:26837774

  4. Catalyst-assisted vapor-liquid-solid growth of single-crystal Ga2O3 nanobelts.

    PubMed

    Zhang, Jun; Jiang, Feihong; Yang, Yongdong; Li, Jianping

    2005-07-14

    Mass production of quasi-one-dimensional gallium oxide nanobelts is accomplished through graphite-thermal reduction of a mixture of gallium oxide powders and SnO2 nanopowders under controlled experimental conditions. Sn nanoparticles are located at or close to the tips of the nanobelts and served as the catalyst for the nanobelt growth by a vapor-liquid-solid mechanism. The morphology and microstructure of the nanobelts were characterized by scanning electron microscopy and high-resolution transmission electron microscopy. The Ga2O3 nanobelts grow along the [104] direction, the widths ranged from several tens to several hundreds of nanometers, and the lengths ranged from several tens to several hundreds of micrometers. The growth of Ga2O3 nanobelts is initiated by Sn nanoparticles via a catalyst-assisted vapor-liquid-solid process, which makes it possible to control the sizes of Ga2O3 nanobelts. PMID:16852636

  5. Effect of three-body interactions on the vapor-liquid phase equilibria of binary fluid mixtures.

    PubMed

    Wang, Liping; Sadus, Richard J

    2006-08-21

    Gibbs-Duhem Monte Carlo simulations are reported for the vapor-liquid phase coexistence of binary argon+krypton mixtures at different temperatures. The calculations employ accurate two-body potentials in addition to contributions from three-body dispersion interactions resulting from third-order triple-dipole interactions. A comparison is made with experiment that illustrates the role of three-body interactions on the phase envelope. In all cases the simulations represent genuine predictions with input parameters obtained independently from sources other than phase equilibria data. Two-body interactions alone are insufficient to adequately describe vapor-liquid coexistence. In contrast, the addition of three-body interactions results in very good agreement with experiment. In addition to the exact calculation of three-body interactions, calculations are reported with an approximate formula for three-body interactions, which also yields good results. PMID:16942347

  6. Vapor-liquid equilibria for the systems difluoromethane + hydrogen fluoride, dichlorodifluoromethane + hydrogen fluoride, and chlorine + hydrogen fluoride

    SciTech Connect

    Kang, Y.W.

    1998-01-01

    Isothermal vapor-liquid equilibria for difluoromethane + hydrogen fluoride, dichlorodifluoromethane + hydrogen fluoride, and chlorine + hydrogen fluoride have been measured. The experimental data for the binary systems are correlated with the NRTL equation with the vapor-phase association model for the mixtures containing hydrogen fluoride, and the relevant parameters are presented. The binary system difluoromethane + hydrogen fluoride forms a homogeneous liquid phase, and the others form minimum boiling heterogeneous azeotropes at the experimental conditions.

  7. Molecular dynamics study on evaporation and reflection of monatomic molecules to construct kinetic boundary condition in vapor-liquid equilibria

    NASA Astrophysics Data System (ADS)

    Kobayashi, Kazumichi; Hori, Kazumasa; Kon, Misaki; Sasaki, Kiyofumi; Watanabe, Masao

    2015-10-01

    Using molecular dynamics simulations, the present study investigates the precise characteristics of evaporating and reflecting monatomic molecules (argon) composing a kinetic boundary condition (KBC) in a vapor-liquid equilibria. We counted the evaporating and reflecting molecules utilizing two boundaries (vapor and liquid boundaries) proposed by the previous studies (Meland et al. in Phys Fluids 16:223-243, 2004; Gu et al. in Fluid Phase Equilib 297:77-89, 2010). In the present study, we improved the method using the two boundaries incorporating the concept of the spontaneously evaporating molecular mass flux. The present method allows us to count the evaporating and reflecting molecules easily, to investigate the detail motion of the evaporating and reflecting molecules, and also to evaluate the velocity distribution function of the KBC at the vapor-liquid interface, appropriately. From the results, we confirm that the evaporating and reflecting molecules in the normal direction to the interface have slightly faster and significantly slower average velocities than that of the Maxwell distribution at the liquid temperature, respectively. Also, the stall time of the reflecting molecules at the interphase that is the region in the vicinity of the vapor-liquid interface is much shorter than those of the evaporating molecules. Furthermore, we discuss our method for constructing the KBC that incorporates condensation and evaporation coefficients. Based on these results, we suggest that the proposed method is appropriate for investigating KBC in various nonequilibrium states or multi-component systems.

  8. Isobar Separator for Anions: Current status

    NASA Astrophysics Data System (ADS)

    Alary, Jean-François; Javahery, Gholamreza; Kieser, William; Zhao, Xiao-Lei; Litherland, Albert; Cousins, Lisa; Charles, Christopher

    2015-10-01

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of 36S from 36Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion-molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  9. Correlation of Zeno (Z = 1) line for supercritical fluids with vapor-liquid rectilinear diameters

    SciTech Connect

    Ben-Amotz, D.; Herschbach, D.R.

    1996-08-01

    For a wide range of substances, extending well beyond the regime of corresponding states behavior, the contour in the temperature-density plane along which the compressibility factor Z = P/{rho}kT is the same as for an ideal gas is nearly linear. This Z = 1 contour, termed the Zeno line, begins deep in the liquid region and ascends as the density decreases to the Boyle point of the supercritical fluid, specified by the temperature T{sub B} for which (dZ/d{rho}){sub T} = 0 as {rho} {r_arrow} 0; equivalent, at T{sub B} the second virial coefficient vanishes. The slope of the Z = 1 line is {minus}B{sub 3}/(dB{sub 2}/dT), in terms of the third virial coefficient and the derivative of the second, evaluated at T{sub B}. Previous work has examined the Zeno line as a means to extend corresponding states and to enhance other practical approximations. Here the authors call attention to another striking aspect, a strong correlation with the line of rectilinear diameters defined by the average of the subcritical vapor and liquid densities. This correlation is obeyed well by empirical data for many substances and computer simulations for a Lennard-jones potential; the ratios of the intercepts and slopes for the Zeno and rectilinear diameter liens are remarkably close to those predicted by the van der Waals equation, 8/9 and 16/9, respectively. Properties of the slightly imperfect fluid far above the critical point thus implicitly determine the diameter of the vapor-liquid coexistence curve below the critical point.

  10. Rational Concept for Designing Vapor-Liquid-Solid Growth of Single Crystalline Metal Oxide Nanowires.

    PubMed

    Klamchuen, Annop; Suzuki, Masaru; Nagashima, Kazuki; Yoshida, Hideto; Kanai, Masaki; Zhuge, Fuwei; He, Yong; Meng, Gang; Kai, Shoichi; Takeda, Seiji; Kawai, Tomoji; Yanagida, Takeshi

    2015-10-14

    Metal oxide nanowires hold great promise for various device applications due to their unique and robust physical properties in air and/or water and also due to their abundance on Earth. Vapor-liquid-solid (VLS) growth of metal oxide nanowires offers the high controllability of their diameters and spatial positions. In addition, VLS growth has applicability to axial and/or radial heterostructures, which are not attainable by other nanowire growth methods. However, material species available for the VLS growth of metal oxide nanowires are substantially limited even though the variety of material species, which has fascinating physical properties, is the most interesting feature of metal oxides. Here we demonstrate a rational design for the VLS growth of various metal oxide nanowires, based on the "material flux window". This material flux window describes the concept of VLS nanowire growth within a limited material flux range, where nucleation preferentially occurs only at a liquid-solid interface. Although the material flux was previously thought to affect primarily the growth rate, we experimentally and theoretically demonstrate that the material flux is the important experimental variable for the VLS growth of metal oxide nanowires. On the basis of the material flux window concept, we discover novel metal oxide nanowires, composed of MnO, CaO, Sm2O3, NiO, and Eu2O3, which were previously impossible to form via the VLS route. The newly grown NiO nanowires exhibited stable memristive properties superior to conventional polycrystalline devices due to the single crystallinity. Thus, this VLS design route offers a useful guideline for the discovery of single crystalline nanowires that are composed of functional metal oxide materials. PMID:26372675

  11. Vapor-liquid equilibria for copolymer+solvent systems: Effect of intramolecular repulsion

    SciTech Connect

    Gupta, R.B.; Prausnitz, J.M.

    1995-03-01

    Role of intramolecular interactions in blend miscibility is well documented for polymer+copolymer mixtures. Some copolymer+polymer mixtures are miscible although their corresponding homopolymers are not miscible; for example, over a range of acrylonitrile content, styrene/acrylonitrile copolymers are miscible with poly(methyl methacrylate) but neither polystyrene nor polyacrylonitrile is miscible with poly(methyl methacrylate). Similarly, over a composition range, butadiene/acrylonitrile copolymers are miscible with poly(vinyl chloride) while none of the binary combinations of the homopolymers [polybutadiene, polyacrylonitrile, and poly(vinyl chloride)] are miscible. This behavior has been attributed to ``intramolecular repulsion`` between unlike copolymer segments. We have observed similar behavior in vapor-liquid equilibria (VLE) of copolymer+solvent systems. We find that acrylonitrile/butadiene copolymers have higher affinity for acetonitrile solvent than do polyacrylonitrile or polybutadiene. We attribute this non-intuitive behavior to ``intramolecular repulsion`` between unlike segments of the copolymer. This repulsive interaction is weakened when acetonitrile molecules are in the vicinity of unlike copolymer segments, favoring copolymer+solvent miscibility. We find similar behavior when acetonitrile is replaced by methyl ethyl ketone. To best knowledge, this effect has not been reported previously for VLE. We have obtained VLE data for mixtures containing a solvent and a copolymer as a function of copolymer composition. It appears that, at a given solvent partial pressure, there may be copolymer composition that yields maximum absorption of the solvent. This highly non-ideal VLE phase behavior may be useful for optimum design of a membrane for a separation process.

  12. System NaCl-H/sub 2/O: relations of vapor-liquid near the critical temperature of water and of vapor-liquid-halite from 300/sup 0/ to 500/sup 0/C

    SciTech Connect

    Bischoff, J.L.; Rosenbauer, R.J.

    1986-07-01

    Vapor-liquid relations (P-T-x) for the system NaCl-H/sub 2/O were determined experimentally at temperatures spanning the critical temperature of water (T/sub c/), the lowest temperature in the system at which critical behavior occurs. In addition, vapor-liquid-halite P-T-x (vapor) relations were determined from 300/sup 0/ to 500/sup 0/C. Results show that at 373.0/sup 0/C, immediately below T/sub c/, the vapor side of the isothermal vapor-liquid P-x boundary has a shape quite different from that previously conceived. The NaCl content of the vapor increases with pressure in a smooth manner from the pressure of the three-phase assemblage (135 bars, 0.0029% NaCl), to a pressure just below that of the vapor pressure of pure water (0.012% NaCl at 184 bars). Above this pressure the boundary abruptly reverses and projects asymptotically to 0% NaCl in a beak-like shape at 218 bars, the vapor pressure of pure water. At 375.5/sup 0/, slightly above T/sub c/, the asymptote disappears, and is replaced by a rounded nose. At progressively higher temperatures, the nose disappears and by 380/sup 0/C the familiar symmetrical bell-shaped curve predominates with the critical point defined by the top of the bell. The P-T curve of the three-phase assemblage determined in the present study is in agreement with previous workers. The NaCl content of the three-phase vapor, however, is much higher than some literature values at temperatures above 410/sup 0/C.

  13. High-pressure vapor-liquid equilibria for propane + 2-butanol, propylene + 2-butanol, and propane + 2-butanol + 2-propanol

    SciTech Connect

    Gros, H.P.; Zabaloy, M.S.; Brignole, E.A.

    1996-03-01

    The use of dual effect solvents (near critical extractant and high-pressure water entrainer), for the recovery and dehydration of alcohols from dilute aqueous solutions, has been proposed by Brignole et al. (1987). The present work is part of an experimental program undertaken to confirm the applicability of light hydrocarbons for this separation problem. Vapor-liquid equilibria have been measured for propane + 2-butanol, propylene + 2-butanol, and propane + 2-butanol + 2-propanol in the temperature range of (328.1 to 368.1) K and at pressures up to 44.45 bar. The data were correlated using a group contribution equation of state for associating mixtures.

  14. Engineering scale development of the Vapor-Liquid-Solid (VLS) process for the production of silicon carbide fibrils

    SciTech Connect

    Hollar, W.E. Jr.; Mills, W.H.

    1993-09-01

    Vapor-liquid-solid (VLS)SiC fibrils are used as reinforcement in ceramic matrix composites (CMC). A program has been completed for determining process scaleup parameters and to produce material for evaluation in a CMC. The scaleup is necessary to lower production cost and increase material availability. Scaleup parameters were evaluated in a reactor with a vertical dimension twice that of the LANL reactor. Results indicate that the scaleup will be possible. Feasibility of recycling process gas was demonstrated and the impact of postprocessing on yields determined.

  15. 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.

  16. First principles Monte Carlo simulations of vapor--liquid equilibria: Density functionals, basis sets, and dispersion corrections

    NASA Astrophysics Data System (ADS)

    Siepmann, J. Ilja; McGrath, Matthew J.; Kuo, I.-F. William; Mundy, Christopher J.

    2012-02-01

    Gibbs ensemble Monte Carlo simulations are used to compute the vapor--liquid equilibria for water, methanol, and methane using Kohn-Sham density functional theory. Results for BLYP and PBE functionals, BLYP with Grimme D2 and D3 dispersion corrections, and various basis sets are compared. Although none of the combinations of functional, dispersive correction, and basis set is found to yield highly accurate predictions for liquid densities, vapor pressures, and heats of vaporization for all three compounds, the results for dispersion corrected BLYP with large basis set are promising.

  17. Middle ear gas exchange in isobaric counterdiffusion.

    PubMed

    Dueker, C W; Lambertsen, C J; Rosowski, J J; Saunders, J C

    1979-12-01

    Nitrous oxide entry into the middle ear gas space was studied in cats in relation to anesthesia and the vestibular dysfunction caused by isobaric inert gas counter-diffusion in diving. A catheter implanted in the auditory bulla was used for direct gas sampling and pressure measurements. Experiments were designed to evaluate the participation of the eustachian tube, mucosal blood vessels, and tympanic membrane in middle ear gas exchange. The eustachian tube did not contribute to N2O entry and the mucosal blood supply only contributed about one-third of the total N2O accumulation. Diffusion across the tympanic membrane accounted for most of the N2O entering the middle ear from ambient and respiratory environments containing N2O. PMID:536296

  18. QUANTITY: An Isobaric Tag for Quantitative Glycomics

    PubMed Central

    Yang, Shuang; Wang, Meiyao; Chen, Lijun; Yin, Bojiao; Song, Guoqiang; Turko, Illarion V.; Phinney, Karen W.; Betenbaugh, Michael J.; Zhang, Hui; Li, Shuwei

    2015-01-01

    Glycan is an important class of macromolecules that play numerous biological functions. Quantitative glycomics - analysis of glycans at global level - however, is far behind genomics and proteomics owing to technical challenges associated with their chemical properties and structural complexity. As a result, technologies that can facilitate global glycan analysis are highly sought after. Here, we present QUANTITY (Quaternary Amine Containing Isobaric Tag for Glycan), a quantitative approach that can not only enhance detection of glycans by mass spectrometry, but also allow high-throughput glycomic analysis from multiple biological samples. This robust tool enabled us to accomplish glycomic survey of bioengineered Chinese Hamster Ovary (CHO) cells with knock-in/out enzymes involved in protein glycosylation. Our results demonstrated QUANTITY is an invaluable technique for glycan analysis and bioengineering. PMID:26616285

  19. Liquid-vapor equilibrium under elevated pressures in the systems formed by pentanes with sulfur compounds

    SciTech Connect

    Shakirzyanov, R.G.; Telyakov, E.S.; Serafimov, L.A.

    1982-10-20

    The possibility of removing sulfur compounds from the pentane fraction was studied. Experimental data obtained on liquid-vapor equilibrium in the system formed by pentanes with sulfur compounds under elevated pressures is presented. Vapor-liquid equilibrium was studied with the aid of a modified Swietoslawski apparatus made of stainless steel. Experimental data on phase equilibria of binary mixtures in the system studied are presented. The compositions and boiling points of binary azeotropes at the pressures studied are also presented.

  20. About the equilibrium speed of sound in a liquid with gas-vapor bubbles

    NASA Astrophysics Data System (ADS)

    Gubaidullin, D. A.; Gubaidullina, D. D.; Fedorov, Yu V.

    2016-01-01

    The general expression of an equilibrium velocity of a sound in vapor-gas-liquid mixtures is presented and influence of concentration of vapor and a volume content of bubbles on the received expression is analyzed. In special cases, for gas-liquid and vapor-liquid mixtures expressions of an equilibrium velocity are presented and the satisfactory consent of the received expressions with known experimental data is discovered.

  1. VAPOR/LIQUID EQUILIBRIA OF CONSTITUENTS FROM COAL GASIFICATION IN REFRIGERATED METHANOL

    EPA Science Inventory

    The report describes a thermodynamic framework, established for the development of a model of the phase equilibria of mixtures of methanol and the major constituents found in gases produced from coal. Two approaches were used to model the equilibrium behavior: (1) an equation of ...

  2. Isothermal vapor-liquid equilibria of 1-pentanol with 2-methyl-1-butanol, 2-methyl-2-butanol, and 3-methyl-2-butanol

    SciTech Connect

    Aucejo, A.; Burguet, M.C.; Monton, J.B.; Munoz, R.; Sanchotello, M.; Vazquez, M.I. . Dept. de Ingenieria Quimica)

    1994-07-01

    The separation of liquid mixtures through distillation is one of the most common operations in chemical industry, and the efficient design of distillation equipment requires a quantitative knowledge of vapor-liquid equilibria (VLE). Vapor-liquid equilibria were measured for binary systems of 1-pentanol + 2-methyl-1-butanol, + 2-methyl-2-butanol, and + 3-methyl-2-butanol at 373.15 K. The results are thermodynamically consistent according to the point-to-point consistency test, and deviation from ideal behavior is small in all cases.

  3. The system NaCl-H2O: relations of vapor-liquid near the critical temperature of water and of vapor-liquid-halite from 300 to 500C

    USGS Publications Warehouse

    Bischoff, James L.; Rosenbauer, Robert J.; Pitzer, Kenneth S.

    1986-01-01

    Vapor-liquid relations (P-T-x) for the system NaCl-H2O were determined experimentally at temperatures spanning the critical temperature of water (Tc), the lowest temperature in the system at which critical behavior occurs. In addition, vapor-liquid-haliteP-T-x(vapor) relations were determined from 300 to 500C. Results show that at 373.0C, immediately belowTc, the vapor side of the isothermal vaporliquid P-x boundary has a shape quite different from that previously conceived. The NaCl content of the vapor increases with pressure in a smooth manner from the pressure of the three-phase assemblage (135 bars, 0.0029% NaCl), to a pressure just below that of the vapor pressure of pure water (0.012% NaCl at 184 bars). Above this pressure the boundary abruptly reverses and projects asymptotically to 0% NaCl in a beak-like shape at 218 bars, the vapor pressure of pure water. At 375.5, slightly aboveTc, the asymptote disappears, and is replaced by a rounded nose. At progressively higher temperatures, the nose disappears and by 380C the familiar symmetrical bell-shaped curve predominates with the critical point defined by the top of the bell. TheP-Tcurve of the three-phase assemblage determined in the present study is in agreement with previous workers. The NaCl content of the three-phase vapor, however, is much higher than some literature values at temperatures above 410C.

  4. Role of local environment relaxation in calculating the rates of elementary processes in vapor-liquid systems

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.; Titov, S. V.

    2013-02-01

    The role of local environment relaxation is studied in calculating the rates of elementary processes in vapor-liquid systems consisting of dipole molecules. It is accepted that the intermolecular interaction potential of reaction system components includes dipole-dipole and Lennard-Jones terms. Two limiting cases of short and long characteristic times of an elementary reaction are considered relative to the thermal progressive and rotational motions of neighboring dipole molecules. It is shown that the condition of long characteristic times for elementary reactions that correspond to the concept of activated complex activity distorts the properties of a system. Good correspondence is obtained for the temperature dependence of the water self-diffusion coefficient.

  5. Vertically Aligned Ge Nanowires on Flexible Plastic Films Synthesized by (111)-Oriented Ge Seeded Vapor-Liquid-Solid Growth.

    PubMed

    Toko, Kaoru; Nakata, Mitsuki; Jevasuwan, Wipakorn; Fukata, Naoki; Suemasu, Takashi

    2015-08-19

    Transfer-free fabrication of vertical Ge nanowires (NWs) on a plastic substrate is demonstrated using a vapor-liquid-solid (VLS) method. The crystal quality of Ge seed layers (50 nm thickness) prepared on plastic substrates strongly influenced the VLS growth morphology, i.e., the density, uniformity, and crystal quality of Ge NWs. The metal-induced layer exchange yielded a (111)-oriented Ge seed layer at 325 C, which allowed for the VLS growth of vertically aligned Ge NWs. The Ge NW array had almost the same quality as that formed on a bulk Ge(111) substrate. Transmission electron microscopy demonstrated that the Ge NWs were defect-free single crystals. The present investigation paves the way for advanced electronic optical devices integrated on a low-cost flexible substrate. PMID:26230716

  6. Structural and electronic properties of InN nanowire network grown by vapor-liquid-solid method

    NASA Astrophysics Data System (ADS)

    Barick, B. K.; Rodrguez-Fernndez, Carlos; Cantarero, Andres; Dhar, S.

    2015-05-01

    Growth of InN nanowires have been carried out on quartz substrates at different temperatures by vapor-liquid-solid (VLS) technique using different thicknesses of Au catalyst layer. It has been found that a narrow window of Au layer thickness and growth temperature leads to multi-nucleation, in which each site acts as the origin of several nanowires. In this multi-nucleation regime, several tens of micrometer long wires with diameter as small as 20 nm are found to grow along [ 11 2 0 ] direction (a-plane) to form a dense network. Structural and electronic properties of these wires are studied. As grown nanowires show degenerate n-type behavior. Furthermore, x-ray photoemission study reveals an accumulation of electrons on the surface of these nanowires. Interestingly, the wire network shows persistence of photoconductivity for several hours after switching off the photoexcitation.

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

    PubMed

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

    2005-01-01

    A new approach to locating the critical point of fluid mixtures is reported, utilizing a shear mode piezoelectric sensor. This technique employs a single piece of quartz crystal that is installed at the bottom of a strongly stirred high-pressure vessel. The sensor response indicates whether liquid or gas is in contact with its surfaces. Thus, the sensor is able to identify vapor-liquid phase separation by registering a discontinuity in the impedance minimum of the sensor as a function of pressure. Two systems (methanol + CO2 and H2 + CO2) have been investigated using this method. The critical point data of the methanol + CO2 system were chosen to validate the approach against a wealth of literature data, and good agreement was obtained. The sensor behavior in the two-phase region, as well as the effect of stirring, is discussed. The method is general and can be used with other sensors. PMID:15623282

  8. Isobaric Labeling-Based Relative Quantification in Shotgun Proteomics

    PubMed Central

    2015-01-01

    Mass spectrometry plays a key role in relative quantitative comparisons of proteins in order to understand their functional role in biological systems upon perturbation. In this review, we review studies that examine different aspects of isobaric labeling-based relative quantification for shotgun proteomic analysis. In particular, we focus on different types of isobaric reagents and their reaction chemistry (e.g., amine-, carbonyl-, and sulfhydryl-reactive). Various factors, such as ratio compression, reporter ion dynamic range, and others, cause an underestimation of changes in relative abundance of proteins across samples, undermining the ability of the isobaric labeling approach to be truly quantitative. These factors that affect quantification and the suggested combinations of experimental design and optimal data acquisition methods to increase the precision and accuracy of the measurements will be discussed. Finally, the extended application of isobaric labeling-based approach in hyperplexing strategy, targeted quantification, and phosphopeptide analysis are also examined. PMID:25337643

  9. Isobar excitation in parity-nonconserving proton-proton scattering

    SciTech Connect

    Iqbal, M.J. ); Niskanen, J.A. )

    1994-01-01

    A parity violating (PV) meson exchange model is applied in the coupled channels formalism to study the effect of isobar excitation on PV [ital pp] scattering. The meson-mixing model used to calculate PV forbids the mixing of [ital S]=0 mesons in particular pions, as well as isospin symmetry violation, so only the [ital pa][sub 1] contribution is considered in isobar excitation. We find a significant contribution to [ital [bar A

  10. The ILIAS project for selective isobar suppression by laser photodetachment

    NASA Astrophysics Data System (ADS)

    Forstner, Oliver; Andersson, Pontus; Hanstorp, Dag; Lahner, Johannes; Martschini, Martin; Pitters, Johanna; Priller, Alfred; Steier, Peter; Golser, Robin

    2015-10-01

    Laser photodetachment is the process when the extra electron of a negative ion is removed by means of laser radiation. This can happen only if the photon energy is larger than the electron affinity of the ion. The process can be used in mass spectrometry to selectively suppress unwanted isobars, provided that the electron affinity of the unwanted isobar is lower than that of the isobar under investigation. At the Ion Laser InterAction Setup (ILIAS) at the University of Vienna laser photodetachment of negative atomic and molecular ions is studied and its applicability for selective isobar suppression in accelerator mass spectrometry (AMS) is evaluated. The setup provides mass separated beams of negative ions with energies up to 30 keV. Negative ions are produced in a Middleton type cesium sputter ion source, mass selected and overlapped with a strong continuous wave laser beam. In order to extend the interaction time of ions and laser, the ion beam is decelerated to thermal energies in a gas-filled radio frequency quadrupole cooler. For an appropriate choice of the photon energy, unwanted isobars are neutralized while the isobar of interest is unaffected and remains negatively charged. A description of the ILIAS setup and results from the commissioning phase of the RFQ cooler are presented. Up to 8% ion beam transmission could be achieved after a recent redesign of the extraction system. Furthermore first results of photodetachment experiments of 63Cu- within the RFQ cooler are presented.

  11. Theoretical study of vapor-liquid homogeneous nucleation using stability analysis of a macroscopic phase.

    PubMed

    Carren-Caldern, Bernardo

    2012-10-14

    Stability analysis is generally used to verify that the solution to phase equilibrium calculations corresponds to a stable state (minimum of the free energy). In this work, tangent plane distance analysis for stability of macroscopic mixtures is also used for analyzing the nucleation process, reconciling thus this analysis with classical nucleation theories. In the context of the revised nucleation theory, the driving force and the nucleation work are expressed as a function of the Lagrange multiplier corresponding to the mole fraction constraint from the minimization problem of stability analysis. Using a van der Waals fluid applied to a ternary mixture, Lagrange multiplier properties are illustrated. In particular, it is shown how the Lagrange multiplier value is equal to one on the binodal and spinodal curves at the same time as the driving force of nucleation vanishes on these curves. Finally, it is shown that, on the spinodal curve, the nucleation work from the revised and generalized nucleation theories are characterized by two different local minima from stability analysis, irrespective of any interfacial tension models. PMID:23061836

  12. Epitaxy-enabled vapor-liquid-solid growth of tin-doped indium oxide nanowires with controlled orientations.

    PubMed

    Shen, Youde; Turner, Stuart; Yang, Ping; Van Tendeloo, Gustaaf; Lebedev, Oleg I; Wu, Tom

    2014-08-13

    Controlling the morphology of nanowires in bottom-up synthesis and assembling them on planar substrates is of tremendous importance for device applications in electronics, photonics, sensing and energy conversion. To date, however, there remain challenges in reliably achieving these goals of orientation-controlled nanowire synthesis and assembly. Here we report that growth of planar, vertical and randomly oriented tin-doped indium oxide (ITO) nanowires can be realized on yttria-stabilized zirconia (YSZ) substrates via the epitaxy-assisted vapor-liquid-solid (VLS) mechanism, by simply regulating the growth conditions, in particular the growth temperature. This robust control on nanowire orientation is facilitated by the small lattice mismatch of 1.6% between ITO and YSZ. Further control of the orientation, symmetry and shape of the nanowires can be achieved by using YSZ substrates with (110) and (111), in addition to (100) surfaces. Based on these insights, we succeed in growing regular arrays of planar ITO nanowires from patterned catalyst nanoparticles. Overall, our discovery of unprecedented orientation control in ITO nanowires advances the general VLS synthesis, providing a robust epitaxy-based approach toward rational synthesis of nanowires. PMID:24971997

  13. Diffusion suppression in vapor-liquid-solid Si nanowire growth by a barrier layer between the Au catalyst and substrate

    NASA Astrophysics Data System (ADS)

    Koto, Makoto; Watanabe, Masatoshi; Sugawa, Etsuko; Shimizu, Tomohiro; Shingubara, Shoso

    2014-10-01

    Nanowires have attracted significant interest because of their unique characteristics. Vapor-liquid-solid (VLS) growth is the standard method for fabricating nanowires and Au is the most commonly used catalyst. However, Au catalyst droplets diffuse over the Si substrate surface with a high migration velocity and agglomerate at relatively low temperatures. In our previous work, we reported a significant improvement in the positioning and diameter distribution of VLS-grown Si nanowires by inserting a diffusion barrier layer and concluded that the barrier layer suppressed the formation of AuSi eutectic droplets and prevented the droplets diffusing on the substrate surface during nucleation. In the present study, we analyzed the nucleation of the Au catalyst and examined its behavior during nucleation. Detailed multidirectional analysis and in situ observations confirmed that the formation and agglomeration of AuSi eutectic droplets was suppressed by the formation of a silicide layer. This because of the higher reaction temperatures between the diffusion barrier and the substrate silicon, and between the catalyst and the diffusion barrier, compared with the reaction between the Au catalyst and substrate silicon.

  14. Effects of nitrogen precursor on the Au-assisted vapor-liquid-solid growth of GaAs(N) nanostructures

    NASA Astrophysics Data System (ADS)

    Suzuki, Hidetoshi; Sakai, Kentaro; Haraguchi, Tomohiro; Yamauchi, Toshihiro; Hijii, Masanobu; Maeda, Kouji; Ikari, Tetsuo

    2014-01-01

    We investigated the effects of the use of a N precursor on the morphology of GaAs(N) nanostructures grown on GaAs (0 0 1) substrates via the vapor-liquid-solid (VLS) method while using Au particles as the catalyst. The synthesized nanostructures were characterized using scanning electron microscopy and X-ray diffraction analyses. When the N precursor was not used, GaAs nanowires grew, mainly along the <1 1 1>A directions, on the surface of the substrate. These nanowires consisted of zincblende (ZB) and wurtzite (WZ) structures, with a number of boundaries being formed at the {1 1 1} planes. When the N precursor was used, isotropic GaAsN nanodots in which 1 2% of the As atoms had been substituted by N atoms were formed. These nanodots consisted of ZB structures having twin boundaries; no WZ structures were formed in this case. Finally, although they remained isotropic in shape, the nanodots grew in a direction along which the substrate was oriented.

  15. Toluene Diisocyanate Reactivity with Glutathione Across a Vapor/Liquid Interface and Subsequent Transcarbamoylation of Human Albumin

    PubMed Central

    Wisnewski, Adam V; Hettick, Justin M.; Siegel, Paul D.

    2012-01-01

    Glutathione has previously been identified as a reaction target for toluene diisocyanate (TDI) in vitro and in vivo, and has been suggested to contribute to toxic and allergic reactions to exposure. In this study, the reactivity of reduced glutathione (GSH) with TDI in vitro was further investigated using a mixed phase (vapor/liquid) exposure system to model the in vivo biophysics of exposure in the lower respiratory tract. HPLC/MS/MS was used to characterize the observed reaction products. Under the conditions tested, the major reaction products between TDI vapor and GSH were S-linked bis(GSH)-TDI and to a lesser extent mono(GSH)-TDI conjugates (with one N=C=O hydrolyzed). The vapor phase generated GSH-TDI conjugates were capable of transcarbamoylating human albumin in a pH-dependent manner, resulting in changes in the self-protein’s conformation/charge, based on electrophoretic mobility under native conditions. Specific sites of human albumin-TDI conjugation, mediated by GSH-TDI, were identified (Lys73, Lys159, Lys190, Lys199, Lys212, Lys351, Lys136/137, Lys413/414, Lys524/525) and overlap with those susceptible to direct conjugation by TDI. Together, the data extend proof-of-principle for GSH to act as a “shuttle” for a reactive form of TDI, which could contribute to clinical responses to exposure. PMID:21806041

  16. Vapor-liquid equilibria of copolymer + solvent and homopolymer + solvent binaries: New experimental data and their correlation

    SciTech Connect

    Gupta, R.B.; Prausnitz, J.M.

    1995-07-01

    Sixty-four isothermal data sets for vapor-liquid equilibria (VLE) for polymer + solvent binaries have been obtained using a gravimetric sorption technique, in the range of 23.5--80 C. Solvents studied were acetone, acetonitrile, 1-butanol, 1,2-dichloroethane, chloroform, cyclohexane, hexane, methanol, octane, pentane, and toluene. Copolymers studied were poly(acrylonitrile-co-butadiene), poly(styrene-co-acrylonitrile), poly(styrene-co-butadiene), poly(styrene-co-butyl methacrylate), poly(vinyl acetate-co-ethylene), and poly(vinyl acetate-co-vinyl chloride). All copolymers were random copolymers. Some homopolymers were also studied: polyacrylonitrile, polybutadiene, poly(butyl methacrylate), poly(ethylene oxide), polystyrene, and poly(vinyl acetate). The composition of the copolymer may have a surprising effect on VLE. Normally, deviation from ideal behavior lies between those of the constituent homopolymers, according to the copolymer composition, as observed for cyclohexane + poly(ethylene-co-vinyl acetate) and chloroform + poly(styrene-co-butyl methacrylate). However, the strong nonideal behavior observed for systems containing hydrocarbons and poly(butadiene-co-acrylonitrile) shows that the effect of acrylonitrile is in excess of that expected form the copolymer composition. The perturbed hard-sphere chain (PHSC) equation of state was used to represent VLE of the copolymer solutions studied here.

  17. Group V sensitive vapor-liquid-solid growth of Au-catalyzed and self-catalyzed III-V nanowires

    NASA Astrophysics Data System (ADS)

    Dubrovskii, Vladimir G.

    2016-04-01

    We present a new theoretical model that treats the group V sensitive growth rates and structures of Au-catalyzed and self-catalyzed III-V nanowires within a single kinetic picture. It is shown that Au-catalyzed III-V nanowires can grow with a time-independent radius within a wide range of parameters. At high V/III flux ratios, the vapor-liquid-solid growth of Au catalyzed III-V nanowires is controlled by surface diffusion of the group III adatoms, while at low V/III flux ratios it becomes nucleation-limited. Conversely, self-catalyzed III-V nanowires cannot grow with a time-independent droplet size and instead such nanowires may either swell or shrink or converge to a certain stationary radius depending on the V/III flux ratio. Quite importantly, the results are presented in a concise analytical form which is convenient for comparison with experimental data or prior theoretical works. We demonstrate how the model fits the data obtained previously for Au- and Ga-catalyzed GaAs nanowires.

  18. Essential role of catalysts (Mn, Au, and Sn) in the vapor liquid solid growth kinematics of ZnS nanowires

    SciTech Connect

    Rehman, S.; Shehzad, M. A.; Hafeez, M.; Bhatti, A. S.

    2014-01-14

    In this paper, we demonstrate that surface energy of the catalyst is a vital parameter for the growth rate, self doping of the self assembled nanowires synthesized by employing vapor liquid solid growth technique. The synthesis of ZnS nanowires was done by selectively using three different catalysts (Mn, Au, and Sn), where Au, is the most common catalyst, was used as a reference. The distinctive difference in the growth rate was due to the surface energy of the metal alloy droplet and the interface energies, as explained theoretically using thermodynamic approach. We have found that the activation energy of diffusion of (Zn, S) species in the catalyst droplet was low in Sn (0.41?eV for Zn and 0.13?eV for S) and high in Mn (1.79?eV for Zn and 0.61?eV for S) compared to Au (0.62?eV for Zn and 0.21?eV for S) catalyzed ZnS nanostructures. The thermodynamic calculations predicted the growth rates of Sn (7.5?nm/s) catalyzed nanowires was faster than Au (5.1?nm/s) and Mn (4.6?nm/s) catalyzed ZnS nanostructures, which were in agreement with the experimental results. Finally, the location of the catalyst as dopant in the grown nanostructure was predicted and compared with experimental observations.

  19. Effects of an applied electric field on the vapor-liquid equilibria of water, methanol, and dimethyl ether.

    PubMed

    Maerzke, Katie A; Siepmann, J Ilja

    2010-04-01

    Gibbs ensemble Monte Carlo simulations are employed to examine the influence of moderately strong electric fields on the vapor-liquid coexistence curves and on structural and energetic properties of the saturated phases of water, methanol, and dimethyl ether. The application of an electric field of 0.1 V/A increases the critical temperature and normal boiling point by approximately 3% compared to the zero field case for all three compounds, whereas the critical density is found to decrease by 1% for methanol and dimethly ether and by 3% for water. For the special case of an electric field applied in only the liquid phase, these effects are magnified with a 4% increase in T(C) and a 13% decrease in rho(C). For the case of an electric field in only the vapor phase, the opposite effect is seen with a 4% decrease in T(C) and a 12% increase in rho(C). Structural analysis shows very little change in the radial distribution functions, but greatly increased orientational ordering with the application of an electric field. The orientational ordering effect is stronger in the liquid phase than in the vapor phase. An examination of the energetics reveals that, in the presence of an electric field, the interactions with the first and second solvation shells become less favorable but these are outweighed by a larger increase in the favorable long-range interactions with more distant molecules and the field. PMID:20201507

  20. Peptide Labeling Using Isobaric Tagging Reagents for Quantitative Phosphoproteomics.

    PubMed

    Cheng, Lei; Pisitkun, Trairak; Knepper, Mark A; Hoffert, Jason D

    2016-01-01

    Isobaric tagging reagents have become an invaluable tool for multiplexed quantitative proteomic analysis. These reagents can label multiple, distinct peptide samples from virtually any source material (e.g., tissue, cell line, purified proteins), allowing users the opportunity to assess changes in peptide abundances across many different time points or experimental conditions. Here, we describe the application of isobaric peptide labeling, specifically 8plex isobaric tags for relative and absolute quantitation (8plex iTRAQ), for quantitative phosphoproteomic analysis of cultured cells or tissue suspensions. For this particular protocol, labeled samples are pooled, fractionated by strong cation exchange chromatography, enriched for phosphopeptides, and analyzed by tandem mass spectrometry (LC-MS/MS) for both peptide identification and quantitation. PMID:26584918

  1. 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

    SciTech Connect

    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.

  2. Vapor-liquid partitioning of alkaline earth and transition metals in NaCl-dominated hydrothermal fluids: An experimental study from 360 to 465 °C, near-critical to halite saturated conditions

    NASA Astrophysics Data System (ADS)

    Pester, Nicholas J.; Ding, Kang; Seyfried, William E.

    2015-11-01

    Multi-phase fluid flow is a common occurrence in magmatic hydrothermal systems; and extensive modeling efforts using currently established P-V-T-x properties of the NaCl-H2O system are impending. We have therefore performed hydrothermal flow experiments (360-465 °C) to observe vapor-liquid partitioning of alkaline earth and first row transition metals in NaCl-dominated source solutions. The data allow extraction of partition coefficients related to the intrinsic changes in both chlorinity and density along the two-phase solvus. The coefficients yield an overall decrease in vapor affinity in the order Cu(I) > Na > Fe(II) > Zn > Ni(II) ⩾ Mg ⩾ Mn(II) > Co(II) > Ca > Sr > Ba, distinguished with 95% confidence for vapor densities greater than ∼0.2 g/cm3. The alkaline earth metals are limited to purely electrostatic interactions with Cl ligands, resulting in an excellent linear correlation (R2 > 0.99) between their partition coefficients and respective ionic radii. Though broadly consistent with this relationship, relative behavior of the transition metals is not well resolved, being likely obscured by complex bonding processes and the potential participation of Na in the formation of tetra-chloro species. At lower densities (at/near halite saturation) partitioning behavior of all metals becomes highly non-linear, where M/Cl ratios in the vapor begin to increase despite continued decreases in chlorinity and density. We refer to this phenomenon as "volatility", which is broadly associated with substantial increases in the HCl/NaCl ratio (eventually to >1) due to hydrolysis of NaCl. Some transition metals (e.g., Fe, Zn) exhibit volatility prior to halite stability, suggesting a potential shift in vapor speciation relative to nearer critical regions of the vapor-liquid solvus. The chemistry of deep-sea hydrothermal fluids appears affected by this process during magmatic events, however, our results do not support suggestions of subseafloor halite precipitation recorded in currently available field data. Ca-Cl systematics in vent fluids are specifically explored, revealing behavior consistent with partitioning due to phase separation. Interestingly, the effect of variable chloride on dissolved Na/Ca ratios associated with plagioclase solubility (in single-phase solutions) appears fundamentally similar to that of phase separation on vapor compositions such that vapors evolved in hydrothermal systems may naturally remain near equilibrium with the host lithology. Conversely, residual liquids/brines left behind in the crust may be undersaturated with metals, enhancing the rate and extent of hydrothermal alteration.

  3. Study of the Vapor-Liquid Coexistence Curve and the Critical Curve for Nonazeotropic Refrigerant Mixture R152a + R114 System

    NASA Astrophysics Data System (ADS)

    Kabata, Yasuo; Higashi, Yukihiro; Uematsu, Masahiko; Watanabe, Koichi

    Measurements of the vapor-liquid coexistence curve in the critical region for the refrigerant mixture of R152a (CH3CHF2: 1, l-difluoroethane) +R 114 (CCIF2CCIF2 :1, 2-dichloro-1, 1, 2, 2-tetrafluoroethane) system were made by visual observation of the disappearance of the meniscus at the vapor-liquid interface within an optical cell. Forty-eight saturated densities along the vapor-liquid coexistence curve between 204 and 861 kg·m-3 for five different compositions of 10, 20, 50, 80 and 90 wt% R 152a were obtained in the temperature range 370 to 409 K. The experimental errors of temperature, density, and mass fraction were estimated within ±10mK, ±0.5% and +0.05 %, respectively. On the basis of these measurements, the critical parameters of five different compositions for the R 152a +R 114 system were determined in consideration of the meniscus disappearance level as well as intensity of the critical opalescence. In accordance with the previous results of three other refrigerant mixtures, i.e., R 12 +R 22 system, R 22 +R 114 system and R 13B1 + R 114 system, the coexistence curve and critical curve on the temperature-density diagram for binary refrigerant mixtures were discussed. In addition, correlations of its composition dependence for this system were proposed.

  4. A flux induced crystal phase transition in the vapor-liquid-solid growth of indium-tin oxide nanowires

    NASA Astrophysics Data System (ADS)

    Meng, Gang; Yanagida, Takeshi; Yoshida, Hideto; Nagashima, Kazuki; Kanai, Masaki; Zhuge, Fuwei; He, Yong; Klamchuen, Annop; Rahong, Sakon; Fang, Xiaodong; Takeda, Seiji; Kawai, Tomoji

    2014-05-01

    Single crystalline metal oxide nanowires formed via a vapor-liquid-solid (VLS) route provide a platform not only for studying fundamental nanoscale properties but also for exploring novel device applications. Although the crystal phase variation of metal oxides, which exhibits a variety of physical properties, is an interesting feature compared with conventional semiconductors, it has been difficult to control the crystal phase of metal oxides during the VLS nanowire growth. Here we show that a material flux critically determines the crystal phase of indium-tin oxide nanowires grown via the VLS route, although thermodynamical parameters, such as temperature and pressure, were previously believed to determine the crystal phase. The crystal phases of indium-tin oxide nanowires varied from the rutile structures (SnO2), the metastable fluorite structures (InxSnyO3.5) and the bixbyite structures (Sn-doped In2O3) when only the material flux was varied within an order of magnitude. This trend can be interpreted in terms of the material flux dependence of crystal phases (rutile SnO2 and bixbyite In2O3) on the critical nucleation at the liquid-solid (LS) interface. Thus, precisely controlling the material flux, which has been underestimated for VLS nanowire growths, allows us to design the crystal phase and properties in the VLS nanowire growth of multicomponent metal oxides.Single crystalline metal oxide nanowires formed via a vapor-liquid-solid (VLS) route provide a platform not only for studying fundamental nanoscale properties but also for exploring novel device applications. Although the crystal phase variation of metal oxides, which exhibits a variety of physical properties, is an interesting feature compared with conventional semiconductors, it has been difficult to control the crystal phase of metal oxides during the VLS nanowire growth. Here we show that a material flux critically determines the crystal phase of indium-tin oxide nanowires grown via the VLS route, although thermodynamical parameters, such as temperature and pressure, were previously believed to determine the crystal phase. The crystal phases of indium-tin oxide nanowires varied from the rutile structures (SnO2), the metastable fluorite structures (InxSnyO3.5) and the bixbyite structures (Sn-doped In2O3) when only the material flux was varied within an order of magnitude. This trend can be interpreted in terms of the material flux dependence of crystal phases (rutile SnO2 and bixbyite In2O3) on the critical nucleation at the liquid-solid (LS) interface. Thus, precisely controlling the material flux, which has been underestimated for VLS nanowire growths, allows us to design the crystal phase and properties in the VLS nanowire growth of multicomponent metal oxides. Electronic supplementary information (ESI) available: STEM mapping of In and Sn in an ISO nanowire (Fig. S1) and homogeneity of a fluorite ISO phase at the full length of a nanowire (Fig. S2). See DOI: 10.1039/c4nr01016g

  5. Removal of the samarium isobaric interference from promethium mass analysis

    SciTech Connect

    Shaw, R.W.; Young, J.P.; Smith, D.H.

    1988-02-01

    Resonance ionization mass spectroscopy (RIMS) is used to eliminate isobaric interference when determining the isotopic abundances of an element. In this application, RIMS is applied to the determination of promethium with the removal of samarium interference. In particular, promethium-147 is separated form samarium-147 and samarium-152.

  6. Isobaric yield ratio difference and Shannon information entropy

    NASA Astrophysics Data System (ADS)

    Ma, Chun-Wang; Wei, Hui-Ling; Wang, Shan-Shan; Ma, Yu-Gang; Wada, Ryoichi; Zhang, Yan-Li

    2015-03-01

    The Shannon information entropy theory is used to explain the recently proposed isobaric yield ratio difference (IBD) probe which aims to determine the nuclear symmetry energy. Theoretically, the difference between the Shannon uncertainties carried by isobars in two different reactions (ΔIn21), is found to be equivalent to the difference between the chemical potentials of protons and neutrons of the reactions [the IBD probe, IB- Δ(βμ)21, with β the reverse temperature]. From the viewpoints of Shannon information entropy, the physical meaning of the above chemical potential difference is interpreted by ΔIn21 as denoting the nuclear symmetry energy or density difference between neutrons and protons in reactions more concisely than from the statistical ablation-abrasion model.

  7. Phase equilibrium measurements on twelve binary mixtures

    SciTech Connect

    Giles, N.F.; Wilson, H.L.; Wilding, W.V.

