Simulation of phase equilibria

NASA Astrophysics Data System (ADS)

Martin, Marcus Gary

The focus of this thesis is on the use of configurational bias Monte Carlo in the Gibbs ensemble. Unlike Metropolis Monte Carlo, which is reviewed in chapter I, configurational bias Monte Carlo uses an underlying Markov chain transition matrix which is asymmetric in such a way that it is more likely to attempt to move to a molecular conformation which has a lower energy than to one with a higher energy. Chapter II explains how this enables efficient simulation of molecules with complex architectures (long chains and branched molecules) for coexisting fluid phases (liquid, vapor, or supercritical), and also presents several of our recent extensions to this method. In chapter III we discuss the development of the Transferable Potentials for Phase Equilibria United Atom (TraPPE-UA) force field which accurately describes the fluid phase coexistence for linear and branched alkanes. Finally, in the fourth chapter the methods and the force field are applied to systems ranging from supercritical extraction to gas chromatography to illustrate the power and versatility of our approach.

Nonlinear dynamics of confined thin liquid-vapor bilayer systems with phase change

NASA Astrophysics Data System (ADS)

Kanatani, Kentaro; Oron, Alexander

2011-03-01

We numerically investigate the nonlinear evolution of the interface of a thin liquid-vapor bilayer system confined by rigid horizontal walls from both below and above. The lateral variation of the vapor pressure arising from phase change is taken into account in the present analysis. When the liquid (vapor) is heated (cooled) and gravity acts toward the liquid, the deflection of the interface monotonically grows, leading to a rupture of the vapor layer, whereas nonruptured stationary states are found when the liquid (vapor) is cooled (heated) and gravity acts toward the vapor. In the latter case, vapor-flow-driven convective cells are found in the liquid phase in the stationary state. The average vapor pressure and interface temperature deviate from their equilibrium values once the interface departs from the flat equilibrium state. Thermocapillarity does not have a significant effect near the thermodynamic equilibrium, but becomes important if the system significantly deviates from it.

Liquid-Vapor Equilibrium of Multicomponent Cryogenic Systems

NASA Technical Reports Server (NTRS)

Thompson, W. Reid; Calado, Jorge C. G.; Zollweg, John A.

1990-01-01

Liquid-vapor and solid-vapor equilibria at low to moderate pressures and low temperatures are important in many solar system environments, including the surface and clouds of Titan, the clouds of Uranus and Neptune, and the surfaces of Mars and Triton. The familiar cases of ideal behavior are limiting cases of a general thermodynamic representation for the vapor pressure of each component in a homogeneous multicomponent system. The fundamental connections of laboratory measurements to thermodynamic models are through the Gibbs-Duhem relation and the Gibbs-Helmholtz relation. Using laboratory measurements of the total pressure, temperature, and compositions of the liquid and vapor phases at equilibrium, the values of these parameters can be determined. The resulting model for vapor-liquid equilibrium can then conveniently and accurately be used to calculate pressures, compositions, condensation altitudes, and their dependencies on changing climatic conditions. A specific system being investigated is CH4-C2H6-N2, at conditions relevant to Titan's surface and atmosphere. Discussed are: the modeling of existing data on CH4-N2, with applications to the composition of Titan's condensate clouds; some new measurements on the CH4-C2H6 binary, using a high-precision static/volumetric system, and on the C2H6-N2 binary, using the volumetric system and a sensitive cryogenic flow calorimeter; and describe a new cryogenic phase-equilibrium vessel with which we are beginning a detailed, systematic study of the three constituent binaries and the ternary CH4-C2H6-N2 system at temperatures ranging from 80 to 105 K and pressures from 0.1 to 7 bar.

Vapor-liquid equilibria for 1,1-difluoroethane + acetylene and 1,1-difluoroethane + 1,1-dichloroethane at 303.2 K and 323.2 K

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

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

1996-09-01

Isothermal vapor-liquid equilibria for 1,1-difluoroethane (HFC-152a) + acetylene and 1,1-difluoroethane + 1,1-dichloroethane (HCC-150a) were measured in a circulation type apparatus at 303.2 K and 323.2 K. The experimental data were correlated with the Peng-Robinson equation of state using the Wong and Sandler mixing rule, and the relevant parameters are presented.

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.

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

PubMed

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

2008-11-01

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

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

NASA Astrophysics Data System (ADS)

Wang, Nan; Upmanyu, Moneesh; Karma, Alain

2018-03-01

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

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.

Comparison of united-atom potentials for the simulation of vapor-liquid equilibria and interfacial properties of long-chain n-alkanes up to n-C100.

PubMed

Müller, Erich A; Mejía, Andrés

2011-11-10

Canonical ensemble molecular dynamics (MD) simulations are reported which compute both the vapor-liquid equilibrium properties (vapor pressure and liquid and vapor densities) and the interfacial properties (density profiles, interfacial tensions, entropy and enthalpy of surface formation) of four long-chained n-alkanes: n-decane (n-C(10)), n-eicosane (n-C(20)), n-hexacontane (n-C(60)), and n-decacontane (n-C(100)). Three of the most commonly employed united-atom (UA) force fields for alkanes (SKS: Smit, B.; Karaborni, S.; Siepmann, J. I. J. Chem. Phys. 1995,102, 2126-2140; J. Chem. Phys. 1998,109, 352; NERD: Nath, S. K.; Escobedo, F. A.; de Pablo, J. J. J. Chem. Phys. 1998, 108, 9905-9911; and TraPPE: Martin M. G.; Siepmann, J. I. J. Phys. Chem. B1998, 102, 2569-2577.) are critically appraised. The computed results have been compared to the available experimental data and those fitted using the square gradient theory (SGT). In the latter approach, the Lennard-Jones chain equation of state (EoS), appropriately parametrized for long hydrocarbons, is used to model the homogeneous bulk phase Helmholtz energy. The MD results for phase equilibria of n-decane and n-eicosane exhibit sensible agreement both to the experimental data and EoS correlation for all potentials tested, with the TraPPE potential showing the lowest deviations. However, as the molecular chain increases to n-hexacontane and n-decacontane, the reliability of the UA potentials decreases, showing notorious subpredictions of both saturated liquid density and vapor pressure. Based on the recommended data and EoS results for the heaviest hydrocarbons, it is possible to attest, that in this extreme, the TraPPE potential shows the lowest liquid density deviations. The low absolute values of the vapor pressure preclude the discrimination among the three UA potentials studied. On the other hand, interfacial properties are very sensitive to the type of UA potential thus allowing a differentiation of the

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

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

1995-01-01

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

Paradoxes of thermodynamics of swelling equilibria of polymers in liquids and vapors.

PubMed

Davankov, Vadim A; Pastukhov, Alexander V

2011-12-29

An automatic registration of the changing size of a single spherical microbead of a cross-linked polymer was applied for studying the swelling process of the bead by the sorption of vapors and/or liquids. Many representatives of all three basic types of polymeric networks, gel-type, hypercrosslinked, and macroporous, were examined. Only the first two display large volume changes and prove suitable for following the kinetics and extent of swelling by the above dilatometric technique. The results unambiguously prove that swelling of all polymeric networks in liquids is always higher than in corresponding saturated vapors (Schroeder's paradox). The general nature of this phenomenon implies that the absolute activity of any sorbate in its liquid form is always larger than in the form of