    1996-11-01

    Phase equilibrium measurements have been performed on twelve binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following binary systems at two temperatures each: ethanethiol + propylene; nitrobenzene + methanol; pyridine + ethyl acetate; octane + tert-amyl methyl ether; diisopropyl ether + butane; 1,3-dichloro-2-propanol + epichlorohydrin; 2,3-dichloro-1-propanol + epichlorohydrin; 2,3-epoxy-1-propanol + epichlorohydrin; 3-chloro-1,2-propanediol + epichlorohydrin; methanol + hydrogen cyanide. For these systems, equilibrium vapor and liquid phase compositions were derived from the PTx data using the Soave equation of state to represent the vapor phase and the Wilson, NRTL, or Redlich-Kister activity coefficient model to represent the liquid phase. The infinite dilution activity coefficient of methylamine in N-methyl-2-pyrrolidone was determined at three temperatures by performing PTx measurements on the N-methyl-2-pyrrolidone was determined at three temperatures by performing PTx measurements on the N-methyl-2-pyrrolidone-rich half of the binary. Liquid-liquid equilibrium studies were made on the triethylene glycol + 1-pentene system at two temperatures by directly analyzing samples taken from each liquid phase.

  8. Reference pressure changes and available potential energy in isobaric coordinates

    NASA Technical Reports Server (NTRS)

    Robertson, F. R.

    1985-01-01

    A formulation of the available potential energy (APE) equation in isobaric coordinates which alleviates the need for computing temporal derivatives of reference pressure and describes how work done relates to changes in the APE of a limited region is presented. The APE budget equation possesses terms analogous to those in Johnson's (1970) isentropic version. It is shown that APE changes result from either mechanical work inside the domain or an exchange of energy via boundary processes with the surrounding environment.

  9. Isobar configurations: ?N correlations versus the independent particle model

    NASA Astrophysics Data System (ADS)

    Glavanakov, I. V.; Tabachenko, A. N.

    2015-05-01

    We present a comparative analysis of two models for the A (?, ?N) B reaction, which take into account the isobar configurations in the ground state of the nuclei: the ?N correlation model and the quasifree pion photoproduction model. The considered models differ in their descriptions of the nucleus states. The ?N correlation model takes into account the dynamic correlations of the nucleon and isobar formed in the virtual transition NN ? ?N, and in the quasifree pion photoproduction model, isobars and nucleons in the nucleus are considered as independent constituents. The predictions of the models are considered for two reactions 16O (?, ?+ p)15C and 16O (?, ?- p)15O. It is shown, that the two models predict the differential cross section significantly differing both in absolute values, and in the shape of the angular dependence. We compare the results of the ?N correlation model for the (?, ?N) and (?, ?NN) reactions with the 16O (?, ?- p) reaction data measured at BNL. Our results give support to the ?N correlation model.

  10. Controlling Axial p-n Heterojunction Abruptness Through Catalyst Alloying in Vapor-Liquid-Solid Grown Semiconductor Nanowires

    SciTech Connect

    Perea, Daniel E.; Schreiber, Daniel K.; Devaraj, Arun; Thevuthasan, Suntharampillai; Yoo, Jinkyoung; Dayeh, Shadi A.; Picraux, Samuel T.

    2012-07-30

    The p-n junction can be regarded as the most important electronic structure that is responsible for the ubiquity of semiconductor microelectronics today. Efforts to continually scale down the size of electronic components is guiding research to explore the use of nanomaterials synthesized from a bottom-up approach - group-IV semiconductor nanowires being one such material. However, Au-catalyzed synthesis of Si/Si1-x-Gex semiconductor nanowire heterojunctions using the commonly-used vapor-liquid-solid (VLS) growth technique results in diffuse heterojunction interfaces [1], leading to doubts of producing compositionally-sharp p-n junctions using this approach. However, we have recently reported the ability to increase Ge-Si nanowire heterojunction abruptness by VLS synthesis from a Au(1-x)Ga(x) catalyst alloy as shown by EDX analysis in an SEM [2]. In this work, we have extended the use of a AuGa catalyst alloy to produce more compositionally abrupt p-n junction interfaces compared to using pure Au as directly measured by atom probe tomography. As shown in Figure 1(a-b), individual Ge-Si heterostructured nanowires were grown vertically atop Ge(111) microposts. Direct growth on the microposts provides a facile approach to nanowire analysis which circumvents the need to use FIB-based sample preparation techniques. Both nanowires grown from pure Au and a AuGa catalyst alloy were analyzed. The corresponding 3D APT reconstruction of an individual heterostructured nanowire is shown in Figure 1(c) with the corresponding materials labeled. A 1-dimensional composition profile along the analysis direction in Figure 1(d) confirms an increase in heterojunction abruptness for nanowires grown from AuGa (~10nm) compared to nanowires grown from pure Au (~65nm). Analysis of the P distribution within the Si region (Figure 1(e)) indicates that P reaches a constant distribution over approximately 10nm when incorporated through the AuGa catalyst, whereas it continually increases over 100’s of nanometers when incorporated through pure Au. The apparent lower overall P concentration within the nanowire grown from the AuGa alloy suggests that the solubility of P in the alloy is lower compared to pure Au. The ability to controllably increase nanowire p-n junction abruptness is important for nanowire applications as solar cells and tunneling field effect transistors where an increase in device performance is expected from shaper p-n junction interfaces. [1] T.E. Clark et al., Nano Lett. 8 (2008) 1246. [2] D.E. Perea et al., Nano Lett. 11 (2011) 3117. [3] The research was supported through the user program at both the Center for Integrated Nanotechnologies at Los Alamos National Laboratory and the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory.

  11. Laser ion source for isobaric heavy ion collider experiment

    NASA Astrophysics Data System (ADS)

    Kanesue, T.; Kumaki, M.; Ikeda, S.; Okamura, M.

    2016-02-01

    Heavy-ion collider experiment in isobaric system is under investigation at Relativistic Heavy Ion Collider. For this experiment, ion source is required to maximize the abundance of the intended isotope. The candidate of the experiment is 96Ru + 96Zr. Since the natural abundance of particular isotope is low and composition of isotope from ion source depends on the composites of the target, an isotope enriched material may be needed as a target. We studied the performance of the laser ion source required for the experiment for Zr ions.

  12. Ultrastructure of the rat hippocampus after isobaric respirative hyperoxia.

    PubMed

    Manthos, A; Tsolaki, M; Kaidoglou, K; Alvanou, A; Hatjinikolaou, K; Hatjiagorakis, A; Giala, M; Foroglou, C

    1991-01-01

    After exposing rats to an environment of isobaric hyperoxia, the ultrastructural alterations of the hippocampus were studied. No major alterations were found in the nerve cells. Of importance was the moderate osmiophilia and the spindle-like transformation of the mitochondria. Vacuolated synapses and neuraxons were found, containing amorphous material. Astrocytic perivascular end feet were found vacuolated in many places. Many endothelial cells of the capillaries presented high osmiophilia, which sometimes prevented structural details. Quantitatively, the findings were proportionally related to the time of exposure in the pure oxygen atmosphere (24, 48 and 65 hours). PMID:1806057

  13. Vapor-liquid phase equilibria of potassium chloride-water mixtures: Equation-of-state representation for KCl-H2O and NaCl-H2O

    USGS Publications Warehouse

    Hovey, J.K.; Pitzer, Kenneth S.; Tanger, J.C., IV; Bischoff, J.L.; Rosenbauer, R.J.

    1990-01-01

    Measurements of isothermal vapor-liquid compositions for KCl-H2O as a function of pressure are reported. An equation of state, which was originally proposed by Pitzer and was improved and used by Tanger and Pitzer to fit the vapor-liquid coexistence surface for NaCl-H2O, has been used for representation of the KCl-H2O system from 300 to 410??C. Improved parameters are also reported for NaCl-H2O from 300 to 500??C. ?? 1990 American Chemical Society.

  14. Isobar Suppression by Photodetachment in a RF Quadrupole Ion Cooler

    NASA Astrophysics Data System (ADS)

    Liu, Yuan; Havener, A. C.; Havener, C. C.; Liang, F.; Beene, J. R.

    2004-11-01

    Selectively removing unwanted isobaric negative ions by electron photodetachment with a pulsed laser beam has been reported. However, the fraction of the negative ions removed was very small due to the short laser pulses used. Continuous wave (CW) lasers are desired for this application, but the photon flux available from CW lasers is too low. We have investigated a novel scheme for efficient suppression of isobar contaminants by photodetachment in a gas-filled RF-only quadrupole (RFQ) ion cooler. Simulation studies have shown that the RFQ ion cooler can significantly increase the laser-ion interaction time, thus, high efficiency of photodetachment is possible with commercially available CW lasers. A proof-of-principle experiment of Co^- and Ni^- ions is underway. A CW Nd:YAG laser beam at 1064 nm wavelength is used to selectively remove Co^- ions inside a RFQ ion cooler. A detailed description of the experimental setup and expected photodetachment efficiencies for Co^- and Ni^- ions will be given in this report. 1. D. Berkovits, et al., Nucl. Instrum. Meth. B52 (1990) 378-333.

  15. Vapor-liquid Equilibria and Polarization Behavior of the GCP Water Model: Gaussian Charge-on-spring versus Dipole Self-consistent Field approaches to induced polarization

    SciTech Connect

    Chialvo, Ariel A; Moucka, Filip; Vlcek, Lukas; Nezbeda, Ivo

    2015-01-01

    We implemented the Gaussian charge-on-spring (GCOS) version of the original self-consistent field implementation of the Gaussian Charge Polarizable water model and test its accuracy to represent the polarization behavior of the original model involving smeared charges and induced dipole moments. For that purpose we adapted the recently developed multiple-particle-move (MPM) within the Gibbs and isochoric-isothermal ensembles Monte Carlo methods for the efficient simulation of polarizable fluids. We assessed the accuracy of the GCOS representation by a direct comparison of the resulting vapor-liquid phase envelope, microstructure, and relevant microscopic descriptors of water polarization along the orthobaric curve against the corresponding quantities from the actual GCP water model.

  16. Remote sensing of atmospheric water vapor, liquid water, and wind speed at the ocean surface by passive microwave techniques from the Nimbus 5 satellite

    NASA Technical Reports Server (NTRS)

    Chang, A. T. C.; Wilheit, T. T.

    1979-01-01

    The microwave brightness temperature measurements for Nimbus 5 electrically scanned microwave radiometer (ESMR) and Nimbus-E microwave spectrometer (NEMS) are used to retrieve the atmospheric water vapor, liquid water, and wind speed by a quasi-statistical retrieval technique. It is shown that the brightness temperature can be utilized to yield these parameters under various weather conditions. Observations at 19.35, 22.235, and 31.4 GHz were input to the regression equations. The retrieved values of these parameters for portions of two Nimbus 5 orbits are presented. Then comparison between the retrieved parameters and the available observations on the total water vapor content and the surface wind speed are made.

  17. Remote sensing of atmospheric water vapor, liquid water and wind speed at the ocean surface by passive microwave techniques from the Nimbus-5 satellite

    NASA Technical Reports Server (NTRS)

    Chang, A. T. C.; Wilheit, T. T.

    1977-01-01

    The microwave brightness temperature measurements for Nimbus-5 electrically scanned microwave radiometer and Nimbus E microwave spectrometer are used to retrieve the atmospheric water vapor, liquid water and wind speed by a quasi-statistical retrieval technique. It is shown that the brightness temperature can be utilized to yield these parameters under various weather conditions. Observations at 19.35 GHz, 22.235 GHz and 31.4 GHz were input to the regression equations. The retrieved values of these parameters for portions of two Nimbus-5 orbits are presented. Then comparison between the retrieved parameters and the available observations on the total water vapor content and the surface wind speed are made. The estimated errors for retrieval are approximately 0.15 g/sq cm for water vapor content, 6.5 mg/sq cm for liquid water content and 6.6 m/sec for surface wind speed.

  18. Nested sampling of isobaric phase space for the direct evaluation of the isothermal-isobaric partition function of atomic systems.

    PubMed

    Wilson, Blake A; Gelb, Lev D; Nielsen, Steven O

    2015-10-21

    Nested Sampling (NS) is a powerful athermal statistical mechanical sampling technique that directly calculates the partition function, and hence gives access to all thermodynamic quantities in absolute terms, including absolute free energies and absolute entropies. NS has been used predominately to compute the canonical (NVT) partition function. Although NS has recently been used to obtain the isothermal-isobaric (NPT) partition function of the hard sphere model, a general approach to the computation of the NPT partition function has yet to be developed. Here, we describe an isobaric NS (IBNS) method which allows for the computation of the NPT partition function of any atomic system. We demonstrate IBNS on two finite Lennard-Jones systems and confirm the results through comparison to parallel tempering Monte Carlo. Temperature-entropy plots are constructed as well as a simple pressure-temperature phase diagram for each system. We further demonstrate IBNS by computing part of the pressure-temperature phase diagram of a Lennard-Jones system under periodic boundary conditions. PMID:26493898

  19. Nested sampling of isobaric phase space for the direct evaluation of the isothermal-isobaric partition function of atomic systems

    NASA Astrophysics Data System (ADS)

    Wilson, Blake A.; Gelb, Lev D.; Nielsen, Steven O.

    2015-10-01

    Nested Sampling (NS) is a powerful athermal statistical mechanical sampling technique that directly calculates the partition function, and hence gives access to all thermodynamic quantities in absolute terms, including absolute free energies and absolute entropies. NS has been used predominately to compute the canonical (NVT) partition function. Although NS has recently been used to obtain the isothermal-isobaric (NPT) partition function of the hard sphere model, a general approach to the computation of the NPT partition function has yet to be developed. Here, we describe an isobaric NS (IBNS) method which allows for the computation of the NPT partition function of any atomic system. We demonstrate IBNS on two finite Lennard-Jones systems and confirm the results through comparison to parallel tempering Monte Carlo. Temperature-entropy plots are constructed as well as a simple pressure-temperature phase diagram for each system. We further demonstrate IBNS by computing part of the pressure-temperature phase diagram of a Lennard-Jones system under periodic boundary conditions.

  20. The isobaric multiplet mass equation for A?71 revisited

    SciTech Connect

    Lam, Yi Hua; Blank, Bertram; Smirnova, Nadezda A.; Bueb, Jean Bernard; Antony, Maria Susai

    2013-11-15

    Accurate mass determination of short-lived nuclides by Penning-trap spectrometers and progress in the spectroscopy of proton-rich nuclei have triggered renewed interest in the isobaric multiplet mass equation (IMME). The energy levels of the members of T=1/2,1,3/2, and 2 multiplets and the coefficients of the IMME are tabulated for A?71. The new compilation is based on the most recent mass evaluation (AME2011) and it includes the experimental results on energies of the states evaluated up to end of 2011. Taking into account the error bars, a significant deviation from the quadratic form of the IMME for the A=9,35 quartets and the A=32 quintet is observed.

  1. Chemical effects during ripple formation with isobaric ion beams

    NASA Astrophysics Data System (ADS)

    Sarkar, S.; Franquet, A.; Moussa, A.; Vandervorst, W.

    2011-05-01

    The formation of nanostructures on SiGe surfaces by erosion using mixed beams of isobaric species (Cs/Xe) is shown to depend on the Cs/Xe ratio. The nanostructures exhibit different wavelengths (longer wavelengths for higher Cs concentrations) contrary to the present theoretical understanding. Moreover, experiments with pure Cs and Xe beams also demonstrate that such differences are enhanced at lower bombarding energies. Such effects are primarily due to the fact that the retentivity and mobility of cesium at the sample surface gets enhanced at lower bombarding energies. The phenomenon could be explained theoretically by including an additional diffusion term in the growth equation describing the mobility of the primary ions on the irradiated surface. Semi-empirical calculations done in this direction also confirm this phenomenon.

  2. Hard breakup of the deuteron into two {Delta} isobars

    SciTech Connect

    Granados, Carlos G.; Sargsian, Misak M.

    2011-05-15

    We study high-energy photodisintegration of the deuteron into two {Delta} isobars at large center of mass angles within the QCD hard rescattering model (HRM). According to the HRM, the process develops in three main steps: the photon knocks a quark from one of the nucleons in the deuteron; the struck quark rescatters off a quark from the other nucleon sharing the high energy of the photon; then the energetic quarks recombine into two outgoing baryons which have large transverse momenta. Within the HRM, the cross section is expressed through the amplitude of pn{yields}{Delta}{Delta} scattering which we evaluated based on the quark-interchange model of hard hadronic scattering. Calculations show that the angular distribution and the strength of the photodisintegration is mainly determined by the properties of the pn{yields}{Delta}{Delta} scattering. We predict that the cross section of the deuteron breakup to {Delta}{sup ++}{Delta}{sup -} is 4-5 times larger than that of the breakup to the {Delta}{sup +}{Delta}{sup 0} channel. Also, the angular distributions for these two channels are markedly different. These can be compared with the predictions based on the assumption that two hard {Delta} isobars are the result of the disintegration of the preexisting {Delta}{Delta} components of the deuteron wave function. In this case, one expects the angular distributions and cross sections of the breakup in both {Delta}{sup ++}{Delta}{sup -} and {Delta}{sup +}{Delta}{sup 0} channels to be similar.

  3. Shear viscosity and thermal conductivity of dipolar real fluids from equilibrium molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Fernndez, Gimmy A.; Vrabec, Jadran; Hasse, Hans

    2006-10-01

    Equilibrium molecular dynamics and the Green-Kubo formalism were used to simultaneously calculate shear viscosity and thermal conductivity for 10 refrigerants: R11, R12, R22, R23, R41, R123, R134a, R142b, R143a, and R152a. The fluids were modelled in previous work of Stoll et al. [J Chem Phys 2003;119:11396-407] using the two-center Lennard-Jones plus point dipole (2CLJD) pair potential, with parameters adjusted to vapor-liquid equilibria only. The predicted shear viscosities and thermal conductivities show an overall average deviation of about 15% and 10%, respectively, from correlations of experimental data.

  4. Effect of polymorphism and dispersity on the crystal-melt phase equilibrium

    NASA Astrophysics Data System (ADS)

    Shablovskii, Ya. O.

    2010-08-01

    The laws of the effect of the dispersity of a polymorphic crystalline substance on the equilibrium with its melt are revealed. The size dependences of the molar volume of a polycrystalline substance, the isothermal-transformation pressure, and the isobaric-transformation temperature are obtained. The Ostwald stage law is analytically generalized to the case of solidification from a melt.

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

    SciTech Connect

    Maimoni, A.

    1980-01-01

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

  6. A solvation model for vapor-liquid equilibria in the system H2O-NaOH from 10 to 85 wt%

    NASA Astrophysics Data System (ADS)

    Peters, R.; Helwig, R.; Keller, J. U.

    1996-01-01

    Vapor-liquid equilibria in the electrolyte system water-sodium hydroxide are described by using a so-called solvation model. In such a model the formation of ion clusters is assumed, consisting of either of the ions Na+ or OH- being surrounded by water molecules, the number of which depends on the overall molar concentration of sodium hydroxide. Activities of the various components in the liquid phase are modeled by local composition models like the nonrandom two-liquid equation (NRTL) and the Wilson's equation. The vapor phase, assumed to consist of water only, is modeled by the equation of state (EOS) of Wagner and Saul. The models include seven parameters fitted to 230 experimental data points taken from the literature in the range 0.18 kPa to 8 M Pa, 273 to 623 K, and 10 to 85 wt% NaOH. The system's pressure resulting from a T x ? p calculation procedure can be represented with a mean relative deviation of 1.3%.

  7. Fabrication and electrical characterization of homo- and hetero-structure Si/SiGe nanowire Tunnel Field Effect Transistor grown by vapor-liquid-solid mechanism

    NASA Astrophysics Data System (ADS)

    Brouzet, V.; Salem, B.; Periwal, P.; Alcotte, R.; Chouchane, F.; Bassani, F.; Baron, T.; Ghibaudo, G.

    2016-04-01

    We demonstrate the fabrication and electrical characterization of Ω -gate Tunnel Field Effect Transistors (TFET) based on p-Si/i-Si/n+Si0.7Ge0.3 heterostructure nanowires grown by Chemical Vapor Deposition (CVD) using the vapor-liquid-solid (VLS) mechanism. The electrical performances of the p-Si/i-Si/n+Si0.7Ge0.3 heterostructure TFET device are presented and compared to Si and Si0.7Ge0.3 homostructure nanowire TFETs. We observe an improvement of the electrical performances of TFET with p-Si/i-Si/n+Si0.7Ge0.3 heterostructure nanowire (HT NW). The optimized devices present an Ion current of about 245 nA at VDS = -0.5 V and VGS = -3 V with a subthreshold swing around 135 mV/dec. Finally, we show that the electrical results are in good agreement with numerical simulation using Kane's Band-to-Band Tunneling model.

  8. Growth mechanism of metal-oxide nanowires synthesized by electron beam evaporation: a self-catalytic vapor-liquid-solid process.

    PubMed

    Yu, Hak Ki; Lee, Jong-Lam

    2014-01-01

    We report the growth mechanism of metal oxide nanostructures synthesized by electron beam evaporation. The condensed electron beam can easily decompose metal oxide sources that have a high melting point, thereby creating a self-catalytic metal nanodot for the vapor-liquid-solid process. The metal oxide nanostructures can be grown at a temperature just above the melting point of the self-catalyst by dissolving oxygen. The morphology of nanostructures, such as density and uniformity, strongly depends on the surface energy and surface migration energy of the substrate. The density of the self-catalytic metal nanodots increased with decreasing surface energies of the substrate due to the perfect wetting phenomenon of the catalytic materials on the high surface energy substrate. However, the surfaces with extremely low surface energy had difficulty producing the high density of self-catalyst nanodot, due to positive line tension, which increases the contact angle to >180. Moreover, substrates with low surface migration energy, such as single layer graphene, make nanodots agglomerate to produce a less-uniform distribution compared to those produced on multi-layer graphene with high surface migration energy. PMID:25300518

  9. Growth mechanism of metal-oxide nanowires synthesized by electron beam evaporation: A self-catalytic vapor-liquid-solid process

    NASA Astrophysics Data System (ADS)

    Yu, Hak Ki; Lee, Jong-Lam

    2014-10-01

    We report the growth mechanism of metal oxide nanostructures synthesized by electron beam evaporation. The condensed electron beam can easily decompose metal oxide sources that have a high melting point, thereby creating a self-catalytic metal nanodot for the vapor-liquid-solid process. The metal oxide nanostructures can be grown at a temperature just above the melting point of the self-catalyst by dissolving oxygen. The morphology of nanostructures, such as density and uniformity, strongly depends on the surface energy and surface migration energy of the substrate. The density of the self-catalytic metal nanodots increased with decreasing surface energies of the substrate due to the perfect wetting phenomenon of the catalytic materials on the high surface energy substrate. However, the surfaces with extremely low surface energy had difficulty producing the high density of self-catalyst nanodot, due to positive line tension, which increases the contact angle to >180. Moreover, substrates with low surface migration energy, such as single layer graphene, make nanodots agglomerate to produce a less-uniform distribution compared to those produced on multi-layer graphene with high surface migration energy.

  10. Effects of transport gradients in a chemical vapor deposition reactor employing vapor-liquid-solid growth of ternary chalcogenide phase-change materials.

    PubMed

    Johnson, Derek C; Morris, Wesley D; Prieto, Amy L

    2010-04-23

    Chemical vapor deposition (CVD) with vapor-liquid-solid (VLS) growth is employed to synthesize individual Ge(2)Sb(2)Te(5) nanowires with the ultimate goal of synthesizing a large scale nanowire array for universal memory storage. A consistent challenge encountered during the synthesis is a lack of control over the composition and morphology across the growth substrate. To better understand the challenges associated with the CVD synthesis of the ternary chalcogenide, computational fluid dynamics simulations are performed to quantify 3D thermal and momentum transients in the growth conditions. While these gradients are qualitatively known to exist, they have not been adequately quantified in both the axial and radial directions when under pressure and flow conditions indicative of VLS growth. These data are not easily acquired by conventional means for the axial direction under vacuum and are a considerable challenge to accurately measure radially. The simulation data shown here provide 3D insights into the gradients which ultimately dictate the region of controllable stoichiometry and morphology. These results help explain the observed inhomogeneity of the characterized ternary chalcogenide growth products at various growth substrate locations. PMID:20351405

  11. Molecular simulation of the shear viscosity and the self-diffusion coefficient of mercury along the vapor-liquid coexistence curve.

    PubMed

    Raabe, Gabriele; Todd, B D; Sadus, Richard J

    2005-07-15

    In earlier work [G. Raabe and R. J. Sadus, J. Chem. Phys. 119, 6691 (2003)] we reported that the combination of an accurate two-body ab initio potential with an empirically determined multibody contribution enables the prediction of the phase coexistence properties, the heats of vaporization, and the pair distribution functions of mercury with reasonable accuracy. In this work we present molecular dynamics simulation results for the shear viscosity and self-diffusion coefficient of mercury along the vapor-liquid coexistence curve using our empirical effective potential. The comparison with experiment and calculations based on a modified Enskog theory shows that our multibody contribution yields reliable predictions of the self-diffusion coefficient at all densities. Good results are also obtained for the shear viscosity of mercury at low to moderate densities. Increasing deviations between the simulation and experimental viscosity data at high densities suggest that not only a temperature-dependent but also a density-dependent multibody contribution is necessary to account for the effect of intermolecular interactions in liquid metals. An analysis of our simulation data near the critical point yields a critical exponent of beta = 0.39, which is identical to the value obtained from the analysis of the experimental saturation densities. PMID:16080748

  12. Interface pn junction arrays with high yielded grown p-Si microneedles by vapor-liquid-solid method at low temperature

    NASA Astrophysics Data System (ADS)

    Islam, Md. Shofiqul; Ishida, Makoto

    2015-01-01

    In this work we report the fabrication and investigation of the properties of interface pn junction arrays formed at the interface of vertically aligned p-Si microneedles and n-Si substrate. Arrays of boron doped p-Si microneedles were grown on n-Si substrate with the maximum yield of 100% by Au-catalysed vapor-liquid-solid (VLS) growth using in-situ doping with the mixed gas of Si2H6 and B2H6 at temperature less than 700 C, which is low as compared to the temperature (1100 C) required by diffusion process to dope Si microneedles after VLS growth. The physical dimension (diameter, length) and position of these p-Si microneedles can be controlled. The variation of growth rate, diameter, conductivity, impurity concentration and hole mobility of these p-Si microneeedles were investigated with the variation of boron doping. The pn junctions, formed with p-Si microneedles having different diameters, were found to exhibit standard diode characteristics. These pn junction embedded Si microneedle arrays might be potential candidate in sensor area applications. Again, low temperature processing would be compatible to integrate these junction arrays with other circuitry on a chip. This work provides one step forward to realize more sophisticated vertical active devices (BJT, MOSFET, etc) with Si microneedles.

  13. Effects of transport gradients in a chemical vapor deposition reactor employing vapor-liquid-solid growth of ternary chalcogenide phase-change materials

    NASA Astrophysics Data System (ADS)

    Johnson, Derek C.; Morris, Wesley D.; Prieto, Amy L.

    2010-04-01

    Chemical vapor deposition (CVD) with vapor-liquid-solid (VLS) growth is employed to synthesize individual Ge2Sb2Te5 nanowires with the ultimate goal of synthesizing a large scale nanowire array for universal memory storage. A consistent challenge encountered during the synthesis is a lack of control over the composition and morphology across the growth substrate. To better understand the challenges associated with the CVD synthesis of the ternary chalcogenide, computational fluid dynamics simulations are performed to quantify 3D thermal and momentum transients in the growth conditions. While these gradients are qualitatively known to exist, they have not been adequately quantified in both the axial and radial directions when under pressure and flow conditions indicative of VLS growth. These data are not easily acquired by conventional means for the axial direction under vacuum and are a considerable challenge to accurately measure radially. The simulation data shown here provide 3D insights into the gradients which ultimately dictate the region of controllable stoichiometry and morphology. These results help explain the observed inhomogeneity of the characterized ternary chalcogenide growth products at various growth substrate locations.

  14. The generation of HCl in the system CaCl2-H2O: Vapor-liquid relations from 380-500C

    USGS Publications Warehouse

    Bischoff, James L.; Rosenbauer, Robert J.; Fournier, Robert O.

    1996-01-01

    We determined vapor-liquid relations (P-T-x) and derived critical parameters for the system CaCl2-H2O from 380-500??C. Results show that the two-phase region of this system is extremely large and occupies a significant portion of the P-T space to which circulation of fluids in the Earth's crust is constrained. Results also show the system generates significant amounts of HCl (as much as 0.1 mol/kg) in the vapor phase buffered by the liquid at surprisingly high pressures (???230 bars at 380??C, <580 bars at 500??C), presumably by hydrolysis of CaCl2: CaCl2 + 2H2O = Ca(OH)2 + 2HCl. We interpret the abundance of HCl in the vapor as due to its preference for the vapor phase, and by the preference of Ca(OH)2 for either the liquid phase or solid. The recent recognition of the abundance of CaCl2 in deep brines of the Earth's crust and their hydrothermal mobilization makes the hydrolysis of CaCl2 geologically important. The boiling of Ca-rich brines produces abundant HCl buffered by the presence of the liquid at moderate pressures. The resultant Ca(OH)2 generated by this process reacts with silicates to form a variety of alteration products, such as epidote, whereas the vapor produces acid-alteration of rocks through which it ascends.

  15. Molecular simulation of the shear viscosity and the self-diffusion coefficient of mercury along the vapor-liquid coexistence curve

    NASA Astrophysics Data System (ADS)

    Raabe, Gabriele; Todd, B. D.; Sadus, Richard J.

    2005-07-01

    In earlier work [G. Raabe and R. J. Sadus, J. Chem. Phys. 119, 6691 (2003)] we reported that the combination of an accurate two-body ab initio potential with an empirically determined multibody contribution enables the prediction of the phase coexistence properties, the heats of vaporization, and the pair distribution functions of mercury with reasonable accuracy. In this work we present molecular dynamics simulation results for the shear viscosity and self-diffusion coefficient of mercury along the vapor-liquid coexistence curve using our empirical effective potential. The comparison with experiment and calculations based on a modified Enskog theory shows that our multibody contribution yields reliable predictions of the self-diffusion coefficient at all densities. Good results are also obtained for the shear viscosity of mercury at low to moderate densities. Increasing deviations between the simulation and experimental viscosity data at high densities suggest that not only a temperature-dependent but also a density-dependent multibody contribution is necessary to account for the effect of intermolecular interactions in liquid metals. An analysis of our simulation data near the critical point yields a critical exponent of ? =0.39, which is identical to the value obtained from the analysis of the experimental saturation densities.

  16. Rapid Analysis of Isobaric Exogenous Metabolites by Differential Mobility Spectrometry Mass Spectrometry

    SciTech Connect

    Parson, Whitney B; Schneider, Bradley B; Kertesz, Vilmos; Corr, Jay; Covey, Thomas R.; Van Berkel, Gary J

    2011-01-01

    The direct separation of isobaric glucuronide metabolites from propranolol dosed tissue extracts by differential mobility spectrometry mass spectrometry (DMS-MS) with the use of a polar gas-phase chemical modifier was demonstrated. The DMS gas-phase separation was able to resolve the isobaric metabolites with separation times on the order of ms instead of mins to hrs typically required when using pre-ionization chromatographic separation methods. Direct separation of isobaric metabolites from the complex tissue extract was validated using standards as well as implementing an HPLC separation prior to the DMS-MS analysis to pre-separate the species of interest. The ability to separate isobaric exogenous metabolites directly from a complex tissue extract is expected to facilitate the drug development process by increasing analytical throughput without the requirement for pre-ionization cleanup or separation strategies.

  17. 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

    SciTech Connect

    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.

  18. Vapor-liquid-solid epitaxial growth of Si1-xGex alloy nanowires: Composition dependence on precursor reactivity and morphology control for vertical forests

    NASA Astrophysics Data System (ADS)

    Choi, S. G.; Manandhar, P.; Picraux, S. T.

    2015-07-01

    Growth of high-density group IV alloy nanowire forests is critical for exploiting their unique functionalities in many applications. Here, the compositional dependence on precursor reactivity and optimized conditions for vertical growth are studied for Si1-xGex alloy nanowires grown by the vapor-liquid-solid method. The nanowire composition versus gas partial-pressure ratio for germane-silane and germane-disilane precursor combinations is obtained at 350 C over a wide composition range (0.05 ? x ? 0.98) and a generalized model to predict composition for alloy nanowires is developed based on the relative precursor partial pressures and reactivity ratio. In combination with germane, silane provides more precise compositional control at high Ge concentrations (x > 0.7), whereas disilane greatly increases the Si concentration for a given gas ratio and enables more precise alloy compositional control at small Ge concentrations (x < 0.3). Vertically oriented, non-kinking nanowire forest growth on Si (111) substrates is then discussed for silane/germane over a wide range of compositions, with temperature and precursor partial pressure optimized by monitoring the nanowire growth front using in-situ optical reflectance. For high Ge compositions (x ? 0.9), a "two-step" growth approach with nucleation at higher temperatures results in nanowires with high-density and uniform vertical orientation. With increasing Si content (x ? 0.8), the optimal growth window is shifted to higher temperatures, which minimizes nanowire kinking morphologies. For Si-rich Si1-xGex alloys (x ? 0.25), vertical nanowire growth is enhanced by single-step, higher-temperature growth at reduced pressures.

  19. The non-Newtonian heat and mass transport of He 2 in porous media used for vapor-liquid phase separation. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Yuan, S. W. K.

    1985-01-01

    This investigation of vapor-liquid phase separation (VLPS) of He 2 is related to long-term storage of cryogenic liquid. The VLPS system utilizes porous plugs in order to generate thermomechanical (thermo-osmotic) force which in turn prevents liquid from flowing out of the cryo-vessel (e.g., Infrared Astronomical Satellite). An apparatus was built and VLPS data were collected for a 2 and a 10 micrometer sintered stainless steel plug and a 5 to 15 micrometer sintered bronze plug. The VLPS data obtained at high temperature were in the nonlinear turbulent regime. At low temperature, the Stokes regime was approached. A turbulent flow model was developed, which provides a phenomenological description of the VLPS data. According to the model, most of the phase separation data are in the turbulent regime. The model is based on concepts of the Gorter-Mellink transport involving the mutual friction known from the zero net mass flow (ZNMF) studies. The latter had to be modified to obtain agreement with the present experimental VLPS evidence. In contrast to the well-known ZNMF mode, the VLPS results require a geometry dependent constant (Gorter-Mellink constant). A theoretical interpretation of the phenomenological equation for the VLPS data obtained, is based on modelling of the dynamics of quantized vortices proposed by Vinen. In extending Vinen's model to the VLPS transport of He 2 in porous media, a correlation between the K*(GM) and K(p) was obtained which permits an interpretation of the present findings. As K(p) is crucial, various methods were introduced to measure the permeability of the porous media at low temperatures. Good agreement was found between the room temperature and the low temperature K(p)-value of the plugs.

  20. Encoding abrupt and uniform dopant profiles in vapor-liquid-solid nanowires by suppressing the reservoir effect of the liquid catalyst.

    PubMed

    Christesen, Joseph D; Pinion, Christopher W; Zhang, Xing; McBride, James R; Cahoon, James F

    2014-11-25

    Semiconductor nanowires (NWs) are often synthesized by the vapor-liquid-solid (VLS) mechanism, a process in which a liquid droplet-supplied with precursors in the vapor phase-catalyzes the growth of a solid, crystalline NW. By changing the supply of precursors, the NW composition can be altered as it grows to create axial heterostructures, which are applicable to a range of technologies. The abruptness of the heterojunction is mediated by the liquid catalyst, which can act as a reservoir of material and impose a lower limit on the junction width. Here, we demonstrate that this "reservoir effect" is not a fundamental limitation and can be suppressed by selection of specific VLS reaction conditions. For Au-catalyzed Si NWs doped with P, we evaluate dopant profiles under a variety of synthetic conditions using a combination of elemental imaging with energy-dispersive X-ray spectroscopy and dopant-dependent wet-chemical etching. We observe a diameter-dependent reservoir effect under most conditions. However, at sufficiently slow NW growth rates (?250 nm/min) and low reactor pressures (?40 Torr), the dopant profiles are diameter independent and radially uniform with abrupt, sub-10 nm axial transitions. A kinetic model of NW doping, including the microscopic processes of (1) P incorporation into the liquid catalyst, (2) P evaporation from the catalyst, and (3) P crystallization in the Si NW, quantitatively explains the results and shows that suppression of the reservoir effect can be achieved when P evaporation is much faster than P crystallization. We expect similar reaction conditions can be developed for other NW systems and will facilitate the development of NW-based technologies that require uniform and abrupt heterostructures. PMID:25363730

  1. Adapting SAFT-γ perturbation theory to site-based molecular dynamics simulation. II. Confined fluids and vapor-liquid interfaces

    SciTech Connect

    Ghobadi, Ahmadreza F.; Elliott, J. Richard

    2014-07-14

    In this work, a new classical density functional theory is developed for group-contribution equations of state (EOS). Details of implementation are demonstrated for the recently-developed SAFT-γ WCA EOS and selective applications are studied for confined fluids and vapor-liquid interfaces. The acronym WCA (Weeks-Chandler-Andersen) refers to the characterization of the reference part of the third-order thermodynamic perturbation theory applied in formulating the EOS. SAFT-γ refers to the particular form of “statistical associating fluid theory” that is applied to the fused-sphere, heteronuclear, united-atom molecular models of interest. For the monomer term, the modified fundamental measure theory is extended to WCA-spheres. A new chain functional is also introduced for fused and soft heteronuclear chains. The attractive interactions are taken into account by considering the structure of the fluid, thus elevating the theory beyond the mean field approximation. The fluctuations of energy are also included via a non-local third-order perturbation theory. The theory includes resolution of the density profiles of individual groups such as CH{sub 2} and CH{sub 3} and satisfies stoichiometric constraints for the density profiles. New molecular simulations are conducted to demonstrate the accuracy of each Helmholtz free energy contribution in reproducing the microstructure of inhomogeneous systems at the united-atom level of coarse graining. At each stage, comparisons are made to assess where the present theory stands relative to the current state of the art for studying inhomogeneous fluids. Overall, it is shown that the characteristic features of real molecular fluids are captured both qualitatively and quantitatively. For example, the average pore density deviates ∼2% from simulation data for attractive pentadecane in a 2-nm slit pore. Another example is the surface tension of ethane/heptane mixture, which deviates ∼1% from simulation data while the theory reproduces the excess accumulation of ethane at the interface.

  2. Vapor-liquid-solid epitaxial growth of Si1-xGex alloy nanowires. Composition dependence on precursor reactivity and morphology control for vertical forests

    DOE PAGESBeta

    Choi, S. G.; Manandhar, P.; Picraux, S. T.

    2015-07-07

    The growth of high-density group IV alloy nanowire forests is critical for exploiting their unique functionalities in many applications. Here, the compositional dependence on precursor reactivity and optimized conditions for vertical growth are studied for Si1- x Ge x alloy nanowires grown by the vapor-liquid-solid method. The nanowire composition versus gas partial-pressure ratio for germane-silane and germane-disilane precursor combinations is obtained at 350°C over a wide composition range (0.05 ≤ x ≤ 0.98) and a generalized model to predict composition for alloy nanowires is developed based on the relative precursor partial pressures and reactivity ratio. In combination with germane, silanemore » provides more precise compositional control at high Ge concentrations (x > 0.7), whereas disilane greatly increases the Si concentration for a given gas ratio and enables more precise alloy compositional control at small Ge concentrations (x < 0.3). Vertically oriented, non-kinking nanowire forest growth on Si (111) substrates is then discussed for silane/germane over a wide range of compositions, with temperature and precursor partial pressure optimized by monitoring the nanowire growth front using in-situ optical reflectance. For high Ge compositions (x ≈ 0.9), a “two-step” growth approach with nucleation at higher temperatures results in nanowires with high-density and uniform vertical orientation. Furthermore, increasing Si content (x ≈ 0.8), the optimal growth window is shifted to higher temperatures, which minimizes nanowire kinking morphologies. For Si-rich Si1- x Ge x alloys (x ≈ 0.25), vertical nanowire growth is enhanced by single-step, higher-temperature growth at reduced pressures.« less

  3. Measurement of vapor/liquid distributions in a binary-component fuel spray using laser imaging of droplet scattering and vapor absorption

    NASA Astrophysics Data System (ADS)

    Li, Shiyan; Zhang, Yuyin; Wu, Shenqi; Xu, Bin

    2014-08-01

    Fuel volatility has a great effect on its evaporation processes and the mixture formation and thus combustion and emissions formation processes in internal combustion engines. To date, however, instead of the actual gasoline or diesel fuel, many researchers have been using single-component fuel in their studies, because the composition of the former is too complicated to understand the real physics behind the evaporation and combustion characteristics. Several research groups have reported their results on droplets evaporation in a spray of multi-component fuel, carried out both numerically and experimentally. However, there are plenty of difficulties in quantitative determination of vapor concentration and droplet distributions of each component in a multicomponent fuel spray. In this study, to determine the vapor phase concentration and droplet distributions in an evaporating binary component fuel spray, a laser diagnostics based on laser extinction by droplet scattering and vapor absorption was developed. In practice, measurements of the vapor concentration distributions of the lower (n-tridencane) and higher (n-octane) volatility components in the binary component fuel sprays have been carried out at ambient temperatures of 473K and 573K, by substituting p-xylene for noctane or α-methylnaphthalene for n-tridecane. p-Xylene and α-methylnaphthalene were selected as the substitutes is because they have strong absorption band near 266nm and transparent near 532nm and, their thermo-physical properties are similar to those of the original component. As a demonstration experiment, vapor/liquid distribution of the lower boiling point (LBP) and higher boiling point (HBP) components in the binary component fuel spray have been obtained.

  4. Finite-size scaling study of the vapor-liquid critical properties of confined fluids: Crossover from three dimensions to two dimensions

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Panagiotopoulos, Athanassios Z.; Debenedetti, Pablo G.

    2010-04-01

    We perform histogram-reweighting grand canonical Monte Carlo simulations of the Lennard-Jones fluid confined between two parallel hard walls and determine the vapor-liquid critical and coexistence properties in the range of ? ?H?6? and 10??Lx,Ly?28?, where H is the wall separation, Lx=Ly is the system size and ? is the characteristic length. By matching the probability distribution of the ordering operator, P(M ), to the three-dimensional (3D) and two-dimensional (2D) Ising universality classes according to the mixed-field finite-size scaling approach, we establish a "phase diagram" in the (H,L) plane, showing the boundary between four types of behavior: 3D, quasi-3D, quasi-2D, and 2D. In order to facilitate 2D critical point calculation, we present a four-parameter analytical expression for the 2D Ising universal distribution. We show that the infinite-system-size critical points obtained by extrapolation from the apparent 3D and 2D critical points have only minor differences with each other. In agreement with recent reports in the literature [Jana et al., J. Chem. Phys. 130, 214707 (2009)], we find departure from linearity in the relationship between critical temperature and inverse wall separation, as well as nonmonotonic dependence of the critical density and the liquid density at coexistence upon wall separation. Additional studies of the ST2 model of water show similar behavior, which suggests that these are quite general properties of confined fluids.

  5. Generation of multiple reporter ions from a single isobaric reagent increases multiplexing capacity for quantitative proteomics.

    PubMed

    Braun, Craig R; Bird, Gregory H; Whr, Martin; Erickson, Brian K; Rad, Ramin; Walensky, Loren D; Gygi, Steven P; Haas, Wilhelm

    2015-10-01

    Isobaric labeling strategies for mass spectrometry-based proteomics enable multiplexed simultaneous quantification of samples and therefore substantially increase the sample throughput in proteomics. However, despite these benefits, current limits to multiplexing capacity are prohibitive for large sample sizes and impose limitations on experimental design. Here, we introduce a novel mechanism for increasing the multiplexing density of isobaric reagents. We present Combinatorial Isobaric Mass Tags (CMTs), an isobaric labeling architecture with the unique ability to generate multiple series of reporter ions simultaneously. We demonstrate that utilization of multiple reporter ion series improves multiplexing capacity of CMT with respect to a commercially available isobaric labeling reagent with preserved quantitative accuracy and depth of coverage in complex mixtures. We provide a blueprint for the realization of 16-plex reagents with 1 Da spacing between reporter ions and up to 28-plex at 6 mDa spacing using only 5 heavy isotopes per reagent. We anticipate that this improvement in multiplexing capacity will further advance the application of quantitative proteomics, particularly in high-throughput screening assays. PMID:26308379

  6. 4C modeling of the supercritical helium loop HELIOS in isobaric configuration

    NASA Astrophysics Data System (ADS)

    Guelfi, F.; Bonifetto, R.; Hoa, C.; Savoldi, L.; Zanino, R.

    2014-11-01

    Superconducting magnets for tokamak fusion reactors are subject to highly variable loads due to the intrinsically pulsed operation of the machine. The refrigerator should, on the contrary, work under conditions as stable as possible and should be sized based on the averaged loads. In this paper, the cryogenic circuit module of the 4C (Cryogenic Circuit Conductor and Coil) code is used to analyze the isobaric configuration of the HELIOS (HElium Loop for hIgh lOads Smoothing) facility at CEA Grenoble, France. The 4C model is validated against experimental data from the isobaric HELIOS configuration: the computed evolution of temperature, pressure and mass flow rate at different circuit locations shows a good agreement with the measurements for two different pulsed heat load scenarios, with and without regulation. The advantages of the (somewhat more complicated) isobaric configuration vs. the isochoric configuration in terms of heat load smoothing are highlighted. 4C simulations are used to propose a new HELIOS layout with helium charging and discharging lines located in such a way that the HELIOS performance in the isobaric configuration is optimized. The paper confirms the importance of the isobaric configuration for a tokamak cryogenic circuit, as well as the accuracy of 4C in modeling the HELIOS operation, even in the presence of complex regulation.

  7. An experimental apparatus proposed for efficient removal of isobaric contaminants in negative ion beams

    NASA Astrophysics Data System (ADS)

    Alton, G. D.; Zhang, Y.

    2008-09-01

    Isobaric contaminants are often problematical in accelerated negative ion beams for research at certain radioactive ion beam (RIB) and accelerator mass spectrometry (AMS) facilities since their presence in low-intensity rare isotopic beams seriously compromise experimental results. This article describes a non-resonant, laser-based photo-detachment apparatus for use at these facilities, which, according to calculations efficiently removes isobaric contaminants from these beams. The advantage of the system for isobaric contaminant removal over other systems proposed to date lies in its ability to efficiently capture easily transportable energetic negative ion beams with low, intermediate or high energy spreads by a superconducting solenoid magnetic field. The ability to change the diameter of captured beams by adjusting the magnetic field strength permits optimum control of the radial overlap of the laser/negative ion beam profiles over an extended interaction region under high vacuum conditions without retarding optical affect, collision-cooling or capture losses.

  8. Thermodynamics of Si(OH)4 in the vapor phase of water: Henrys and vapor-liquid distribution constants, fugacity and cross virial coefficients

    NASA Astrophysics Data System (ADS)

    Plyasunov, Andrey V.

    2012-01-01

    The fugacity coefficients of Si(OH)4 are evaluated from solubilities of solid phases of SiO2 in the vapor phase of water. The virial equation of state, truncated at the third virial coefficient, is employed to describe the fugacity coefficients of Si(OH)4. The temperature dependencies of the second, B12, and the third, C112, cross virial coefficients for H2O-Si(OH)4 interactions are approximated by empirical relations. It is found that silica-water interactions in the vapor phase are significantly more non-ideal compared to water-water interactions. Knowledge of B12 and C112 allows calculation of solubilities of quartz (Q) and amorphous silica (AS) in steam up to the density of 200 kg m-3 in satisfactory agreement with available data, and should provide reasonable solubility values at temperatures where no experimental results exist. The calculated values of the solubility of Q and AS in saturated vapor up to the critical temperature of water, Tc, are tabulated. The partial molar properties of dilute solutes close to the critical point of water are governed by the Krichevskii parameter, the value of which for Si(OH)4 is evaluated from available data (mainly vapor-liquid distribution constants for silica) to be equal to -187 10 MPa. The knowledge of the thermodynamic properties of Si(OH)4 in the ideal gas state and in the state of the standard solution in liquid water allows calculating Henrys constant, kH, for Si(OH)4 up to 623.15 K at water saturation pressure P1?. The theoretically-based equation, containing the Krichevskii parameter, allows extrapolating kH values all the way toward the critical temperature of water. This, in turn, makes possible calculation of the solubility of quartz and amorphous silica in liquid water at P1? at all temperatures up to Tc. The presented results should be useful for modeling solid-liquid-vapor, solid-vapor and liquid-vapor equilibria in the H2O-SiO2 system at steam densities up to 200 kg m-3.

  9. Probing Temperature from Intermediate Mass Fragment by Isobaric Yield Ratio in Heavy-Ion Collisions

    NASA Astrophysics Data System (ADS)

    Yu, Mian; Wei, Hui-Ling; Ma, Chun-Wang

    2015-12-01

    A probe to extract the temperature (TIYR) from intermediate-mass fragment has been proposed using the isobaric yield ratio (IYR) difference based on the modified Fisher model. By analyzing the isobaric cross section in the measured 140A MeV 40,48Ca+9Be reactions, the TIYR can well fit the IYR difference for the large mass fragments. Because of the fragments are produced in different colliding regions, it is also suggested to select the fragments according to different mechanisms when using TIYR. Supported by Program for Science & Technology Innovation Talents in Universities of Henan Province under Grant No. 13HASTIT046

  10. Vapor-liquid equilibria for hydrogen fluoride + difluoromethane, + 1,1,1,2-tetrafluoroethane, and + 1-chloro-1,2,2,2-tetrafluoromethane at 283.3 and 298.2 K

    SciTech Connect

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

    1996-01-01

    The production of refrigerants involves the separation of multicomponent mixtures containing hydrogen fluoride, hydrogen chloride, and various chlorinated and fluorinated hydrocarbons. Therefore, it is essential to known the phase behavior of these mixtures. Isothermal vapor-liquid equilibria for hydrogen fluoride (HF) + difluoromethane (HFC-32), HF + 1,1,1,2-tetrafluoroethane (HFC-134a), and HF + 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124) were measured by the P-T-x method at 283.3 and 298.2 K. Vapor compositions were calculated from these results. Among these systems, the HF + HFC-134a and HF + HCFC-124 systems exhibit minimum boiling azeotropes at both temperatures.

  11. High-Throughput Quantitative Proteomics Enabled by Mass Defect-Based 12-Plex DiLeu Isobaric Tags.

    PubMed

    Frost, Dustin C; Li, Lingjun

    2016-01-01

    Isobaric labeling has become a popular technique for high-throughput, mass spectrometry (MS)-based relative quantification of peptides and proteins. However, widespread use of the approach for large-scale proteomics applications has been limited by the high cost of commercial isobaric tags. To address this, we have developed our own N,N-dimethyl leucine (DiLeu) multiplex isobaric tags as a cost-effective alternative that can be synthesized with ease using readily available isotopic reagents. When paired with high-resolution tandem mass (MS (n) ) acquisition, mass defect-based DiLeu isobaric tags allow relative quantification of up to twelve samples in a single liquid chromatography (LC)-MS(2) experiment. Herein, we present detailed methods for synthesis of 12-plex DiLeu isobaric tags, labeling of complex protein digest samples, analysis by high-resolution nanoLC-MS (n) , and processing of acquired data. PMID:26867744

  12. Residue Coulomb Interaction Among Isobars and Its Influence in Symmetry Energy of Neutron-Rich Fragment

    NASA Astrophysics Data System (ADS)

    Ma, Chun-Wang; Wang, Shan-Shan; Zhang, Yan-Li; Zhao, Yi-Long; Wei, Hui-Ling

    2015-09-01

    The residue Coulomb interaction (RCI), which affects the result of symmetry-energy coefficient of neutron-rich nucleus in isobaric yield ratio (IYR) method, is difficult to be determined. Four RCI approximations are investigated: (i) The M1-RCI adopting the ac/T (the ratio of Coulomb energy coefficient to temperature) determined from the IYR of mirror-nucleus fragments; (ii) The M2-RCI by fitting the difference between IYRs; (iii) The M3-RCI adopting the standard Coulomb energy at a temperature T = 2 MeV; and (iv) Neglecting the RCI among isobars. The M1-, M2- and M3-RCI are no larger than 0.4. In particular, the M2-RCI is very close to zero. The effects of RCI in asym/T of fragment are also studied. The M1- and M4-asym/T are found to be the lower and upper limitations of asym/T, respectively. The M2-asym/T overlaps the M4-asym/T, which indicates that the M2-RCI is negligible in the IYR method, and the RCI among the three isobars can be neglected. The relative consistent low values of M3-asym/T (7.5 2.5) are found in very neutron-rich isobars. Supported by the Program for Science & Technology Innovation Talents in Universities of Henan Province (13HASTIT046), and Young Teacher Project in Henan Normal University (HNU), China

  13. Formation of isobaric discontinuities in large-scale flute drift motions

    SciTech Connect

    Dreizin, Y.A.; Sokolov, E.P.

    1982-05-01

    The flute drift motion in MHD-stable plasma configurations with closed lines of force is analyzed qualitatively. The onset of this motion can lead to isobaric discontinuities in experimentally observable quantitites: the electric potential and the electron and ion densities and temperatures.

  14. Tandem mass spectrometric analysis of a mixture of isobars using the survival yield technique.

    PubMed

    Memboeuf, Antony; Jullien, Laure; Lartia, Rémy; Brasme, Bernard; Gimbert, Yves

    2011-10-01

    Collision induced dissociation tandem mass spectrometry experiments were performed to unequivocally separate compounds from an isobaric mixture of two products. The Survival Yield curve was obtained and is shown to consist in a linear combination of the curves corresponding to the two components separately. For such a mixture, a plateau appears on the diagram in lieu of the continuous decrease expected allowing for the structural study of the two components separately. The width of the plateau critically relates to the fragmentation parameters of the two molecular ions, which need to be sufficiently different structurally for the plateau to be observed. However, at constant fragmentation parameters, we have observed the width significantly increases at large m/z. This makes the separation more and more efficient as isobars have larger m/z and the technique complementary to those applicable at low m/z only. We have observed that the vertical position of the plateau relates linearly to the relative concentration of the two compounds that may be useful for quantification. Repeatability was estimated at 2% on a quadrupole ion trap. An advantage of using survival yield curves only, is that a priori knowledge of the respective fragmentation patterns of the two isobars becomes unnecessary. Consequently, similar performances are obtained if fragments are isobaric, which is also demonstrated in our study. The critical case of reverse peptides, at low m/z and similar fragmentation parameters, is also presented as a limitation of the method. PMID:21952888

  15. High-Resolution Enabled 12-Plex DiLeu Isobaric Tags for Quantitative Proteomics

    PubMed Central

    2015-01-01

    Multiplex isobaric tags (e.g., tandem mass tags (TMT) and isobaric tags for relative and absolute quantification (iTRAQ)) are a valuable tool for high-throughput mass spectrometry based quantitative proteomics. We have developed our own multiplex isobaric tags, DiLeu, that feature quantitative performance on par with commercial offerings but can be readily synthesized in-house as a cost-effective alternative. In this work, we achieve a 3-fold increase in the multiplexing capacity of the DiLeu reagent without increasing structural complexity by exploiting mass defects that arise from selective incorporation of 13C, 15N, and 2H stable isotopes in the reporter group. The inclusion of eight new reporter isotopologues that differ in mass from the existing four reporters by intervals of 6 mDa yields a 12-plex isobaric set that preserves the synthetic simplicity and quantitative performance of the original implementation. We show that the new reporter variants can be baseline-resolved in high-resolution higher-energy C-trap dissociation (HCD) spectra, and we demonstrate accurate 12-plex quantitation of a DiLeu-labeled Saccharomyces cerevisiae lysate digest via high-resolution nano liquid chromatographytandem mass spectrometry (nanoLCMS2) analysis on an Orbitrap Elite mass spectrometer. PMID:25405479

  16. Study of Isobaric Interference in Quantification of Citrulline by Parallel Fragmentation Monitoring

    PubMed Central

    Ng, Eddy Wing Yin; Lam, Hugh Simon; Ng, Pak Cheung; Poon, Terence Chuen Wai

    2014-01-01

    Parallel Fragmentation Monitoring (PFM), which is an analogue of selected reaction monitoring (SRM), is a recently developed method for quantification of small molecules by MALDI-TOF/TOF mass spectrometry (MS). It is well known that isobaric interference substances can be occasionally present in complex biological samples, and affect the accuracy of measurement by SRM. Unfortunately, by design it is not possible to assess whether isobaric interference happens in a SRM analysis. In contrast, the unique design of PFM should allow quick inspection for isobaric interference and subsequent correction. In this study, using arginine as an example, interference effect of isobaric structural analogs on the quantification of citrulline by PFM was evaluated. Our results showed that the presence of arginine affected the measured concentrations of citrulline standard solutions in a concentration dependent manner. Such interference could be observed readily in the MS/MS spectra, and contributed by [arginine+HNH3]+ fragment ion. Because of having highly similar mass, 13C-isotope of [arginine+HNH3]+ fragment ion overlapped with monoisotope of [citrulline+HNH3]+ fragment ion, which was used as the report ion for quantification. However, such interference could be mathematically eliminated or minimized through estimation of the signal intensity of the 13C-isotopic peak of [arginine+HNH3]+ from the intensity of the corresponding monoisotopic peak according to isotope distribution of elements. Furthermore, the presence of interfering fragment ions could be avoided by optimizing MALDI ionization condition. In conclusion, isobaric interference can happen in PFM, but can be easily identified in the mass spectra and eliminated (minimized) with simple methods.

  17. Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption

    NASA Astrophysics Data System (ADS)

    Hhener, Patrick; Yu, Xianjing

    2012-03-01

    Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from - 0.13 0.04 (benzene) to - 0.52 0.19 (trichloroethene at 5-15 C). Hydrogen enrichment factors for sorption of 14 different compounds were between - 2.4 and - 9.2. For perdeuterated hydrocarbons the predicted enrichment factors ranged from - 19 5.4 (benzene) to - 64 30 (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for 13C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants.

  18. PVT measurements on tetrafluoroethane (R134a) along the vapor-liquid equilibrium boundary between 288 and 373 K and in the liquid state from the triple point to 265 K

    SciTech Connect

    Blanke, W.; Klingenberg, G.; Weiss, R.

    1995-09-01

    For the investigations of the gas-liquid phase equilibria, a new apparatus has been developed capable of simultaneously determining the pressure and the liquid and vapor densities using Archmiedes` principle. The relative measurement uncertainties of the liquid and vapor densities of R134a (purity, 99.999%) at 313 K are 2 X 10 {sup -4} and 7 X 10{sup -4}, respectively (95% confidence level). For the measurements in the liquid region along nine quasi-isochores at pressures up to 5MPa, an isochoric apparatus was used. The relative measurement uncertainty of pv/(RT) is less than 1X10{sup -3}. In addition to the investigation of the (p,v,T) properties, the temperature and pressure at the triple point and the vapor pressure between the triple point and 265 K were measured. On the basis of these data, a vapor pressure correlation has been developed that reproduces the measured vapor pressures within the uncertainty of measurement. The results of our measurements of other research groups.

  19. Isobars of an ideal Bose gas within the grand canonical ensemble

    NASA Astrophysics Data System (ADS)

    Jeon, Imtak; Kim, Sang-Woo; Park, Jeong-Hyuck

    2011-08-01

    We investigate the isobar of an ideal Bose gas confined in a cubic box within the grand canonical ensemble for a large yet finite number of particles, N. After solving the equation of the spinodal curve, we derive precise formulas for the supercooling and the superheating temperatures that reveal an N-1/3 or N-1/4 power correction to the known Bose-Einstein condensation temperature in the thermodynamic limit. Numerical computations confirm the accuracy of our analytical approximation, and further show that the isobar zigzags on the temperature-volume plane if N?14393. In particular, for the Avogadros number of particles, the volume expands discretely about 105 times. Our results quantitatively agree with a previous study on the canonical ensemble within 0.1% error.

  20. Isobars of an ideal Bose gas within the grand canonical ensemble

    SciTech Connect

    Jeon, Imtak; Park, Jeong-Hyuck; Kim, Sang-Woo

    2011-08-15

    We investigate the isobar of an ideal Bose gas confined in a cubic box within the grand canonical ensemble for a large yet finite number of particles, N. After solving the equation of the spinodal curve, we derive precise formulas for the supercooling and the superheating temperatures that reveal an N{sup -1/3} or N{sup -1/4} power correction to the known Bose-Einstein condensation temperature in the thermodynamic limit. Numerical computations confirm the accuracy of our analytical approximation, and further show that the isobar zigzags on the temperature-volume plane if N{>=}14 393. In particular, for the Avogadro's number of particles, the volume expands discretely about 10{sup 5} times. Our results quantitatively agree with a previous study on the canonical ensemble within 0.1% error.

  1. Revalidation of the isobaric multiplet mass equation for the A =20 quintet

    NASA Astrophysics Data System (ADS)

    Glassman, B. E.; Prez-Loureiro, D.; Wrede, C.; Allen, J.; Bardayan, D. W.; Bennett, M. B.; Brown, B. A.; Chipps, K. A.; Febbraro, M.; Fry, C.; Hall, M. R.; Hall, O.; Liddick, S. N.; O'Malley, P.; Ong, W.; Pain, S. D.; Schwartz, S. B.; Shidling, P.; Sims, H.; Thompson, P.; Zhang, H.

    2015-10-01

    An unexpected breakdown of the isobaric multiplet mass equation in the A =20 ,T =2 quintet was recently reported, presenting a challenge to modern theories of nuclear structure. In the present work, the excitation energy of the lowest T =2 state in 20Na has been measured to be 6498.4 0 .2stat0 .4syst keV by using the superallowed 0+?0+ beta decay of 20Mg to access it and an array of high-purity germanium detectors to detect its ? -ray deexcitation. This value differs by 27 keV (1.9 standard deviations) from the recommended value of 6525 14 keV and is a factor of 28 more precise. The isobaric multiplet mass equation is shown to be revalidated when the new value is adopted.

  2. Phase Structure of the T-matrix and Multichannel Unitary Isobar Model

    NASA Astrophysics Data System (ADS)

    Razavi, S.; Nakayama, K.

    2015-04-01

    By exploiting the full phase structure of the meson-baryon coupled channels reaction amplitude-here including also the photon-baryon channel-an isobar model is constructed which fulfills automatically the unitarity and analyticity conditions of the S-matrix, in addition to gauge invariance in the case of photoproduction. In particular, it is shown that the unitarity of the (resonance) pole amplitude arises from the dressing mechanism inherent in the basic T-matrix equation, requiring no extra unitarity condition on the pole amplitude as is the case in earlier works on isobar models. As an example, the present model is applied in the description of the meson-nucleon reactions including the πN , ηN , σN , ρN and πΔ channels. The latter three account effectively for the ππN channel. FFE-COSY Grant No. 41788390.

  3. Isobar model analysis of {pi}{sup 0{eta}} photoproduction on protons

    SciTech Connect

    Fix, A.; Lee, A.; Kashevarov, V. L.; Ostrick, M.

    2010-09-15

    Photoproduction of {pi}{sup 0{eta}} on protons in the energy range from threshold to 1.4 GeV is discussed. The data for representative angular distributions recently obtained at MAMI C are analyzed using an isobar model. The isobars considered are {Delta}(1232) and S{sub 11}(1535) for {pi}{sup 0}p and {eta}p states, respectively. In accordance with the results of earlier works, the main features of the reaction are explained through the dominance of the D{sub 33} wave with a relatively small admixture of positive parity resonances. Comparison with recent experimental results for the photon beam asymmetry is carried out.

  4. Resonance ionization mass spectrometric study of the promethium/samarium isobaric pair

    SciTech Connect

    Shaw, R.W.; Young, J.P.; Smith, D.H.

    1988-01-01

    Samarium daughters are problematic in isotope ratio measurements of promethium because they are isobaric. Resonance ionization mass spectrometry was utilized to circumvent this problem. An ionization selectivity factor of at least 1000:1 has been measured for promethium over samarium at 584.6 nm. Resonance ionization spectra have been recorded for both elements over the 528-560 and 580-614 nm wavelength ranges.

  5. Densities, isobaric thermal expansion coefficients and isothermal compressibilities of linear alkylbenzene

    NASA Astrophysics Data System (ADS)

    Zhou, X.; Zhang, Q. M.; Liu, Q.; Zhang, Z. Y.; Ding, Y. Y.; Zhou, L.; Cao, J.

    2015-05-01

    We report the measurements of the densities of linear alkylbenzene at three temperatures over 4 to 23 C with pressures up to 10 MPa. The measurements have been analysed to yield the isobaric thermal expansion coefficients and, so far for the first time, isothermal compressibilities of linear alkylbenzene. Relevance of results for current generation (i.e., Daya Bay) and next generation (i.e. JUNO) large liquid scintillator neutrino detectors are discussed.

  6. Resonant scattering of isobaric [sup 19]Ne and [sup 19]F beams on an H target

    SciTech Connect

    Coszach, R.; Delbar, T.; Galster, W.; Leleux, P.; Licot, I.; Lienard, E.; Lipnik, P.; Michotte, C.; Ninane, A.; Vervier, J. ); Bain, C.R.; Davinson, T.; Page, R.D.; Shotter, A.C.; Woods, P.J. ); Baye, D.; Binon, F.; Descouvemont, P.; Duhamel, P.; Vanhorenbeeck, J.; Vincke, M. ); Decrock, P.; Huyse, M.; Van Duppen, P.; Vancraeynest, G. ); Barker, F.C. )

    1994-09-01

    Resonances in [sup 20]Na above the proton threshold have been studied by scattering radioactive [sup 19]Ne beams off thick polyethylene targets. The isobaric [sup 19]F+[ital p] scattering was also examined. The analysis of the data under different theoretical approaches is discussed. The energy, total width, spin, and parity of two resonances in [sup 20]Na were assigned unambiguously. The results are compared to those obtained by indirect methods.

  7. A regression model for calculating the boiling point isobars of tetrachloromethane-based binary solutions

    NASA Astrophysics Data System (ADS)

    Preobrazhenskii, M. P.; Rudakov, O. B.

    2016-01-01

    A regression model for calculating the boiling point isobars of tetrachloromethane-organic solvent binary homogeneous systems is proposed. The parameters of the model proposed were calculated for a series of solutions. The correlation between the nonadditivity parameter of the regression model and the hydrophobicity criterion of the organic solvent is established. The parameter value of the proposed model is shown to allow prediction of the potential formation of azeotropic mixtures of solvents with tetrachloromethane.

  8. Spinal Anesthesia for Knee Arthroscopy Using Isobaric Bupivacaine and Levobupivacaine: Anesthetic and Neuroophthalmological Assessment

    PubMed Central

    del-Rio-Vellosillo, Monica; Garcia-Medina, Jose Javier; Abengochea-Cotaina, Antonio; Barbera-Alacreu, Manuel

    2014-01-01

    Introduction. The aim of the study was to compare the sensory, motor, and neuroophthalmological effects of isobaric levobupivacaine and bupivacaine when intrathecally administered. Materials and Methods. A prospective, double-blind, randomized study with 60 ASA grade I-II patients aged 1865 years awaiting knee arthroscopy under spinal anesthesia. Patients received 12.5?mg of isobaric bupivacaine or levobupivacaine. Several features were recorded. Results. No significant intergroup differences were observed for ASA classification, time to micturate, demographic data, surgery duration, and patient/surgeon satisfaction. Similar hemodynamic parameters and sensory/motor blockade duration were found for both groups. There were no neuroophthalmological effects in either group. Sensory (P = 0.018) and motor blockade onset (P = 0.003) was faster in the bupivacaine group. T6 (T2T12) and T3 (T2T12) were the highest sensory block levels for the levobupivacaine and bupivacaine groups, respectively (P = 0.008). It took less time to regain maximum motor blockade in the bupivacaine group (P = 0.014), and the levobupivacaine group required use of analgesia earlier (P = 0.025). Conclusions. Isobaric bupivacaine and levobupivacaine are analogous and well-tolerated anesthetics for knee arthroscopy. However, for bupivacaine, sensory and motor blockade onset was faster, and greater sensory blockade with a longer postoperative painless period was achieved. PMID:24701571

  9. Discrimination of large maltooligosaccharides from isobaric dextran and pullulan using ion mobility mass spectrometry

    PubMed Central

    Rashid, Abdul M; Saalbach, Gerhard; Bornemann, Stephen

    2013-01-01

    RATIONALE Ion mobility mass spectrometry (IMMS) has previously been shown to resolve small isobaric oligosaccharides, but larger alpha-oligoglucans are also abundant in biology and are of industrial importance. If conformational differences between such isomers are retained in the gas phase, IMMS could be used to address questions in biology and industry. METHODS Negative mode electrospray ionization (ESI) travelling-wave IMMS was used to resolve large isobaric ?-glucan ions on the basis of their different gas-phase conformations. ?,?-Dicarboxy-terminated polystyrene was used to calibrate the instrument allowing the collision cross-sections (CCSs) of ions to be determined. RESULTS ?-1,4-Linked maltooligosaccharides with a degree of polymerisation of up to 35 could be discriminated from ?-1,6-linked dextran and ?-1,4/1,6-linked pullulan using IMMS. Fragmentation spectra of ions separated by IMMS could also distinguish isomers. Two conformational isomers of maltohexaose were resolvable by IMMS, likely reflecting extended and V6 helical conformations. IMMS was also able to identify a product within a mixture of maltooligosaccharides treated with the potential anti-tuberculosis drug target Mycobacterium tuberculosis GlgB branching enzyme. CONCLUSIONS Biological samples of complex isobaric oligosaccharides can be analysed using IMMS in the negative mode providing facile analyses and high sensitivity without the need for either derivatisation or chromatographic separation. 2013 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:24338967

  10. MTOF - A High Resolution Isobar Separator for Studies of Exotic Decays

    SciTech Connect

    Piechaczek, Andreas Paul Albert; Shchepunov, Viatcheslav A; Carter, H Kennon; Batchelder, Jon Charles; Zganjar, Edward F; Liddick, S. N.; Wollnik, Hermann; Hu, Y.; Griffith, Boyce O

    2009-01-01

    A compact high resolution, isobar separator, based on the Multi-pass-Time-of-Flight (MTOF) principle, is being built by the University Radioactive Ion Beam (UNIRIB) Consortium. MTOF as a spectroscopy tool will have the capability to suppress a contaminating nuclear species with a relative mass difference of M/dM > 40,000 by a factor of >> 100. MTOF has high transmission (20% - 50%), is not chemistry dependent and fast (2-10 milliseconds of analysis time per ion bunch of {approx} 10{sup 4} ions). The commissioning of and first experiments with MTOF will take place at the UNISOR mass separator of HRIBF, which acts as a low resolving power pre-separator. At this location, MTOF will provide isobarically pure samples of nuclei for decay spectroscopy produced in fusion-evaporation reactions with stable beams from the 25-MV tandem accelerator or by fission of UC. MTOF is capable of providing isobarically pure samples of all masses. Initially, our experimental program will focus on the region around 100Sn.

  11. Enhanced sample multiplexing for nitrotyrosine-modified proteins using combined precursor isotopic labeling and isobaric tagging.

    PubMed

    Robinson, Ren A S; Evans, Adam R

    2012-06-01

    Current strategies for identification and quantification of 3-nitrotyrosine (3NT) post-translationally modified proteins (PTM) generally rely on biotin/avidin enrichment. Quantitative approaches have been demonstrated which employ isotopic labeling or isobaric tagging in order to quantify differences in the relative abundances of 3NT-modified proteins in two or potentially eight samples, respectively. Here, we present a novel strategy which uses combined precursor isotopic labeling and isobaric tagging (cPILOT) to increase the multiplexing capability of quantifying 3NT-modified proteins to 12 or 16 samples using commercially available tandem mass tags (TMT) or isobaric tags for relative and absolute quantification (iTRAQ), respectively. This strategy employs "light" and "heavy" labeled acetyl groups to block both N-termini and lysine residues of tryptic peptides. Next, 3NT is reduced to 3-aminotyrosine (3AT) using sodium dithionite followed by derivatization of light and heavy labeled 3AT-peptides with either TMT or iTRAQ multiplex reagents. We demonstrate the proof-of-principle utility of cPILOT with in vitro nitrated bovine serum albumin (BSA) and mouse splenic proteins using TMT(0), TMT(6), and iTRAQ(8) reagents and discuss limitations of the strategy. PMID:22509719

  12. Coupled-channel Treatment of Isobaric Analog Resonances in (p,p?) Capture Processes

    NASA Astrophysics Data System (ADS)

    Thompson, I. J.; Arbanas, G.

    2014-04-01

    With the advent of nuclear reactions on unstable isotopes, there has been a renewed interest in using isobaric analogue resonances (IAR) as a tool for probing the nuclear structure. The position and width of isobaric analogue resonances in nucleon-nucleus scattering are accurate and detailed indicators of the positions of resonances and bound states with good single-particle characters. We report on implementation within our coupled-channels code FRESCO of the charge-exchange interaction term that transforms an incident proton into a neutron. Isobaric analog resonances are seen as peaks in ?-ray spectrum when the proton is transformed into a neutron at an energy near a neutron bound state. The Lane coupled-channels formalism was extended to follow the non-orthogonality of this neutron channel with that configuration of an inelastic outgoing proton, and the target being left in a particle-hole excited state. This is tested for 208Pb, for which good (p,p'?) coincidence data exists.

  13. Coupled-channel treatment of Isobaric Analog Resonances in (p,p') Capture Processes

    SciTech Connect

    Thompson, I J; Arbanas, Goran

    2013-01-01

    With the advent of nuclear reactions on unstable isotopes, there has been a renewed interest in using isobaric analogue resonances (IAR) as a tool for probing the nuclear structure. The position and width of isobaric analogue resonances in nucleon-nucleus scattering are accurate and detailed indicators of the positions of resonances and bound states with good single-particle characters. We report on implementation within our coupled-channels code FRESCO of the charge-exchange interaction term that transforms an incident proton into a neutron. Isobaric analog resonances are seen as peaks in gamma-ray spectrum when the proton is transformed into a neutron at an energy near a neutron bound state. The Lane coupled-channels formalism was extended to follow the nonorthogonality of this neutron channel with that configuration of an inelastic outgoing proton, and the target being left in a particle-hole excited state. This is tested for 208Pb, for which good (p,p g)

  14. Multicomponent vapor-liquid equilibria measurements for the development of an extractive distillation process for the processing of gas issuing from a CO/sub 2/ enhanced oil recovery project

    SciTech Connect

    Hong, J.H.; Kobayashi, R.

    1987-02-01

    This paper provides vapor-liquid equilibria data for the design of the upper section of the all-important column treating the stabilized feed gas from CO/sub 2/ enhanced oil recovery (EOR) projects. Again, the extractive agent is represented by n-pentane. The simulated feed gas containing the methane, liquified petroleum gas (LPG) components, and H/sub 2/S is added to n-pentane to form quasi-binary mixtures. A comparison of the K values obtained by the addition of methane to an otherwise similar methane-free gas shows that the effect of methane on the K values of the other constituents becomes increasingly pronounced as the pressure increases.

  15. Vapor-liquid equilibria for the systems composed of 1-chloro-1,1-difluoroethane, 1,1-dichloro-1-fluoroethane, and 1,1,1-trichloroethane at 50.1 C

    SciTech Connect

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

    1996-03-01

    Isothermal vapor-liquid equilibria for the three binary systems 1-chloro-1,1-difluoroethane + 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane + 1,1,1-trichloroethane, and 1,1-dichloro-1-fluoroethane + 1,1,1-trichloroethane and the ternary system 1-chloro-1,1-difluoromethane + 1,1-dichloro-1-fluoroethane + 1,1,1-trichloroethane have been measured at 50.1 C. The experimental data for the binary systems are correlated with the Peng-Robinson equation of state, and the relevant parameters are presented. The predicted results for the ternary system were found to be in good agreement with the experimental data.

  16. Relative protein quantification by isobaric SILAC with immonium ion splitting (ISIS).

    PubMed

    Colzani, Mara; Schütz, Frédéric; Potts, Alexandra; Waridel, Patrice; Quadroni, Manfredo

    2008-05-01

    Metabolic labeling techniques have recently become popular tools for the quantitative profiling of proteomes. Classical stable isotope labeling with amino acids in cell cultures (SILAC) uses pairs of heavy/light isotopic forms of amino acids to introduce predictable mass differences in protein samples to be compared. After proteolysis, pairs of cognate precursor peptides can be correlated, and their intensities can be used for mass spectrometry-based relative protein quantification. We present an alternative SILAC approach by which two cell cultures are grown in media containing isobaric forms of amino acids, labeled either with 13C on the carbonyl (C-1) carbon or 15N on backbone nitrogen. Labeled peptides from both samples have the same nominal mass and nearly identical MS/MS spectra but generate upon fragmentation distinct immonium ions separated by 1 amu. When labeled protein samples are mixed, the intensities of these immonium ions can be used for the relative quantification of the parent proteins. We validated the labeling of cellular proteins with valine, isoleucine, and leucine with coverage of 97% of all tryptic peptides. We improved the sensitivity for the detection of the quantification ions on a pulsing instrument by using a specific fast scan event. The analysis of a protein mixture with a known heavy/light ratio showed reliable quantification. Finally the application of the technique to the analysis of two melanoma cell lines yielded quantitative data consistent with those obtained by a classical two-dimensional DIGE analysis of the same samples. Our method combines the features of the SILAC technique with the advantages of isobaric labeling schemes like iTRAQ. We discuss advantages and disadvantages of isobaric SILAC with immonium ion splitting as well as possible ways to improve it. PMID:18165257

  17. Three-pion exchange nucleon-nucleon potentials with virtual ? -isobar excitation

    NASA Astrophysics Data System (ADS)

    Kaiser, N.

    2015-08-01

    The nucleon-nucleon interaction arising from the exchange of three pions and the excitation of ? (1232 ) isobars in intermediate states is studied. Approximating the ? propagator by the inverse ? N mass-splitting, analytical expressions are derived for the spectral functions of the isoscalar and isovector central, spin-spin, and tensor N N potentials in momentum-space. A translation of the spectral functions into coordinate-space potentials reveals that the main effect of these specific exchange and excitation mechanisms is a repulsive isoscalar central N N potential.

  18. Isobaric thermal expansivity and isothermal compressibility of several nonsaturated hydrocarbons at 298.15 K

    SciTech Connect

    Aicart, E.; Junquera, E.; Letcher, T.M.

    1995-11-01

    The isobaric thermal expansivity and the isothermal compressibility have been measured at 298.15 K for several nonsaturated hydro bons: 1-hexene, 1-hexyne, 1-heptene, 1-heptyne, 1-octene, 1-octyne, o-xylene, m-xylene, p-xylene, and mesitylene (1,3,5-trimethylbenzene). The results, together with previous data from their laboratory, are discussed in terms of the chain length of the hydrocarbons, the degree of unsaturation (-ane, -ene, -yne), the degree of methylation, and the position of the methyl groups on the aromatic ring.

  19. A universal method for calculating isobaric-isothermal sections of ternary system phase diagrams

    NASA Astrophysics Data System (ADS)

    Voskov, A. L.; Voronin, G. F.

    2010-04-01

    A method for calculating and constructing isobaric-isothermal sections of ternary system phase diagrams with the use of convex hulls was developed. The method is based on the projection of the singularities of the lower part of the Gibbs energy convex hull onto the plane of component mole fractions followed by a geometric analysis of the properties of this projection. The method is applicable to a wide range of ternary systems, it can be used to find tie-line coordinates and determine the phase compositions of all the diagram regions. The quality of the suggested algorithm was estimated, and examples of the construction of several phase diagrams are given.

  20. Coefficients of the isobaric mass equation and their correlations with various nuclear parameters

    SciTech Connect

    Britz, J.; Pape, A.; Antony, M.S.

    1998-05-01

    The coefficients of the isobaric multiplet mass equation M = a + bT{sub z} + cT{sub z}{sup 2} have been calculated for the 430 identified T = 1/2, 1, 3/2, 2 multiplets and correlations of its b, c coefficients with various nuclear parameters have been sought. For most mass numbers A there is a tendency for b to increase, and for c to decrease, with the average excitation energy of the multiplet. There seems to be no separate dependence of b or c on spin, but there could be a dependence of b on parity.

  1. Getting Freshman in Equilibrium.

    ERIC Educational Resources Information Center

    Journal of Chemical Education, 1983

    1983-01-01

    Various aspects of chemical equilibrium were discussed in six papers presented at the Seventh Biennial Conference on Chemical Education (Stillwater, Oklahoma 1982). These include student problems in understanding hydrolysis, helping students discover/uncover topics, equilibrium demonstrations, instructional strategies, and flaws to kinetic…

  2. Getting Freshman in Equilibrium.

    ERIC Educational Resources Information Center

    Journal of Chemical Education, 1983

    1983-01-01

    Various aspects of chemical equilibrium were discussed in six papers presented at the Seventh Biennial Conference on Chemical Education (Stillwater, Oklahoma 1982). These include student problems in understanding hydrolysis, helping students discover/uncover topics, equilibrium demonstrations, instructional strategies, and flaws to kinetic

  3. The MR-TOF-MS isobar separator for the TITAN facility at TRIUMF

    NASA Astrophysics Data System (ADS)

    Jesch, Christian; Dickel, Timo; Pla, Wolfgang R.; Short, Devin; Ayet San Andres, Samuel; Dilling, Jens; Geissel, Hans; Greiner, Florian; Lang, Johannes; Leach, Kyle G.; Lippert, Wayne; Scheidenberger, Christoph; Yavor, Mikhail I.

    2015-05-01

    At TRIUMF's Ion Trap for Atomic and Nuclear Science (TITAN) a multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) will extend TITAN's capabilities and facilitate mass measurements and in-trap decay spectroscopy of exotic nuclei that so far have not been possible due to strong isobaric contamination. This MR-TOF-MS will also enable mass measurements of very short-lived nuclides (half-life > 1 ms) that are produced in very low quantities (a few detected ions overall). In order to allow the installation of an MR-TOF-MS in the restricted space on the platform, on which the TITAN facility is located, novel mass spectrometric methods have been developed. Transport, cooling and distribution of the ions inside the device is done using a buffer gas-filled RFQ-based ion beam switchyard. Mass selection is achieved using a dynamic retrapping technique after time-of-flight analysis in an electrostatic isochronous reflector system. Only due to the combination of these novel methods the realization of an MR-TOF-MS based isobar separator at TITAN has become possible. The device has been built, commissioned off-line and is currently under installation at TITAN.

  4. The MR-TOF-MS isobar separator for the TITAN facility at TRIUMF

    NASA Astrophysics Data System (ADS)

    Jesch, Christian; Dickel, Timo; Plaß, Wolfgang R.; Short, Devin; Ayet San Andres, Samuel; Dilling, Jens; Geissel, Hans; Greiner, Florian; Lang, Johannes; Leach, Kyle G.; Lippert, Wayne; Scheidenberger, Christoph; Yavor, Mikhail I.

    2015-11-01

    At TRIUMF's Ion Trap for Atomic and Nuclear Science (TITAN) a multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) will extend TITAN's capabilities and facilitate mass measurements and in-trap decay spectroscopy of exotic nuclei that so far have not been possible due to strong isobaric contamination. This MR-TOF-MS will also enable mass measurements of very short-lived nuclides (half-life > 1 ms) that are produced in very low quantities (a few detected ions overall). In order to allow the installation of an MR-TOF-MS in the restricted space on the platform, on which the TITAN facility is located, novel mass spectrometric methods have been developed. Transport, cooling and distribution of the ions inside the device is done using a buffer gas-filled RFQ-based ion beam switchyard. Mass selection is achieved using a dynamic retrapping technique after time-of-flight analysis in an electrostatic isochronous reflector system. Only due to the combination of these novel methods the realization of an MR-TOF-MS based isobar separator at TITAN has become possible. The device has been built, commissioned off-line and is currently under installation at TITAN.

  5. Zr/Nb isobar separation experiment for future 93Zr AMS measurement

    NASA Astrophysics Data System (ADS)

    Lu, W.; Anderson, T.; Bowers, M.; Bauder, W.; Collon, P.; Kutschera, W.; Kashiv, Y.; Lachner, J.; Martschini, M.; Ostdiek, K.; Robertson, D.; Schmitt, C.; Skulski, M.; Steier, P.

    2015-10-01

    93Zr (t1/2 = 1.6 Ma) is mostly produced by the main s-process in low-to-intermediate mass AGB stars. Large uncertainty exists in the current 92Zr(n,γ)93Zr Maxwellian Average cross section. This could have significant impact on nucleosynthesis calculations. Large amounts of 93Zr are also produced in nuclear reactors and pose long-term environmental radioactivity. Hence, measurement of 93Zr by the AMS is important for both fields above. We report here on progress in the development of AMS method to measure 93Zr. Compared with 98 MeV beam energy, Zr/Nb isobar position separation was improved using 155.2 MeV beam energy and Gas-Filled Magnet. Energy loss measurement with increased beam energy inside the detector indicates that higher beam energy can improve isobar energy loss separation. A chemical procedure to reduce the Nb content in Zr samples has been developed and tested. It reduces the 93Nb content by a factor of 1000.

  6. Isobaric-isothermal Monte Carlo simulations from first principles: Application to liquid water at ambient conditions

    SciTech Connect

    McGrath, M; Siepmann, J I; Kuo, I W; Mundy, C J; VandeVondele, J; Hutter, J; Mohamed, F; Krack, M

    2004-12-02

    A series of first principles Monte Carlo simulations in the isobaric-isothermal ensemble were carried out for liquid water at ambient conditions (T = 298 K and p = 1 atm). The Becke-Lee-Yang-Parr (BLYP) exchange and correlation energy functionals and norm-conserving Goedecker-Teter-Hutter (GTH) pseudopotentials were employed with the CP2K simulation package to examine systems consisting of 64 water molecules. The fluctuations in the system volume encountered in simulations in the isobaric-isothermal ensemble requires a reconsideration of the suitability of the typical charge density cutoff and the regular grid generation method previously used for the computation of the electrostatic energy in first principles simulations in the microcanonical or canonical ensembles. In particular, it is noted that a much higher cutoff is needed and that the most computationally efficient method of creating grids can result in poor simulations. Analysis of the simulation trajectories using a very large charge density cutoff at 1200 Ry and four different grid generation methods point to a substantially underestimated liquid density of about 0.85 g/cm{sup 3} resulting in a somewhat understructured liquid (with a value of about 2.7 for the height of the first peak in the oxygen/oxygen radial distribution function) for BLYP-GTH water at ambient conditions.

  7. Rapid differentiation of isobaric and positional isomers of structurally related glycosides from Phytolacca bogotensis.

    PubMed

    Montoya, Guillermo; Arango, Gabriel J; Ramrez-Pineda, Jos R

    2009-11-01

    Through the action of glycosyltransferases, a plant can biosynthetically assemble small different aglycons or 'templates' to various polysaccharides to produce numerous glycoconjugates differing in the type of the attached aglycon, the anomeric configuration of C-1 of the glycosylating sugar, the type of sugar and the different position of attachments of the sugar unit present in the polysaccharide chain. The position of attachments and the anomeric configuration of the different sugar present in the polysaccharide create the opportunity to generate molecules with either the same or very close molecular weights, which have relative structural similarity--forming isobaric and positional isomers. Although isomeric differentiation was once considered outside of the domain of mass spectrometry, this task can now be resolved using tandem mass spectrometry. In a standardized purified glycoconjugate fraction (SPT01) from Phytolacca bogotensis, we report conventional electrospray ionization mass spectrometry and collision-induced dissociation (CID) MS/MS parameters which favored the formation of characteristic product ions. This allowed us to suggest the type of sugar linkages present in a specific glycoconjugate. Ten new glycoconjugate are described from this plant and another twelve known saponins were structurally characterized using the automatic MSn acquisition mode. The differentiation of two pairs of positional isomers and four isobaric glycosides and the production of a library of 30 glycosides present in P. bogotensis were accomplished. PMID:19785003

  8. Breakdown of the Isobaric Multiplet Mass Equation for the A =20 and 21 Multiplets

    NASA Astrophysics Data System (ADS)

    Gallant, A. T.; Brodeur, M.; Andreoiu, C.; Bader, A.; Chaudhuri, A.; Chowdhury, U.; Grossheim, A.; Klawitter, R.; Kwiatkowski, A. A.; Leach, K. G.; Lennarz, A.; Macdonald, T. D.; Schultz, B. E.; Lassen, J.; Heggen, H.; Raeder, S.; Teigelhfer, A.; Brown, B. A.; Magilligan, A.; Holt, J. D.; Menndez, J.; Simonis, J.; Schwenk, A.; Dilling, J.

    2014-08-01

    Using the Penning trap mass spectrometer TITAN, we performed the first direct mass measurements of Mg20,21, isotopes that are the most proton-rich members of the A =20 and A=21 isospin multiplets. These measurements were possible through the use of a unique ion-guide laser ion source, a development that suppressed isobaric contamination by 6 orders of magnitude. Compared to the latest atomic mass evaluation, we find that the mass of Mg21 is in good agreement but that the mass of Mg20 deviates by 3?. These measurements reduce the uncertainties in the masses of Mg20,21 by 15 and 22 times, respectively, resulting in a significant departure from the expected behavior of the isobaric multiplet mass equation in both the A =20 and A=21 multiplets. This presents a challenge to shell model calculations using either the isospin nonconserving universal sd USDA and USDB Hamiltonians or isospin nonconserving interactions based on chiral two- and three-nucleon forces.

  9. Transverse electron scattering response function of {sup 3}He with {Delta}-isobar degrees of freedom

    SciTech Connect

    Yuan Luping; Efros, Victor D.; Leidemann, Winfried; Tomusiak, Edward L.

    2010-11-15

    A calculation of the {sup 3}He transverse (e,e{sup '}) inclusive response function, R{sub T}, which includes {Delta} degrees of freedom, is performed using the Lorentz integral transform method. The resulting coupled equations are treated in impulse approximation, where the NNN and NN{Delta} channels are solved separately. As NN and NNN potentials, we use the Argonne V18 and Urbana IX models, respectively. Electromagnetic currents include the {Delta}-isobar currents, one-body N currents with relativistic corrections, and two-body currents consistent with the Argonne V18 potential. R{sub T} is calculated for the breakup threshold region at momentum transfers near 900 MeV/c. Our results are similar to those of Deltuva et al. in that large {Delta}-isobar current contributions are found. However, we find that these are largely canceled by the relativistic contribution from the one-body N currents. Finally, a comparison is made between theoretical results and experimental data.

  10. Structure of heavy helium isotopes via the isobaric analog states in Lithium.

    NASA Astrophysics Data System (ADS)

    Rogachev, G. V.; Aprahamian, A.; Boutachkov, P.; Quinn, M.; Kolata, J. J.; Skorodumov, B.; Woehr, A.; Goldberg, V. Z.; Chubarian, G.; Fomichev, A.; Golovkov, M. S.; Oganessian, Yu. Ts.; Rodin, A.; Slepnev, R. S.; Ter-Akopian, G.; Wolski, R.; Trzaska, W. H.; Aleksandrov, D. V.; Deyoung, P. A.; Peaslee, G. F.; Mears, P. J.; Becchetti, F. D.; Chen, Y.

    2003-10-01

    Study of nuclei far removed from the valley of stability provide an opportunity to test the models of nuclear structure. In particular, heavy isotopes of helium attract much attention due to their extreme neutron to proton ratio. In this work we studied the T=5/2 states in ^9Li and T=3/2 states in ^7Li, isobaric analog states of ^9He and ^7He respectively. Experiment on investigation of T=5/2 states in ^9Li was performed on ACCULINA spectrometer in Dubna, Russia. Excitation function for ^8He+p elastic scattering was measured in the center-of-momentum (cm) energy range from 1.6 to 5.8 MeV. Three T=5/2 states in ^9Li (isobaric analogs of ^9He) were observed. Restrictions on the spin-parity assignments to these states are provided according to R-matrix calculations, and conclusions regarding the structure of ^9He are given. T=3/2 states in ^7Li was populated in interaction of ^6He with protons using the ^6He beam provided by TWINSOL RNB facility at the University of Notre Dame. Neutron decay channel of T=3/2 resonances in ^7Li (n+^6Li(T=1)) was observed in a combination of ?-ray and neutron detectors. Preliminary results of this experiment will be reported.

  11. Breakdown of the isobaric multiplet mass equation for the A = 20 and 21 multiplets.

    PubMed

    Gallant, A T; Brodeur, M; Andreoiu, C; Bader, A; Chaudhuri, A; Chowdhury, U; Grossheim, A; Klawitter, R; Kwiatkowski, A A; Leach, K G; Lennarz, A; Macdonald, T D; Schultz, B E; Lassen, J; Heggen, H; Raeder, S; Teigelhfer, A; Brown, B A; Magilligan, A; Holt, J D; Menndez, J; Simonis, J; Schwenk, A; Dilling, J

    2014-08-22

    Using the Penning trap mass spectrometer TITAN, we performed the first direct mass measurements of (20,21)Mg, isotopes that are the most proton-rich members of the A = 20 and A = 21 isospin multiplets. These measurements were possible through the use of a unique ion-guide laser ion source, a development that suppressed isobaric contamination by 6 orders of magnitude. Compared to the latest atomic mass evaluation, we find that the mass of (21)Mg is in good agreement but that the mass of (20)Mg deviates by 3 ?. These measurements reduce the uncertainties in the masses of (20,21)Mg by 15 and 22 times, respectively, resulting in a significant departure from the expected behavior of the isobaric multiplet mass equation in both the A = 20 and A = 21 multiplets. This presents a challenge to shell model calculations using either the isospin nonconserving universal sd USDA and USDB Hamiltonians or isospin nonconserving interactions based on chiral two- and three-nucleon forces. PMID:25192091

  12. Chemical Principles Revisited: Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Mickey, Charles D.

    1980-01-01

    Describes: (1) Law of Mass Action; (2) equilibrium constant and ideal behavior; (3) general form of the equilibrium constant; (4) forward and reverse reactions; (5) factors influencing equilibrium; (6) Le Chatelier's principle; (7) effects of temperature, changing concentration, and pressure on equilibrium; and (8) catalysts and equilibrium. (JN)

  13. TEA: Thermal Equilibrium Abundances

    NASA Astrophysics Data System (ADS)

    Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver

    2015-05-01

    TEA (Thermal Equilibrium Abundances) calculates gaseous molecular abundances under thermochemical equilibrium conditions. Given a single T,P point or a list of T,P pairs (the thermal profile of an atmosphere) and elemental abundances, TEA calculates mole fractions of the desired molecular species. TEA uses 84 elemental species and thermodynamical data for more then 600 gaseous molecular species, and can adopt any initial elemental abundances.

  14. Computing Equilibrium Chemical Compositions

    NASA Technical Reports Server (NTRS)

    Mcbride, Bonnie J.; Gordon, Sanford

    1995-01-01

    Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

  15. An ion guide laser ion source for isobar-suppressed rare isotope beams

    SciTech Connect

    Raeder, Sebastian Ames, Friedhelm; Bishop, Daryl; Bricault, Pierre; Kunz, Peter; Mjs, Anders; Heggen, Henning; Institute of Applied Physics, TU Darmstadt, Schlossgartenstr. 7, 64289 Darmstadt ; Lassen, Jens Teigelhfer, Andrea; Department of Physics and Astronomy, University of Manitoba, Winnipeg, Manitoba R3T 2N2

    2014-03-15

    Modern experiments at isotope separator on-line (ISOL) facilities like ISAC at TRIUMF often depend critically on the purity of the delivered rare isotope beams. Therefore, highly selective ion sources are essential. This article presents the development and successful on-line operation of an ion guide laser ion source (IG-LIS) for the production of ion beams free of isobaric contamination. Thermionic ions from the hot ISOL target are suppressed by an electrostatic potential barrier, while neutral radio nuclides effusing out are resonantly ionized by laser radiation within a quadrupole ion guide behind this barrier. The IG-LIS was developed through detailed thermal and ion optics simulation studies and off-line tests with stable isotopes. In a first on-line run with a SiC target a suppression of surface-ionized Na contaminants in the ion beam of up to six orders of magnitude was demonstrated.

  16. The Defect Diffusion Model and Isochoric Energy and Isobaric Enthalpy for Glass Formers

    NASA Astrophysics Data System (ADS)

    Shlesinger, Michael; Bendler, John; Fontanella, John; Wintersgill, Mary

    2009-03-01

    The defect diffusion model produces stretched exponential relaxation, in supercooled liquids, through the sub-diffusive motion of defects. The aggregation of the defects produces a Vogel-Fulcher type law for the divergence of the time scale at a critical temperature. The model is employed to calculate the ratio of the apparent isochoric activation energy to the isobaric activation enthalpy, EV*/H* or EV/EP,. This ratio measures the relative sensitivity of kinetic processes to changes in volume and temperature respectively. This ratio equation is tested using dielectric relaxation data for poly(vinyl acetate), viscosity data for glycerol and ionic conductivity data for poly(propylene glycol) containing LiCF3SO3. Good agreement between theory and experiment is found using model parameters previously published.

  17. Nucleon resonances with spin 3 /2 and 5 /2 in the isobar model for kaon photoproduction

    NASA Astrophysics Data System (ADS)

    Mart, T.; Clymton, S.; Arifi, A. J.

    2015-11-01

    We compare two different propagator and vertex factor formulations of spin-3 /2 and -5 /2 nucleon resonances by using isobar models for kaon photoproduction on the proton ? +p ?K++? . All nucleon resonances listed in the Particle Data Group listing with spin up to 5 /2 and with at least a two-star rating are included in the model. The unknown coupling constants are extracted from fitting to around 7400 data points. It is found that the gauge-invariant formulation of the spin-3 /2 and -5 /2 interactions leads to a better agreement with experimental data. An extensive comparison of model calculation with experimental data and comparison with the previous analyses are presented. A short discussion on the cross section near the production threshold is also provided.

  18. Density functional theory of fluids in the isothermal-isobaric ensemble.

    PubMed

    Gonzlez, A; White, J A; Romn, F L; Velasco, S

    2004-06-01

    We present a density functional theory for inhomogeneous fluids at constant external pressure. The theory is formulated for a volume-dependent density, n(r,V), defined as the conjugate variable of a generalized external potential, nu(r,V), that conveys the information on the pressure. An exact expression for the isothermal-isobaric free-energy density functional is obtained in terms of the corresponding canonical ensemble functional. As an application we consider a hard-sphere system in a spherical pore with fluctuating radius. In general we obtain very good agreement with simulation. However, in some situations a peak develops in the center of the cavity and the agreement between theory and simulation becomes worse. This happens for systems where the number of particles is close to the magic numbers N=13, 55, and 147. PMID:15268089

  19. The current status of Zr-Nb isobar separation experiments for future 93Zr AMS measurement

    NASA Astrophysics Data System (ADS)

    Lu, Wenting; Collon, Philippe; Kashiv, Yoav; Robertson, Daniel; Schmitt, Christopher; Bowers, Matthew; Ostdiek, Karen; Bauder, William

    2013-10-01

    The rare isotope 93Zr (t1/2 = 1.6 Ma) can be produced (1) in the s-process, (2) by the spontaneous fission of Uranium and Plutonium, and (3) by the activation of cladding Zr in nuclear reactors. The production method (1) makes it relevant in astrophysical modeling of nucleosynthesis processes, while (2) and (3) makes it of interest to people dealing with nuclear waste management and transmutation study. The main challenge in AMS detection of 93Zr is the adequate separation from its stable isobar 93Nb which is only one atomic number away. The nuclear Science Laboratory at the University of Notre Dame is developing the capability to measure 93Zr by AMS, featuring the combination of gas-filled magnet with the position-sensitive parallel grid avalanche counter and gas chamber (ionization chamber and Bragg curve detector). The chemical reduction and the suppression in the ion source of 93Nb have been deemed as necessary.

  20. Excitation of ? and N* resonances in isobaric charge-exchange reactions of heavy nuclei

    NASA Astrophysics Data System (ADS)

    Vidaa, I.; Benlliure, J.; Geissel, H.; Lenske, H.; Scheidenberger, C.; Vargas, J.

    2016-01-01

    We present a model for the study of the excitation of ?(1232) and N*(1440) resonances in isobaric charge-exchange (AZ, A(Z 1)) reactions of heavy nuclei. Quasi-elastic and inelastic elementary processes contributing to the double differential cross sections of the reactions are described in terms of the exchange of virtual pions. The inelastic channel includes processes where the resonances are excited both in the target and in the projectile nucleus. We present results for reactions of 112Sn and 124Sn on different targets. Our results confirm that the position of the ? peak is insensitive to targets with mass number A ? 12, and show that the origin of the ? peak shift towards low excitation energies, with respect to its position in reactions with a proton target, can be easily explained in terms of the superposition of the different excitation mechanisms contributing to the reaction.

  1. Weather maps classification over Greek domain based on isobaric line patterns. A pattern recognition approach

    NASA Astrophysics Data System (ADS)

    Zagouras, Athanassios; Argiriou, Athanassios A.; Economou, George; Fotopoulos, Spiros; Flocas, Helena A.

    2013-11-01

    The paper presents a semi-supervised weather classification method based on 850-hPa isobaric level maps. A preprocessing step is employed, where isolines of geopotential height are extracted from weather map images via an image processing procedure. Α feature extraction stage follows where two techniques are applied. The first technique implements phase space reconstruction, and yields multidimensional delay distributions. The second technique is based on chain code representation of signals, from which histogram features are derived. Similarity measures are used to compare multidimensional data and the k-means algorithm is applied in the final stage. The method is applied over the area of Greece, and the resulting catalogues are compared to a subjective classification for this area. Numerical experiments with datasets derived from the European Meteorological Bulletin archives exhibit an up to 91 % accurate agreement with the subjective weather patterns.

  2. Gamow-Teller strength studied through {Gamma}-excitation of isobaric analog states

    SciTech Connect

    Boswell, M. S.; Young, A. R.; Ejiri, H.

    2013-04-19

    We consider a measurement of isobaric analog states (IAS) of 76As in 76Se as a method for measuring the Gamow-Teller (GT) strength important to constrain and possibly help normalize calculations of double beta ({beta}{beta}) decay matrix elements. We show that photo-nuclear reactions via IAS can provide valuable information about the parent and daughter states of {beta}{beta}-decay not currently available from measurements of charge exchange reactions. Several experiments have been proposed at the HI{open_square} Sfacility at the Triangle Nuclear Research Laboratory in Durham, NC, the first of which will measure the lowest 1{sup -}, 1{sup +} and 2{sup +} IAS in {sup 76}Se.

  3. Split isobaric analog state in 55Ni: case of strong isospin mixing.

    PubMed

    Tripathi, Vandana; Tabor, S L; Volya, A; Liddick, S N; Bender, P C; Larson, N; Prokop, C; Suchyta, S; Tai, P-L; Vonmoss, J M

    2013-12-27

    Study of ?+ decay of the exotic Tz=-3/2 nucleus 55Cu, via delayed ? rays, has revealed a strongly isospin mixed doublet (4599-4579 keV) in 55Ni, which represents the fragmented and previously unknown isobaric analog of the ground state of 55Cu. The observed small log?ft values to both states in the doublet confirm the superallowed Fermi ? decay. The near degeneracy of a pair of 3/2- levels in 55Ni results in the strong isospin mixing. The isospin mixing matrix element between the T=3/2 and T=1/2 levels is inferred from the experiment to be 9(1) keV, which agrees well with the matrix element of the charge symmetry breaking shell model Hamiltonian of Ormand and Brown. A precise value of the half-life of 55Cu at 57(3) ms was also obtained. PMID:24483792

  4. A new gas lesion syndrome in man, induced by 'isobaric gas counterdiffusion'

    NASA Technical Reports Server (NTRS)

    Lambertsen, C. J.; Idicula, J.

    1975-01-01

    Normal men have been found to develop pruritis and gas bubble lesions in the skin, and disruption of vestibular function, when breathing nitrogen or neon with oxygen while surrounded by helium at increased ambient pressure. This phenomenon, which occurs at stable ambient pressures, at 1 or many ATA, has been designated the isobaric gas counterdiffusion syndrome. In a series of analyses and experiments in vivo and in vitro the cause of the syndrome has been established as due to gas accumulation and development of gas bubbles in tissues as a result of differences in selective diffusivities, for various respired and ambient gases, in the tissue substances between capillary blood and the surrounding atmosphere. The phenomenon described in man is an initial stage of a process shown later in animals to progress to continuous, massive, lethal, intravascular gas embolization.

  5. Isobar channels in the production of π+π- pairs on a proton by virtual photons

    SciTech Connect

    Burkert, V D; Mokeev, V I; Shvedunov, N V; Boluchevskii, A A; Battaglieri, M; Golovach, E N; Elouardrhiri, L; Joo, K; Isupov, E L; Ishkhanov, B S; Markov, N S; Ripani, M; Ricco, J; Sapunenko, V V; Taiuti, M; Fedotov, G V

    2007-03-01

    A new approach is developed for evaluating contributions of various isobar channels to the double charged-pion production in the reactions γ r,v p → π + π - p. This approach makes it possible to determine both respective cross sections and amplitudes for quasi-two-particle channels from a fit to data on cross sections for a three-particle final state. The diffractive anzatz, which is widely used to describe rho-meson production, is modified to meet the purpose of the description of data in the near-threshold and subthreshold regions. The cross sections for rho-meson electroproduction in the energy region of nucleon-resonance excitation are determined for the first time on the basis of the latest data of the CLAS Collaboration.

  6. N, N-Dimethyl Leucines as Novel Isobaric Tandem Mass Tags for Quantitative Proteomics and Peptidomics

    PubMed Central

    Xiang, Feng; Ye, Hui; Chen, Ruibing; Fu, Qiang; Li, Lingjun

    2010-01-01

    Herein we describe the development and application of a set of novel N, N-dimethyl leucine (DiLeu) 4-plex isobaric tandem mass (MS2) tagging reagents with high quantitation efficacy and greatly reduced cost for neuropeptide and protein analysis. DiLeu reagents serve as attractive alternatives for isobaric tag for relative and absolute quantitation (iTRAQ) and tandem mass tags (TMTs) due to their synthetic simplicity, labeling efficiency and improved fragmentation efficiency. DiLeu reagent resembles the general structure of a tandem mass tag in that it contains an amine reactive group (triazine ester) targeting the N-terminus and ?-amino group of the lysine side-chain of a peptide, a balance group, and a reporter group. A mass shift of m/z 145.1 is observed for each incorporated label. Intense a1 reporter ions at m/z 115.1, 116.1, 117.1, and 118.1 are observed for all pooled samples upon MS2. All labeling reagents are readily synthesized from commercially available chemicals with greatly reduced cost. Labels 117 and 118 can be synthesized in one step and labels 115 and 116 can be synthesized in two steps. Both DiLeu and iTRAQ reagents show comparable protein sequence coverage (~43%) and quantitation accuracy (<15%) for tryptically digested protein samples. Furthermore, enhanced fragmentation of DiLeu labeling reagents offers greater confidence in protein identification and neuropeptide sequencing from complex neuroendocrine tissue extracts from a marine model organism, Callinectes sapidus. PMID:20218596

  7. Premixed hydrogen-oxygen flames. Part II: Quasi-isobaric ignition near the flammability limits

    SciTech Connect

    He, Longting; Clavin, P. Univ. d'Aix-Marseille )

    1993-06-01

    A numerical study of one-dimensional and time-dependent problems in quasi-isobaric combustion of H2-02 mixtures is carried out with a complex chemical network and detailed molecular transport mechanisms. A first numerical result shows that a diffusive-thermal instability corresponding to a Hopf bifurcation appears in the propagation of planar flames in the neighborhood of the H2-rich flammability limit. The corresponding critical mole fraction of H2 is 0.947 at ordinary conditions with a flame velocity of about 45 cm/s, compared with 0.96 for the flammability limit. The quasi-isobaric ignition by a hot pocket of combustion products is also investigated numerically. The critical size of the hot pockets is determined as a function of the equivalence ratio. It is found that when the H2-rich flammability limit is approached, the critical radius becomes much larger than the flame thickness and moreover, it diverges before reaching the planar flammability limit, at a critical H2 mole fraction about 0.945 at ordinary conditions (compared with 0.96). Thus, planar flames cannot be ignited in this way in the range of H2 mole fractions between 0.945 and 0.96 where the burning velocity varies from about 50 cm/s to few millimeters per second. Near the H2 lean flammability limit the situation is quite different. The critical size is smaller than the planar flame thickness, and spherical flames with a very small initial radius may grow in lean mixtures even beyond the flammability limit of planar flames. These phenomena are explained by an elementary analytical study of a minimal model coupling preferential diffusion mechanisms with the kinetic effects controlling the planar flammability limits.

  8. Ultrahigh-temperature metamorphism under isobaric heating: New evidence from the North China Craton

    NASA Astrophysics Data System (ADS)

    Yang, Qiong-Yan; Santosh, M.; Tsunogae, Toshiaki

    2014-12-01

    The Khondalite Belt within Inner Mongolia Suture Zone (IMSZ) in the North China Craton (NCC) preserves evidence for extreme crustal metamorphism under ultra-high temperature (UHT) conditions at ca. 1.92 Ga, associated with the subduction-collision tectonics between the Yinshan and Ordos Blocks. Here we report a new locality in Hongsigou where cordierite- and spinel-bearing granulites record UHT metamorphism. The prograde, peak, and retrograde mineral assemblages in these pelitic granulites have been identified based on petrography and mineral chemistry as: Bt1 + Grt1 + Sil1 + Kfs1 + Pl1 + Ilm + Qtz1, Grt1 + Sil2 + Kfs2 + Pl2 + Spl + Ilm + Qtz2 + Liq, and Crd + Grt2 + Sil3 + Kfs2 + Pl2 + Ilm + Qtz2 respectively. The peak metamorphic conditions of the pelitic granulite were estimated as 930-1050 C and 6.5-7.5 kbar based on pseudosection analysis in the system NCKFMASHTO, suggesting extreme thermal metamorphism. We report LA-ICPMS zircon U-Pb data from the granulite which show weighted mean 207Pb/206Pb age of 1881 6.6 Ma, marking the timing of UHT metamorphism. Lu-Hf analyses of the zircons show ?Hf(t) values within a restricted range of -4.2 to 0.3 and together with Hf model ages, a Paleoproterozoic arc magmatic source is inferred for the detrital zircons. The estimated P-T path for the UHT granulite suggests isobaric heating followed by cooling and decompression along a clockwise trajectory, different from the anti-clockwise P-T paths defined in earlier studies for the 1.92 Ga UHT rocks from the IMSZ. The younger age and the isobaric heating trajectory suggest that the Hongsigou UHT rocks are related to heat input from underplated mafic magmas following continental collision.

  9. A Precise, Simple, and Low-Cost Experiment to Determine the Isobaric Expansion Coefficient for Physical Chemistry Students

    ERIC Educational Resources Information Center

    Perez, Eduardo

    2015-01-01

    The procedure of a physical chemistry experiment for university students must be designed in a way that the accuracy and precision of the measurements is properly maintained. However, in many cases, that requires costly and sophisticated equipment not readily available in developing countries. A simple, low-cost experiment to determine isobaric

  10. Finite-size and truncation effects for microscopic expressions for the temperature at equilibrium and nonequilibrium.

    PubMed

    Lervik, Anders; Wilhelmsen, ivind; Trinh, Thuat T; Nagel, Henrik Rojas

    2015-09-21

    Several expressions have been proposed for the temperature in molecular simulations, where some of them have configurational contributions. We investigate how their accuracy is influenced by the number of particles in the simulation and the discontinuity in the derivatives of the interaction potential introduced by truncation. For equilibrium molecular dynamics with fixed total volume and fixed average total energy per particle, all the evaluated expressions including that for the kinetic temperature give a dependence on the total number of particles in the simulation. However, in a partitioned simulation volume under the same conditions, the mean temperature of each bin is independent of the number of bins. This finding is important for consistently defining a local temperature for use in nonequilibrium simulations. We identify the configurational temperature expressions which agree most with the kinetic temperature and find that they give close to identical results in nonequilibrium molecular dynamics (NEMD) simulations with a temperature gradient, for high and low density bulk-systems (both for transient and steady-state conditions), and across vapor-liquid interfaces, both at equilibrium and during NEMD simulations. The work shows that the configurational temperature is equivalent to the kinetic temperature in steady-state molecular dynamics simulations if the discontinuity in the derivatives of the interaction potential is handled properly, by using a sufficiently long truncation-distance or tail-corrections. PMID:26395686

  11. Phase equilibrium of liquid mixtures: experimental and modeled data using statistical associating fluid theory for potential of variable range approach.

    PubMed

    Giner, Beatriz; Bandrs, Isabel; Lpez, M Carmen; Lafuente, Carlos; Galindo, Amparo

    2007-10-14

    A study of the phase equilibrium (experimental and modeled) of mixtures formed by a cyclic ether and haloalkanes has been derived. Experimental data for the isothermal vapor liquid equilibrium of mixtures formed by tetrahydrofuran and tetrahydropyran and isomeric chlorobutanes at temperatures of 298.15, 313.15, and 328.15 K are presented. Experimental results have been discussed in terms of both molecular characteristics of pure compounds and potential intermolecular interaction between them using thermodynamic information of the mixtures obtained earlier. The statistical associating fluid theory for potential of variable range (SAFT-VR) approach together with standard combining rules without adjustable parameters has been used to model the phase equilibrium. Good agreement between experiment and the prediction is found with such a model. Mean absolute deviations for pressures are of the order of 1 kPa, while less than 0.013 mole fraction for vapor phase compositions. In order to improve the results obtained, a new modeling has been carried out by introducing a unique transferable parameter k(ij), which modifies the strength of the dispersion interaction between unlike components in the mixtures, and is valid for all the studied mixtures being not temperature or pressure dependent. This parameter together with the SAFT-VR approach provides a description of the vapor-liquid equilibrium of the mixtures that is in excellent agreement with the experimental data for most cases. The absolute deviations are of the order of 0.005 mole fraction for vapor phase compositions and less than 0.3 kPa for pressure, excepting for mixtures containing 2-chloro-2-methylpropane which deviations for pressure are larger. Results obtained in this work in the modeling of the phase equilibrium with the SAFT-VR equation of state have been compared to the ones obtained in a previous study when the approach was used to model similar mixtures with clear differences in the thermodynamic behavior. We show how the SAFT-VR approach is capable of differentiating the molecular features of a relatively wide set of different mixtures. PMID:17935415

  12. Nonisothermal filaments in equilibrium

    NASA Astrophysics Data System (ADS)

    Recchi, S.; Hacar, A.; Palestini, A.

    2013-10-01

    Context. The physical properties of the so-called Ostriker isothermal filament have been classically used as a benchmark to interpret the stability of the filaments observed in nearby clouds. However, recent continuum studies have shown that the internal structure of the filaments depart from the isothermality, typically exhibiting radially increasing temperature gradients. Aims: The presence of internal temperature gradients within filaments suggests that the equilibrium configuration of these objects should be therefore revisited. The main goal of this work is to theoretically explore how the equilibrium structure of a filament changes in a nonisothermal configuration. Methods: We solve the hydrostatic equilibrium equation by assuming temperature gradients similar to those derived from observations. Results: We obtain a new set of equilibrium solutions for nonisothermal filaments with both linear and asymptotically constant temperature gradients. For sufficiently large internal temperature gradients, our results show that a nonisothermal filament could present significantly larger masses per unit length and shallower density profiles than the isothermal filament without collapsing by its own gravity. Conclusions: We conclude that filaments can reach an equilibrium configuration under nonisothermal conditions. Detailed studies of both the internal mass distribution and temperature gradients within filaments are then needed to judge the physical state of filaments.

  13. Equilibrium games in networks

    NASA Astrophysics Data System (ADS)

    Li, Angsheng; Zhang, Xiaohui; Pan, Yicheng; Peng, Pan

    2014-12-01

    It seems a universal phenomenon of networks that the attacks on a small number of nodes by an adversary player Alice may generate a global cascading failure of the networks. It has been shown (Li et al., 2013) that classic scale-free networks (Barabsi and Albert, 1999, Barabsi, 2009) are insecure against attacks of as small as O(logn) many nodes. This poses a natural and fundamental question: Can we introduce a second player Bob to prevent Alice from global cascading failure of the networks? We proposed a game in networks. We say that a network has an equilibrium game if the second player Bob has a strategy to balance the cascading influence of attacks by the adversary player Alice. It was shown that networks of the preferential attachment model (Barabsi and Albert, 1999) fail to have equilibrium games, that random graphs of the Erds-Rnyi model (Erds and Rnyi, 1959, Erds and Rnyi, 1960) have, for which randomness is the mechanism, and that homophyly networks (Li et al., 2013) have equilibrium games, for which homophyly and preferential attachment are the underlying mechanisms. We found that some real networks have equilibrium games, but most real networks fail to have. We anticipate that our results lead to an interesting new direction of network theory, that is, equilibrium games in networks.

  14. Comparison between intrathecal isobaric ropivacaine-fentanyl and bupivacaine-fentanyl in elective infraumbilical orthopedic surgery: A randomized controlled study

    PubMed Central

    Layek, Amitava; Maitra, Souvik; Gozi, Nitish K; Bhattacharjee, Sulagna; Pal, Sugata; Sen, Suvadeep; Hazra, Avijit

    2015-01-01

    Background and Aims: We aimed to evaluate and compare the block characteristics and duration of analgesia of intrathecal isobaric ropivacaine-fentanyl and bupivacaine-fentanyl combination in adult patients undergoing lower limb orthopedic surgery. Material and Methods: Seventy-four American Society of Anesthesiologists I and II adult patients undergoing lower limb orthopedic surgery under subarachnoid block were randomized to receive either 3 ml 0.5% isobaric ropivacaine and 25 mcg fentanyl (Group R) or 3 ml 0.5% isobaric bupivacaine and 25 mcg fentanyl (Group B). The hemodynamic profiles, maximum upper level of sensory block height, time to reach peak block height, two dermatome regression time, and duration of motor block were recorded. Results: There was no statistically significant difference regarding the hemodynamic parameters between the groups. The median (range) peak sensory block height was T7 (T4-T9) in Group R and T7 (T4-T10) in Group B. Time to reach peak block height (13.2 2.3 min in Group R vs. 13.7 2.2 min in Group B; P = 0.385) was similar between the groups. Two dermatome regression time in sensory block (median 120 min vs. 85 min; P < 0.001) and duration of motor block (median 245 min vs. 150 min; P < 0.001) was significantly higher in Group B. The duration of analgesia (median 360 min vs. 245 min; P < 0.001) was significantly higher in the bupivacaine group. Conclusion: Intrathecal isobaric bupivacaine-fentanyl combination produces a significantly longer duration of analgesia, sensory block and motor block than isobaric ropivacaine-fentanyl combination. As ropivacaine has a shorter duration of sensory and motor block, it may be preferred in day care surgery. PMID:26702216

  15. Beyond Equilibrium Thermodynamics

    NASA Astrophysics Data System (ADS)

    Öttinger, Hans Christian

    2005-01-01

    Beyond Equilibrium Thermodynamics fills a niche in the market by providing a comprehensive introduction to a new, emerging topic in the field. The importance of non-equilibrium thermodynamics is addressed in order to fully understand how a system works, whether it is in a biological system like the brain or a system that develops plastic. In order to fully grasp the subject, the book clearly explains the physical concepts and mathematics involved, as well as presenting problems and solutions; over 200 exercises and answers are included. Engineers, scientists, and applied mathematicians can all use the book to address their problems in modelling, calculating, and understanding dynamic responses of materials.

  16. Vapor-liquid-solid epitaxial growth of Si1-xGex alloy nanowires. Composition dependence on precursor reactivity and morphology control for vertical forests

    SciTech Connect

    Choi, S. G.; Manandhar, P.; Picraux, S. T.

    2015-07-07

    The growth of high-density group IV alloy nanowire forests is critical for exploiting their unique functionalities in many applications. Here, the compositional dependence on precursor reactivity and optimized conditions for vertical growth are studied for Si1- x Ge x alloy nanowires grown by the vapor-liquid-solid method. The nanowire composition versus gas partial-pressure ratio for germane-silane and germane-disilane precursor combinations is obtained at 350°C over a wide composition range (0.05 ≤ x ≤ 0.98) and a generalized model to predict composition for alloy nanowires is developed based on the relative precursor partial pressures and reactivity ratio. In combination with germane, silane provides more precise compositional control at high Ge concentrations (x > 0.7), whereas disilane greatly increases the Si concentration for a given gas ratio and enables more precise alloy compositional control at small Ge concentrations (x < 0.3). Vertically oriented, non-kinking nanowire forest growth on Si (111) substrates is then discussed for silane/germane over a wide range of compositions, with temperature and precursor partial pressure optimized by monitoring the nanowire growth front using in-situ optical reflectance. For high Ge compositions (x ≈ 0.9), a “two-step” growth approach with nucleation at higher temperatures results in nanowires with high-density and uniform vertical orientation. Furthermore, increasing Si content (x ≈ 0.8), the optimal growth window is shifted to higher temperatures, which minimizes nanowire kinking morphologies. For Si-rich Si1- x Ge x alloys (x ≈ 0.25), vertical nanowire growth is enhanced by single-step, higher-temperature growth at reduced pressures.

  17. An Updated Equilibrium Machine

    ERIC Educational Resources Information Center

    Schultz, Emeric

    2008-01-01

    A device that can demonstrate equilibrium, kinetic, and thermodynamic concepts is described. The device consists of a leaf blower attached to a plastic container divided into two chambers by a barrier of variable size and form. Styrofoam balls can be exchanged across the barrier when the leaf blower is turned on and various air pressures are

  18. Equilibrium CO bond lengths

    NASA Astrophysics Data System (ADS)

    Demaison, Jean; Csszr, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 within the full range of 1.10-1.43 , corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  19. Isobar suppression for measurement of silicon-32 by accelerator mass spectrometry at low energy

    NASA Astrophysics Data System (ADS)

    Treacy, Donald John, Jr.

    2000-10-01

    Development of a method to suppress the isobaric interference, 32S, for the purpose of measuring 32Si by Accelerator Mass Spectrometry (AMS) at low energy was undertaken. The differential energy loss of the ions when transmitted through a thin carbon foil was the basis of the isobaric suppression. A new silica reduction technique was developed for the purpose of increasing ion source output for silicon samples. The energy loss and energy straggle of the transmitted ions, the charge state distributions, and beamline transmission were measured for the stable isotopes of silicon and 32S for the development of the method. The data are compared to the predictions that were made for the ion beam energy loss and energy straggle using the Monte Carlo simulation program TRIM. The charge state distribution data are compared to predictions made using empirical formulas developed by Chaki and Elmore in 1980. The negative silicon ion beam source output for chemically prepared Mg 2Si samples was increased from approximately 10 nA to approximately 15 ?A. This was an increase of a factor of approximately 103 over naturally occurring SiO2 samples. The observed energy loss profiles of the silicon and sulfur ions through carbon foils of 50-?g/cm2, 75-?g/cm2, and 100-?g/cm2 are in good agreement with the predicted values, with absolute percent error results ranging from 0.1% to 2.5%. The measured energy straggling for the silicon and sulfur ions in the thin carbon foils ranged from approximately 150 keV to 450 keV. This is much larger than the values of 21 keV to 30 keV that were predicted using simulations from the TRIM code. The measured charge state distributions were in very good agreement with the predicted distributions for silicon and sulfur. The overall system ion beam transmission efficiency was 0.2% for the transmission to the spectrograph, and 0.02% to the silicon surface barrier detector in the spectrograph. The results indicate that enacting the differential energy loss for the silicon- sulfur pair suppressed the sulfur interference by a factor of 106 relative to the silicon count rate.

  20. Vapor-liquid phase separator studies

    NASA Technical Reports Server (NTRS)

    Yuan, S. W. K.; Lee, J. M.; Kim, Y. I.; Hepler, W. A.; Frederking, T. H. K.

    1983-01-01

    Porous plugs serve as both entropy rejection devices and phase separation components separating the vapor phase on the downstream side from liquid Helium 2 upstream. The liquid upstream is the cryo-reservoir fluid needed for equipment cooling by means of Helium 2, i.e Helium-4 below its lambda temperature in near-saturated states. The topics outlined are characteristic lengths, transport equations and plug results.

  1. An Updated Equilibrium Machine

    NASA Astrophysics Data System (ADS)

    Schultz, Emeric

    2008-08-01

    A device that can demonstrate equilibrium, kinetic, and thermodynamic concepts is described. The device consists of a leaf blower attached to a plastic container divided into two chambers by a barrier of variable size and form. Styrofoam balls can be exchanged across the barrier when the leaf blower is turned on and various air pressures are applied. Equilibrium can be approached from different distributions of balls in the container under different conditions. The Le Chtelier principle can be demonstrated. Kinetic concepts can be demonstrated by changing the nature of the barrier, either changing the height or by having various sized holes in the barrier. Thermodynamic concepts can be demonstrated by taping over some or all of the openings and restricting air flow into container on either side of the barrier.

  2. Absolute Equilibrium Entropy

    NASA Technical Reports Server (NTRS)

    Shebalin, John V.

    1997-01-01

    The entropy associated with absolute equilibrium ensemble theories of ideal, homogeneous, fluid and magneto-fluid turbulence is discussed and the three-dimensional fluid case is examined in detail. A sigma-function is defined, whose minimum value with respect to global parameters is the entropy. A comparison is made between the use of global functions sigma and phase functions H (associated with the development of various H-theorems of ideal turbulence). It is shown that the two approaches are complimentary though conceptually different: H-theorems show that an isolated system tends to equilibrium while sigma-functions allow the demonstration that entropy never decreases when two previously isolated systems are combined. This provides a more complete picture of entropy in the statistical mechanics of ideal fluids.

  3. Solving isobaric interferences in Secondary Ion Mass Spectrometry: The case of Am and Pu in irradiated thorium-based fuel

    NASA Astrophysics Data System (ADS)

    Portier, S.; Degueldre, C.; Kivel, N.

    2012-07-01

    Secondary Ion Mass Spectrometry (SIMS) is routinely used to provide radial isotopic distribution of actinides in irradiated nuclear fuel samples but the measurements are mainly qualitative because many isobaric interferences remain. A simple method to solve the isobaric interferences between Am and Pu for mass 241 and 242 is proposed in this work. The method is based on isotope ratio measurements currently gained by SIMS. The discussion of the results includes the evaluation of the limit of utilization of this approach as well as the enhancement possibility. The method is applied on thorium-based fuels, which represent a sustainable alternative to the classical uranium-based fuels commonly used in most of power plants around the world.

  4. The manometric sorptomat—an innovative volumetric instrument for sorption measurements performed under isobaric conditions

    NASA Astrophysics Data System (ADS)

    Kudasik, Mateusz

    2016-03-01

    The present paper discusses the concept of measuring the process of sorption by means of the volumetric method, developed in such a way as to allow measurements performed under isobaric conditions. On the basis of the concept in question, a prototype of a sorption instrument was built: the manometric sorptomat. The paper provides a detailed description of the idea of the instrument, and of the way it works. In order to evaluate the usefulness of the device in sorption measurements carried out under laboratory conditions, comparative studies were conducted, during which the results of sorption measurements obtained with the developed instrument were compared with the results Mateusz obtained with a reference device. The objects of comparison were the sorption capacities of hard coal samples, calculated on the basis of the established courses of the methane sorption process. The results were regarded as compatible if the compared values fell within the range of the measurement uncertainty of the two devices. For the sake of the comparative studies, fifteen granular samples of hard coal—representing the 0.20–0.25 mm grain fraction and coming from various mines of the Upper Silesian Coal Basin—were used. After comparing the results obtained with the original manometric sorptomat with the results obtained with the gravimetric reference device, it was observed that the compatibility of measurements of sorption capacities was over 90%, based on the defined criterion of the measurement compatibility.

  5. Search for isobar-analog states of superheavy hydrogen isotopes5-7He

    NASA Astrophysics Data System (ADS)

    Chernyshev, B. A.; Gurov, Yu B.; Korotkova, L. Yu; Kuznetsov, D. S.; Lapushkin, S. V.; Tel'kushev, M. V.; Schurenkova, T. D.

    2016-02-01

    Search for isobar-analog states (IAS) of superheavy hydrogen isotopes 5-7H was performed among the high-excited states of helium isotopes 5-7He. The excited spectra were measured in stopped pion absorption by light nuclei. The experiment was performed at low energy pion channel of LANL with two-arm multilayer semiconductor spectrometer. Excited states of 5-7He were observed in three-body reaction channels on 10,11B nuclei. Several excited levels were observed for the first time. 6He excited state with Ex = 27.0(8) MeV observed in 10B(π-,pt)X channel is an IAS candidate for 6H with Er ∼ 5.5 MeV. 7He excited state with Ex = 24.8(4) MeV observed in 10B(π-,pd)X, nB(π-,pt)X and nB(π-,dd)X channels is an IAS candidate for 7H with Er ∼ 3 MeV.

  6. Efficient Isobar Suppression by Photodetachment in a RF Quadrupole Ion Cooler

    SciTech Connect

    Liu, Y.; Havener, C. C.; Beene, J. R.; Lewis, T. L.; Galindo-Uribarri, A.

    2009-03-10

    A highly efficient method for suppressing isobar contaminants in negative radioactive ion beams by photodetachment is demonstrated. A laser beam having the appropriate photon energy is used to selectively neutralize the contaminant if the electron affinity of the contaminant is lower than the electron affinity of the desired radioactive ions. The photodetachment efficiency can be dramatically increased when the laser-ion interaction is made inside a radio frequency quadrupole ion beam cooler where the ion residence time can be a few milliseconds. In off-line experiments with ion beams of stable isotopes, more than 99.9% suppression of S{sup -} and O{sup -} ions by photodetachment has been obtained. These ions would be the contaminants of desired beams of Cl{sup -} and F{sup -}, respectively. Under similar conditions no reduction in Cl{sup -} and F{sup -} ions was observed. The off-line results demonstrate the potential of this technique for on-line purification of a number of interesting radioactive beams and possible applications in accelerator mass spectrometry.

  7. Efficient Isobar Suppression by Photodetachment in a RF Quadrupole Ion Cooler

    SciTech Connect

    Liu, Yuan; Havener, Charles C; Lewis, Thomas L.; Galindo-Uribarri, Alfredo {nmn}; Beene, James R

    2009-01-01

    A highly efficient method for suppressing isobar contaminants in negative radioactive ion beams by photodetachment is demonstrated. A laser beam having the appropriate photon energy is used to selectively neutralize the contaminant if the electron affinity of the contaminant is lower than the electron affinity of the desired radioactive ions. The photodetachment efficiency can be dramatically increased when the laser-ion interaction is made inside a radio frequency quadrupole ion beam cooler where the ion residence time can be a few milliseconds. In off-line experiments with ion beams of stable isotopes, more than 99.9% suppression of S- and O- ions by photodetachment has been obtained. These ions would be the contaminants of desired beams of Cl- and F-, respectively. Under similar conditions no reduction in Cl- and F- ions was observed. The off-line results demonstrate the potential of this technique for on-line purification of a number of interesting radioactive beams and possible applications in accelerator mass spectrometry.

  8. Analysis of abscisic acid responsive proteins in Brassica napus guard cells by multiplexed isobaric tagging.

    PubMed

    Zhu, Mengmeng; Simons, Brigitte; Zhu, Ning; Oppenheimer, David G; Chen, Sixue

    2010-02-10

    Guard cells, which form stomata on the leaf epidermis, play important roles in plant gas exchange and defense against pathogens. Abscisic acid (ABA) is a phytohormone that can be induced by drought and leads to stomatal closure. Guard cells have been a premier model system for studying ABA signal transduction. Despite significant progress on the identification of molecular components in the ABA signaling pathway, our knowledge of the protein components is very limited. Here, we employ a recently developed multiplexed isobaric tagging technology to identify ABA-responsive proteins in Brassica napus guard cells. A total of 431 unique proteins were identified with relative quantitative information in control and ABA-treated samples. Proteins involved in stress and defense constituted a major group among the 66 proteins with increased abundance. Thirty-eight proteins were decreased in abundance and fell into several functional groups including metabolism and protein synthesis. Many of the proteins have not been reported as being ABA responsive or involved in stomatal movement. A large percentage of the protein-coding genes contained ABA-responsive elements. This study not only established a comprehensive inventory of ABA-responsive proteins, but also identified new proteins for further investigation of their functions in guard cell ABA signaling. PMID:19913118

  9. Optimized proteomic analysis of a mouse model of cerebellar dysfunction using amine-specific isobaric tags.

    PubMed

    Hu, Jun; Qian, Jin; Borisov, Oleg; Pan, Sanqiang; Li, Yan; Liu, Tong; Deng, Longwen; Wannemacher, Kenneth; Kurnellas, Michael; Patterson, Christa; Elkabes, Stella; Li, Hong

    2006-08-01

    Recent proteomic applications have demonstrated their potential for revealing the molecular mechanisms underlying neurodegeneration. The present study quantifies cerebellar protein changes in mice that are deficient in plasma membrane calcium ATPase 2 (PMCA2), an essential neuronal pump that extrudes calcium from cells and is abundantly expressed in Purkinje neurons. PMCA2-null mice display motor dyscoordination and unsteady gait deficits observed in neurological diseases such as multiple sclerosis and ataxia. We optimized an amine-specific isobaric tags (iTRAQ)-based shotgun proteomics workflow for this study. This workflow took consideration of analytical variance as a function of ion signal intensity and employed biological repeats to aid noise reduction. Even with stringent protein identification criteria, we could reliably quantify nearly 1000 proteins, including many neuronal proteins that are important for synaptic function. We identified 21 proteins that were differentially expressed in PMCA2-null mice. These proteins are involved in calcium homeostasis, cell structure and chromosome organization. Our findings shed light on the molecular changes that underlie the neurological deficits observed in PMCA2-null mice. The optimized workflow presented here will be valuable for others who plan to implement the iTRAQ method. PMID:16800037

  10. Pion absorption reaction on 2H and 3He in the ?-isobar region

    NASA Astrophysics Data System (ADS)

    Kamada, H.; Locher, M. P.; Lee, T.-S. H.; Golak, J.; Markushin, V. E.; Glckle, W.; Wita? A, H.

    1998-03-01

    By using Faddeev equations the absorption of ?+ on 3He in the ?-isobar region is investigated with the final state three-nucleon interaction. We calculated the NN - N?t-matrix and ?N ? ? vertex from a phenomenological model for NN and ?d reactions. In case of neglecting the initial pion scattering effects the theoretically predicted peaks of the pion absorption cross sections for 2H and 3He occur at too high an energy with respect to the data. It is shown that the final state three-nucleon interactions have a negligible effect on the magnitude and the shift of the peak position. By a small modification of the ? bare mass and the ?N? coupling strength the peak positions of the absorption cross sections of 2H and 3He are simultaneously brought to the correct peak position. The Dalitz plots of the outgoing three protons are shown and compared to the recent PSI measurements using kinematics cuts which almost eliminate the contribution from quasi free pion absorption.

  11. Proteomic analysis of astrocytic secretion that regulates neurogenesis using quantitative amine-specific isobaric tagging

    SciTech Connect

    Yan, Hu; Zhou, Wenhao; Wei, Liming; Zhong, Fan; Yang, Yi

    2010-01-08

    Astrocytes are essential components of neurogenic niches that affect neurogenesis through membrane association and/or the release of soluble factors. To identify factors released from astrocytes that could regulate neural stem cell differentiation and proliferation, we used mild oxygen-glucose deprivation (OGD) to inhibit the secretory capacity of astrocytes. Using the Transwell co-culture system, we found that OGD-treated astrocytes could not promote neural stem cell differentiation and proliferation. Next, isobaric tagging for the relative and absolute quantitation (iTRAQ) proteomics techniques was performed to identify the proteins in the supernatants of astrocytes (with or without OGD). Through a multi-step analysis and gene ontology classification, 130 extracellular proteins were identified, most of which were involved in neuronal development, the inflammatory response, extracellular matrix composition and supportive functions. Of these proteins, 44 had never been reported to be produced by astrocytes. Using ProteinPilot software analysis, we found that 60 extracellular proteins were significantly altered (27 upregulated and 33 downregulated) in the supernatant of OGD-treated astrocytes. Among these proteins, 7 have been reported to be able to regulate neurogenesis, while others may have the potential to regulate neurogenesis. This study profiles the major proteins released by astrocytes, which play important roles in the modulation of neurogenesis.

  12. Aqua ions-graphene interfacial and confinement behavior: Insights from isobaric-isothermal molecular dynamics

    SciTech Connect

    Chialvo, A. A.; Cummings, Peter T.

    2011-06-16

    We carry out a systematic microstructural characterization of the solidfluid interface (SFI) of water and simple metal chloride aqueous solutions in contact with a free-standing plate or with two such plates separated by an interplate distance 0 ? h () ? 30 at ambient conditions via isothermalisobaric molecular dynamics. With this characterization, we target the interrogation of the system in search for answers to fundamental questions regarding the structure of the external and internal (confined) SFIs, the effect of the differential hydration behavior among species, and its link to species expulsion from confinement. For water at ambient conditions, we found that the structure of the external SFIs is independent of the interplate distance h in the range 0 ? h () ? 30, that is, the absence of wall-mediated correlation effects between external and internal SFIs, and that for h < 9 the slit-pores dewet. Moreover, we observed a selective expulsion of ions caused by the differential hydration between the anion and the cations with a consequent charging of the slit-pore. All these observations were interpreted in terms of the axial profiles for precisely defined order parameters, including tetrahedral configuration, hydrogen bonding, and species coordination numbers.

  13. Excitation energies of double isobar-analog states in heavy nuclei

    SciTech Connect

    Poplavskii, I. V.

    1988-12-01

    Several new relationships are established for isomultiplets on the basis of a theory in which the Coulomb coupling constant (CCC) is allowed to be complex. In particular, the following rule is formulated: the energies for fission or decay of members of an isomultiplet into a charged cluster and members of the corresponding daughter isomultiplet are equidistant. This relationship is well satisfied for isomultiplets with /ital A/less than or equal to60. By extrapolating the rule for fission and decay energies to the region of heavy nuclei, the excitation energies /ital E//sub /ital x// of double isobar-analog states (DIASs) are found for the nuclei /sup 197,199/Hg, /sup 205/Pb, /sup 205 - -209/Po, /sup 209/At, and /sup 238/Pu. A comparison of the computed energies /ital E//sub /ital x// with the experimentally measured values for /sup 208/Po attest to the reliability and good accuracy of the method proposed here when used to determine the excitation energies of DIASs in heavy nuclei.

  14. Differentiating Isobaric Steroid Hormone Metabolites Using Multi-Stage Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Tedmon, Lauren; Barnes, Jeremy S.; Nguyen, Hien P.; Schug, Kevin A.

    2013-03-01

    Steroid hormones and their metabolites are currently undergoing clinical trials as potential therapeutics for traumatic brain injury (TBI). To support this work, it is necessary to develop improved procedures for differentiating isobaric species in this compound class. Equilin sulfate (E-S), estrone sulfate (E1-S), 17α-dihydroequilin sulfate (ADHE-S), and 17β-dihydroequilin sulfate (BDHE-S) are primary constituents in hormone replacement therapies, such as Premarin, which are among pharmaceuticals being investigated for TBI treatment. The latter three compounds are isomers and can be difficult to differentiate in trace analytical determinations. In this work, a systematic study of the fragmentation of ADHE-S, BDHE-S, E1-S, and E-S under different stages of higher order tandem mass spectrometry (MSn) and variation of collision energy, allowed optimization of conditions for distinguishing the isomeric structures. For epimeric variants (e.g., ADHE-S versus BDHE-S; α- versus β-stereoisomerization in the C-17 position), differentiation was achieved at MS4 and fragmentation was demonstrated through MS5. Computational analysis was performed to further explore differences in the fragmentation pathways due to changes in stereochemistry.

  15. Improved Isobaric Tandem Mass Tag Quantification by Ion Mobility-Mass Spectrometry

    PubMed Central

    Li, Lingjun

    2014-01-01

    Isobaric tandem mass tags are an attractive alternative to mass difference tags and label free approaches for quantitative proteomics due to the high degree of multiplexing that can be performed with their implementation. A drawback of tandem mass tags are that the co-isolation and co-fragmentation of labeled peptide precursors can result in chimeric MS/MS spectra that can underestimate the fold-change expression of each peptide. Two methods (QuantMode and MS3) have addressed this concern for ion trap and orbitrap instruments, but there is still a need to solve this problem for quadrupole time-of-flight (Q-TOF) instruments. Ion mobility (IM) separations coupled to Q-TOF instruments have the potential to mitigate MS/MS spectra chimeracy since IM-MS has the ability to separate ions based on charge, m/z, and collision cross section (CCS). This work presents results that showcase the power of IM-MS to improve tandem mass tag peptide quantitation accuracy by resolving co-isolated differently charged and same charged peptides prior to MS/MS fragmentation. PMID:24677527

  16. Equilibrium Electroconvective Instability

    NASA Astrophysics Data System (ADS)

    Rubinstein, I.; Zaltzman, B.

    2015-03-01

    Since its prediction 15 years ago, hydrodynamic instability in concentration polarization at a charge-selective interface has been attributed to nonequilibrium electro-osmosis related to the extended space charge which develops at the limiting current. This attribution had a double basis. On the one hand, it has been recognized that neither equilibrium electro-osmosis nor bulk electroconvection can yield instability for a perfectly charge-selective solid. On the other hand, it has been shown that nonequilibrium electro-osmosis can. The first theoretical studies in which electro-osmotic instability was predicted and analyzed employed the assumption of perfect charge selectivity for the sake of simplicity and so did the subsequent studies of various time-dependent and nonlinear features of electro-osmotic instability. In this Letter, we show that relaxing the assumption of perfect charge selectivity (tantamount to fixing the electrochemical potential of counterions in the solid) allows for the equilibrium electroconvective instability. In addition, we suggest a simple experimental test for determining the true, either equilibrium or nonequilibrium, origin of instability in concentration polarization.

  17. Systematic Comparison of Label-Free, Metabolic Labeling, and Isobaric Chemical Labeling for Quantitative Proteomics on LTQ Orbitrap Velos

    SciTech Connect

    Li, Zhou; Adams, Rachel M; Chourey, Karuna; Hurst, Gregory {Greg} B; Hettich, Robert {Bob} L; Pan, Chongle

    2012-01-01

    A variety of quantitative proteomics methods have been developed, including label-free, metabolic labeling, and isobaric chemical labeling using iTRAQ or TMT. Here, these methods were compared in terms of the depth of proteome coverage, quantification accuracy, precision, and reproducibility using a high-performance hybrid mass spectrometer, LTQ Orbitrap Velos. Our results show that (1) the spectral counting method provides the deepest proteome coverage for identification, but its quantification performance is worse than labeling-based approaches, especially the quantification reproducibility; (2) metabolic labeling and isobaric chemical labeling are capable of accurate, precise, and reproducible quantification and provide deep proteome coverage for quantification. Isobaric chemical labeling surpasses metabolic labeling in terms of quantification precision and reproducibility; (3) iTRAQ and TMT perform similarly in all aspects compared in the current study using a CID-HCD dual scan configuration. Based on the unique advantages of each method, we provide guidance for selection of the appropriate method for a quantitative proteomics study.

  18. Structural design using equilibrium programming

    NASA Technical Reports Server (NTRS)

    Scotti, Stephen J.

    1992-01-01

    Multiple nonlinear programming methods are combined in the method of equilibrium programming. Equilibrium programming theory has been appied to problems in operations research, and in the present study it is investigated as a framework to solve structural design problems. Several existing formal methods for structural optimization are shown to actually be equilibrium programming methods. Additionally, the equilibrium programming framework is utilized to develop a new structural design method. Selected computational results are presented to demonstrate the methods.

  19. MRI analysis of the ISOBAR TTL internal fixation system for the dynamic fixation of intervertebral discs: a comparison with rigid internal fixation

    PubMed Central

    2014-01-01

    Objectives Using magnetic resonance imaging (MRI), we analyzed the efficacy of the posterior approach lumbar ISOBAR TTL internal fixation system for the dynamic fixation of intervertebral discs, with particular emphasis on its effects on degenerative intervertebral disc disease. Methods We retrospectively compared the MRIs of 54 patients who had previously undergone either rigid internal fixation of the lumbar spine or ISOBAR TTL dynamic fixation for the treatment of lumbar spondylolisthesis. All patients had received preoperative and 6-, 12-, and 24-month postoperative MRI scans of the lumbar spine with acquisition of both routine and diffusion-weighted images (DWI). The upper-segment discs of the fusion were subjected to Pfirrmann grading, and the lumbar intervertebral discs in the DWI sagittal plane were manually drawn; the apparent diffusion coefficient (ADC) value was measured. Results ADC values in the ISOBAR TTL dynamic fixation group measured at the 6-, 12-, and 24-month postoperative MRI studies were increased compared to the preoperative ADC values. The ADC values in the ISOBAR TTL dynamic fixation group at 24months postoperatively were significantly different from the preoperative values (P?ISOBAR TTL dynamic fixation group (P?ISOBAR TTL internal fixation system can prevent or delay the degeneration of intervertebral discs. PMID:24898377

  20. High-pressure vapor-liquid equilibria for CO[sub 2] + benzonitrile, CO[sub 2] + benzyl alcohol, CO[sub 2] + 2-tert-butylphenol, CO[sub 2] + methoxybenzene, and CO[sub 2] + 1,2,3,4-Tetrahydronaphthalene at temperatures between 313 and 393 K and pressures up to 20 MPa

    SciTech Connect

    Walther, D.; Maurer, G. )

    1993-04-01

    High-pressure vapor-liquid equilibria are reported for CO[sub 2] + benzonitrile, CO[sub 2] + benzyl alcohol, CO[sub 2] + 1-tert-butylphenol, CO[sub 2] + methoxybenzene, and CO[sub 2] + 1,2,3,4-tetrahydronaphthalene at three temperatures from 313 to 393 K and pressures up to 20 MPa. The investigations were made by using a flow-type apparatus. The results for CO[sub 2] + methoxybenzene are compared to literature values. On the other systems no literature values are available.

  1. Principles of the equilibrium theory of small multicomponent systems in three aggregate states

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.

    2015-11-01

    Principles of the molecular statistical theory of small multicomponent drops/microcrystals in a three-dimensional bulk and in two-dimensional adsorption systems are developed. Equations of the theory are derived using the cluster approach. The theory describes discrete distributions of molecules in space (on a size scale comparable to the molecular size) and continuous molecular distributions (at short distances inside cells) upon their translational and vibrational motions. The theory provides a unified description of the equilibrium molecular distributions in three aggregate states and at their interfaces. Pair intermolecular interaction potentials (such as the Mie potential) in several coordination spheres that determine lattice structure compressibility are taken into account. For simplicity, it is considered that the sizes of mixture components are virtually the same. Structural cell distribution functions for the transition region of curved interfaces are derived. Expressions for the pressure tensor components inside small bodies are obtained, allowing us to calculate the thermodynamic characteristics of a vapor-liquid interface, including surface tension. Questions regarding the consistency between the theory of phase transitions in small systems and the traditional theory of associate (cluster) formation and the transition to systems limited in the total volume value are discussed.

  2. Step free energies at faceted solid-liquid interfaces from equilibrium molecular dynamics simulations.

    PubMed

    Frolov, T; Asta, M

    2012-12-01

    In this work a method is proposed for computing step free energies for faceted solid-liquid interfaces based on atomistic simulations. The method is demonstrated in an application to (111) interfaces in elemental Si, modeled with the classical Stillinger-Weber potential. The approach makes use of an adiabatic trapping procedure, and involves simulations of systems with coexisting solid and liquid phases separated by faceted interfaces containing islands with different sizes, for which the corresponding equilibrium temperatures are computed. We demonstrate that the calculated coexistence temperature is strongly affected by the geometry of the interface. We find that island radius is inversely proportional to superheating, allowing us to compute the step free energy by fitting simulation data within the formalism of classical nucleation theory. The step free energy value is computed to be ?(st) = 0.103 0.005 10(-10) J/m. The approach outlined in this work paves the way to the calculation of step free energies relevant to the solidification of faceted crystals from liquid mixtures, as encountered in nanowire growth by the vapor-liquid-solid mechanism and in alloy casting. The present work also shows that at low undercoolings the Stillinger-Weber interatomic potential for Si tends to crystallize in the wurtzite, rather than the diamond-cubic structure. PMID:23231218

  3. Step free energies at faceted solid-liquid interfaces from equilibrium molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Frolov, T.; Asta, M.

    2012-12-01

    In this work a method is proposed for computing step free energies for faceted solid-liquid interfaces based on atomistic simulations. The method is demonstrated in an application to (111) interfaces in elemental Si, modeled with the classical Stillinger-Weber potential. The approach makes use of an adiabatic trapping procedure, and involves simulations of systems with coexisting solid and liquid phases separated by faceted interfaces containing islands with different sizes, for which the corresponding equilibrium temperatures are computed. We demonstrate that the calculated coexistence temperature is strongly affected by the geometry of the interface. We find that island radius is inversely proportional to superheating, allowing us to compute the step free energy by fitting simulation data within the formalism of classical nucleation theory. The step free energy value is computed to be ?st = 0.103 0.005 10-10 J/m. The approach outlined in this work paves the way to the calculation of step free energies relevant to the solidification of faceted crystals from liquid mixtures, as encountered in nanowire growth by the vapor-liquid-solid mechanism and in alloy casting. The present work also shows that at low undercoolings the Stillinger-Weber interatomic potential for Si tends to crystallize in the wurtzite, rather than the diamond-cubic structure.

  4. Statistical physics ""Beyond equilibrium

    SciTech Connect

    Ecke, Robert E

    2009-01-01

    The scientific challenges of the 21st century will increasingly involve competing interactions, geometric frustration, spatial and temporal intrinsic inhomogeneity, nanoscale structures, and interactions spanning many scales. We will focus on a broad class of emerging problems that will require new tools in non-equilibrium statistical physics and that will find application in new material functionality, in predicting complex spatial dynamics, and in understanding novel states of matter. Our work will encompass materials under extreme conditions involving elastic/plastic deformation, competing interactions, intrinsic inhomogeneity, frustration in condensed matter systems, scaling phenomena in disordered materials from glasses to granular matter, quantum chemistry applied to nano-scale materials, soft-matter materials, and spatio-temporal properties of both ordinary and complex fluids.

  5. Equilibrium of nematic vesicles

    NASA Astrophysics Data System (ADS)

    Napoli, Gaetano; Vergori, Luigi

    2010-11-01

    A variational scheme is proposed which allows the derivation of a concise and elegant formulation of the equilibrium equations for closed fluid membranes, endowed with a nematic microstructure. The nematic order is described by an in-plane nematic director and a degree of orientation, as customary in the theory of uniaxial nematics. The only constitutive ingredient in this scheme is a free-energy density which depends on the vesicle geometry and order parameters. The stress and the couple stress tensors related to this free-energy density are provided. As an application of the proposed scheme, a certain number of special theories are deduced: soap bubbles, lipid vesicles, chiral and achiral nematic membranes, and nematics on curved substrates.

  6. Improved thermometer for intermediate-mass fragments in heavy-ion collisions with isobaric yield ratio difference

    NASA Astrophysics Data System (ADS)

    Ma, Chun-Wang; Ding, Tian-Tian; Qiao, Chun-Yuan; Cao, Xi-Guang

    2015-12-01

    Background: Temperature is an important parameter in studying many important questions in heavy-ion collisions. A thermometer based on the isobaric yield ratio (IYR) has been proposed [Ma et al., Phys. Rev. C 86, 054611 (2012), 10.1103/PhysRevC.86.054611; Phys. Rev. C 88, 014609 (2013), 10.1103/PhysRevC.88.014609]. Purpose: An improved thermometer (TI B) is proposed based on the difference between IYRs. TI B obtained from isobars in different reactions will be compared. Methods: The yields of three isobars are employed in TI B. The residual free energy of the three isobars are replaced by that of the binding energy. No secondary decay modification for odd A fragment is used in TI B. Results: The measured fragment yields in the 140 A MeV40,48Ca+(181Ta9Be) and 58,64Ni+(181Ta9Be), the 1 A GeV124,136Xe+Pb+, and the 112,124Sn+,112,124Sn reactions have been analyzed to obtain TI B from IMFs. TI B from most of the fragments in the 40,48Ca and 58,64Ni reactions is in the range of 0.6 MeV

  7. Microscopic nuclear-structure calculations for the solar-neutrino detector 71Ga and close-lying isobars

    NASA Astrophysics Data System (ADS)

    Holmlund, E.; Suhonen, J.

    2003-02-01

    In the present solar-neutrino experiments, mainly observing the pp contribution of the solar-neutrino flux, an important role is played by 71Ga. The structure of this detector nucleus and three of its isobars have been calculated by using the microscopic quasiparticle-phonon model. Using a realistic effective two-body interaction in a realistic valence space, the method yielded energy spectra in good agreement with experiments. The calculated log ft values for a number of spontaneous and neutrino-induced Gamow-Teller transitions, when compared with the experimental results, gave qualitatively correct but overestimated transition-strength values in most cases.

  8. Observation of a double isobaric analog state in the reaction /sup 209/Bi(. pi. /sup +/,. pi. /sup -/)/sup 209/At

    SciTech Connect

    Morris, C.L.; Thiessen, H.A.; Braithwaite, W.J.; Cottingame, W.B.; Greene, S.J.; Holtkamp, D.B.; Moore, I.B.; Moore, C.F.; Burleson, G.R.; Blanpied, G.S.; Daw, G.H.; Viescas, A.J.

    1980-10-13

    Pion double charge exchange has been used to populate the double isobaric analog state in /sup 209/At with use of the neutron-rich target /sup 209/Bi. The data were obtained at an energy of 292 MeV and at an angle of 5/sup 0/, as the double-charge-eschange reaction mechanism has been shown to be dominated by analog transitions under these conditions in previous work on light nuclei. The measured cross section is found to be in good agreement with semiclassical predictions by Johnson.

  9. The Isospin Admixture of The Ground State and The Properties of The Isobar Analog Resonances In Deformed Nuclei

    SciTech Connect

    Aygor, H. Ali; Maras, Ismail; Cakmak, Necla; Selam, Cevad

    2008-11-11

    Within quasiparticle random phase approximation (QRPA), Pyatov-Salamov method for the self-consistent determination of the isovector effective interaction strength parameter, restoring a broken isotopic symmetry for the nuclear part of the Hamiltonian, is used. The isospin admixtures in the ground state of the parent nucleus, and the isospin structure of the isobar analog resonance (IAR) state are investigated by including the pairing correlations between nucleons for {sup 72-80}Kr isotopes. Our results are compared with the spherical case and with other theoretical results.

  10. Grinding kinetics and equilibrium states

    NASA Technical Reports Server (NTRS)

    Opoczky, L.; Farnady, F.

    1984-01-01

    The temporary and permanent equilibrium occurring during the initial stage of cement grinding does not indicate the end of comminution, but rather an increased energy consumption during grinding. The constant dynamic equilibrium occurs after a long grinding period indicating the end of comminution for a given particle size. Grinding equilibrium curves can be constructed to show the stages of comminution and agglomeration for certain particle sizes.

  11. Structure, thermodynamics, and liquid-vapor equilibrium of ethanol from molecular-dynamics simulations using nonadditive interactions.

    PubMed

    Patel, Sandeep; Brooks, Charles L

    2005-10-22

    We present a molecular-dynamics simulation study of the bulk and liquid-vapor interfacial properties of ethanol using a polarizable force field based on the fluctuating charge (FQ) formalism, as well as the nonpolarizable CHARMM22 force field. Both models are competitive with respect to the prediction of ambient liquid properties such as liquid density, enthalpy of vaporization, dielectric constant, and self-diffusion constants. The polarizable model predicts an average condensed-phase dipole moment of 2.2 D associated with an induced liquid-phase dipole moment of 0.6 D; though qualitatively in agreement with earlier nonadditive models as well as recent Car-Parinello calculations, the current FQ model underestimates the condensed-phase dipole moment. In terms of liquid structure, both models are in agreement with recent neutron-diffraction results of liquid ethanol structure, although the polarizable model predicts the hydroxyl-hydrogen-hydroxyl-hydrogen structure factor in closer agreement with the experimental data. In terms of interfacial properties, both models predict ambient surface tension to within 4% of the experimental value of 22.8 dyncm, while overestimating the surface excess entropy by almost a factor of 2. Both models display the characteristic preferential orientation of interfacial molecules. The polarizable model allows for a monotonic variation of the average molecular dipole moment from the bulk value to that of the vapor phase. Consequently, there is a dramatic difference in the surface potential predicted by the polarizable and nonpolarizable models. The polarizable model estimates a surface potential of -209+/-3 mV, while the nonpolarizable model yields a value of -944+/-10 mV. Finally, based on the vapor-liquid equilibrium simulation data from several temperatures, we estimate the critical properties of both models. As observed with other FQ models for associating fluids (such as water and methanol), and counter to what one would anticipate by modeling more physically the electrostatic response to local environment, the current FQ model underestimates the critical temperature and overestimates the critical density of ethanol; moreover, the FQ model is, in this respect, equivalent to the underlying fixed-charge model. These results further suggest the need to revisit polarizable models in terms of quantitative vapor-liquid equilibrium prediction. PMID:16268707

  12. Structure, thermodynamics, and liquid-vapor equilibrium of ethanol from molecular-dynamics simulations using nonadditive interactions

    NASA Astrophysics Data System (ADS)

    Patel, Sandeep; Brooks, Charles L.

    2005-10-01

    We present a molecular-dynamics simulation study of the bulk and liquid-vapor interfacial properties of ethanol using a polarizable force field based on the fluctuating charge (FQ) formalism, as well as the nonpolarizable CHARMM22 force field. Both models are competitive with respect to the prediction of ambient liquid properties such as liquid density, enthalpy of vaporization, dielectric constant, and self-diffusion constants. The polarizable model predicts an average condensed-phase dipole moment of 2.2D associated with an induced liquid-phase dipole moment of 0.6D; though qualitatively in agreement with earlier nonadditive models as well as recent Car-Parinello calculations, the current FQ model underestimates the condensed-phase dipole moment. In terms of liquid structure, both models are in agreement with recent neutron-diffraction results of liquid ethanol structure, although the polarizable model predicts the hydroxyl-hydrogen-hydroxyl-hydrogen structure factor in closer agreement with the experimental data. In terms of interfacial properties, both models predict ambient surface tension to within 4% of the experimental value of 22.8dyn/cm, while overestimating the surface excess entropy by almost a factor of 2. Both models display the characteristic preferential orientation of interfacial molecules. The polarizable model allows for a monotonic variation of the average molecular dipole moment from the bulk value to that of the vapor phase. Consequently, there is a dramatic difference in the surface potential predicted by the polarizable and nonpolarizable models. The polarizable model estimates a surface potential of -2093mV, while the nonpolarizable model yields a value of -94410mV. Finally, based on the vapor-liquid equilibrium simulation data from several temperatures, we estimate the critical properties of both models. As observed with other FQ models for associating fluids (such as water and methanol), and counter to what one would anticipate by modeling more physically the electrostatic response to local environment, the current FQ model underestimates the critical temperature and overestimates the critical density of ethanol; moreover, the FQ model is, in this respect, equivalent to the underlying fixed-charge model. These results further suggest the need to revisit polarizable models in terms of quantitative vapor-liquid equilibrium prediction.

  13. Napoleon Is in Equilibrium

    NASA Astrophysics Data System (ADS)

    Phillips, Rob

    2015-03-01

    It has been said that the cell is the test tube of the twenty-first century. If so, the theoretical tools needed to quantitatively and predictively describe what goes on in such test tubes lag sorely behind the stunning experimental advances in biology seen in the decades since the molecular biology revolution began. Perhaps surprisingly, one of the theoretical tools that has been used with great success on problems ranging from how cells communicate with their environment and each other to the nature of the organization of proteins and lipids within the cell membrane is statistical mechanics. A knee-jerk reaction to the use of statistical mechanics in the description of cellular processes is that living organisms are so far from equilibrium that one has no business even thinking about it. But such reactions are probably too hasty given that there are many regimes in which, because of a separation of timescales, for example, such an approach can be a useful first step. In this article, we explore the power of statistical mechanical thinking in the biological setting, with special emphasis on cell signaling and regulation. We show how such models are used to make predictions and describe some recent experiments designed to test them. We also consider the limits of such models based on the relative timescales of the processes of interest.

  14. Single and double beta decays in the A=100, A=116 and A=128 triplets of isobars

    NASA Astrophysics Data System (ADS)

    Suhonen, J.; Civitarese, O.

    2014-04-01

    In this paper we analyze the ground-state-to-ground-state two-neutrino double beta (2νββ) decays and single EC and β- decays for the A=100 (100Mo-100Tc-100Ru), A=116 (116Cd-116In-116Sn) and A=128 (128Te-128I-128Xe) triplets of isobars. We use the proton-neutron quasiparticle random-phase approximation (pnQRPA) with realistic G-matrix-derived effective interactions in very large single-particle bases. The purpose is to access the effective value of the axial-vector coupling constant gA in the pnQRPA calculations. We show that the three triplets of isobars represent systems with different characteristics of orbital occupancies and cumulative 2νββ nuclear matrix elements. Our analysis points to a considerably quenched averaged effective value of ≈0.6±0.2 in the pnQRPA calculations.

  15. Comparison of two different doses of intrathecal dexmedetomidine as adjuvant with isobaric ropivacaine in lower abdominal surgery

    PubMed Central

    Singh, Atul Kumar; Singh, Yashpal; Jain, Gaurav; Verma, Ravi Kumar

    2015-01-01

    Background: To augment the subarachnoid block utility, the efficacy of newer molecules as an adjuvant is investigated constantly. Considering the favorable profile of dexmedetomidine, it could have a potential role as an adjuvant to ropivacaine. Aim: We evaluated the efficacy of two different doses of dexmedetomidine as an adjuvant to isobaric ropivacaine, intrathecally. Methods: Ninety patients scheduled for lower abdominal surgery under spinal anesthesia were randomized into three groups to receive 2.5 ml of isobaric ropivacaine (0.75%, 7.5 mg/ml) added to 5 g (10 g/ml) or 10 g (20 g/ml) of dexmedetomidine or 0.5 ml of normal saline in group A, B or C, respectively. Block characteristics were compared as a primary outcome. Statistical Analysis: One-way analysis of variance test, Fisher's exact test/Chi-square test, whichever appropriate. A P < 0.05 was considered significant. Results: Time to achieve desired block was least in group B and maximum in group C. The sensory-motor blockade remained significantly prolonged in group B compared to other groups. Hemodynamic parameters remained stable in all three groups. Conclusion: Among the investigated doses, dexmedetomidine augments the efficacy of intrathecal ropivacaine in a dose-dependent manner, without any untoward side effects. PMID:26712971

  16. Thermodynamic properties of supercritical n-m Lennard-Jones fluids and isochoric and isobaric heat capacity maxima and minima.

    PubMed

    Mairhofer, Jonas; Sadus, Richard J

    2013-10-21

    Molecular dynamics simulations are reported for the thermodynamic properties of n-m Lennard-Jones fluids, where n = 10 and 12, and m = 5 and 6. Results are reported for the thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound at supercritical conditions covering a wide range of fluid densities. The thermodynamic criteria for maxima?minima in the isochoric and isobaric heat capacities are identified and the simulation results are also compared with calculations from Lennard-Jones equations of state. The Johnson et al. [Mol. Phys. 78, 591 (1993)] equation of state can be used to reproduce all heat capacity phenomena reported [T. M. Yigzawe and R. J. Sadus, J. Chem. Phys. 138, 194502 (2013)] from molecular dynamics simulations for the 12-6 Lennard-Jones potential. Significantly, these calculations and molecular dynamics results for other n-m Lennard-Jones potentials support the existence of Cp minima at supercritical conditions. The values of n and m also have a significant influence on many other thermodynamic properties. PMID:24160523

  17. Thermodynamic properties of supercritical n-m Lennard-Jones fluids and isochoric and isobaric heat capacity maxima and minima

    NASA Astrophysics Data System (ADS)

    Mairhofer, Jonas; Sadus, Richard J.

    2013-10-01

    Molecular dynamics simulations are reported for the thermodynamic properties of n-m Lennard-Jones fluids, where n = 10 and 12, and m = 5 and 6. Results are reported for the thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound at supercritical conditions covering a wide range of fluid densities. The thermodynamic criteria for maxima/minima in the isochoric and isobaric heat capacities are identified and the simulation results are also compared with calculations from Lennard-Jones equations of state. The Johnson et al. [Mol. Phys. 78, 591 (1993)] equation of state can be used to reproduce all heat capacity phenomena reported [T. M. Yigzawe and R. J. Sadus, J. Chem. Phys. 138, 194502 (2013)] from molecular dynamics simulations for the 12-6 Lennard-Jones potential. Significantly, these calculations and molecular dynamics results for other n-m Lennard-Jones potentials support the existence of Cp minima at supercritical conditions. The values of n and m also have a significant influence on many other thermodynamic properties.

  18. Rapid-Equilibrium Enzyme Kinetics

    ERIC Educational Resources Information Center

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

  19. Rapid-Equilibrium Enzyme Kinetics

    ERIC Educational Resources Information Center

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is

  20. Equilibrium Shape of Colloidal Crystals.

    PubMed

    Sehgal, Ray M; Maroudas, Dimitrios

    2015-10-27

    Assembling colloidal particles into highly ordered configurations, such as photonic crystals, has significant potential for enabling a broad range of new technologies. Facilitating the nucleation of colloidal crystals and developing successful crystal growth strategies require a fundamental understanding of the equilibrium structure and morphology of small colloidal assemblies. Here, we report the results of a novel computational approach to determine the equilibrium shape of assemblies of colloidal particles that interact via an experimentally validated pair potential. While the well-known Wulff construction can accurately capture the equilibrium shape of large colloidal assemblies, containing O(10(4)) or more particles, determining the equilibrium shape of small colloidal assemblies of O(10) particles requires a generalized Wulff construction technique which we have developed for a proper description of equilibrium structure and morphology of small crystals. We identify and characterize fully several "magic" clusters which are significantly more stable than other similarly sized clusters. PMID:26439330

  1. A randomized controlled study comparing intrathecal hyperbaric bupivacaine-fentanyl mixture and isobaric bupivacaine-fentanyl mixture in common urological procedures

    PubMed Central

    Upadya, Madhusudan; Neeta, S; Manissery, Jesni Joseph; Kuriakose, Nigel; Singh, Rakesh Raushan

    2016-01-01

    Background and Aims: Bupivacaine is available in isobaric and hyperbaric forms for intrathecal use and opioids are used as additives to modify their effects. The aim of this study was to compare the efficacy and haemodynamic effect of intrathecal isobaric bupivacaine-fentanyl mixture and hyperbaric bupivacaine-fentanyl mixture in common urological procedures. Methods: One hundred American Society of Anesthesiologists physical status 1 and 2 patients undergoing urological procedures were randomized into two groups. Group 1 received 3 ml of 0.5% isobaric bupivacaine with 25 μg fentanyl while Group 2 received 3 ml of 0.5% hyperbaric bupivacaine with 25 μg fentanyl. The parameters measured include heart rate, blood pressure, respiratory rate, onset and duration of motor and sensory blockade. Student's unpaired t-test and the χ2 test were used to analyse the results, using the SPSS version 11.5 software. Results: The haemodynamic stability was better with isobaric bupivacaine fentanyl mixture (Group 1) than with hyperbaric bupivacaine fentanyl mixture (Group 2). The mean onset time in Group 1 for both sensory block (4 min) and motor block (5 min) was longer compared with Group 2. The duration of sensory block (127.8 ± 38.64 min) and motor block (170.4 ± 27.8 min) was less with isobaric bupivacaine group compared with hyperbaric bupivacaine group (sensory blockade 185.4 ± 16.08 min and motor blockade 201.6 ± 14.28 min). Seventy percent of patients in Group 2 had maximum sensory block level of T6 whereas it was 53% in Group 1. More patients in Group 1 required sedation compared to Group 2. Conclusion: Isobaric bupivacaine fentanyl mixture was found to provide adequate anaesthesia with minimal incidence of haemodynamic instability. PMID:26962255

  2. Equilibrium and Non-Equilibrium Dust Cluster Modes

    SciTech Connect

    Melzer, Andre; Ivanov, Yuriy; Wolter, Matthias

    2005-10-31

    Simulations of the melting transition of 2D clusters are presented. Equilibrium melting is obtained by increasing the kinetic temperature of the dust particles. Non-equilibrium melting occurs when an additional particle is placed in a layer below the cluster plane. The presence of the lower particle drives the transition by the onset of unstable oscillations. The mode spectra of the two melting processes allow detailed insight into the governing mechanisms.

  3. Understanding thermal equilibrium through activities

    NASA Astrophysics Data System (ADS)

    Pathare, Shirish; Huli, Saurabhee; Nachane, Madhura; Ladage, Savita; Pradhan, Hemachandra

    2015-03-01

    Thermal equilibrium is a basic concept in thermodynamics. In India, this concept is generally introduced at the first year of undergraduate education in physics and chemistry. In our earlier studies (Pathare and Pradhan 2011 Proc. episteme-4 Int. Conf. to Review Research on Science Technology and Mathematics Education pp 169-72) we found that students in India have a rather unsatisfactory understanding of thermal equilibrium. We have designed and developed a module of five activities, which are presented in succession to the students. These activities address the students’ alternative conceptions that underlie their lack of understanding of thermal equilibrium and aim at enhancing their understanding of the concept.

  4. Helical axis stellarator equilibrium model

    SciTech Connect

    Koniges, A.E.; Johnson, J.L.

    1985-02-01

    An asymptotic model is developed to study MHD equilibria in toroidal systems with a helical magnetic axis. Using a characteristic coordinate system based on the vacuum field lines, the equilibrium problem is reduced to a two-dimensional generalized partial differential equation of the Grad-Shafranov type. A stellarator-expansion free-boundary equilibrium code is modified to solve the helical-axis equations. The expansion model is used to predict the equilibrium properties of Asperators NP-3 and NP-4. Numerically determined flux surfaces, magnetic well, transform, and shear are presented. The equilibria show a toroidal Shafranov shift.

  5. Simulations for Teaching Chemical Equilibrium

    NASA Astrophysics Data System (ADS)

    Huddle, Penelope A.; White, Margaret Dawn; Rogers, Fiona

    2000-07-01

    This paper outlines a systematic approach to teaching chemical equilibrium using simulation experiments that address most known alternate conceptions in the topic. Graphs drawn using the data from the simulations are identical to those obtained using real experimental data for reactions that go to equilibrium. This allows easy mapping of the analogy to the target. The requirements for the simulations are simple and inexpensive, making them accessible to even the poorest schools. The simulations can be adapted for all levels, from pupils who are first encountering equilibrium through students in tertiary education to qualified teachers who have experienced difficulty in teaching the topic. The simulations were piloted on four very different audiences. Minor modifications were then made before the Equilibrium Games as reported in this paper were tested on three groups of subjects: a Grade 12 class, college students, and university Chemistry I students. Marked improvements in understanding of the concept were shown in two of the three sets of subjects.

  6. Equilibrium and Orientation in Cephalopods.

    ERIC Educational Resources Information Center

    Budelmann, Bernd-Ulrich

    1980-01-01

    Describes the structure of the equilibrium receptor system in cephalopods, comparing it to the vertebrate counterpart--the vestibular system. Relates the evolution of this complex system to the competition of cephalopods with fishes. (CS)

  7. NUMERICAL VERIFICATION OF EQUILIBRIUM CHEMISTRY

    SciTech Connect

    Piro, Markus; Lewis, Brent; Thompson, Dr. William T.; Simunovic, Srdjan; Besmann, Theodore M

    2010-01-01

    A numerical tool is in an advanced state of development to compute the equilibrium compositions of phases and their proportions in multi-component systems of importance to the nuclear industry. The resulting software is being conceived for direct integration into large multi-physics fuel performance codes, particularly for providing boundary conditions in heat and mass transport modules. However, any numerical errors produced in equilibrium chemistry computations will be propagated in subsequent heat and mass transport calculations, thus falsely predicting nuclear fuel behaviour. The necessity for a reliable method to numerically verify chemical equilibrium computations is emphasized by the requirement to handle the very large number of elements necessary to capture the entire fission product inventory. A simple, reliable and comprehensive numerical verification method is presented which can be invoked by any equilibrium chemistry solver for quality assurance purposes.

  8. Edge equilibrium code for tokamaks

    SciTech Connect

    Li, Xujing; Drozdov, Vladimir V.

    2014-01-15

    The edge equilibrium code (EEC) described in this paper is developed for simulations of the near edge plasma using the finite element method. It solves the Grad-Shafranov equation in toroidal coordinate and uses adaptive grids aligned with magnetic field lines. Hermite finite elements are chosen for the numerical scheme. A fast Newton scheme which is the same as implemented in the equilibrium and stability code (ESC) is applied here to adjust the grids.

  9. Phase equilibrium data for development of correlations for coal fluids

    SciTech Connect

    Robinson, R.L. Jr.; Gasem, K.A.M.; Darwish, N.A.; Raff, A.M.

    1991-02-01

    The overall objective of the authors' work is to develop accurate predictive methods for representations of vapor-liquid equilibria in systems encountered in coal-conversion processes. The objectives pursued in the present project include: (1) Measurements of binary vapor-liquid phase behavior data for selected solute gases (e.g., C{sub 2}H{sub 6}, CH{sub 4}) in a series of paraffinic, naphthenic, and aromatic hydrocarbon solvents to permit evaluations of interaction parameters in models for phase behavior. Solubilities of the gases in the liquid phase have been determined. (2) Evaluation of existing equations of state and other models for representations of phase behavior in systems of the type studied experimentally; development of new correlation frameworks as needed. (3) Generalization of the interaction parameters for the solutes studied to a wide spectrum of heavy solvents; presentation of final results in formats useful in the design/optimization of coal liquefaction processes.

  10. Relevance of equilibrium in multifragmentation

    SciTech Connect

    Furuta, Takuya; Ono, Akira

    2009-01-15

    The relevance of equilibrium in a multifragmentation reaction of very central {sup 40}Ca + {sup 40}Ca collisions at 35 MeV/nucleon is investigated by using simulations of antisymmetrized molecular dynamics (AMD). Two types of ensembles are compared. One is the reaction ensemble of the states at each reaction time t in collision events simulated by AMD, and the other is the equilibrium ensemble prepared by solving the AMD equation of motion for a many-nucleon system confined in a container for a long time. The comparison of the ensembles is performed for the fragment charge distribution and the excitation energies. Our calculations show that there exists an equilibrium ensemble that well reproduces the reaction ensemble at each reaction time t for the investigated period 80{<=}t{<=}300 fm/c. However, there are some other observables that show discrepancies between the reaction and equilibrium ensembles. These may be interpreted as dynamical effects in the reaction. The usual static equilibrium at each instant is not realized since any equilibrium ensemble with the same volume as that of the reaction system cannot reproduce the fragment observables.

  11. The kinetic chemical equilibrium regime

    NASA Astrophysics Data System (ADS)

    Ern, Alexandre; Giovangigli, Vincent

    We investigate reactive gas mixtures in the kinetic chemical equilibrium regime. Our starting point is a generalized Boltzmann equation with a chemical source term valid for arbitrary reaction mechanisms and yielding a positive entropy production. We first study the Enskog expansion in the kinetic chemical equilibrium regime. We derive a new set of macroscopic equations in the zeroth- and first-order regimes, expressing conservation of element densities, momentum and energy. The transport fluxes arising in the Navier-Stokes equilibrium regime are the element diffusion velocities, the heat flux vector and the pressure tensor and are written in terms of transport coefficients. Upon introducing species diffusion velocities, the kinetic equilibrium regime appears to be formally equivalent to the one obtained for gas mixtures in chemical nonequilibrium and then letting the chemical reactions approach equilibrium. The actual values of the transport coefficients are, however, different. Finally, we derive the entropy conservation equation in the Navier-Stokes equilibrium regime and show that the source term is positive and that it is compatible with Onsagers reciprocal relations.

  12. Measurement of Isobaric Heat Capacity of Gaseous Trans-1,3,3,3-tetrafluoropropene (HFO 1234ze (E) )

    NASA Astrophysics Data System (ADS)

    Kagawa, Noboru; Matsuguchi, Atsushi; Watanabe, Koichi

    The specific isobaric heat capacity (cp) was measured for HFO-1234ze(E) (trans-1,3,3,3-tetrafluoropropene) in the gas phase. HFO-1234ze(E) has a lower GWP value of 6 and is one of new environment-friendly refrigerants. Nineteen measurements for HFO-1234ze(E) were obtained at temperatures from 303 K to 363 K and at pressures from 0.35 MPa to 1.3 MPa. The expanded uncertainty (k=2) of the temperature measurements is estimated to be less 22 mK, and that of the pressure measurements is less 4.4 kPa. The expanded uncertainty for cp is estimated to range from 14 to 21 J.kg-1.K-1.

  13. The separation and analysis of symmetric and asymmetric dimethylarginine and other hydrophilic isobaric compounds using aqueous normal phase chromatography.

    PubMed

    Pesek, Joseph J; Matyksa, Maria T; Modereger, Brent; Hasbun, Alejandra; Phan, Vy T; Mehr, Zahra; Guzman, Mariano; Watanable, Seiichiro

    2016-04-01

    Two biologically important compounds with clinical relevance, asymmetric dimethylarginine and symmetric dimethylarginine, are analyzed using aqueous normal phase chromatography on silica hydride-based columns. Two different stationary phases were tested, a commercially available Diamond Hydride™ and a 2-acrylamido-2-methylpropane sulfonic acid experimental column. Two types of analytical protocols were investigated: analysis of the compounds when separation was achieved and analysis of the compounds with partial chromatographic separation. Urine samples from tuberculosis patients were tested for levels of asymmetric and symmetric dimethylarginine. The mass spectrometric technique of in-source fragmentation that can provide data similar to a tandem mass analyzer was evaluated as a means of identification and quantitation of the two compounds when complete separation is not achieved. This same protocol was also evaluated for two other isobaric compounds, glucose-1 and glucose-6 phohsphate, and leucine and isoleucine. PMID:26952368

  14. A vibrational spectroscopic study of structure evolution of water dissolved in supercritical carbon dioxide under isobaric heating.

    PubMed

    Oparin, R; Tassaing, T; Danten, Y; Besnard, M

    2004-06-01

    A combination of Raman scattering spectroscopy and infrared absorption was applied to investigate the structural evolution of water dissolved in supercritical carbon dioxide under isobaric heating (T=40-340 degrees C, P=250 bar). Quantitative analysis of experimental spectra allowed us to determine that at relatively moderate temperatures water dissolved in CO(2)-rich phase exists only under monomeric form (solitary water surrounding by CO(2) molecules), but hydrogen-bonded species, namely, dimers, begin to appear upon heating. At the same time, the ratio of dimers to monomers concentration increases with further temperature increase and at temperatures close to the temperature of total miscibility of the mixture (T=366 degrees C, P=250 bar), water dimers only are present in the CO(2)-rich phase. PMID:15268095

  15. Spectroscopy of the neutron-deficient isobars {sup 163}Re and {sup 163}W using tagging techniques

    SciTech Connect

    Joss, D. T.; Thomson, J.; Page, R. D.; Bianco, L.; Darby, I. G.; Grahn, T.; Pakarinen, J.; Paul, E. S.; Scholey, C.; Eeckhaudt, S.; Greenlees, P. T.; Jones, P. M.; Julin, R.; Juutinen, S.; Ketelhut, S.; Leino, M.; Leppaennen, A.-P.; Nyman, M.; Rahkila, P.; Sorri, J.

    2008-11-11

    Selective tagging techniques have been used to establish new band structures in the transitional isobars {sup 163}Re and {sup 163}W. These nuclei were produced in the {sup 106}Cd({sup 60}Ni, xp yn {gamma}) reaction at a bombarding energy of 270 MeV. Prompt {gamma} rays were detected at the target position using the JUROGAM spectrometer while recoiling ions were separated by the RITU separator and implanted into the GREAT spectrometer. At low spin, the yrast band of {sup 163}Re is shown to be a strongly coupled collective band based on a proton h{sub 11/2} configuration. In {sup 163}W, the decay path of the 13/2{sup +} isomeric state to the ground state has been identified and negative parity structures based on the ground state established.

  16. Isobar channels in the production of {pi}{sup +}{pi}{sup -} pairs on a proton by virtual photons

    SciTech Connect

    Burkert, V. D.; Mokeev, V. I.; Shvedunov, N. V.; Boluchevskii, A. A.; Battaglieri, M.; Golovach, E. N.; Elouardrhiri, L.; Joo, K.; Isupov, E. L.; Ishkhanov, B. S.; Markov, N. S.; Ripani, M.; Ricco, J.; Sapunenko, V. V.; Taiuti, M.; Fedotov, G. V.

    2007-03-15

    A new approach is developed for evaluating contributions of various isobar channels to the double charged-pion production in the reactions {gamma}{sub r,v}p {sup {yields}} {pi}{sup +}{pi}{sup -}p. This approach makes it possible to determine both respective cross sections and amplitudes for quasi-two-particle channels from a fit to data on cross sections for a three-particle final state. The diffractive anzatz, which is widely used to describe rho-meson production, is modified to meet the purpose of the description of data in the near-threshold and subthreshold regions. The cross sections for rho-meson electroproduction in the energy region of nucleon-resonance excitation are determined for the first time on the basis of the latest data of the CLAS Collaboration.

  17. Proteomic Identification and Quantification of S-glutathionylation in Mouse Macrophages Using Resin-Assisted Enrichment and Isobaric Labeling

    SciTech Connect

    Su, Dian; Gaffrey, Matthew J.; Guo, Jia; Hatchell, Kayla E.; Chu, Rosalie K.; Clauss, Therese RW; Aldrich, Joshua T.; Wu, Si; Purvine, Samuel O.; Camp, David G.; Smith, Richard D.; Thrall, Brian D.; Qian, Weijun

    2014-02-11

    Protein S-glutathionylation (SSG) is an important regulatory posttranslational modification of protein cysteine (Cys) thiol redox switches, yet the role of specific cysteine residues as targets of modification is poorly understood. We report a novel quantitative mass spectrometry (MS)-based proteomic method for site-specific identification and quantification of S-glutathionylation across different conditions. Briefly, this approach consists of initial blocking of free thiols by alkylation, selective reduction of glutathionylated thiols and enrichment using thiol affinity resins, followed by on-resin tryptic digestion and isobaric labeling with iTRAQ (isobaric tags for relative and absolute quantitation) for MS-based identification and quantification. The overall approach was validated by application to RAW 264.7 mouse macrophages treated with different doses of diamide to induce glutathionylation. A total of 1071 Cys-sites from 690 proteins were identified in response to diamide treatment, with ~90% of the sites displaying >2-fold increases in SSG-modification compared to controls.. This approach was extended to identify potential SSG modified Cys-sites in response to H2O2, an endogenous oxidant produced by activated macrophages and many pathophysiological stimuli. The results revealed 364 Cys-sites from 265 proteins that were sensitive to S-glutathionylation in response to H2O2 treatment. These proteins covered a range of molecular types and molecular functions with free radical scavenging, and cell death and survival included as the most significantly enriched functional categories. Overall the results demonstrate that our approach is effective for site-specific identification and quantification of S-glutathionylated proteins. The analytical strategy also provides a unique approach to determining the major pathways and cell processes most susceptible to glutathionylation at a proteome-wide scale.

  18. Molecular dynamics in the isothermal-isobaric ensemble: the requirement of a "shell" molecule. III. Discontinuous potentials.

    PubMed

    Uline, Mark J; Corti, David S

    2008-07-01

    Based on the approach of Gruhn and Monson [Phys. Rev. E 63, 061106 (2001)], we present a new method for deriving the collisions dynamics for particles that interact via discontinuous potentials. By invoking the conservation of the extended Hamiltonian, we generate molecular dynamics (MD) algorithms for simulating the hard-sphere and square-well fluids within the isothermal-isobaric (NpT) ensemble. Consistent with the recent rigorous reformulation of the NpT ensemble partition function, the equations of motion impose a constant external pressure via the introduction of a shell particle of known mass [M. J. Uline and D. S. Corti, J. Chem. Phys. 123, 164101 (2005); 123, 164102 (2005)], which serves to define uniquely the volume of the system. The particles are also connected to a temperature reservoir through the use of a chain of Nose-Hoover thermostats, the properties of which are not affected by a hard-sphere or square-well collision. By using the Liouville operator formalism and the Trotter expansion theorem to integrate the equations of motion, the update of the thermostat variables can be decoupled from the update of the positions of the particles and the momentum changes upon a collision. Hence, once the appropriate collision dynamics for the isobaric-isenthalpic (NpH) equations of motion is known, the adaptation of the algorithm to the NpT ensemble is straightforward. Results of MD simulations for the pure component square-well fluid are presented and serve to validate our algorithm. Finally, since the mass of the shell particle is known, the system itself, and not a piston of arbitrary mass, controls the time scales for internal pressure and volume fluctuations. We therefore consider the influence of the shell particle algorithm on the dynamics of the square-well fluid. PMID:18624470

  19. Shape characteristics of equilibrium and non-equilibrium fractal clusters

    NASA Astrophysics Data System (ADS)

    Mansfield, Marc L.; Douglas, Jack F.

    2013-07-01

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other between the viscosity and hydrodynamic radii, as potential measures of shape anisotropy. We also find a strong correlation between anisotropy and effective fractal dimension. These observations should provide new practical methods for quantifying the nature of particle clustering in diverse contexts.

  20. Drop tower experiment for performance evaluation of gas-liquid equilibrium thruster for small spacecraft

    NASA Astrophysics Data System (ADS)

    Motooka, Norizumi; Yamamoto, Takayuki; Mori, Osamu; Okano, Yoshinobu; Kishino, Yoshihiro; Kawaguchi, Junichiro

    JAXA/ISAS is developing the gas-liquid equilibrium thruster for a small spacecraft. In small spacecrafts, the thruster system must be simple and its weight must be light. This thruster system uses HFC-134a (1,1,1,2-tetrafluoroethane) , a kind of liquefied gas, as propellant because of its harmlessness and ease of handling. And this thruster stores propellant as liquid in the tank and ejects propellant as gas using the gas-liquid equilibrium pressure to produce thrust, so the propellant tank only needs to resist the vapor pressure of propellant. In this thruster system, the porous metal is also equipped in the tank for the following performance advantages: (1) liquid fuel retention: The porous metal reduces sloshing problems which cause bad effects on spacecraft attitude by retaining liquid propellant inside the porous metal: (2) vapor-liquid separation: The porous metal also helps propellant separate gas from liquid by advancing propellant vaporization on its large surface area and retaining liquid propellant using its surface tension. In last autumn, we carried out the experiment to evaluate these two advantages of porous metal under micro gravity condition using 50 meters drop tower in Hokkaido, Japan. The system of this experiment divides into two different systems. The first one evaluates liquid propellant retention performance by adding disturbance to liquid propellant absorbed in porous metal. The disturbance is centrifugal force and angular acceleration worked on the liquid propellant by rotating propellant tank controlled by motor. A high speed camera records the behavior of the liquid propellant. The other one evaluates the ability of gas-liquid separation on the case of propellant ejection. In this evaluation, the parameters are full filling porous metal or some ullage in the tank, nozzle diameters and the filling ratio of liquid propellant in the tank. As for (1) liquid fuel retention, in all conducted cases without propellant ejection, liquid propellant was retained in the porous metal. It is obvious that the porous metal is effective for decreasing of sloshing problems. We evaluated this effectiveness analytically based on head pressure worked on liquid propellant as centrifugal force and angular acceleration. As for (2)vapor-liquid separation, liquid propellant retained inside the porous metal started to boil right after propellant ejection occurred and propellant was ejected mixed with liquid. And after propellant ejection, it takes some time to recover tank pressure into saturated vapor pressure. To obtain stable thrust force, it is required to halt the propellant ejection just before the tank pressure reaches to the break point pressure and to take enough ejection intervals to recover the tank pressure. From these experiments, for practical use of this thruster system, that is, to avoid liquid propellant ejection, it is important to ensure adequate ullage volume of tank to achieve mission requirement.

  1. Tuning universality far from equilibrium

    PubMed Central

    Karl, Markus; Nowak, Boris; Gasenzer, Thomas

    2013-01-01

    Possible universal dynamics of a many-body system far from thermal equilibrium are explored. A focus is set on meta-stable non-thermal states exhibiting critical properties such as self-similarity and independence of the details of how the respective state has been reached. It is proposed that universal dynamics far from equilibrium can be tuned to exhibit a dynamical transition where these critical properties change qualitatively. This is demonstrated for the case of a superfluid two-component Bose gas exhibiting different types of long-lived but non-thermal critical order. Scaling exponents controlled by the ratio of experimentally tuneable coupling parameters offer themselves as natural smoking guns. The results shed light on the wealth of universal phenomena expected to exist in the far-from-equilibrium realm. PMID:23928853

  2. Detecting temperature fluctuations at equilibrium.

    PubMed

    Dixit, Purushottam D

    2015-05-21

    The Gibbs and the Boltzmann definition of temperature agree only in the macroscopic limit. The ambiguity in identifying the equilibrium temperature of a finite-sized 'small' system exchanging energy with a bath is usually understood as a limitation of conventional statistical mechanics. We interpret this ambiguity as resulting from a stochastically fluctuating temperature coupled with the phase space variables giving rise to a broad temperature distribution. With this ansatz, we develop the equilibrium statistics and dynamics of small systems. Numerical evidence using an analytically tractable model shows that the effects of temperature fluctuations can be detected in the equilibrium and dynamical properties of the phase space of the small system. Our theory generalizes statistical mechanics to small systems relevant in biophysics and nanotechnology. PMID:25912565

  3. General equilibrium of an ecosystem.

    PubMed

    Tschirhart, J

    2000-03-01

    Ecosystems and economies are inextricably linked: ecosystem models and economic models are not linked. Consequently, using either type of model to design policies for preserving ecosystems or improving economic performance omits important information. Improved policies would follow from a model that links the systems and accounts for the mutual feedbacks by recognizing how key ecosystem variables influence key economic variables, and vice versa. Because general equilibrium economic models already are widely used for policy making, the approach used here is to develop a general equilibrium ecosystem model which captures salient biological functions and which can be integrated with extant economic models. In the ecosystem model, each organism is assumed to be a net energy maximizer that must exert energy to capture biomass from other organisms. The exerted energies are the "prices" that are paid to biomass, and each organism takes the prices as signals over which it has no control. The maximization problem yields the organism's demand for and supply of biomass to other organisms as functions of the prices. The demands and supplies for each biomass are aggregated over all organisms in each species which establishes biomass markets wherein biomass prices are determined. A short-run equilibrium is established when all organisms are maximizing and demand equals supply in every biomass market. If a species exhibits positive (negative) net energy in equilibrium, its population increases (decreases) and a new equilibrium follows. The demand and supply forces in the biomass markets drive each species toward zero stored energy and a long-run equilibrium. Population adjustments are not based on typical Lotka-Volterra differential equations in which one entire population adjusts to another entire population thereby masking organism behavior; instead, individual organism behavior is central to population adjustments. Numerical simulations use a marine food web in Alaska to illustrate the model and to show several simultaneous predator/prey relationships, prey switching by the top predator, and energy flows through the web. PMID:10677274

  4. Equilibrium in a Production Economy

    SciTech Connect

    Chiarolla, Maria B.; Haussmann, Ulrich G.

    2011-06-15

    Consider a closed production-consumption economy with multiple agents and multiple resources. The resources are used to produce the consumption good. The agents derive utility from holding resources as well as consuming the good produced. They aim to maximize their utility while the manager of the production facility aims to maximize profits. With the aid of a representative agent (who has a multivariable utility function) it is shown that an Arrow-Debreu equilibrium exists. In so doing we establish technical results that will be used to solve the stochastic dynamic problem (a case with infinite dimensional commodity space so the General Equilibrium Theory does not apply) elsewhere.

  5. Adiabatic evolution of plasma equilibrium

    PubMed Central

    Grad, H.; Hu, P. N.; Stevens, D. C.

    1975-01-01

    A new theory of plasma equilibrium is introduced in which adiabatic constraints are specified. This leads to a mathematically nonstandard structure, as compared to the usual equilibrium theory, in which prescription of pressure and current profiles leads to an elliptic partial differential equation. Topologically complex configurations require further generalization of the concept of adiabaticity to allow irreversible mixing of plasma and magnetic flux among islands. Matching conditions across a boundary layer at the separatrix are obtained from appropriate conservation laws. Applications are made to configurations with planned islands (as in Doublet) and accidental islands (as in Tokamaks). Two-dimensional, axially symmetric, helically symmetric, and closed line equilibria are included. PMID:16578729

  6. Equilibrium problems for Raney densities

    NASA Astrophysics Data System (ADS)

    Forrester, Peter J.; Liu, Dang-Zheng; Zinn-Justin, Paul

    2015-07-01

    The Raney numbers are a class of combinatorial numbers generalising the Fuss-Catalan numbers. They are indexed by a pair of positive real numbers (p, r) with p > 1 and 0 < r ⩽ p, and form the moments of a probability density function. For certain (p, r) the latter has the interpretation as the density of squared singular values for certain random matrix ensembles, and in this context equilibrium problems characterising the Raney densities for (p, r) = (θ + 1, 1) and (θ/2 + 1, 1/2) have recently been proposed. Using two different techniques—one based on the Wiener-Hopf method for the solution of integral equations and the other on an analysis of the algebraic equation satisfied by the Green's function—we establish the validity of the equilibrium problems for general θ > 0 and similarly use both methods to identify the equilibrium problem for (p, r) = (θ/q + 1, 1/q), θ > 0 and q \\in Z+ . The Wiener-Hopf method is used to extend the latter to parameters (p, r) = (θ/q + 1, m + 1/q) for m a non-negative integer, and also to identify the equilibrium problem for a family of densities with moments given by certain binomial coefficients.

  7. Understanding Thermal Equilibrium through Activities

    ERIC Educational Resources Information Center

    Pathare, Shirish; Huli, Saurabhee; Nachane, Madhura; Ladage, Savita; Pradhan, Hemachandra

    2015-01-01

    Thermal equilibrium is a basic concept in thermodynamics. In India, this concept is generally introduced at the first year of undergraduate education in physics and chemistry. In our earlier studies (Pathare and Pradhan 2011 "Proc. episteme-4 Int. Conf. to Review Research on Science Technology and Mathematics Education" pp 169-72) we

  8. An investigation of equilibrium concepts

    NASA Technical Reports Server (NTRS)

    Prozan, R. J.

    1982-01-01

    A different approach to modeling of the thermochemistry of rocket engine combustion phenomena is presented. The methodology described is based on the hypothesis of a new variational principle applicable to compressible fluid mechanics. This hypothesis is extended to treat the thermochemical behavior of a reacting (equilibrium) gas in an open system.

  9. Thermodynamic theory of equilibrium fluctuations

    NASA Astrophysics Data System (ADS)

    Mishin, Y.

    2015-12-01

    The postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different from that of statistical mechanics and represents an expanded version of thermodynamics. Based on this theory, we present a regular procedure for calculations of equilibrium fluctuations of extensive parameters, intensive parameters and densities in systems with any number of fluctuating parameters. The proposed fluctuation formalism is demonstrated by four applications: (1) derivation of the complete set of fluctuation relations for a simple fluid in three different ensembles; (2) fluctuations in finite-reservoir systems interpolating between the canonical and micro-canonical ensembles; (3) derivation of fluctuation relations for excess properties of grain boundaries in binary solid solutions, and (4) derivation of the grain boundary width distribution for pre-melted grain boundaries in alloys. The last two applications offer an efficient fluctuation-based approach to calculations of interface excess properties and extraction of the disjoining potential in pre-melted grain boundaries. Possible future extensions of the theory are outlined.

  10. Quantifying mixing using equilibrium reactions

    SciTech Connect

    Wheat, Philip M.; Posner, Jonathan D.

    2009-03-15

    A method of quantifying equilibrium reactions in a microchannel using a fluorometric reaction of Fluo-4 and Ca{sup 2+} ions is presented. Under the proper conditions, equilibrium reactions can be used to quantify fluid mixing without the challenges associated with constituent mixing measures such as limited imaging spatial resolution and viewing angle coupled with three-dimensional structure. Quantitative measurements of CaCl and calcium-indicating fluorescent dye Fluo-4 mixing are measured in Y-shaped microchannels. Reactant and product concentration distributions are modeled using Green's function solutions and a numerical solution to the advection-diffusion equation. Equilibrium reactions provide for an unambiguous, quantitative measure of mixing when the reactant concentrations are greater than 100 times their dissociation constant and the diffusivities are equal. At lower concentrations and for dissimilar diffusivities, the area averaged fluorescence signal reaches a maximum before the species have interdiffused, suggesting that reactant concentrations and diffusivities must be carefully selected to provide unambiguous, quantitative mixing measures. Fluorometric equilibrium reactions work over a wide range of pH and background concentrations such that they can be used for a wide variety of fluid mixing measures including industrial or microscale flows.

  11. Understanding Thermal Equilibrium through Activities

    ERIC Educational Resources Information Center

    Pathare, Shirish; Huli, Saurabhee; Nachane, Madhura; Ladage, Savita; Pradhan, Hemachandra

    2015-01-01

    Thermal equilibrium is a basic concept in thermodynamics. In India, this concept is generally introduced at the first year of undergraduate education in physics and chemistry. In our earlier studies (Pathare and Pradhan 2011 "Proc. episteme-4 Int. Conf. to Review Research on Science Technology and Mathematics Education" pp 169-72) we…

  12. Non-Equilibrium Properties from Equilibrium Free Energy Calculations

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew; Wilson, Michael A.

    2012-01-01

    Calculating free energy in computer simulations is of central importance in statistical mechanics of condensed media and its applications to chemistry and biology not only because it is the most comprehensive and informative quantity that characterizes the eqUilibrium state, but also because it often provides an efficient route to access dynamic and kinetic properties of a system. Most of applications of equilibrium free energy calculations to non-equilibrium processes rely on a description in which a molecule or an ion diffuses in the potential of mean force. In general case this description is a simplification, but it might be satisfactorily accurate in many instances of practical interest. This hypothesis has been tested in the example of the electrodiffusion equation . Conductance of model ion channels has been calculated directly through counting the number of ion crossing events observed during long molecular dynamics simulations and has been compared with the conductance obtained from solving the generalized Nernst-Plank equation. It has been shown that under relatively modest conditions the agreement between these two approaches is excellent, thus demonstrating the assumptions underlying the diffusion equation are fulfilled. Under these conditions the electrodiffusion equation provides an efficient approach to calculating the full voltage-current dependence routinely measured in electrophysiological experiments.

  13. Measurements of the Isobaric Specific Heat Capacity and Formulation of an Equation of State for Refrigerant 23 in the Gaseous Region

    NASA Astrophysics Data System (ADS)

    Takanuma, Akihiro; Uematsu, Masahiko; Watanabe, Koichi

    The isobaric specific heat capacity of Refrigerant 23 (CHF3) has been measured by the flow calorimeter. Forty-five measurements were obtained in the gaseous region for temperatures 253 to 383 K and for pressures 0.5 to 3.0 MPa including the region near the saturation line. The sample purity used was 99.99 wt%. The uncertainty of the measurements was estimated to be less than l.5%. Based on the present results in addition to the isobaric specific heat capacity at the ideal gas state, the second virial coefficients and the available PVT data, an equation of state has been formulated as a function of pressure and temperature for the region of the present study. The equation of state expressed by the form of Gibbs free energy reproduces the present results with an average deviation of l.0% and most of the available PVT data within a deviation of 1%.

  14. Isobaric tags for relative and absolute quantitation (iTRAQ)-based proteomic analysis of Cryptococcus humicola response to aluminum stress.

    PubMed

    Zhang, Jingjing; Zhang, Lei; Qiu, Jinkui; Nian, Hongjuan

    2015-10-01

    Cryptococcus humicola is a highly aluminum (Al) tolerant yeast strain isolated from a tea field. Here the relative changes of protein expression in C.humicola undergoing aluminum stress were analyzed to understand the genetic basis of aluminum tolerance. In this work, iTRAQ-based (isobaric tags for relative and absolute quantification) quantitative proteomic technology was used to detect statistically significant proteins associated with the response to aluminum stress. A total of 625 proteins were identified and were mainly involved in translation/ribosomal structure and biogenesis, posttranslational modification/protein turnover/chaperones, energy production and conversion, and amino acid transport and metabolism. Of these proteins, 59 exhibited differential expression during aluminum stress. Twenty-nine proteins up-regulated by aluminum were mainly involved in translation/ribosomal structure and biogenesis, posttranslational modification/protein turnover and chaperones, and lipid transport and metabolism. Thirty proteins down-regulated by aluminum were mainly associated with energy transport and metabolism, translation/ribosomal structure and biogenesis, posttranslational modification/protein turnover/chaperones, and lipid transport and metabolism. The potential functions of some proteins in aluminum tolerance are discussed. These functional changes may be beneficial for cells to protect themselves from aluminum toxic conditions. PMID:25747181

  15. Differential proteomic analysis of cancer stem cell properties in hepatocellular carcinomas by isobaric tag labeling and mass spectrometry.

    PubMed

    Ko, Ching-Huai; Cheng, Chieh-Fang; Lai, Chin-Pen; Tzu, Te-Hui; Chiu, Chih-Wei; Lin, Mei-Wei; Wu, Si-Yuan; Sun, Chung-Yuan; Tseng, Hsiang-Wen; Wang, Chun-Chung; Kuo, Zong-Keng; Wang, Ling-Mei; Chen, Sung-Fang

    2013-08-01

    Malignant tumors are relatively resistant to treatment due to their heterogeneous nature, drug resistance, and tendency for metastasis. Recent studies suggest that a subpopulation of cancer cells is responsible for the malignant outcomes. These cells are considered as cancer stem cells (CSC). Although a number of molecules have been identified in different cancer cells as markers for cancer stem cells, no promising markers are currently available for hepatocellular carcinoma cells. In this study, two clones of Hep3B cell lines were functionally characterized as control or CSC-like cells, based on properties including spheroid formation, drug resistance, and tumor initiation. Furthermore, their protein expression profiles were investigated by isobaric tags for relative and absolute quantitation (iTRAQ), and a total of 1,127 proteins were identified and quantified from the combined fractions; 50 proteins exhibited at least 2-fold differences between these two clones. These 50 proteins were analyzed by GeneGo and were found to be associated with liver neoplasms, hepatocellular carcinoma (HCC), and liver diseases. They were also components of metabolic pathways, immune responses, and cytoskeleton remodeling. Among these proteins, the expressions of S100P, S100A14, and vimentin were verified in several HCC cell lines, and their expressions were correlated with tumorigenicity in HCC cell lines. The functional significance of vimentin and S100A14 were also investigated and verified. PMID:23782096

  16. Elastic and Inelastic Scattering of Polarized Protons from LEAD-206 and LEAD-208 Near Isobaric Analog Resonances.

    NASA Astrophysics Data System (ADS)

    Back, Norman Lee

    Excitation functions have been measured for elastic scattering of polarized protons from ('206)Pb and ('208)Pb, and for inelastic scattering to collective states in ('206)Pb (2('+), 0.8033 MeV; 3('-), 2.647 MeV) and ('208)Pb (3(' -), 2.6145 MeV). Both differential cross sections and analyzing powers were measured at (theta)(,lab) = 120(DEGREES), 135(DEGREES), 150(DEGREES), and 165(DEGREES), for E(,p) = 14.25 to 18 MeV. Fits to the excitation-function data were obtained using scattering amplitudes consisting of sums of resonant and non-resonant parts. The resonances are the isobaric analogs (IARs) of 7 low-lying states in ('209)Pb and 35 in ('207)Pb. The fits to the elastic-scattering data are excellent; for the inelastic scattering the fit is very good for the 2('+) state but only fair for the 3('-) states. For each IAR, the energy, the total width, and the partial width and mixing phase in each channel were obtained. Also, new spin assignments were made for a number of parent states in ('207)Pb. The theory of Bund and Blair was used to find the spectroscopic amplitudes, which provide information on the wave functions for the parent states in ('207)Pb and ('209)Pb and for the 3('-) states in ('206)Pb and ('208)Pb. These spectroscopic amplitudes were then checked for internal consistency and compared with the results of other experiments and with theoretical predictions.

  17. Separation of Isobaric Compounds Using a Spiral Orbit Type Time-of-Flight Mass Spectrometer, MALDI-SpiralTOF

    PubMed Central

    Satoh, Takaya; Kubo, Ayumi; Hazama, Hisanao; Awazu, Kunio; Toyoda, Michisato

    2014-01-01

    The development of a MALDI-TOF mass spectrometer that utilizes spiral ion trajectory, SpiralTOF, is reported. The total flight path length was 17?m, which is five times longer than that in commonly used reflectron ion optical system. The SpiralTOF reduced the dependence of the mass resolving power on the mass of the analyte, while improving the accuracy of the mass measurements. Furthermore, SpiralTOF has two advantages that can be exploited for the separation of minor abundant isobaric components in mass spectra. One is the reduction in chemical background due to the post source decay (PSD), which is achieved through PSD ion elimination by electrostatic sectors contained within the SpiralTOF. The other is that the stabilities of peak positions are improved during mass spectrum accumulation. The peak drift caused by the fine structure of matrix crystals and the small irregularities on the sample surface can be reduced by extending the flight path. In this study, these advantages are demonstrated via the analysis of a block copolymer and mass spectrometry imaging (MSI) of lipids.

  18. Isobaric labeling approach to the tracking and relative quantitation of peptide damage at the primary structural level.

    PubMed

    Grosvenor, Anita J; Morton, James D; Dyer, Jolon M

    2010-12-22

    Protein oxidative damage lies behind skin and hair degradation and the deterioration of protein-based products, such as wool and meat, in addition to a range of serious health problems. Effective strategies to ameliorate degenerative processes require detailed fundamental knowledge of the chemistry at the molecular level, including specific residue-level products and their relative abundance. This paper presents a new means of tracking damage-induced side-chain modification in peptides using a novel application for isobaric label quantification. Following exposure to heat and UVA and UVB irradiation, tryptophan and tyrosine damage products in synthetic peptides were characterized and tracked using ESI-MS/MS and iTRAQ labeling-based relative quantification. An in-depth degradation profile of these peptides was generated, enabling the formation of even low-abundance single-residue-level modifications to be sensitively monitored. The development of this novel approach to profiling and tracking residue-level protein damage offers significant potential for application in the development and validation of protein protection treatments. PMID:21087046

  19. Superconducting Electrons and Equilibrium Patterns

    NASA Astrophysics Data System (ADS)

    Khushalani, Bharat

    2004-05-01

    Rotation of superfluid generates quantized vortices. Movement of magnetic vortices through superconductors produces unwanted resistance. Such vortices are generated when the magnetic field penetrates some superconductors as narrow flux tubes. Electrical current due to superconducting electrons is generated around these vortices. Externally applied electrical current produces the motion of this quantized magnetic flux. For a vortex in a container filled with superfluid He3 mounted on a rotating turntable, the vortex begins to align itself along the rotational axis. Such ordering is also seen in spinning electron clouds within a superconducting magnet which settle down into geometric patterns. It has been shown recently that movement of the vortex is influenced by sum of direction of supercurrents at the vortex location and the law of interaction of these vortices is governed by Euler equations. In this paper, we will obtain the equilibrium discretizations of Euler equations and derive the frequency of rotating patterns in the case of relative equilibrium configurations.

  20. Non-equilibrium steady states

    NASA Astrophysics Data System (ADS)

    Nicolas, J.

    2002-11-01

    This paper deals with some thermodynamical aspects of a class of models in non equilibrium quantum statistical mechanics (QSM) which are commonly used to describe the behaviour of infinite quantum systems perturbed by a time-dependent periodic force. We are interested to the thermodynamical properties of the set of non-equilibrium steady states (NESS) of the perturbed system. We extend the construction of the C-Liouvillean originally introduce in [1] to our time-dependent situation to define the C-Liouvillean of Floquet KF. The NESS are thus described by zero-resonance eigenvectors of KF*. We also give a time dependent version of the rate of entropy production [2] for the perturbed system based on the relative entropy as defined by Araki [3] in terms of the relative modular operator.

  1. Phonon Mapping in Flowing Equilibrium

    NASA Astrophysics Data System (ADS)

    Ruff, J. P. C.

    2015-03-01

    When a material conducts heat, a modification of the phonon population occurs. The equilibrium Bose-Einstein distribution is perturbed towards flowing-equilibrium, for which the distribution function is not analytically known. Here I argue that the altered phonon population can be efficiently mapped over broad regions of reciprocal space, via diffuse x-ray scattering or time-of-flight neutron scattering, while a thermal gradient is applied across a single crystal sample. When compared to traditional transport measurements, this technique offers a superior, information-rich new perspective on lattice thermal conductivity, wherein the band and momentum dependences of the phonon thermal current are directly resolved. The proposed method is benchmarked using x-ray thermal diffuse scattering measurements of single crystal diamond under transport conditions. CHESS is supported by the NSF & NIH/NIGMS via NSF Award DMR-1332208.

  2. Punctuated equilibrium comes of age

    NASA Astrophysics Data System (ADS)

    Gould, Stephan Jay; Eldredge, Niles

    1993-11-01

    The intense controversies that surrounded the youth of punctuated equilibrium have helped it mature to a useful extension of evolutionary theory. As a complement to phyletic gradualism, its most important implications remain the recognition of stasis as a meaningful and predominant pattern within the history of species, and in the recasting of macroevolution as the differential success of certain species (and their descendants) within clades.

  3. Long-term equilibrium tides

    NASA Astrophysics Data System (ADS)

    Shaffer, John A.; Cerveny, Randall S.

    1998-08-01

    Extreme equilibrium tides, or ``hypertides,'' are computed in a new equilibrium tidal model combining algorithms of a version of the Chapront ELP-2000/82 Lunar Theory with the BER78 Milankovitch astronomical expansions. For the recent past, a high correspondence exists between computed semidiurnal tide levels and a record of coastal flooding demonstrating that astronomical alignment is a potential influence on such flooding. For the Holocene and near future, maximum tides demonstrate cyclic variations with peaks at near 5000 B.P. and 4000 A.P. On the late Quaternary timescale, variations in maximum equilibrium tide level display oscillations with periods of approximately 10,000, 100,000 and 400,000 years, because of precessional shifts in tidal maxima between vernal and autumnal equinoxes. While flooding occurs under the combined effects of tides and storms via ``storm surges,'' the most extensive flooding will occur with the coincidence of storms and the rarer hypertides and is thus primarily influenced by hypertides. Therefore we suggest that astronomical alignment's relationship to coastal flooding is probabilistic rather than deterministic. Data derived from this model are applicable to (1) archaeological and paleoclimatic coastal reconstructions, (2) long-term planning, for example, radioactive waste site selection, (3) sealevel change and paleoestuarine studies or (4) ocean-meteorological interactions.

  4. Equilibrium and Stability of Stellarators.

    NASA Astrophysics Data System (ADS)

    Anania, Giorgio

    There is strong interest in the stellarator concept for containment of a thermonuclear plasma. Very little is known about stellarator equilibrium and stability. Of the three main approaches now available to answer these questions the stellarator expansion provides the greatest simplification. An equilibrium code and a stability code which incorporate the stellarator expansion have been developed. The equilibrium code uses an Eulerian grid and can be used to study free-boundary equilibria. The stability code uses flux coordinates and employs a Lagrangian formulation suitable for the investigation of the normal modes of the plasma. This code can be used to study the stability of both free-boundary and fixed-boundary modes. Appplication is made to existing devices, modular coil stellarators, a proposed device (ATF), and a tokamak -torsatron hybrid. For the modular-soil configurations it is found that a large lateral distortion of the coils from planar is needed to obtain a high rotational transform so as to support a high plasma pressure. For a given maximum coil deformation it is possible to improve the equilibrium properties of the plasma by modifying the harmonics in the coil winding law. Among the existing stellarator devices it is found that the Heliotron-E device is limited by localized, pressure -driven interchanges, while the dominant instabilities in the Wendelstein VII-A device are large-scale modes which are driven both by parallel currents and by pressure gradients. The effects of a vertical field, of changes in the vacuum rotational transform, and of the presence of a conducting wall near the plasma are investigated. The proposed ATF device is stable with average betas greater than 2.5% if a parabolic pressure distribution is assumed. It is unstable to a free-boundary kink mode if the pressure distribution is sufficiently broad. This instability persists even in the absence of a net toroidal current. The addition of helical windings to an axisymmetric tokamak configuration is shown to increase plasma elongation and increase the plasma rotational transform near the plasma surface. Too much helical field produces surface breakup. For a particular equilibrium it is found that the addition of helical windings reduces the connection length for ballooning modes and thereby stabilizes some non-axisymmetric modes at the expense of increasing the growth-rate of the vertical instability.

  5. Morphodynamic equilibrium of alluvial estuaries

    NASA Astrophysics Data System (ADS)

    Tambroni, Nicoletta; Bolla Pittaluga, Michele; Canestrelli, Alberto; Lanzoni, Stefano; Seminara, Giovanni

    2014-05-01

    The evolution of the longitudinal bed profile of an estuary, with given plan-form configuration, subject to given tidal forcing at the mouth and prescribed values of water and sediment supply from the river is investigated numerically. Our main goal is to ascertain whether, starting from some initial condition, the bed evolution tends to reach a unique equilibrium configuration asymptotically in time. Also, we investigate the morphological response of an alluvial estuary to changes in the tidal range and hydrologic forcing (flow and sediment supply). Finally, the solution helps characterizing the transition between the fluvially dominated region and the tidally dominated region of the estuary. All these issues play an important role also in interpreting how the facies changes along the estuary, thus helping to make correct paleo-environmental and sequence-stratigraphic interpretations of sedimentary successions (Dalrymple and Choi, 2007). Results show that the model is able to describe a wide class of settings ranging from tidally dominated estuaries to fluvially dominated estuaries. In the latter case, the solution is found to compare satisfactory with the analytical asymptotic solution recently derived by Seminara et al. (2012), under the hypothesis of fairly 'small' tidal oscillations. Simulations indicate that the system always moves toward an equilibrium configuration in which the net sediment flux in a tidal cycle is constant throughout the estuary and equal to the constant sediment flux discharged from the river. For constant width, the bed equilibrium profile of the estuarine channel is characterized by two distinct regions: a steeper reach seaward, dominated by the tide, and a less steep upstream reach, dominated by the river and characterized by the undisturbed bed slope. Although the latter reach, at equilibrium, is not directly affected by the tidal wave, however starting from an initial uniform stream with the constant 'fluvial' slope, the final equilibrium state is reached through an erosional wave, which leads to bed degradation of the upstream 'fluvial reach'. For a given river discharge, the length of the tidal reach increases quite rapidly with tidal amplitude, up to some threshold value of the tidal amplitude above which the length of the estuary becomes comparable with the length of the tidal wave. When the channel plan-form is convergent, deposition of sediments of fluvial origin in the funnel-shaped region drastically changes the equilibrium configuration. The effect of an increasing channel convergence is thus to induce bed aggradation close to the inlet. Nevertheless, tidal forcing only slightly changes the non-tidal profile. The effect of increasing tidal oscillations again leads to an increase of the bed slope at the inlet and to a general bed degradation upstream. The effects of varying sediment supply, flow discharge and river width in the upstream reach have also been investigated and play an important role. Further geomorphological implications of these results will be discussed at the meeting. References Dalrymple, R. W., and K. Choi (2007), Morphologic and facies trends through the fluvialmarine transition in tide-dominated depositional systems: A schematic framework for environmental and sequence-stratigraphic interpretation, Earth-Science Reviews, 81(3-4), 135-174, doi:10.1016/j.earscirev.2006.10.002. Seminara, G., M. Bolla Pittaluga, and N. Tambroni (2012), Morphodynamic equilibrium of tidal channels, Environmental Fluid Mechanics: Memorial Volume in Honour of Prof. Gerhard H. Jirka, 153-174

  6. Torque equilibrium attitude control for Skylab reentry

    NASA Technical Reports Server (NTRS)

    Glaese, J. R.; Kennel, H. F.

    1979-01-01

    All the available torque equilibrium attitudes (most were useless from the standpoint of lack of electrical power) and the equilibrium seeking method are presented, as well as the actual successful application during the 3 weeks prior to Skylab reentry.

  7. Accelerating Multiagent Reinforcement Learning by Equilibrium Transfer.

    PubMed

    Hu, Yujing; Gao, Yang; An, Bo

    2015-07-01

    An important approach in multiagent reinforcement learning (MARL) is equilibrium-based MARL, which adopts equilibrium solution concepts in game theory and requires agents to play equilibrium strategies at each state. However, most existing equilibrium-based MARL algorithms cannot scale due to a large number of computationally expensive equilibrium computations (e.g., computing Nash equilibria is PPAD-hard) during learning. For the first time, this paper finds that during the learning process of equilibrium-based MARL, the one-shot games corresponding to each state's successive visits often have the same or similar equilibria (for some states more than 90% of games corresponding to successive visits have similar equilibria). Inspired by this observation, this paper proposes to use equilibrium transfer to accelerate equilibrium-based MARL. The key idea of equilibrium transfer is to reuse previously computed equilibria when each agent has a small incentive to deviate. By introducing transfer loss and transfer condition, a novel framework called equilibrium transfer-based MARL is proposed. We prove that although equilibrium transfer brings transfer loss, equilibrium-based MARL algorithms can still converge to an equilibrium policy under certain assumptions. Experimental results in widely used benchmarks (e.g., grid world game, soccer game, and wall game) show that the proposed framework: 1) not only significantly accelerates equilibrium-based MARL (up to 96.7% reduction in learning time), but also achieves higher average rewards than algorithms without equilibrium transfer and 2) scales significantly better than algorithms without equilibrium transfer when the state/action space grows and the number of agents increases. PMID:25181517

  8. X-ray continuum as a measure of pressure and fuel–shell mix in compressed isobaric hydrogen implosion cores

    SciTech Connect

    Epstein, R.; Goncharov, V. N.; Marshall, F. J.; Betti, R.; Nora, R.; Christopherson, A. R.; Golovkin, I. E.; MacFarlane, J. J.

    2015-02-15

    Pressure, by definition, characterizes the conditions within an isobaric implosion core at peak compression [Gus'kov et al., Nucl. Fusion 16, 957 (1976); Betti et al., Phys. Plasmas 8, 5257 (2001)] and is a key parameter in quantifying its near-ignition performance [Lawson, Proc. Phys. Soc. London, B 70, 6 (1957); Betti et al., Phys. Plasmas 17, 058102 (2010); Goncharov et al., Phys. Plasmas 21, 056315 (2014); and Glenzer et al., Phys. Plasmas 19, 056318 (2012)]. At high spectral energy, where the x-ray emission from an imploded hydrogen core is optically thin, the emissivity profile can be inferred from the spatially resolved core emission. This emissivity, which can be modeled accurately under hot-core conditions, is dependent almost entirely on the pressure when measured within a restricted spectral range matched to the temperature range anticipated for the emitting volume. In this way, the hot core pressure at the time of peak emission can be inferred from the measured free-free emissivity profile. The pressure and temperature dependences of the x-ray emissivity and the neutron-production rate explain a simple scaling of the total filtered x-ray emission as a constant power of the total neutron yield for implosions of targets of similar design over a broad range of shell implosion isentropes. This scaling behavior has been seen in implosion simulations and is confirmed by measurements of high-isentrope implosions [Sangster et al., Phys. Plasmas 20, 056317 (2013)] on the OMEGA laser system [Boehly et al., Opt. Commun. 133, 495 (1997)]. Attributing the excess emission from less-stable, low-isentrope implosions, above the level expected from this neutron-yield scaling, to the higher emissivity of shell carbon mixed into the implosion's central hot spot, the hot-spot “fuel–shell” mix mass can be inferred.

  9. X-ray continuum as a measure of pressure and fuel-shell mix in compressed isobaric hydrogen implosion cores

    NASA Astrophysics Data System (ADS)

    Epstein, R.; Goncharov, V. N.; Marshall, F. J.; Betti, R.; Nora, R.; Christopherson, A. R.; Golovkin, I. E.; MacFarlane, J. J.

    2015-02-01

    Pressure, by definition, characterizes the conditions within an isobaric implosion core at peak compression [Gus'kov et al., Nucl. Fusion 16, 957 (1976); Betti et al., Phys. Plasmas 8, 5257 (2001)] and is a key parameter in quantifying its near-ignition performance [Lawson, Proc. Phys. Soc. London, B 70, 6 (1957); Betti et al., Phys. Plasmas 17, 058102 (2010); Goncharov et al., Phys. Plasmas 21, 056315 (2014); and Glenzer et al., Phys. Plasmas 19, 056318 (2012)]. At high spectral energy, where the x-ray emission from an imploded hydrogen core is optically thin, the emissivity profile can be inferred from the spatially resolved core emission. This emissivity, which can be modeled accurately under hot-core conditions, is dependent almost entirely on the pressure when measured within a restricted spectral range matched to the temperature range anticipated for the emitting volume. In this way, the hot core pressure at the time of peak emission can be inferred from the measured free-free emissivity profile. The pressure and temperature dependences of the x-ray emissivity and the neutron-production rate explain a simple scaling of the total filtered x-ray emission as a constant power of the total neutron yield for implosions of targets of similar design over a broad range of shell implosion isentropes. This scaling behavior has been seen in implosion simulations and is confirmed by measurements of high-isentrope implosions [Sangster et al., Phys. Plasmas 20, 056317 (2013)] on the OMEGA laser system [Boehly et al., Opt. Commun. 133, 495 (1997)]. Attributing the excess emission from less-stable, low-isentrope implosions, above the level expected from this neutron-yield scaling, to the higher emissivity of shell carbon mixed into the implosion's central hot spot, the hot-spot "fuel-shell" mix mass can be inferred.

  10. High-Field Asymmetric-Waveform Ion Mobility Spectrometry and Electron Detachment Dissociation of Isobaric Mixtures of Glycosaminoglycans

    NASA Astrophysics Data System (ADS)

    Kailemia, Muchena J.; Park, Melvin; Kaplan, Desmond A.; Venot, Andre; Boons, Geert-Jan; Li, Lingyun; Linhardt, Robert J.; Amster, I. Jonathan

    2013-11-01

    High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of glycosaminoglycans (GAGs). However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4-10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other.

  11. A quantitative tool to distinguish isobaric leucine and isoleucine residues for mass spectrometry-based de novo monoclonal antibody sequencing.

    PubMed

    Poston, Chloe N; Higgs, Richard E; You, Jinsam; Gelfanova, Valentina; Hale, John E; Knierman, Michael D; Siegel, Robert; Gutierrez, Jesus A

    2014-07-01

    De novo sequencing by mass spectrometry (MS) allows for the determination of the complete amino acid (AA) sequence of a given protein based on the mass difference of detected ions from MS/MS fragmentation spectra. The technique relies on obtaining specific masses that can be attributed to characteristic theoretical masses of AAs. A major limitation of de novo sequencing by MS is the inability to distinguish between the isobaric residues leucine (Leu) and isoleucine (Ile). Incorrect identification of Ile as Leu or vice versa often results in loss of activity in recombinant antibodies. This functional ambiguity is commonly resolved with costly and time-consuming AA mutation and peptide sequencing experiments. Here, we describe a set of orthogonal biochemical protocols, which experimentally determine the identity of Ile or Leu residues in monoclonal antibodies (mAb) based on the selectivity that leucine aminopeptidase shows for n-terminal Leu residues and the cleavage preference for Leu by chymotrypsin. The resulting observations are combined with germline frequencies and incorporated into a logistic regression model, called Predictor for Xle Sites (PXleS) to provide a statistical likelihood for the identity of Leu at an ambiguous site. We demonstrate that PXleS can generate a probability for an Xle site in mAbs with 96% accuracy. The implementation of PXleS precludes the expression of several possible sequences and, therefore, reduces the overall time and resources required to go from spectra generation to a biologically active sequence for a mAb when an Ile or Leu residue is in question. PMID:24845350

  12. High-Field Asymmetric-Waveform Ion Mobility Spectrometry and Electron Detachment Dissociation of Isobaric Mixtures of Glycosaminoglycans

    PubMed Central

    Kailemia, Muchena J.; Park, Melvin; Kaplan, Desmond A.; Venot, Andre; Boons, Geert-Jan; Li, Lingyun; Linhardt, Robert J.; Amster, I. Jonathan

    2014-01-01

    High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions, and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of GAGs. However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 410 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other. PMID:24254578

  13. A Quantitative Tool to Distinguish Isobaric Leucine and Isoleucine Residues for Mass Spectrometry-Based De Novo Monoclonal Antibody Sequencing

    NASA Astrophysics Data System (ADS)

    Poston, Chloe N.; Higgs, Richard E.; You, Jinsam; Gelfanova, Valentina; Hale, John E.; Knierman, Michael D.; Siegel, Robert; Gutierrez, Jesus A.

    2014-07-01

    De novo sequencing by mass spectrometry (MS) allows for the determination of the complete amino acid (AA) sequence of a given protein based on the mass difference of detected ions from MS/MS fragmentation spectra. The technique relies on obtaining specific masses that can be attributed to characteristic theoretical masses of AAs. A major limitation of de novo sequencing by MS is the inability to distinguish between the isobaric residues leucine (Leu) and isoleucine (Ile). Incorrect identification of Ile as Leu or vice versa often results in loss of activity in recombinant antibodies. This functional ambiguity is commonly resolved with costly and time-consuming AA mutation and peptide sequencing experiments. Here, we describe a set of orthogonal biochemical protocols, which experimentally determine the identity of Ile or Leu residues in monoclonal antibodies (mAb) based on the selectivity that leucine aminopeptidase shows for n-terminal Leu residues and the cleavage preference for Leu by chymotrypsin. The resulting observations are combined with germline frequencies and incorporated into a logistic regression model, called Predictor for Xle Sites (PXleS) to provide a statistical likelihood for the identity of Leu at an ambiguous site. We demonstrate that PXleS can generate a probability for an Xle site in mAbs with 96% accuracy. The implementation of PXleS precludes the expression of several possible sequences and, therefore, reduces the overall time and resources required to go from spectra generation to a biologically active sequence for a mAb when an Ile or Leu residue is in question.

  14. Equilibrium Sampling in Biomolecular Simulation

    PubMed Central

    2015-01-01

    Equilibrium sampling of biomolecules remains an unmet challenge after more than 30 years of atomistic simulation. Efforts to enhance sampling capability, which are reviewed here, range from the development of new algorithms to parallelization to novel uses of hardware. Special focus is placed on classifying algorithms — most of which are underpinned by a few key ideas — in order to understand their fundamental strengths and limitations. Although algorithms have proliferated, progress resulting from novel hardware use appears to be more clear-cut than from algorithms alone, partly due to the lack of widely used sampling measures. PMID:21370970

  15. Hard spheres out of equilibrium

    NASA Astrophysics Data System (ADS)

    Hermes, M.

    2010-05-01

    In this thesis, experiments and simulations are combined to investigate the nonequilibrium behaviour of hard spheres. In the first chapters we use Molecular Dynamics simulations to investigate the dynamic glass transition of polydisperse hard spheres. We show that this dynamic transition is accompanied by a thermodynamic signature. The higher-order derivatives of the pressure change abruptly at the dynamic glass transition. If a system is compressed beyond this dynamic transition, the pressure increases until it diverges when the system is completely jammed. The density at which the pressure diverges depends on the compression speed. We proceed with experiments on colloidal polymethylmethacrylate (PMMA) particles which closely resemble hard spheres. We investigate the effect of compression using gravity and electric field gradients on the nucleation and on the glass transition. The transition from glass to crystal is gradual and is strongly effected by gravity. We go back to computer simulations to investigate two different techniques to calculate the rate at which a hard-sphere system nucleates. We find that the two techniques yield similar results for the nucleation rate as well as the critical nucleus shape. From this we conclude that the simulation techniques are valid. A combination of simulations and experiments is used to study the nucleation of hard spheres on seed structures. We initiate the nucleation with a seed of particles kept in place by optical tweezers. We show that whereas the nucleation itself can be well described as an equilibrium process, the growth after nucleation can not. We demonstrate that defects play an important role in the growth of the crystal. Colloidal hard spheres can also be driven out of equilibrium using shear. We perform experiments on an equilibrium fluid phase below the coexistence density of the fluid. We show that we can induce order in an equilibrium fluid using oscillatory shear. We find five different phases for varying frequency and amplitude: four known phases and one new phase. The formation of all phases occurs via nucleation and growth and the melting, when the shear is stopped, starts on the edges and near the defects of the crystal phases. In the final chapter, we investigate the interactions between rough colloidal particles in the presence of polymers. We investigate whether surface roughness can be used to reduce the depletion attraction. We find that when the polymer is smaller than the surface roughness the attraction can be reduced significantly compared to smooth colloids.

  16. Thermal equilibrium in Einstein's elevator.

    PubMed

    Snchez-Rey, Bernardo; Chacn-Acosta, Guillermo; Dagdug, Leonardo; Cubero, David

    2013-05-01

    We report fully relativistic molecular-dynamics simulations that verify the appearance of thermal equilibrium of a classical gas inside a uniformly accelerated container. The numerical experiments confirm that the local momentum distribution in this system is very well approximated by the Jttner function-originally derived for a flat spacetime-via the Tolman-Ehrenfest effect. Moreover, it is shown that when the acceleration or the container size is large enough, the global momentum distribution can be described by the so-called modified Jttner function, which was initially proposed as an alternative to the Jttner function. PMID:23767501

  17. Princeton spectral equilibrium code: PSEC

    SciTech Connect

    Ling, K.M.; Jardin, S.C.

    1984-03-01

    A fast computer code has been developed to calculate free-boundary solutions to the plasma equilibrium equation that are consistent with the currents in external coils and conductors. The free-boundary formulation is based on the minimization of a mean-square error epsilon while the fixed-boundary solution is based on a variational principle and spectral representation of the coordinates x(psi,theta) and z(psi,theta). Specific calculations using the Columbia University Torus II, the Poloidal Divertor Experiment (PDX), and the Tokamak Fusion Test Reactor (TFTR) geometries are performed.

  18. Critical and phase-equilibrium properties of an ab initio based potential model of methanol and 1-propanol using two-phase molecular dynamics simulations.

    PubMed

    Patel, Sonal; Wilding, W Vincent; Rowley, Richard L

    2011-12-21

    Two-phase molecular dynamics simulations employing a Monte Carlo volume sampling method were performed using an ab initio based force field model parameterized to reproduce quantum-mechanical dimer energies for methanol and 1-propanol at temperatures approaching the critical temperature. The intermolecular potential models were used to obtain the binodal vapor-liquid phase dome at temperatures to within about 10 K of the critical temperature. The efficacy of two all-atom, site-site pair potential models, developed solely from the energy landscape obtained from high-level ab initio pair interactions, was tested for the first time. The first model was regressed from the ab initio landscape without point charges using a modified Morse potential to model the complete interactions; the second model included point charges to separate Coulombic and dispersion interactions. Both models produced equivalent phase domes and critical loci. The model results for the critical temperature, density, and pressure, in addition to the sub-critical equilibrium vapor and liquid densities and vapor pressures, are compared to experimental data. The model's critical temperature for methanol is 77 K too high while that for 1-propanol is 80 K too low, but the critical densities are in good agreement. These differences are likely attributable to the lack of multi-body interactions in the true pair potential models used here. PMID:22191893

  19. Critical and phase-equilibrium properties of an ab initio based potential model of methanol and 1-propanol using two-phase molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Patel, Sonal; Wilding, W. Vincent; Rowley, Richard L.

    2011-12-01

    Two-phase molecular dynamics simulations employing a Monte Carlo volume sampling method were performed using an ab initio based force field model parameterized to reproduce quantum-mechanical dimer energies for methanol and 1-propanol at temperatures approaching the critical temperature. The intermolecular potential models were used to obtain the binodal vapor-liquid phase dome at temperatures to within about 10 K of the critical temperature. The efficacy of two all-atom, site-site pair potential models, developed solely from the energy landscape obtained from high-level ab initio pair interactions, was tested for the first time. The first model was regressed from the ab initio landscape without point charges using a modified Morse potential to model the complete interactions; the second model included point charges to separate Coulombic and dispersion interactions. Both models produced equivalent phase domes and critical loci. The model results for the critical temperature, density, and pressure, in addition to the sub-critical equilibrium vapor and liquid densities and vapor pressures, are compared to experimental data. The model's critical temperature for methanol is 77 K too high while that for 1-propanol is 80 K too low, but the critical densities are in good agreement. These differences are likely attributable to the lack of multi-body interactions in the true pair potential models used here.

  20. Pre-equilibrium plasma dynamics

    SciTech Connect

    Heinz, U.

    1986-01-01

    Approaches towards understanding and describing the pre-equilibrium stage of quark-gluon plasma formation in heavy-ion collisions are reviewed. Focus is on a kinetic theory approach to non-equilibrium dynamics, its extension to include the dynamics of color degrees of freedom when applied to the quark-gluon plasma, its quantum field theoretical foundations, and its relationship to both the particle formation stage at the very beginning of the nuclear collision and the hydrodynamic stage at late collision times. The usefulness of this approach to obtain the transport coefficients in the quark-gluon plasma and to derive the collective mode spectrum and damping rates in this phase are discussed. Comments are made on the general difficulty to find appropriated initial conditions to get the kinetic theory started, and a specific model is given that demonstrates that, once given such initial conditions, the system can be followed all the way through into the hydrodynamical regime. 39 refs., 7 figs. (LEW)

  1. Non-equilibrium phase transitions

    SciTech Connect

    Mottola, E.; Cooper, F.M.; Bishop, A.R.; Habib, S.; Kluger, Y.; Jensen, N.G.

    1998-12-31

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Non-equilibrium phase transitions play a central role in a very broad range of scientific areas, ranging from nuclear, particle, and astrophysics to condensed matter physics and the material and biological sciences. The aim of this project was to explore the path to a deeper and more fundamental understanding of the common physical principles underlying the complex real time dynamics of phase transitions. The main emphasis was on the development of general theoretical tools to deal with non-equilibrium processes, and of numerical methods robust enough to capture the time-evolving structures that occur in actual experimental situations. Specific applications to Laboratory multidivisional efforts in relativistic heavy-ion physics (transition to a new phase of nuclear matter consisting of a quark-gluon plasma) and layered high-temperature superconductors (critical currents and flux flow at the National High Magnetic Field Laboratory) were undertaken.

  2. Are the Concepts of Dynamic Equilibrium and the Thermodynamic Criteria for Spontaneity, Nonspontaneity, and Equilibrium Compatible?

    ERIC Educational Resources Information Center

    Silverberg, Lee J.; Raff, Lionel M.

    2015-01-01

    Thermodynamic spontaneity-equilibrium criteria require that in a single-reaction system, reactions in either the forward or reverse direction at equilibrium be nonspontaneous. Conversely, the concept of dynamic equilibrium holds that forward and reverse reactions both occur at equal rates at equilibrium to the extent allowed by kinetic…

  3. Are the Concepts of Dynamic Equilibrium and the Thermodynamic Criteria for Spontaneity, Nonspontaneity, and Equilibrium Compatible?

    ERIC Educational Resources Information Center

    Silverberg, Lee J.; Raff, Lionel M.

    2015-01-01

    Thermodynamic spontaneity-equilibrium criteria require that in a single-reaction system, reactions in either the forward or reverse direction at equilibrium be nonspontaneous. Conversely, the concept of dynamic equilibrium holds that forward and reverse reactions both occur at equal rates at equilibrium to the extent allowed by kinetic

  4. Vadose zone isobaric well

    DOEpatents

    Hubbell, Joel M. (Idaho Falls, ID); Sisson, James B. (Idaho Falls, ID)

    2001-01-01

    A deep tensiometer is configured with an outer guide tube having a vented interval along a perforate section at its lower end, which is isolated from atmospheric pressure at or above grade. A transducer having a monitoring port and a reference port is located within a coaxial inner guide tube. The reference port of the transducer is open to the vented interval of the outer guide tube, which has the same gas pressure as in the sediment surrounding the tensiometer. The reference side of the pressure transducer is thus isolated from the effects of atmospheric pressure changes and relative to pressure changes in the material surrounding the tensiometer measurement location and so it is automatically compensated for such pressure changes.

  5. String fluid in local equilibrium

    NASA Astrophysics Data System (ADS)

    Schubring, Daniel; Vanchurin, Vitaly

    2014-10-01

    We study the solutions of string fluid equations under the assumption of a local equilibrium which was previously obtained in the context of the kinetic theory. We show that the fluid can be foliated into noninteracting submanifolds whose equations of motion are exactly that of the wiggly strings considered previously by Vilenkin and Carter. In a special case of negligible statistical variance in either the left- or the right-moving directions of microscopic strings, the submanifolds are described by the action of a null-current-carrying chiral string. When both variances vanish the submanifolds are described by the Nambu-Goto action and the string fluid reduces to the string dust introduced by Stachel.

  6. Local non-equilibrium thermodynamics

    PubMed Central

    Jinwoo, Lee; Tanaka, Hajime

    2015-01-01

    Local Shannon entropy lies at the heart of modern thermodynamics, with much discussion of trajectory-dependent entropy production. When taken at both boundaries of a process in phase space, it reproduces the second law of thermodynamics over a finite time interval for small scale systems. However, given that entropy is an ensemble property, it has never been clear how one can assign such a quantity locally. Given such a fundamental omission in our knowledge, we construct a new ensemble composed of trajectories reaching an individual microstate, and show that locally defined entropy, information, and free energy are properties of the ensemble, or trajectory-independent true thermodynamic potentials. We find that the Boltzmann-Gibbs distribution and Landauer's principle can be generalized naturally as properties of the ensemble, and that trajectory-free state functions of the ensemble govern the exact mechanism of non-equilibrium relaxation. PMID:25592077

  7. Radon equilibrium factor and aerosols

    NASA Astrophysics Data System (ADS)

    Planini?, J.; Radoli?, V.; Faj, Z.; uveljak, B.

    1997-02-01

    Equilibrium factor values ( F) were measured in the NRPB radon chamber and corresponding track densities of the bare ( D) and diffusion ( D0) LR-115 nuclear track detectors were determined. The obtained empirical function, F( {D}/{D 0}) , has agreed with the theoretical one, that had been derived by using concentration equations for the radon and its short-lived decay products. Measurements of the detector track densities and aerosol concentrations ( ca) made possible a fitting of the {D}/{D 0}(c a) function, that after introducing into the F( {D}/{D 0}) gave a relationship for aerosol concentration, F( ca). So, it was possible to assess a radon dose equivalent if concentrations of radon and aerosols in the air were known (measured).

  8. Neoclassical equilibrium in gyrokinetic simulations

    SciTech Connect

    Garbet, X.; Dif-Pradalier, G.; Nguyen, C.; Sarazin, Y.; Grandgirard, V.; Ghendrih, Ph.

    2009-06-15

    This paper presents a set of model collision operators, which reproduce the neoclassical equilibrium and comply with the constraints of a full-f global gyrokinetic code. The assessment of these operators is based on an entropy variational principle, which allows one to perform a fast calculation of the neoclassical diffusivity and poloidal velocity. It is shown that the force balance equation is recovered at lowest order in the expansion parameter, the normalized gyroradius, hence allowing one to calculate correctly the radial electric field. Also, the conventional neoclassical transport and the poloidal velocity are reproduced in the plateau and banana regimes. The advantages and drawbacks of the various model operators are discussed in view of the requirements for neoclassical and turbulent transport.

  9. Equilibrium calculations of firework mixtures

    SciTech Connect

    Hobbs, M.L.; Tanaka, Katsumi; Iida, Mitsuaki; Matsunaga, Takehiro

    1994-12-31

    Thermochemical equilibrium calculations have been used to calculate detonation conditions for typical firework components including three report charges, two display charges, and black powder which is used as a fuse or launch charge. Calculations were performed with a modified version of the TIGER code which allows calculations with 900 gaseous and 600 condensed product species at high pressure. The detonation calculations presented in this paper are thought to be the first report on the theoretical study of firework detonation. Measured velocities for two report charges are available and compare favorably to predicted detonation velocities. However, the measured velocities may not be true detonation velocities. Fast deflagration rather than an ideal detonation occurs when reactants contain significant amounts of slow reacting constituents such as aluminum or titanium. Despite such uncertainties in reacting pyrotechnics, the detonation calculations do show the complex nature of condensed phase formation at elevated pressures and give an upper bound for measured velocities.

  10. Isobar separation of 93Zr and 93Nb at 24 MeV with a new multi-anode ionization chamber

    NASA Astrophysics Data System (ADS)

    Martschini, Martin; Buchriegler, Josef; Collon, Philippe; Kutschera, Walter; Lachner, Johannes; Lu, Wenting; Priller, Alfred; Steier, Peter; Golser, Robin

    2015-10-01

    93Zr with a half-life of 1.6 Ma is produced with high yield in nuclear fission, and thus should be present as a natural or anthropogenic trace isotope in all compartments of the general environment. Sensitive measurements of this isotope would immediately find numerous applications, however, its detection at sufficiently low levels has not yet been achieved. AMS measurements of 93Zr suffer from the interference of the stable isobar 93Nb. At the Vienna Environmental Research Accelerator VERA a new multi-anode ionization chamber was built. It is optimized for isobar separation in the medium mass range and is based on the experience from AMS experiments of 36Cl at our 3-MV tandem accelerator facility. The design provides high flexibility in anode configuration and detector geometry. After validating the excellent energy resolution of the detector with 36S, it was recently used to study iron-nickel and zirconium-niobium-molybdenum isobar separation. To our surprise, the separation of 94Zr (Z = 40) from 94Mo (Z = 42) was found to be much better than that of 58Fe (Z = 26) from 58Ni (Z = 28), despite the significantly larger ΔZ/Z of the latter pair. This clearly contradicts results from SRIM-simulations and suggests that differences in the stopping behavior may unexpectedly favor identification of 93Zr. At 24 MeV particle energy, a 93Nb (Z = 41) suppression factor of 1000 is expected based on a synthetic 93Zr spectrum obtained by interpolation between experimental spectra from the two neighboring stable isotopes 92Zr and 94Zr. Assuming realistic numbers for chemical niobium reduction, a detection level of 93Zr/Zr below 10-9 seems feasible.

  11. Simultaneous quantification of protein phosphorylation sites using liquid chromatography-tandem mass spectrometry-based targeted proteomics: a linear algebra approach for isobaric phosphopeptides.

    PubMed

    Xu, Feifei; Yang, Ting; Sheng, Yuan; Zhong, Ting; Yang, Mi; Chen, Yun

    2014-12-01

    As one of the most studied post-translational modifications (PTM), protein phosphorylation plays an essential role in almost all cellular processes. Current methods are able to predict and determine thousands of phosphorylation sites, whereas stoichiometric quantification of these sites is still challenging. Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS)-based targeted proteomics is emerging as a promising technique for site-specific quantification of protein phosphorylation using proteolytic peptides as surrogates of proteins. However, several issues may limit its application, one of which relates to the phosphopeptides with different phosphorylation sites and the same mass (i.e., isobaric phosphopeptides). While employment of site-specific product ions allows for these isobaric phosphopeptides to be distinguished and quantified, site-specific product ions are often absent or weak in tandem mass spectra. In this study, linear algebra algorithms were employed as an add-on to targeted proteomics to retrieve information on individual phosphopeptides from their common spectra. To achieve this simultaneous quantification, a LC-MS/MS-based targeted proteomics assay was first developed and validated for each phosphopeptide. Given the slope and intercept of calibration curves of phosphopeptides in each transition, linear algebraic equations were developed. Using a series of mock mixtures prepared with varying concentrations of each phosphopeptide, the reliability of the approach to quantify isobaric phosphopeptides containing multiple phosphorylation sites (≥ 2) was discussed. Finally, we applied this approach to determine the phosphorylation stoichiometry of heat shock protein 27 (HSP27) at Ser78 and Ser82 in breast cancer cells and tissue samples. PMID:25403019

  12. Measurement and isobar-model analysis of the doubly differential cross section for the. pi. /sup +/ produced in. pi. /sup -/p. -->. pi. /sup +/. pi. /sup -/n

    SciTech Connect

    Manley, D.M.

    1981-11-01

    The doubly differential cross section d/sup 2/sigma/d..cap omega..dT for ..pi../sup +/ mesons produced in the reaction ..pi../sup -/p ..-->.. ..pi../sup +/..pi../sup -/n was measured at 203, 230, 256, and 358 MeV with a single-arm magnetic spectrometer. A set of five previous measurements at 254, 280, 292, 331, and 356 MeV was reanalyzed with the new measurements. Integrated cross sections were calculated for the combined data set with unprecedented accuracy for this energy range. The chiral-symmetry-breaking parameter was determined to be epsilon = -0.03 +- 0.26 by extrapolating the mean square modulus of the matrix element to threshold and comparing the threshold matrix element with the prediction of soft-pion theory. This value of epsilon is consistent with zero as required by the Weinberg Lagrangian. Measurements at the three highest energies were compared with the results of an isobar-model analysis of bubble-chamber events by an LBL-SLAC collaboration. After allowing for an overall normalization difference, the measurements at 331 and 358 MeV were in excellent agreement with the results of their analysis. The measurement at 292 MeV required variation of the PS11(epsilonN) amplitude, as well as the overall normalization, which could be due to the limited number of bubble-chamber events available for the LBL-SLAC analysis at this energy. A partial-wave analysis of the measurements was also carried out with the VPI isobar model. Within this model, the matrix element contains a background term calculated from a phenomenological ..pi..N Lagrangian that is consistent with the hypotheses of current algebra and PCAC. The reaction was found to be dominated by the initial P11 wave. Production of the ..delta.. isobar from initial D waves was found to be significant at the two highest energies.

  13. Rare evidence for formation of garnet + corundum during isobaric cooling of ultrahigh temperature metapelites: New insights for retrograde P-T trajectory of the Highland Complex, Sri Lanka

    NASA Astrophysics Data System (ADS)

    Dharmapriya, P. L.; Malaviarachchi, Sanjeeva P. K.; Galli, Andrea; Su, Ben-Xun; Subasinghe, N. D.; Dissanayake, C. B.

    2015-04-01

    We report the occurrence of coexisting garnet + corundum in spinel- and corundum-bearing, garnet-sillimanite-biotite-graphite gneiss (pelitic granulites) from the Highland Complex (HC), Sri Lanka. In the investigated pelitic granulites, two domains such as quartz-saturated and quartz-undersaturated are distinguishable. The quartz-saturated domains consist of porphyroblastic garnet, quartz, plagioclase, alkali-feldspar and biotite flakes rimming garnet. The quartz-undersaturated domains are constituted of two generations of garnet (Grt1 and Grt2), sillimanite, plagioclase, alkali-feldspar, corundum, spinel and biotite. Grt1 encloses rare Ti-rich biotite and numerous rutile needles and apatite rods. Grt2 contains rare sillimanite and/or spinel inclusions. Corundum occurs in mutual contact with Grt2, partially embedded at the rim or as an inclusions in Grt2. Thermobarometry on inclusion phases in Grt1 indicates that during the prograde history pelitic granulites attained a P of 10.5-11 kbar at T of ~ 850 C. Textural observations coupled with both pseudosections calculated in the NCKFMASHTMnO system and Ti-in-Garnet geothermobarometry suggest that peak metamorphism occurred at ultrahigh temperature (UHT) conditions of 950-975 C and pressures of 9-9.5 kbar. Peak T was followed by a period of isobaric cooling that formed corundum and Grt2 at approx. 930 C along with exsolution of rutile needles and apatite rods in Grt1. Thermodynamic modelling confirms that corundum appears along an isobaric cooling path at about 920-930 C and 9-9.5 kbar. Therefore, the investigated granulites provide a rare example of post-peak crystallization of garnet + corundum along a retrograde metamorphic trajectory under UHT conditions. Thus, isobaric cooling at the base of the crust could be regarded as an alternative process to form coexisting garnet + corundum.

  14. A comparison of thoracic spinal anesthesia with low-dose isobaric and low-dose hyperbaric bupivacaine for orthopedic surgery: A randomized controlled trial

    PubMed Central

    Imbelloni, Luiz Eduardo; Gouveia, Marildo A.

    2014-01-01

    Background: The thoracic spinal anesthesia was first described in 1909 and recently revised for various surgical procedures. This is a prospective study aims to evaluate the parameters of the thoracic spinal anesthesia (latency, motor block and paresthesia), the incidence of cardiovascular changes and complications comparing low doses of isobaric and hyperbaric bupivacaine. Materials and Methods: A total of 200 orthopedic patients operated under spinal anesthesia were included in this study. Spinal anesthesia was between T9-T10, with a 27G cutting point or pencil tip in lateral or sitting. Spinal anesthesia was performed with 0.5% bupivacaine isobaric or hyperbaric. Patients remained in cephalad or head down position 10-20 for 10 minutes. We evaluated the demographics, analgesia, and degree of motor block, incidence of paresthesia, bradycardia, hypotension, anesthesia success and neurological complications. Results: All patients developed spinal and there was no failure. The solution did not affect the onset of the blockade. The duration of motor block was greater than the sensitive with isobaric. The duration of sensory block was greater than the motor block with hyperbaric solution. The incidence of paresthesia was 4%, with no difference between the needles. The incidence of hypotension was 12.5% with no difference between the solutions. There was no neurological damage in all patients. Conclusion: The beginning of the block is fast regardless of the solution used. By providing a sensory block of longer duration than the motor block hyperbaric bupivacaine is reflected in a better indication. Thoracic spinal anesthesia provides excellent anesthesia for lower limb orthopedic surgery PMID:25886099

  15. Relativistic equilibrium distribution by relative entropy maximization

    NASA Astrophysics Data System (ADS)

    Nakamura, T. K.

    2009-11-01

    The equilibrium state of a relativistic gas has been calculated based on the maximum entropy principle. Though the relativistic equilibrium state was long believed to be the Jttner distribution, a number of papers have been published in recent years proposing alternative equilibrium states. Some of these papers do not pay enough attention to the covariance of distribution functions, resulting in confusion in equilibrium states. Starting from a fully covariant expression, it has been shown in the present paper that the Jttner distribution is the maximum entropy state if we assume the Lorentz symmetry.

  16. 1-D EQUILIBRIUM DISCRETE DIFFUSION MONTE CARLO

    SciTech Connect

    T. EVANS; ET AL

    2000-08-01

    We present a new hybrid Monte Carlo method for 1-D equilibrium diffusion problems in which the radiation field coexists with matter in local thermodynamic equilibrium. This method, the Equilibrium Discrete Diffusion Monte Carlo (EqDDMC) method, combines Monte Carlo particles with spatially discrete diffusion solutions. We verify the EqDDMC method with computational results from three slab problems. The EqDDMC method represents an incremental step toward applying this hybrid methodology to non-equilibrium diffusion, where it could be simultaneously coupled to Monte Carlo transport.

  17. EASI - EQUILIBRIUM AIR SHOCK INTERFERENCE

    NASA Technical Reports Server (NTRS)

    Glass, C. E.

    1994-01-01

    New research on hypersonic vehicles, such as the National Aero-Space Plane (NASP), has raised concerns about the effects of shock-wave interference on various structural components of the craft. State-of-the-art aerothermal analysis software is inadequate to predict local flow and heat flux in areas of extremely high heat transfer, such as the surface impingement of an Edney-type supersonic jet. EASI revives and updates older computational methods for calculating inviscid flow field and maximum heating from shock wave interference. The program expands these methods to solve problems involving the six shock-wave interference patterns on a two-dimensional cylindrical leading edge with an equilibrium chemically reacting gas mixture (representing, for example, the scramjet cowl of the NASP). The inclusion of gas chemistry allows for a more accurate prediction of the maximum pressure and heating loads by accounting for the effects of high temperature on the air mixture. Caloric imperfections and specie dissociation of high-temperature air cause shock-wave angles, flow deflection angles, and thermodynamic properties to differ from those calculated by a calorically perfect gas model. EASI contains pressure- and temperature-dependent thermodynamic and transport properties to determine heating rates, and uses either a calorically perfect air model or an 11-specie, 7-reaction reacting air model at equilibrium with temperatures up to 15,000 K for the inviscid flowfield calculations. EASI solves the flow field and the associated maximum surface pressure and heat flux for the six common types of shock wave interference. Depending on the type of interference, the program solves for shock-wave/boundary-layer interaction, expansion-fan/boundary-layer interaction, attaching shear layer or supersonic jet impingement. Heat flux predictions require a knowledge (from experimental data or relevant calculations) of a pertinent length scale of the interaction. Output files contain flow-field information for the various shock-wave interference patterns and their associated maximum surface pressure and heat flux predictions. EASI is written in FORTRAN 77 for a DEC VAX 8500 series computer using the VAX/VMS operating system, and requires 75K of memory. The program is available on a 9-track 1600 BPI magnetic tape in DEC VAX BACKUP format. EASI was developed in 1989. DEC, VAX, and VMS are registered trademarks of the Digital Equipment Corporation.

  18. Equilibrium coexistence of three amphiboles

    USGS Publications Warehouse

    Robinson, P.; Jaffe, H.W.; Klein, C., Jr.; Ross, M.

    1969-01-01

    Electron probe and wet chemical analyses of amphibole pairs from the sillimanite zone of central Massachusetts and adjacent New Hampshire indicated that for a particular metamorphic grade there should be a restricted composition range in which three amphiboles can coexist stably. An unequivocal example of such an equilibrium three amphibole rock has been found in the sillimanite-orthoclase zone. It contains a colorless primitive clinoamphibole, space group P21/m, optically and chemically like cummingtonite with blue-green hornblende exsolution lamellae on (100) and (-101) of the host; blue-green hornblende, space group C2/m, with primitive cummingtonite exsolution lamellae on (100) and (-101) of the host; and pale pinkish tan anthophyllite, space group Pnma, that is free of visible exsolution lamellae but is a submicroscopic intergrowth of two orthorhombic amphiboles. Mutual contacts and coarse, oriented intergrowths of two and three host amphiboles indicate the three grew as an equilibrium assemblage prior to exsolution. Electron probe analyses at mutual three-amphibole contacts showed little variation in the composition of each amphibole. Analyses believed to represent most closely the primary amphibole compositions gave atomic proportions on the basis of 23 oxygens per formula unit as follows: for primitive cummingtonite (Na0.02Ca0.21- Mn0.06Fe2+2.28Mg4.12Al0.28) (Al0.17Si7.83), for hornblende (Na0.35Ca1.56Mn0.02Fe1.71Mg2.85Al0.92) (Al1.37Si6.63), and for anthophyllite (Na0.10Ca0.06Mn0.06Fe2.25Mg4.11Al0.47) (Al0.47Si7.53). The reflections violating C-symmetry, on X-ray single crystal photographs of the primitive cummingtonite, are weak and diffuse, and suggest a partial inversion from a C-centered to a primitive clinoamphibole. Single crystal photographs of the anthophyllite show split reflections indicating it is an intergrowth of about 80% anthophyllite and about 20% gedrite which differ in their b crystallographic dimensions. Split reflections are characteristic of all analyzed orthorhombic amphiboles so far examined from Massachusetts and New Hampshire except the most aluminous gedrites, and the relative intensity of the gedrite reflections is roughly proportional to the degree of Na and Al substitution. Thin sections of a few of these anthophyllite specimens show lamellae parallel to (010) that are just resolved with a high power objective. ?? 1969 Springer-Verlag.

  19. Ringed Accretion Disks: Equilibrium Configurations

    NASA Astrophysics Data System (ADS)

    Pugliese, D.; Stuchlík, Z.

    2015-12-01

    We investigate a model of a ringed accretion disk, made up by several rings rotating around a supermassive Kerr black hole attractor. Each toroid of the ringed disk is governed by the general relativity hydrodynamic Boyer condition of equilibrium configurations of rotating perfect fluids. Properties of the tori can then be determined by an appropriately defined effective potential reflecting the background Kerr geometry and the centrifugal effects. The ringed disks could be created in various regimes during the evolution of matter configurations around supermassive black holes. Therefore, both corotating and counterrotating rings have to be considered as being a constituent of the ringed disk. We provide constraints on the model parameters for the existence and stability of various ringed configurations and discuss occurrence of accretion onto the Kerr black hole and possible launching of jets from the ringed disk. We demonstrate that various ringed disks can be characterized by a maximum number of rings. We present also a perturbation analysis based on evolution of the oscillating components of the ringed disk. The dynamics of the unstable phases of the ringed disk evolution seems to be promising in relation to high-energy phenomena demonstrated in active galactic nuclei.

  20. Cluster size distributions in equilibrium

    NASA Astrophysics Data System (ADS)

    Hendriks, E. M.

    1984-12-01

    Equilibrium size distributions for finite system containing M monomers in a volume V undergoing coagulation (polymerization)/fragmentation, are determined for coagulation rate K ij and fragmentation rate F ij , corresponding to the process A i + A j ⇄ A i+j (here A k denotes a cluster containing k monomeric units). It is shown that microscopic detailed balance implies F ij / K ij = λa i a j / a i+j , where λ and a k are arbitrary. The mean and most probable size distribution c k = λρ -1 a k e -μk coincide in the thermodynamic limit M, V→∞, ρ= M/V fixed. Ifa_k ˜ e^{μ _c k} k^{ - δ } (k to infty ), 2<δ<3, then the theory predicts a (solgel) phase transition at a well defined value of q = λ ρ -1, with critical exponents γ = δ and σ = δ-2. The gel fraction exponent β assumes its classical value unity, probably due to the neglect of spatial fluctuations. Finally it is indicated how the theory can in principle be extended to account for isomerism and cyclization.

  1. Delayed fragmentation and optimized isolation width settings for improvement of protein identification and accuracy of isobaric mass tag quantification on Orbitrap-type mass spectrometers.

    PubMed

    Savitski, Mikhail M; Sweetman, Gavain; Askenazi, Manor; Marto, Jarrod A; Lang, Manja; Zinn, Nico; Bantscheff, Marcus

    2011-12-01

    Fragmentation of multiple peptides in a single tandem mass scan impairs accuracy of isobaric mass tag based quantification. Consequently, practitioners aim at fragmenting peptide ions with the highest possible purity without compromising on sensitivity and coverage achieved in the experiment. Here we report the first systematic study optimizing delayed fragmentation options on Orbitrap instruments. We demonstrate that by delaying peptide fragmentation to occur closer to the apex of the chromatographic peak in liquid chromatography-tandem mass spectrometry (LC-MS/MS) experiments cofragmentation is reduced by 2-fold and peptides are fragmented with 2.8-fold better signal-to-noise ratios. This results in significantly improved accuracy of isobaric mass tag quantification. Further, we measured cofragmentation dependence on isolation width. In comparison to Orbitrap XL instruments the reduced space charging in the Orbitrap Velos enables isolation widths as narrow as 1 Th without impairing coverage, thus substantially reducing cofragmentation. When delayed peptide fragmentation and narrow isolation width settings were both applied, cofragmentation-induced ratio compression could be reduced by 32% on a log2 scale under otherwise identical conditions. PMID:22017476

  2. Prediction of the plate height of capillary columns operated at any inlet pressure of the carrier gas by using few retention data measured under isobaric conditions.

    PubMed

    Vezzani, S; Moretti, P; Castello, G

    2003-04-25

    Programming inlet pressure in gas chromatography permits to decrease the analysis time without changing the elution order of compounds of different polarity whose relative retention changes with changing temperature. The choice of the best values of the inlet pressure and flow-rate of the carrier gas often requires many preliminary analyses with different parameters to be carried out. A method for the prediction of the separation by starting from few experimental data measured in isothermal and isobaric conditions decreases the time required for the optimisation of the analysis. The efficiency of the separation depends on the change of the theoretical plate height at various pressures and temperatures, due to pressure drop along the column. By calculation of the diffusion coefficients of the analysed compounds into the mobile and stationary phase it is possible to evaluate the column efficiency and predict the number of theoretical plates at any inlet pressure. A procedure for the prediction of the plate height of a capillary column at any inlet pressure of the carrier gas and column temperature by using retention data of polar and non-polar compounds (1-alcohols and linear alkanes) obtained in few isobaric runs is described. PMID:12779223

  3. Custom 4-Plex DiLeu Isobaric Labels Enable Relative Quantification of Urinary Proteins in Men with Lower Urinary Tract Symptoms (LUTS)

    PubMed Central

    Greer, Tyler; Hao, Ling; Nechyporenko, Anatoliy; Lee, Sanghee; Vezina, Chad M.; Ricke, Will A.; Marker, Paul C.; Bjorling, Dale E.; Bushman, Wade; Li, Lingjun

    2015-01-01

    The relative quantification of proteins using liquid chromatography mass spectrometry (LC-MS) has allowed researchers to compile lists of potential disease markers. These complex quantitative workflows often include isobaric labeling of enzymatically-produced peptides to analyze their relative abundances across multiple samples in a single LC-MS run. Recent efforts by our lab have provided scientists with cost-effective alternatives to expensive commercial labels. Although the quantitative performance of these dimethyl leucine (DiLeu) labels has been reported using known ratios of complex protein and peptide standards, their potential in large-scale proteomics studies using a clinically relevant system has never been investigated. Our work rectifies this oversight by implementing 4-plex DiLeu to quantify proteins in the urine of aging human males who suffer from lower urinary tract symptoms (LUTS). Protein abundances in 25 LUTS and 15 control patients were compared, revealing that of the 836 proteins quantified, 50 were found to be differentially expressed (>20% change) and statistically significant (p-value <0.05). Gene ontology (GO) analysis of the differentiated proteins showed that many were involved in inflammatory responses and implicated in fibrosis. While confirmation of individual protein abundance changes would be required to verify protein expression, this study represents the first report using the custom isobaric label, 4-plex DiLeu, to quantify protein abundances in a clinically relevant system. PMID:26267142

  4. A Stochastic Algorithm for the Isobaric-Isothermal Ensemble with Ewald Summations for All Long Range Forces.

    PubMed

    Di Pierro, Michele; Elber, Ron; Leimkuhler, Benedict

    2015-12-01

    We present an algorithm termed COMPEL (COnstant Molecular Pressure with Ewald sum for Long range forces) to conduct simulations in the NPT ensemble. The algorithm combines novel features recently proposed in the literature to obtain a highly efficient and accurate numerical integrator. COMPEL exploits the concepts of molecular pressure, rapid stochastic relaxation to equilibrium, exact calculation of the contribution to the pressure of long-range nonbonded forces with Ewald summation, and the use of Trotter expansion to generate a robust, highly stable, symmetric, and accurate algorithm. Explicit implementation in the MOIL program and illustrative numerical examples are discussed. PMID:26616351

  5. Microwave Remote Sensing Techniques for Vapor, Liquid and Ice Parameters.

    NASA Astrophysics Data System (ADS)

    Li, Li.

    The objective of this dissertation is to develop a comprehensive physical inverse model for microwave remote sensing of atmospheric components. This novel approach provides a rigorous basis for understanding and extracting the physical information content of radiometer and/or radar measurements of the atmospheric media. To this end, a comprehensive parametric radiative transfer model (forward model) is developed first and then used to examine the sensitivity of downwelling microwave radiation to realistic variations of environments and to evaluate the information content carried in the ground-based radiometer observations. A physical inversion approach is designed using Artificial Neural Network (ANN) inversion techniques. Both explicit and iterative inverse methods are used to study the non -uniqueness and non-convexness of the inversion on synthetic data. This physical inverse approach is applied to model NOAA's two- and three-channel ground-based radiometers (20.6, 31.65 and 90 GHz). The new physical inverse model is able to retrieve vertically integrated water vapor, cloud liquid water and ice water content simultaneously. Excellent model validations on water vapor and liquid water path retrievals were obtained based on radiosonde observations and NOAA's operational statistical models. A combined iterative radar/radiometer method is further developed to vertically profile cloud microphysics. The combined model use retrievals from radiometer as initial guess and search iteratively for desired microphysical profiles which are consistent with radar measurements. Case studies found that this radar/radiometer technique agrees very well with aircraft in situ measurement of liquid drop size spectra and reasonably well with other published studies on empirical relationships between radar reflectivity and ice or liquid cloud parameters. The predominant feature of a physical inverse model developed in this dissertation is that it can easily handle the non-linearity of radiative transfer and address the non-uniqueness of inversion. Besides, the physical model does not depend on in situ measurements and is thus site-independent. In principle, different remote sensor observations and climatological statistics can be incorporated into the inversion model.

  6. Catalytic hydrogenation process and apparatus with improved vapor liquid separation

    DOEpatents

    Chervenak, Michael C. (Pennington, NJ); Comolli, Alfred G. (Trenton, NJ)

    1980-01-01

    A continuous hydrogenation process and apparatus wherein liquids are contacted with hydrogen in an ebullated catalyst reaction zone with the liquids and gas flowing vertically upwardly through that zone into a second zone substantially free of catalyst particles and wherein the liquid and gases are directed against an upwardly inclining surface through which vertical conduits are placed having inlet ends at different levels in the liquid and having outlet ends at different levels above the inclined surface, such that vapor-rich liquid is collected and discharged through conduits terminating at a higher level above the inclined surface than the vapor-poor liquid which is collected and discharged at a level lower than the inclined surface.

  7. Two-Step Vapor/Liquid/Solid Purification

    NASA Technical Reports Server (NTRS)

    Holland, L. R.

    1986-01-01

    Vertical distillation system combines in single operation advantages of multiple zone refining with those of distillation. Developed specifically to load Bridgman-Stockbarger (vertical-solidification) growth ampoules with ultrapure tellurium and cadmium, system, with suitable modifications, serves as material refiner. In first phase of purification process, ampoule heated to drive off absorbed volatiles. Second phase, evaporator heated to drive off volatiles in charge. Third phase, slowly descending heater causes distillation from evaporator to growing crystal in ampoule.

  8. Effect of dimensionality on vapor-liquid phase transition

    SciTech Connect

    Singh, Sudhir Kumar

    2014-04-24

    Dimensionality play significant role on ‘phase transitions’. Fluids in macroscopic confinement (bulk or 3-Dimensional, 3D) do not show significant changes in their phase transition properties with extent of confinement, since the number of molecules away from the surrounding surfaces is astronomically higher than the number of molecules in close proximity of the confining surfaces. In microscopic confinement (quasi 3D to quasi-2D), however, the number of molecules away from the close proximity of the surface is not as high as is the case with macroscopic (3D) confinement. Hence, under the same thermodynamic conditions ‘phase transition’ properties at microscopic confinement may not remain the same as the macroscopic or 3D values. Phase transitions at extremely small scale become very sensitive to the dimensions as well as the surface characteristics of the system. In this work our investigations reveal the effect of dimensionality on the phase transition from 3D to quasi-2D to 2D behavior. We have used grand canonical transition matrix Monte Carlo simulation to understand the vapor–liquid phase transitions from 3D to quasi-2D behavior. Such studies can be helpful in understanding and controlling the fluid film behaviour confined between solid surfaces of few molecular diameters, for example, in lubrication applications.

  9. Equilibrium swelling of elastomers in solvents

    NASA Technical Reports Server (NTRS)

    Fedors, R. F.

    1980-01-01

    Two proposed empirical equations, developed from Eilers-VanDijk equation to characterize relative modulus of filled elastomers as function of filler content, describe: (1) equilibrium swelling for cases where fillers are composed of permanent aggregates of primary particles; and (2) equilibrium swelling when filler material is composed of non-aggregated particles.

  10. Zeroth Law, Entropy, Equilibrium, and All That

    ERIC Educational Resources Information Center

    Canagaratna, Sebastian G.

    2008-01-01

    The place of the zeroth law in the teaching of thermodynamics is examined in the context of the recent discussion by Gislason and Craig of some problems involving the establishment of thermal equilibrium. The concept of thermal equilibrium is introduced through the zeroth law. The relation between the zeroth law and the second law in the…

  11. Zeroth Law, Entropy, Equilibrium, and All That

    ERIC Educational Resources Information Center

    Canagaratna, Sebastian G.

    2008-01-01

    The place of the zeroth law in the teaching of thermodynamics is examined in the context of the recent discussion by Gislason and Craig of some problems involving the establishment of thermal equilibrium. The concept of thermal equilibrium is introduced through the zeroth law. The relation between the zeroth law and the second law in the

  12. The Equilibrium of Life-Career Planning

    NASA Astrophysics Data System (ADS)

    Byars-Winston, Angela

    Over a 100 years ago, fixed wing aircraft flight was made possible by Orville and Wilbur Wright's breakthrough invention of a three-axis control that allowed effective steering and maintenance of airplanes' equilibrium. The significance of the Wright brothers' control invention is that it facilitated recovery of lateral balance, or equilibrium, when the wind tilts the aircraft to one side or another.

  13. Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

    ERIC Educational Resources Information Center

    Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

    2015-01-01

    A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

  14. Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

    ERIC Educational Resources Information Center

    Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

    2015-01-01

    A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of

  15. A general equilibrium analysis of partial-equilibrium welfare measures: The case of climate change

    SciTech Connect

    Kokoski, M.F.; Smith, V.K. )

    1987-06-01

    This paper uses computable general equilibrium models to demonstrate that partial-equilibrium welfare measures can offer reasonable approximations of the true welfare changes for large exogenous changes. With consistency in the size and direction of the indirect price effects associated with large shocks, single sector partial-equilibrium measures will exhibit small errors. Otherwise the errors can be substantial and difficult to sign.

  16. Disturbances in equilibrium function after major earthquake

    PubMed Central

    Honma, Motoyasu; Endo, Nobutaka; Osada, Yoshihisa; Kim, Yoshiharu; Kuriyama, Kenichi

    2012-01-01

    Major earthquakes were followed by a large number of aftershocks and significant outbreaks of dizziness occurred over a large area. However it is unclear why major earthquake causes dizziness. We conducted an intergroup trial on equilibrium dysfunction and psychological states associated with equilibrium dysfunction in individuals exposed to repetitive aftershocks versus those who were rarely exposed. Greater equilibrium dysfunction was observed in the aftershock-exposed group under conditions without visual compensation. Equilibrium dysfunction in the aftershock-exposed group appears to have arisen from disturbance of the inner ear, as well as individual vulnerability to state anxiety enhanced by repetitive exposure to aftershocks. We indicate potential effects of autonomic stress on equilibrium function after major earthquake. Our findings may contribute to risk management of psychological and physical health after major earthquakes with aftershocks, and allow development of a new empirical approach to disaster care after such events. PMID:23087814

  17. Probing local equilibrium in nonequilibrium fluids.

    PubMed

    del Pozo, J J; Garrido, P L; Hurtado, P I

    2015-08-01

    We use extensive computer simulations to probe local thermodynamic equilibrium (LTE) in a quintessential model fluid, the two-dimensional hard-disks system. We show that macroscopic LTE is a property much stronger than previously anticipated, even in the presence of important finite-size effects, revealing a remarkable bulk-boundary decoupling phenomenon in fluids out of equilibrium. This allows us to measure the fluid's equation of state in simulations far from equilibrium, with an excellent accuracy comparable to the best equilibrium simulations. Subtle corrections to LTE are found in the fluctuations of the total energy which strongly point to the nonlocality of the nonequilibrium potential governing the fluid's macroscopic behavior out of equilibrium. PMID:26382354

  18. Thermodynamics of nonlinear bolometers near equilibrium

    NASA Astrophysics Data System (ADS)

    Irwin, K. D.

    2006-04-01

    We present the first thermodynamically correct calculation of the noise in a simple nonlinear resistive bolometer or calorimeter operated out of equilibrium. The solution is rigorous only for first- and second-order deviations from equilibrium, and for the linear and quadratic terms of dissipative elements. In contrast, existing models of noise in resistive bolometers are based on the application of equilibrium theories to a system that is often nonlinear and out of equilibrium. We derive solutions applicable both in and out of steady state. The noise has power spectral density different from the equilibrium theory, and it has higher-order correlations and non-Gaussian characteristics. The results do not apply to non-Markovian hidden variables in the bolometer.

  19. Relativistic Equilibrium Distribution by Relative Entropy Maximization

    NASA Astrophysics Data System (ADS)

    Nakamura, T. K.

    2009-12-01

    The equilibrium distribution function of relativistic plasmas has been calculated based on the maximum entropy principle. The equilibrium distribution function is a necessary ingredient for theoretical or numerical study of various plasma processes. Though the relativistic equilibrium state has been long believed to be the Juttner distribution, a number of papers have been published in recent years proposing alternative equilibrium states. However, some of these papers do not pay enough attention to the covariance of distribution functions, resulting confusion in equilibrium states. Starting from a fully covariant expression to avoid this confusion, it has been shown in the present study that the Juttner distribution is the maximum entropy state if we assume the Lorentz symmetry.

  20. Disturbances in equilibrium function after major earthquake

    NASA Astrophysics Data System (ADS)

    Honma, Motoyasu; Endo, Nobutaka; Osada, Yoshihisa; Kim, Yoshiharu; Kuriyama, Kenichi

    2012-10-01

    Major earthquakes were followed by a large number of aftershocks and significant outbreaks of dizziness occurred over a large area. However it is unclear why major earthquake causes dizziness. We conducted an intergroup trial on equilibrium dysfunction and psychological states associated with equilibrium dysfunction in individuals exposed to repetitive aftershocks versus those who were rarely exposed. Greater equilibrium dysfunction was observed in the aftershock-exposed group under conditions without visual compensation. Equilibrium dysfunction in the aftershock-exposed group appears to have arisen from disturbance of the inner ear, as well as individual vulnerability to state anxiety enhanced by repetitive exposure to aftershocks. We indicate potential effects of autonomic stress on equilibrium function after major earthquake. Our findings may contribute to risk management of psychological and physical health after major earthquakes with aftershocks, and allow development of a new empirical approach to disaster care after such events.

  1. The Sulfur-Iodine Cycle: Process Analysis and Design Using Comprehensive Phase Equilibrium Measurements and Modeling

    SciTech Connect

    Thies, Mark C.; O'Connell, J. P.; Gorensek, Maximilian B.

    2010-01-10

    Of the 100+ thermochemical hydrogen cycles that have been proposed, the Sulfur-Iodine (S-I) Cycle is a primary target of international interest for the centralized production of hydrogen from nuclear power. However, the cycle involves complex and highly nonideal phase behavior at extreme conditions that is only beginning to be understood and modeled for process simulation. The consequence is that current designs and efficiency projections have large uncertainties, as they are based on incomplete data that must be extrapolated from property models. This situation prevents reliable assessment of the potential viability of the system and, even more, a basis for efficient process design. The goal of this NERI award (05-006) was to generate phase-equilibrium data, property models, and comprehensive process simulations so that an accurate evaluation of the S-I Cycle could be made. Our focus was on Section III of the Cycle, where the hydrogen is produced by decomposition of hydroiodic acid (HI) in the presence of water and iodine (I2) in a reactive distillation (RD) column. The results of this project were to be transferred to the nuclear hydrogen community in the form of reliable flowsheet models for the S-I process. Many of the project objectives were achieved. At Clemson University, a unique, tantalum-based, phase-equilibrium apparatus incorporating a view cell was designed and constructed for measuring fluid-phase equilibria for mixtures of iodine, HI, and water (known as HIx) at temperatures to 350 C and pressures to 100 bar. Such measurements were of particular interest for developing a working understanding of the expected operation of the RD column in Section III. The view cell allowed for the IR observation and discernment of vapor-liquid (VL), liquid-liquid, and liquid-liquid-vapor (LLVE) equilibria for HIx systems. For the I2-H2O system, liquid-liquid equilibrium (LLE) was discovered to exist at temperatures up to 310-315 C, in contrast to the models and predictions of earlier workers. For the I2-HI-H2O ternary, LLE and LLVE were all observed for the first time at temperatures of 160 and 200 C. Three LLE tie-lines were measured at 160 C, and preliminary indications are that the underlying phase behavior could result in further improvements in the performance of the S-I Cycle. Unfortunately, these new results were obtained too late in the project to be incorporated into the modeling and simulation work described below. At the University of Virginia, a uniquely complete and reliable model was developed for the thermodynamic properties of HIx, covering the range of conditions expected for the separation of product hydrogen and recycled iodine in the RD column located in Section III. The model was validated with all available property spectroscopy data. The results provide major advances over prior understanding of the chemical speciation involved. The model was implemented in process simulation studies of the S-I Cycle, which showed improvement in energy efficiency to 42%, as well as significantly smaller capital requirements due to lower pressure operation and much smaller equipment sizes. The result is that the S-I Cycle may be much more economically feasible than was previously thought. If both the experimental and modeling work described above were to be continued to ultimate process optimization, both the American public and the global community would benefit from this alternative energy source that does not produce carbon emissions.

  2. Local Nash Equilibrium in Social Networks

    PubMed Central

    Zhang, Yichao; Aziz-Alaoui, M. A.; Bertelle, Cyrille; Guan, Jihong

    2014-01-01

    Nash equilibrium is widely present in various social disputes. As of now, in structured static populations, such as social networks, regular, and random graphs, the discussions on Nash equilibrium are quite limited. In a relatively stable static gaming network, a rational individual has to comprehensively consider all his/her opponents' strategies before they adopt a unified strategy. In this scenario, a new strategy equilibrium emerges in the system. We define this equilibrium as a local Nash equilibrium. In this paper, we present an explicit definition of the local Nash equilibrium for the two-strategy games in structured populations. Based on the definition, we investigate the condition that a system reaches the evolutionary stable state when the individuals play the Prisoner's dilemma and snow-drift game. The local Nash equilibrium provides a way to judge whether a gaming structured population reaches the evolutionary stable state on one hand. On the other hand, it can be used to predict whether cooperators can survive in a system long before the system reaches its evolutionary stable state for the Prisoner's dilemma game. Our work therefore provides a theoretical framework for understanding the evolutionary stable state in the gaming populations with static structures. PMID:25169150

  3. Local Nash equilibrium in social networks.

    PubMed

    Zhang, Yichao; Aziz-Alaoui, M A; Bertelle, Cyrille; Guan, Jihong

    2014-01-01

    Nash equilibrium is widely present in various social disputes. As of now, in structured static populations, such as social networks, regular, and random graphs, the discussions on Nash equilibrium are quite limited. In a relatively stable static gaming network, a rational individual has to comprehensively consider all his/her opponents' strategies before they adopt a unified strategy. In this scenario, a new strategy equilibrium emerges in the system. We define this equilibrium as a local Nash equilibrium. In this paper, we present an explicit definition of the local Nash equilibrium for the two-strategy games in structured populations. Based on the definition, we investigate the condition that a system reaches the evolutionary stable state when the individuals play the Prisoner's dilemma and snow-drift game. The local Nash equilibrium provides a way to judge whether a gaming structured population reaches the evolutionary stable state on one hand. On the other hand, it can be used to predict whether cooperators can survive in a system long before the system reaches its evolutionary stable state for the Prisoner's dilemma game. Our work therefore provides a theoretical framework for understanding the evolutionary stable state in the gaming populations with static structures. PMID:25169150

  4. Teaching Chemical Equilibrium with the Jigsaw Technique

    NASA Astrophysics Data System (ADS)

    Doymus, Kemal

    2008-03-01

    This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students’ understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes was randomly assigned as the non-jigsaw group (control) and other as the jigsaw group (cooperative). Students participating in the jigsaw group were divided into four “home groups” since the topic chemical equilibrium is divided into four subtopics (Modules A, B, C and D). Each of these home groups contained four students. The groups were as follows: (1) Home Group A (HGA), representin g the equilibrium state and quantitative aspects of equilibrium (Module A), (2) Home Group B (HGB), representing the equilibrium constant and relationships involving equilibrium constants (Module B), (3) Home Group C (HGC), representing Altering Equilibrium Conditions: Le Chatelier’s principle (Module C), and (4) Home Group D (HGD), representing calculations with equilibrium constants (Module D). The home groups then broke apart, like pieces of a jigsaw puzzle, and the students moved into jigsaw groups consisting of members from the other home groups who were assigned the same portion of the material. The jigsaw groups were then in charge of teaching their specific subtopic to the rest of the students in their learning group. The main data collection tool was a Chemical Equilibrium Achievement Test (CEAT), which was applied to both the jigsaw and non-jigsaw groups The results indicated that the jigsaw group was more successful than the non-jigsaw group (individual learning method).

  5. The Conceptual Change Approach to Teaching Chemical Equilibrium

    ERIC Educational Resources Information Center

    Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

    2006-01-01

    This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

  6. The Conceptual Change Approach to Teaching Chemical Equilibrium

    ERIC Educational Resources Information Center

    Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

    2006-01-01

    This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This

  7. Negative thermal expansion of ScF3: Insights from density-functional molecular dynamics in the isothermal-isobaric ensemble

    NASA Astrophysics Data System (ADS)

    Lazar, Petr; Bučko, Tomáš; Hafner, Jürgen

    2015-12-01

    Scandium trifluoride (ScF3) is a rare example of a material with a simple structure exhibiting a large negative thermal expansion over a wide range of temperatures. In the present work, the thermal behavior of this material has been studied by means of density-functional molecular dynamics in the isothermal-isobaric ensemble. Our simulations reproduce the experimentally observed trends: thermal expansion is negative at low temperatures, approaches zero at ≈1000 K, and is positive at higher temperatures. The simulations permit us to develop an atomistic scenario of the observed phenomena, which arises from the correlated dynamics of ScF6 octahedra. The relation between the cubic-to-rhombohedral transformation under a very modest compression and the thermal behavior of ScF3 is demonstrated.

  8. Nuclear structure beyond the neutron drip line: The lowest energy states in 9He via their T = 5/2 isobaric analogs in 9Li

    NASA Astrophysics Data System (ADS)

    Uberseder, E.; Rogachev, G. V.; Goldberg, V. Z.; Koshchiy, E.; Roeder, B. T.; Alcorta, M.; Chubarian, G.; Davids, B.; Fu, C.; Hooker, J.; Jayatissa, H.; Melconian, D.; Tribble, R. E.

    2016-03-01

    The level structure of the very neutron rich and unbound 9He nucleus has been the subject of significant experimental and theoretical study. Many recent works have claimed that the two lowest energy 9He states exist with spins Jπ = 1 /2+ and Jπ = 1 /2- and widths on the order of 100-200 keV. These findings cannot be reconciled with our contemporary understanding of nuclear structure. The present work is the first high-resolution study with low statistical uncertainty of the relevant excitation energy range in the 8He+n system, performed via a search for the T = 5 / 2 isobaric analog states in 9Li populated through 8He+p elastic scattering. The present data show no indication of any narrow structures. Instead, we find evidence for a broad Jπ = 1 /2+ state in 9He located approximately 3 MeV above the neutron decay threshold.

  9. A new working mode for molecular springs: water intrusion induced by cooling and associated isobaric heat capacity change of a {ZIF-8 + water} system.

    PubMed

    Grosu, Ya; Eroshenko, V; Nedelec, J M; Grolier, J P E

    2015-01-21

    Hydrophobic microporous metal-organic framework ZIF-8 combined with water forms a molecular spring (MS), which by the forced intrusion of water into the pores and its spontaneous extrusion can store and restore large amounts of mechanical and thermal energy. Using scanning transitiometry technique, we demonstrate that the simultaneous effect of temperature and pressure on the porosity of ZIF-8 leads to a non-standard temperature dependence of intrusion and extrusion pressures of MS, which allows to provoke water intrusion into the hydrophobic pores of ZIF-8 by decreasing the temperature of the system under constant pressure. A remarkably strong effect of intrusion on the isobaric heat-capacity of {ZIF-8 + water} MS is discovered. PMID:25473935

  10. Formation of garnet + corundum during isobaric cooling at UHT conditions: an example from pelitic granulites of the Highland Complex, Sri Lanka

    NASA Astrophysics Data System (ADS)

    Laksthitha Dharmapriya, Prasanna; Galli, Andrea; Prabath Malaviarachchi, Sanjeeva; Su, Ben-Xun

    2014-05-01

    Coexisting garnet and corundum have been reported from different rock types such as UHP rocks, aluminous eclogites, kimberlites and numerous granulites worldwide which experienced UHT conditions of 900-1050 C at relatively high but not eclogitic pressures of 10-12 kbar. In pelitic granulites the assemblage garnet + corundum is usually interpreted to form at peak P during prograde heating along a clock-wise metamorphic path and subsequently breaks down during decompression to form sapphirine, cordierite-sapphirine-spinel or spinel-sillimanite bearing assemblages, depending on the PT-trajectory and bulk rock composition. In any cases, coexisting garnet + corundum are rarely preserved. Even less usual is the occurrence of garnet + corundum in pyroxene-free rocks. In this study, we report the occurrence of coexisting garnet + corundum within spinel- and corundum-bearing, orthopyroxene-free garnet-sillimanite-biotite-graphite gneisses from the Highland Complex (HC), Sri Lanka. In the investigated pelitic granulites, quartz-saturated domains and quartz-deficient domains are distinguishable. Quartz-saturated domains consist of quartz, plagioclase, alkali-feldspar, garnet-porphyroblasts and biotite flakes around garnet. Quartz-deficient domains are constituted of sillimanite, plagioclase, alkali-feldspar, corundum, spinel, biotite and two generations of garnet. Grt1 is coarse- to medium-grained (0.5-3 cm in diameter) and encloses rare Ti-rich biotite and numerous rutile needles and apatite rods. Grt2 is medium- to fine-grained (0.25-1 cm in diameter), contains rare sillimanite and/or spinel inclusions and is always associated with corundum. Corundum occurs in mutual contact with Grt2, partially embedded within rim area of Grt2 or as inclusions in Grt2. Rarely, tiny spinel inclusions can be observed in corundum. The chemistry of minerals preserved as inclusion in Grt1 indicates that pelitic granulites attained maximal P of 10.5-11 kbar at T around 850C during their prograde history. Further heating induced a series of biotite-melting reactions which progressively consumed biotite and quartz from the rock matrix and produced garnet-porphyroblasts and spinel. Textural observations coupled with both pseudosections calculated in the CNKFMASHTMnO system and Ti-in-garnet geothermobarometry suggest that peak metamorphic temperature occurred at UHT conditions of 950-975 0C and pressures of 9-9.5 kbar. Peak T was followed by a period of isobaric cooling responsible for the formation of corundum and Grt2 via the reaction Spl + Sil = Grt2 + Crn at around 930 C, as well as exsolution of rutile needles and apatite rods from Grt1. Modelling of the mode of spinel, sillimanite, corundum and garnet confirms that along an isobaric cooling path at about 920-930 C and 9-9.5 kbar corundum appears and spinel contemporaneously disappears. At the same PT conditions, our model predicts a decrease of sillimanite and an increase of garnet content. Further isobaric cooling produced a second generation of biotite at the rim of large Grt1-porphyroblasts at ca. 800 C. Therefore, the investigated granulites provide a rare but meaningful example where garnet + corundum formed along a retrograde metamorphic trajectory under UHT conditions, forcing to consider isobaric cooling at the base of the crust as an alternative process to explain the formation of coexisting garnet + corundum, especially if the studied rock lacks of cordierite or orthopyroxene.

  11. Assessment of Instrumental Mass Bias and Isobaric Interference Corrections for Hf-Lu-Nd Isotopic Geochemistry on Zircon by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Goolaerts, A.; Scoates, J. S.; Weis, D.; de Jong, J.; Mattielli, N.

    2002-12-01

    We present (1) a simple approach to correct the mass bias as well as isobaric interferences for Hf-Lu isotopic geochemistry of spiked and unspiked zircon samples, (2) new Lu and Nd isotopic data on the zircon standard 91500, and (3) a new 176Hf/177Hf reference value on the zircon standard 91500 specific for MC-ICP-MS instruments. The chemical procedure follows that reported previously for determining the Hf isotopic composition in zircon by MC-ICP-MS (Goolaerts et al., AGU, 2001). Potential Hf-Yb-Lu isobaric interferences and instrumental mass bias were investigated by chemical simulations, which were carried out on different mixed standard solutions with variable elemental ratios (Lu/Hf, Lu/Yb, Hf/Yb). All of the data collected from these experiments were then used for iterative modeling of either 187Re/185Re or 176Yb/173Yb to optimize the correction procedures. These experiments highlight the stability of the Nu Plasma MC-ICP-MS with respect to isobaric interferences and complex external normalization. The results also show that instrumental mass bias and strong isobaric interferences due to high Yb/Hf or Yb/Lu ratios are not simply corrected. This is an especially important issue for chemically untreated zircons (i.e. laser ablation studies) or pelagic sediments and Mn-nodules. The instruments were calibrated using standard solutions for Hf (JMC-475 250 ppb: 176Hf/177Hf = 0.282161 +/- 16), Nd (Rennes 300 ppb: 143Nd/144Nd = 0.511934 +/- 23; 50 ppb: 143Nd/144Nd = 0.511952 +/- 16) and Lu (JMC 50 ppb: 175Lu/176Lu = 37.72 +/- 2); all errors are 2sd. The entire analytical method was calibrated by processing 59 Hf measurements on the zircon standard 91500, including four independent complete dissolution procedures and two Nu Plasma MC-ICP-MS instruments (Nu15-ULB, Nu21-UBC). The average 176Hf/177Hf is 0.282302 +/- 8 (2sd) and the Gaussian distribution of our data confirms the absence of systematic analytical error. These high precision data - external error: 27.3 ppm (2sd) for 59 measurements and 10 ppm for a single day; internal error: 10 ppm (2sd) - show excellent reproducibility between duplicates and underscore the stability of our analytical protocol. Comparison with published data on the zircon standard 91500 highlights the significant improvement in precision provided by our method and suggests that the previous reference value (176Hf/177Hf = 0.282284 +/- 14 (2sd), Wiedenbeck et al., Geostand. Newslett., 1995) should be revised for MC-ICP-MS instruments. We have also determined precisely the Lu and Nd isotopic compositions on the zircon standard 91500. With the growing use of in situ measurement techniques using MC-ICP-MS technology, such precise reference values will become critical for the calibration of laser ablation-MC-ICP-MS analyses in the future.

  12. Rapid Equilibrium-Ordered Enzyme Mechanisms.

    ERIC Educational Resources Information Center

    Chauncey, Thomas R.; And Others

    1985-01-01

    Discusses: (1) characteristic initial velocity behavior (considering the five-step reaction sequence for rapid equilibrium-order bisubstrate mechanisms); (2) dead-end inhibition; (3) inhibition by single products; and (4) an activator as a leading reactant. (JN)

  13. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    PubMed

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions. PMID:25974471

  14. Equilibrium Reconstruction on the Large Helical Device

    SciTech Connect

    Samuel A. Lazerson, D. Gates, D. Monticello, H. Neilson, N. Pomphrey, A. Reiman S. Sakakibara, and Y. Suzuki

    2012-07-27

    Equilibrium reconstruction is commonly applied to axisymmetric toroidal devices. Recent advances in computational power and equilibrium codes have allowed for reconstructions of three-dimensional fields in stellarators and heliotrons. We present the first reconstructions of finite beta discharges in the Large Helical Device (LHD). The plasma boundary and magnetic axis are constrained by the pressure profile from Thomson scattering. This results in a calculation of plasma beta without a-priori assumptions of the equipartition of energy between species. Saddle loop arrays place additional constraints on the equilibrium. These reconstruction utilize STELLOPT, which calls VMEC. The VMEC equilibrium code assumes good nested flux surfaces. Reconstructed magnetic fields are fed into the PIES code which relaxes this constraint allowing for the examination of the effect of islands and stochastic regions on the magnetic measurements.

  15. Stochastic approach to equilibrium and nonequilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Tomé, Tânia; de Oliveira, Mário J.

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

  16. Spreadsheet Templates for Chemical Equilibrium Calculations.

    ERIC Educational Resources Information Center

    Joshi, Bhairav D.

    1993-01-01

    Describes two general spreadsheet templates to carry out all types of one-equation chemical equilibrium calculations encountered by students in undergraduate chemistry courses. Algorithms, templates, macros, and representative examples are presented to illustrate the approach. (PR)

  17. An Elementary Discussion of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    David, Carl W.

    1988-01-01

    This discussion uses a more difficult reaction as the prototype to derive the standard equation for chemical equilibrium. It can be used by students who can understand and use partial derivatives. (CW)

  18. Isobaric yield ratio difference between the 140 A MeV 58Ni + 9Be and 64Ni +9Be reactions studied by the antisymmetric molecular dynamics model

    NASA Astrophysics Data System (ADS)

    Qiao, C. Y.; Wei, H. L.; Ma, C. W.; Zhang, Y. L.; Wang, S. S.

    2015-07-01

    Background: The isobaric yield ratio difference (IBD) method is found to be sensitive to the density difference of neutron-rich nucleus induced reaction around the Fermi energy. Purpose: An investigation is performed to study the IBD results in the transport model. Methods: The antisymmetric molecular dynamics (AMD) model plus the sequential decay model gemini are adopted to simulate the 140 A MeV 58 ,64Ni +9Be reactions. A relative small coalescence radius Rc= 2.5 fm is used for the phase space at t = 500 fm/c to form the hot fragment. Two limitations on the impact parameter (b 1 =0 -2 fm and b 2 =0 -9 fm) are used to study the effect of central collisions in IBD. Results: The isobaric yield ratios (IYRs) for the large-A fragments are found to be suppressed in the symmetric reaction. The IBD results for fragments with neutron excess I = 0 and 1 are obtained. A small difference is found in the IBDs with the b 1 and b 2 limitations in the AMD simulated reactions. The IBD with b 1 and b 2 are quite similar in the AMD + GEMINI simulated reactions. Conclusions: The IBDs for the I =0 and 1 chains are mainly determined by the central collisions, which reflects the nuclear density in the core region of the reaction system. The increasing part of the IBD distribution is found due to the difference between the densities in the peripheral collisions of the reactions. The sequential decay process influences the IBD results. The AMD + GEMINI simulation can better reproduce the experimental IBDs than the AMD simulation.

  19. Edge Equilibrium Code (EEC) For Tokamaks

    SciTech Connect

    Li, Xujling

    2014-02-24

    The edge equilibrium code (EEC) described in this paper is developed for simulations of the near edge plasma using the finite element method. It solves the Grad-Shafranov equation in toroidal coordinate and uses adaptive grids aligned with magnetic field lines. Hermite finite elements are chosen for the numerical scheme. A fast Newton scheme which is the same as implemented in the equilibrium and stability code (ESC) is applied here to adjust the grids

  20. Dynamically defined measures and equilibrium states

    NASA Astrophysics Data System (ADS)

    Werner, Ivan

    2011-12-01

    A technique of dynamically defined measures is developed and its relation to the theory of equilibrium states is shown. The technique uses Carathodory's method and the outer measure introduced in a previous work by I. Werner [Math. Proc. Camb. Phil. Soc. 140(2), 333-347 (2006), 10.1017/S0305004105009072]. As an application, equilibrium states for contractive Markov systems [I. Werner, J. London Math. Soc. 71(1), 236-258 (2005), 10.1112/S0024610704006088] are obtained.

  1. Approaches to the Treatment of Equilibrium Perturbations

    NASA Astrophysics Data System (ADS)

    Canagaratna, Sebastian G.

    2003-10-01

    Perturbations from equilibrium are treated in the textbooks by a combination of Le Chtelier's principle, the comparison of the equilibrium constant K with the reaction quotient Q,and the kinetic approach. Each of these methods is briefly reviewed. This is followed by derivations of the variation of the equilibrium value of the extent of reaction, ?eq, with various parameters on which it depends. Near equilibrium this relationship can be represented by a straight line. The equilibrium system can be regarded as moving on this line as the parameter is varied. The slope of the line depends on quantities like enthalpy of reaction, volume of reaction and so forth. The derivation shows that these quantities pertain to the equilibrium system, not the standard state. Also, the derivation makes clear what kind of assumptions underlie our conclusions. The derivation of these relations involves knowledge of thermodynamics that is well within the grasp of junior level physical chemistry students. The conclusions that follow from the derived relations are given as subsidiary rules in the form of the slope of ?eq, with T, p, et cetera. The rules are used to develop a visual way of predicting the direction of shift of a perturbed system. This method can be used to supplement one of the other methods even at the introductory level.

  2. Theory for non-equilibrium statistical mechanics.

    PubMed

    Attard, Phil

    2006-08-21

    This paper reviews a new theory for non-equilibrium statistical mechanics. This gives the non-equilibrium analogue of the Boltzmann probability distribution, and the generalization of entropy to dynamic states. It is shown that this so-called second entropy is maximized in the steady state, in contrast to the rate of production of the conventional entropy, which is not an extremum. The relationships of the new theory to Onsager's regression hypothesis, Prigogine's minimal entropy production theorem, the Langevin equation, the formula of Green and Kubo, the Kawasaki distribution, and the non-equilibrium fluctuation and work theorems, are discussed. The theory is worked through in full detail for the case of steady heat flow down an imposed temperature gradient. A Monte Carlo algorithm based upon the steady state probability density is summarized, and results for the thermal conductivity of a Lennard-Jones fluid are shown to be in agreement with known values. Also discussed is the generalization to non-equilibrium mechanical work, and to non-equilibrium quantum statistical mechanics. As examples of the new theory two general applications are briefly explored: a non-equilibrium version of the second law of thermodynamics, and the origin and evolution of life. PMID:16883388

  3. Equilibrium free energy measurement of a confined electron driven out of equilibrium

    NASA Astrophysics Data System (ADS)

    Hofmann, A.; Maisi, V. F.; Rssler, C.; Basset, J.; Krhenmann, T.; Mrki, P.; Ihn, T.; Ensslin, K.; Reichl, C.; Wegscheider, W.

    2016-01-01

    The Jarzynski equality relates nonequilibrium thermodynamics and equilibrium states. We realize a coupled quantum dot-electron reservoir system in which the time resolved observation of the tunneling dynamics is used to explicitly measure the exerted work and dissipated heat per single charge. We determine accurate values of the equilibrium free energy change over a large range of final state energies by driving the system far from equilibrium.

  4. Non-Equilibrium Transitions of Heliospheric plasma

    NASA Astrophysics Data System (ADS)

    Livadiotis, G.; McComas, D. J.

    2011-12-01

    Recent advances in Space Physics theory have established the connection between non-extensive Statistical Mechanics and space plasmas by providing a theoretical basis for the empirically derived kappa distributions commonly used to describe the phase space distribution functions of these systems [1]. The non-equilibrium temperature and the kappa index that govern these distributions are the two independent controlling parameters of non-equilibrium systems [1-3]. The significance of the kappa index is primarily given by its role in identifying the non-equilibrium stationary states, and measuring their "thermodynamic distance" from thermal equilibrium [4], while its physical meaning is connected to the correlation between the system's particles [5]. For example, analysis of the IBEX high Energetic Neutral Atom spectra [6] showed that the vast majority of measured kappa indices are between ~1.5 and ~2.5, consistent with the far-equilibrium "cavity" of minimum entropy discovered by Livadiotis & McComas [2]. Spontaneous procedures that can increase the entropy, move the system gradually toward equilibrium, that is the state with the maximum (infinite) kappa index. Other external factors that may decrease the entropy, move the system back to states further from equilibrium where the kappa indices are smaller. Newly formed pick-up ions can play this critical role in the solar wind and other space plasmas. We have analytically shown that their highly ordered motion can reduce the average entropy in the plasma beyond the termination shock, inside the inner heliosheath [7]. Non-equilibrium transitions have a key role in understanding the governing thermodynamical processes of space plasmas. References 1. Livadiotis, G., & McComas, D. J. 2009, JGR, 114, 11105. 2. Livadiotis, G., & McComas, D. J. 2010a, ApJ, 714, 971. 3. Livadiotis, G., & McComas, D. J. 2010c, in AIP Conf. Proc. 9, Pickup Ions Throughout the Heliosphere and Beyond, ed. J. LeRoux, V. Florinski, G. P. Zank, & A. Coates (Melville, NY: AIP), 70. 4. Livadiotis, G., & McComas, D. J. 2010b, PhyS, 82, 035003. 5. Livadiotis, G., & McComas, D. J. 2011, ApJ, Invariant kappa distribution in space plasmas out of equilibrium, in press. 6. Livadiotis, G., McComas, D. J., Dayeh, M. A., Funsten, H. O., Schwadron, N. A. 2011, ApJ.., 734, 1. 7. Livadiotis, G., & McComas, D. J. 2011, ApJ, The influence of pick-up ions on space plasma distributions, in press.

  5. Torque equilibrium attitude control for Skylab reentry

    NASA Technical Reports Server (NTRS)

    Glaese, J. R.; Kennel, H. F.

    1980-01-01

    The method of torque equilibrium attitude control used to control the reentry of Skylab to an altitude below 150 km without the use of thruster fuel once the attitude was established is discussed. The Skylab attitude and pointing control system, which included rate gyros, sun sensors, star tracker, the Apollo telescope mount digital computer, control moment gyros and cold-gas attitude thrusters, is presented. The 12 torque equilibrium attitudes found at which aerodynamic, gravity gradient and gyroscopic torques would balance are indicated, and the three of those at which the solar power supply would be adequate for attitude control are illustrated. The equilibrium seeking method employed is then examined, and the operation and performance of the torque equilibrium attitude control system during the three weeks prior to Skylab reentry are discussed. It is concluded that the torque equilibrium attitude control method developed for Skylab was successful in performing its assigned mission, and will be valuable for the design of future, low-altitude spacecraft or tethered vehicles.

  6. Adult performance on three tests of equilibrium.

    PubMed

    Fisher, A G; Wietlisbach, S E; Wilbarger, J L

    1988-01-01

    The purpose of this investigation was twofold: (a) to determine preliminary norms for young adult males and young adult females on three clinical tests of equilibrium, Tilt Board Tip (TBT), Tilt Board Reach (TBR), and Flat Board Reach (FBR), and (b) to determine sex differences in equilibrium performance. The three equilibrium tests were administered to a sample of 25 men and 29 women between the ages of 20 and 30 years. The results revealed a significant sex difference on TBT, with men obtaining significantly higher scores than women. FBR approached significance, and no significant difference was found on the TBR. These results support earlier findings of sex differences in performance on a variety of equilibrium measures and suggest that different normative criteria should be used to evaluate the performance of males and females on some tests of equilibrium. Possible reasons for males obtaining higher scores on TBT and for lack of differences between male and female performance on FBR and TBR are discussed. PMID:3354626

  7. Efficiency of muscle contraction. The chemimechanic equilibrium

    NASA Astrophysics Data System (ADS)

    Becker, E. W.

    1991-10-01

    Although muscle contraction is one of the principal themes of biological research, the exact mechanism whereby the chemical free energy of ATP hydrolysis is converted into mechanical work remains elusive. The high thermodynamic efficiency of the process, above all, is difficult to explain on the basis of present theories. A model of the elementary effect in muscle contraction is proposed which aims at high thermodynamic efficiency based on an approximate equilibrium between chemical and mechanical forces throughout the transfer of free energy. The experimental results described in the literature support the assumption that chemimechanic equilibrium is approximated by a free energy transfer system based on the binding of divalent metal ions to the myosin light chains. Muscle contraction demonstrated without light chains is expected to proceed with a considerably lower efficiency. Free energy transfer systems based on the binding of ions to proteins seem to be widespread in the cell. By establishing an approximate chemimechanic equilibrium, they could facilitate biological reactions considerably and save large amounts of free energy. The concept of chemimechanic equilibrium is seen as a supplementation to the concept of chemiosmotic equilibrium introduced for the membrane transport by P. Mitchell.

  8. Radiative Equilibrium - Photochemical Model of Titan's Atmosphere

    NASA Astrophysics Data System (ADS)

    Adams, E. Y.; Atreya, S. K.; Kuhn, W. R.

    2004-12-01

    Titan's thermal structure has been characterized and studied by radiative/convective models [1,2,3,4] that are based on an assumed height distribution of species. Likewise, photochemical models [5,6,7,8,9] also employ a temperature profile as basis for the calculations. In this presentation, we discuss preliminary results of a coupled self-consistent radiative equilibrium/photochemical model for the middle and lower atmosphere of Titan. The radiative equilibrium model includes CH4 as the principal absorbent of thermal radiation, minor constituents, and the effect of pressure - induced absorption. The vertical distribution of species is calculated by a comprehensive photochemical model [9]. Our coupled radiative equilibrium/photochemical model is self-consistent, so that the temperature calculated in the radiative equilibrium model is used in the photochemical model to calculate the species vertical distribution, and this produced vertical distribution - in the radiation code, reiterating until both reach equilibrium. We are in the process of adding haze contribution to the radiative model for it serves as a main source of heating in the stratosphere. 1. Samuelson et al., Icarus, 53, 1983; 2. McKay et al., Icarus, 80, 1989; 3. Samuelson and Mayo, Icarus, 91, 1991; 4. McKay et al., Science, 253, 1991; 5.Yung et al., Astrophys. J. Suppl.,55,1984; 6. Toublanc, Icarus, 113, 1995; 7. Lara et al., JGR, 101, E10, 1996; 8. Lebonnois et al., Icarus,152, 2001; 9. Wilson and Atreya, JGR, E06002, 2004.

  9. Planetary cratering 2: Studies of saturation equilibrium

    NASA Astrophysics Data System (ADS)

    Hartmann, William K.; Gaskell, Robert W.

    1997-01-01

    A realistic computer model has been developed to display images of imaginary cratered surfaces, taking into account empirically measured input size distributions of primary and secondary craters, ejecta blanket morphology including feathering with distance, obliteration due to ejecta from outside the imaged area, lighting effects, etc. The model allows us to track surface evolution of morphology as new craters are added. Using the model as well as lunar photos, we have studied the approach to saturation equilibrium (defined as a condition when no further proportionate increase in crater density occurs as input cratering increases). We find that an identifiable saturation equilibrium occurs close to a level previously identified for this state (Hartmann 1984), typically fluctuating around a crater density from about 0.4 to 2 times that level. This result is fairly robust vis-a-vis the range of model parameters we have chosen. Flooding, basin ejecta blankets, and other obliterative effects can introduce structure and oscillations within this range, even after saturation equilibrium is achieved. These findings may constrain or revise certain earlier interpretations of satellite and planet surface evolution and impactor populations which were predicated on the assumed absence of saturation equilibrium. In our fourth experimental run, we found that suppression of "sandblasting" by sub-resolution impacts allows the smallest secondaries to rise above the saturation equilibrium line, a result that might be relevant to a similar situation on Gaspra and perhaps some other asteroids.

  10. Quasilocal energy and thermodynamic equilibrium conditions

    NASA Astrophysics Data System (ADS)

    Uzun, Nezihe; Wiltshire, David L.

    2015-08-01

    Equilibrium thermodynamic laws are typically applied to horizons in general relativity without stating the conditions that bring them into equilibrium. We fill this gap by applying a new thermodynamic interpretation to a generalized Raychaudhuri equation for a worldsheet orthogonal to a closed spacelike two-surface, the screen, which encompasses a system of arbitrary size in nonequilibrium with its surroundings in general. In the case of spherical symmetry this enables us to identify quasilocal thermodynamic potentials directly related to standard quasilocal energy definitions. Quasilocal thermodynamic equilibrium is defined by minimizing the mean extrinsic curvature of the screen. Moreover, without any direct reference to surface gravity, we find that the system comes into quasilocal thermodynamic equilibrium when the screen is located at a generalized apparent horizon. Examples of the Schwarzschild, Friedmann-Lematre and Lematre-Tolman geometries are investigated and compared. Conditions for the quasilocal thermodynamic and hydrodynamic equilibrium states to coincide are also discussed, and a quasilocal virial relation is suggested as a potential application of this approach.

  11. Equilibrium versus disequilibrium of barchan dunes

    NASA Astrophysics Data System (ADS)

    El belrhiti, Hicham; Douady, Stphane

    2011-02-01

    Barchans are crescentic dunes which occur in mainly mono-directional winds. Shape, aspect ratios and velocities of these dunes have been studied as if they were in equilibrium. However, following a study of the shape and migration of 11 barchans of different sizes for 18 months in the field on Moroccan Atlantic Sahara, we show that they only appear to be in a stationary state if studied over a long timeframe (at the scale of the year or several years), but are never in equilibrium at the scale of weeks or months. Rather, they are always 'trying' to reach a possible equilibrium state but never have enough time to accomplish this. This may be the main reason for the large variation observed in previous measurements, and justifies some caution in what can be deduced from them.

  12. MCNP modelling of the PBMR equilibrium core

    SciTech Connect

    Albornoz, F.; Korochinsky, S.

    2006-07-01

    A complete MCNP model of the PBMR equilibrium core is presented, which accounts for the same fuel regions defined in the PBMR core management code, as well as for complete fuel and reflector temperature distributions. This comprehensive 3D model is the means to calculate and characterize the neutron and photon boundary sources of the equilibrium core, and is also used to support some specific core neutronic studies needing detailed geometry modelling. Due to the geometrical modelling approach followed, an unrealistic partial cutting of fuel kernels and pebbles is introduced in the model. The variations introduced by this partial cutting both on the packing fraction and on the uranium load of the modelled core and its corresponding effect on core reactivity and flux levels, have been investigated and quantified. A complete set of high-temperature cross-section data was applied to the calculation of the PBMR equilibrium core, and its effect on the calculated core reactivity is also reported. (authors)

  13. Non-equilibrium quantum heat machines

    NASA Astrophysics Data System (ADS)

    Alicki, Robert; Gelbwaser-Klimovsky, David

    2015-11-01

    Standard heat machines (engine, heat pump, refrigerator) are composed of a system (working fluid) coupled to at least two equilibrium baths at different temperatures and periodically driven by an external device (piston or rotor) sometimes called the work reservoir. The aim of this paper is to go beyond this scheme by considering environments which are stationary but cannot be decomposed into a few baths at thermal equilibrium. Such situations are important, for example in solar cells, chemical machines in biology, various realizations of laser cooling or nanoscopic machines driven by laser radiation. We classify non-equilibrium baths depending on their thermodynamic behavior and show that the efficiency of heat machines powered by them is limited by the generalized Carnot bound.

  14. Analytic prediction of airplane equilibrium spin characteristics

    NASA Technical Reports Server (NTRS)

    Adams, W. M., Jr.

    1972-01-01

    The nonlinear equations of motion are solved algebraically for conditions for which an airplane is in an equilibrium spin. Constrained minimization techniques are employed in obtaining the solution. Linear characteristics of the airplane about the equilibrium points are also presented and their significance in identifying the stability characteristics of the equilibrium points is discussed. Computer time requirements are small making the method appear potentially applicable in airplane design. Results are obtained for several configurations and are compared with other analytic-numerical methods employed in spin prediction. Correlation with experimental results is discussed for one configuration for which a rather extensive data base was available. A need is indicated for higher Reynolds number data taken under conditions which more accurately simulate a spin.

  15. A carbene-carbene complex equilibrium.

    PubMed

    Moss, Robert A; Wang, Lei; Odorisio, Christina M; Krogh-Jespersen, Karsten

    2010-08-11

    Phenylchlorocarbene, generated by laser flash photolysis of phenylchlorodiazirine, formed highly stable pi-type complexes with 1,3,5-trimethoxybenzene in pentane. The carbene and carbene complexes were in equilibrium. We measured the equilibrium constant (K = 1264 M(-1) at 294 K) and, from its temperature dependence, extracted the associated thermodynamic parameters: DeltaH(o) = -7.1 kcal/mol, DeltaS(o) = -10.2 eu, and DeltaG(o) = -4.1 kcal/mol. The carbene complexes were characterized by UV-vis spectroscopy and computational analysis. PMID:20681697

  16. Algorithm For Hypersonic Flow In Chemical Equilibrium

    NASA Technical Reports Server (NTRS)

    Palmer, Grant

    1989-01-01

    Implicit, finite-difference, shock-capturing algorithm calculates inviscid, hypersonic flows in chemical equilibrium. Implicit formulation chosen because overcomes limitation on mathematical stability encountered in explicit formulations. For dynamical portion of problem, Euler equations written in conservation-law form in Cartesian coordinate system for two-dimensional or axisymmetric flow. For chemical portion of problem, equilibrium state of gas at each point in computational grid determined by minimizing local Gibbs free energy, subject to local conservation of molecules, atoms, ions, and total enthalpy. Major advantage: resulting algorithm naturally stable and captures strong shocks without help of artificial-dissipation terms to damp out spurious numerical oscillations.

  17. Equilibrium partition function for nonrelativistic fluids

    NASA Astrophysics Data System (ADS)

    Banerjee, Nabamita; Dutta, Suvankar; Jain, Akash

    2015-10-01

    We construct an equilibrium partition function for a nonrelativistic fluid and use it to constrain the dynamics of the system. The construction is based on light cone reduction, which is known to reduce the Poincar symmetry to Galilean in one lower dimension. We modify the constitutive relations of a relativistic fluid, and find that its symmetry broken phase"null fluid" is equivalent to the nonrelativistic fluid. In particular, their symmetries, thermodynamics, constitutive relations, and equilibrium partition function match exactly to all orders in derivative expansion.

  18. Return to equilibrium in the XY model

    SciTech Connect

    Hume, L.; Robinson, D.W.

    1986-09-01

    We prove that the locally perturbed XY model returns to equilibrium under the unperturbed evolution but the unperturbed model does not necessarily approach equilibrium under the perturbed evolution. In fact this latter property is false for perturbation by a local magnetization. The failure is directly attributable to the formation of bound states. If the perturbation is quadratic these problems are reduced to spectral analysis of the one-particle Hamiltonian. We demonstrate that the perturbed Hamiltonian has a finite set of eigenvalues of finite multiplicity together with some absolutely continuous spectrum. Eigenvalues can occur in the continuum if, and only if, the perturbation dislocates the system. Singular continuous spectrum cannot occur.

  19. Far-from-equilibrium kinetic processes

    NASA Astrophysics Data System (ADS)

    Rub, J. Miguel; Prez-Madrid, Agustin

    2015-12-01

    We analyze the kinetics of activated processes that take place under far-from-equilibrium conditions, when the system is subjected to external driving forces or gradients or at high values of affinities. We use mesoscopic non-equilibrium thermodynamics to show that when a force is applied, the reaction rate depends on the force. In the case of a chemical reaction at high affinity values, the reaction rate is no longer constant but depends on affinity, which implies that the law of mass action is no longer valid. This result is in good agreement with the kinetic theory of reacting gases, which uses a Chapman-Enskog expansion of the probability distribution.

  20. Computing Properties Of Chemical Mixtures At Equilibrium

    NASA Technical Reports Server (NTRS)

    Mcbride, B. J.; Gordon, S.

    1995-01-01

    Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

  1. Putting A Human Face on Equilibrium

    NASA Astrophysics Data System (ADS)

    Glickstein, Neil

    2005-03-01

    A short biography of chemist Fritz Haber is used to personalize the abstract concepts of equilibrium chemistry for high school students in an introductory course. In addition to giving the Haber Bosch process an historic, an economic, and a scientific background the reading and subsequent discussion allows students for whom the human perspective is of paramount importance a chance to investigate the irony of balance or equilibrium in Haber's life story. Since the inclusion of the Haber biography, performance in the laboratory and on examinations for those students who are usually only partially engaged has dramatically improved.

  2. Isodynamic axisymmetric equilibrium near the magnetic axis

    SciTech Connect

    Arsenin, V. V.

    2013-08-15

    Plasma equilibrium near the magnetic axis of an axisymmetric toroidal magnetic confinement system is described in orthogonal flux coordinates. For the case of a constant current density in the vicinity of the axis and magnetic surfaces with nearly circular cross sections, expressions for the poloidal and toroidal magnetic field components are obtained in these coordinates by using expansion in the reciprocal of the aspect ratio. These expressions allow one to easily derive relationships between quantities in an isodynamic equilibrium, in which the absolute value of the magnetic field is constant along the magnetic surface (Palumbo’s configuration)

  3. Equilibrium stellar systems with genetic algorithms

    NASA Astrophysics Data System (ADS)

    Gularte, E.; Carpintero, D. D.

    In 1979, M Schwarzschild showed that it is possible to build an equilibrium triaxial stellar system. However, the linear programmation used to that goal was not able to determine the uniqueness of the solution, nor even if that solution was the optimum one. Genetic algorithms are ideal tools to find a solution to this problem. In this work, we use a genetic algorithm to reproduce an equilibrium spherical stellar system from a suitable set of predefined orbits, obtaining the best solution attainable with the provided set. FULL TEXT IN SPANISH

  4. Isobaric heating and cooling path of the lower crust of a Variscan exotic unit: evidences from P -T estimates in NW Iberian metapelitic granulites

    NASA Astrophysics Data System (ADS)

    Alampi, A.; Gomez Barreiro, J.; Alvarez Valero, A.; Castieiras, P.

    2012-12-01

    Allochthonous complexes (AC) in NW Iberia consist of a pile of exotic units characterized by distinct tectonothermal evolution and lithological association, and separated from each other by tectonic contacts, either thrust or extensional detachments. In the rdenes AC, three groups of units are recognized from bottom to top in the pile: Basal, Ophiolitic and Upper units. Upper units comprise an ensemble of arc-related rocks with a lower section that underwent a high-P and high-T (HP-HT) evolution, and an upper section with an intermediate - pressure (IP) evolution. Extensional detachments have been commonly identifying at the boundary between HP-HT and IP Upper units, like the Forns and Corredoiras detachments. Pelitic granulites from one IP upper unit, the O Pino unit, have been investigated. Petrologic studies reveal an isobaric tectono-metamorphic crustal evolution throughout a multidisciplinary integration of: (i) detailed microstructural analysis; (ii) EMP mineral chemistry; (iii) mass-balance of the key and representative chemical reactions observed in the microstructures and subsequent interpretation of the reaction sequence; (iv) P-T estimates and paths from phase diagram modeling. Results in the NCKFMASHT system describe an isobaric (c. 7 kbar) continuous heating (and later cooling) evolution ranging from c. 620 to 680 C crossing into the melt-bearing stability fields. These achieved anatectic conditions are evidenced by the presence of both leucosomes (quartz, plagioclase and muscovite) and glass inclusions, mainly in local garnet cores through the dehydration/melting reactions of muscovite first and biotite later. Chemically distinct generations of garnet and plagioclase are evident and stoichiometrically balance each other in continuous reactions. They are consistent with the observations of both a garnet overgrowth and large patches of plagioclase which host euhedral, smaller garnets. In the cooling episode, the newly-grown garnet reacted with melt and formed a retrograde biotite + aluminosilicate + muscovite generation wrapping around the leucosomes or within the matrix. This implicates the existence of a localized thermal event in the base of the O Pino unit. The structural context of these rocks may represent the origin of the isobaric path as an important extensional shear zone (Forns detachment) has been localized below the pelitic granulites. The Forns detachment put in contact the O Pino unit from the HP-HT rocks of the Forns unit (> 750C,15kbar). The thermal contrast between both units may generate a localized heating at the base of the O Pino unit which is a recognized effect in other extensional detachments. This fact is in accordance with the description of syn-kinematic melts intruded into the Forns detachment in other NW Iberian areas. We may also speculate with a different scenario where the evolution of the pelitic granulites represent a relic of primitive thermal event barely recognized across the IP Upper units for which more geohronological constraint is still needed.

  5. Applications of 3D Equilibrium Reconstruction

    NASA Astrophysics Data System (ADS)

    Lazerson, Samuel; Geiger, Joachim; Gribov, Yuri; Hudson, Stuart; Gates, David

    2013-10-01

    The STELLOPT 3D equilibrium reconstruction code has utilized to model the W7-X diagnostic response to bootstrap current profile variation, the ITER diagnostic response to +/-2 cm boundary variations, and full 3D equilibrium reconstructions for the DIII-D plasma with applied RMP fields. Field line tracing codes indicate a +/-5 cm ability to shift divertor strike points providing limited capabilities to control divertor heat loads in W7-X. Parameter space maps of bootstrap current variation suggest a diagnostic set capable of predicting bootstrap current evolution and providing feedback control of the plasma. Modeling of the ITER 15MA scenario suggests such coils will perturb the plasma edge up to +/-2 cm, with significant effects on magnetic diagnostic response. Full 3D reconstructions of the DIII-D plasma with applied RMP's have been carried out with STELLOPT. Forward modeling of the equilibrium using the Stepped Pressure Equilibrium Code (SPEC) suggests the presence of islands and corroborates the notion of mode penetration in this shot. This presentation has been authored by Princeton University under Contract Number DE-AC02-09CH11466 with the US Department of Energy.

  6. Teaching Chemical Equilibrium with the Jigsaw Technique

    ERIC Educational Resources Information Center

    Doymus, Kemal

    2008-01-01

    This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students' understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes

  7. A Progression of Static Equilibrium Laboratory Exercises

    ERIC Educational Resources Information Center

    Kutzner, Mickey; Kutzner, Andrew

    2013-01-01

    Although simple architectural structures like bridges, catwalks, cantilevers, and Stonehenge have been integral in human societies for millennia, as have levers and other simple tools, modern students of introductory physics continue to grapple with Newton's conditions for static equilibrium. As formulated in typical introductory physics…

  8. Generalized convective quasi-equilibrium principle

    NASA Astrophysics Data System (ADS)

    Yano, Jun-Ichi; Plant, Robert S.

    2016-03-01

    A generalization of Arakawa and Schubert's convective quasi-equilibrium principle is presented for a closure formulation of mass-flux convection parameterization. The original principle is based on the budget of the cloud work function. This principle is generalized by considering the budget for a vertical integral of an arbitrary convection-related quantity. The closure formulation includes Arakawa and Schubert's quasi-equilibrium, as well as both CAPE and moisture closures as special cases. The formulation also includes new possibilities for considering vertical integrals that are dependent on convective-scale variables, such as the moisture within convection. The generalized convective quasi-equilibrium is defined by a balance between large-scale forcing and convective response for a given vertically-integrated quantity. The latter takes the form of a convolution of a kernel matrix and a mass-flux spectrum, as in the original convective quasi-equilibrium. The kernel reduces to a scalar when either a bulk formulation is adopted, or only large-scale variables are considered within the vertical integral. Various physical implications of the generalized closure are discussed. These include the possibility that precipitation might be considered as a potentially-significant contribution to the large-scale forcing. Two dicta are proposed as guiding physical principles for the specifying a suitable vertically-integrated quantity.

  9. EQUILIBRIUM MOISTURE CONTENT OF PEARL MILLET

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Moisture content has a significant influence in the storability of cereal grains. The relationship of temperature, relative humidity, and equilibrium moisture can indicate the need for drying grain to improve storability and prevent grain mold development. This information is available for many grai...

  10. Local Thermodynamic Equilibrium at Three Levels

    NASA Astrophysics Data System (ADS)

    Sewell, Geoffrey L.

    2013-12-01

    We present coordinated formulations of local thermodynamical equilibrium conditions at three levels, namely the macroscopic one of classical thermodynamics, the mesoscopic one of hydrodynamical fluctuations and the microscopic one of quantum statistical mechanics. These conditions are all expressed in terms of the hydrodynamical variables of the macroscopic picture, and the quantum statistical ones are shown to imply a local version of the zeroth law.

  11. On the equilibrium of rotating filaments

    NASA Astrophysics Data System (ADS)

    Recchi, S.; Hacar, A.; Palestini, A.

    2014-10-01

    The physical properties of the so-called Ostriker isothermal, non-rotating filament have been classically used as benchmark to interpret the stability of the filaments observed in nearby clouds. However, such static picture seems to contrast with the more dynamical state observed in different filaments. In order to explore the physical conditions of filaments under realistic conditions, in this work we theoretically investigate how the equilibrium structure of a filament changes in a rotating configuration. To do so, we solve the hydrostatic equilibrium equation assuming both uniform and differential rotations independently. We obtain a new set of equilibrium solutions for rotating and pressure truncated filaments. These new equilibrium solutions are found to present both radial and projected column density profiles shallower than their Ostriker-like counterparts. Moreover, and for rotational periods similar to those found in the observations, the centrifugal forces present in these filaments are also able to sustain large amounts of mass (larger than the mass attained by the Ostriker filament) without being necessary unstable. Our results indicate that further analysis on the physical state of star-forming filaments should take into account rotational effects as stabilizing agents against gravity.

  12. General Equilibrium Models: Improving the Microeconomics Classroom

    ERIC Educational Resources Information Center

    Nicholson, Walter; Westhoff, Frank

    2009-01-01

    General equilibrium models now play important roles in many fields of economics including tax policy, environmental regulation, international trade, and economic development. The intermediate microeconomics classroom has not kept pace with these trends, however. Microeconomics textbooks primarily focus on the insights that can be drawn from the

  13. Teaching Chemical Equilibrium with the Jigsaw Technique

    ERIC Educational Resources Information Center

    Doymus, Kemal

    2008-01-01

    This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students' understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes…

  14. Generalized Equilibrium Problem with Mixed Relaxed Monotonicity

    PubMed Central

    Rizvi, Haider Abbas; K?l?man, Adem

    2014-01-01

    We extend the concept of relaxed ?-monotonicity to mixed relaxed ?-?-monotonicity. The concept of mixed relaxed ?-?-monotonicity is more general than many existing concepts of monotonicities. Finally, we apply this concept and well known KKM-theory to obtain the solution of generalized equilibrium problem. PMID:25121137

  15. Spontaneity and Equilibrium II: Multireaction Systems

    ERIC Educational Resources Information Center

    Raff, Lionel M.

    2014-01-01

    The thermodynamic criteria for spontaneity and equilibrium in multireaction systems are developed and discussed. When N reactions are occurring simultaneously, it is shown that G and A will depend upon N independent reaction coordinates, ?a (a = 1,2, ..., N), in addition to T and p for G or T and V for A. The general criteria for spontaneity and

  16. Spontaneity and Equilibrium II: Multireaction Systems

    ERIC Educational Resources Information Center

    Raff, Lionel M.

    2014-01-01

    The thermodynamic criteria for spontaneity and equilibrium in multireaction systems are developed and discussed. When N reactions are occurring simultaneously, it is shown that G and A will depend upon N independent reaction coordinates, ?a (a = 1,2, ..., N), in addition to T and p for G or T and V for A. The general criteria for spontaneity and…

  17. The 'Schwarzschild-Kerr' Equilibrium Configurations

    SciTech Connect

    Manko, V. S.; Ruiz, E.

    2010-12-07

    We discuss the possibility of equilibrium between a Schwarzschild black hole possessing zero intrinsic angular momentum and a hyperextreme Kerr source. The balance occurs due to frame-dragging exerted by the latter source on the black-hole constituent, thus giving rise to a non-zero horizon's angular velocity parallel to the angular momentum of the Kerr object.

  18. Exploring Equilibrium Chemistry for Hot Exoplanets

    NASA Astrophysics Data System (ADS)

    Blumenthal, Sarah; Harrington, Joseph; Mandell, Avi; Hébrard, Eric; Venot, Olivia; Cubillos, Patricio; Challener, Ryan

    2015-11-01

    It has been established that equilibrium chemistry is usually achieved deep in the atmosphere of hot Jovians where timescales are short (Line and Young 2013). Thus, equilibrium chemistry has been used as a starting point (setting initial conditions) for evaluating disequilibrium processes. We explore parameters of setting these initial conditions including departures from solar metallicity, the number of species allowed in a system, the types of species allowed in a system, and different thermodynamic libraries in an attempt to create a standard for evaluating equilibrium chemistry. NASA's open source code Chemical Equilibrium and Applications (CEA) is used to calculate model planet abundances by varying the metallicity, in the pressure regime of 0.1 to 1 bar. These results are compared to a variety of exoplanets (Teq between 600 and 2100K) qualitatively by color maps of the dayside with different temperature redistributions. Additionally, CEA (with an updated thermodynamic library) is validated with the thermochemical model presented in Venot et al. (2012) for HD 209458b and HD 189733b. This same analysis has then been extended to the cooler planet HD 97658b. Spectra are generated from both models’ abundances using the open source code transit (https://github.com/exosports/transit) using the opacities of 15 molecules. We make the updated CEA thermodyanamic library and supporting Python scripts to do the CEA analyses available open source. This work was supported by NASA Planetary Atmospheres grant NNX12AI69G.

  19. A Progression of Static Equilibrium Laboratory Exercises

    ERIC Educational Resources Information Center

    Kutzner, Mickey; Kutzner, Andrew

    2013-01-01

    Although simple architectural structures like bridges, catwalks, cantilevers, and Stonehenge have been integral in human societies for millennia, as have levers and other simple tools, modern students of introductory physics continue to grapple with Newton's conditions for static equilibrium. As formulated in typical introductory physics

  20. Assessing Students' Conceptual Understanding of Solubility Equilibrium.

    ERIC Educational Resources Information Center

    Raviolo, Andres

    2001-01-01

    Presents a problem on solubility equilibrium which involves macroscopic, microscopic, and symbolic levels of representation as a resource for the evaluation of students, and allows for assessment as to whether students have acquired an adequate conceptual understanding of the phenomenon. Also diagnoses difficulties with regard to previous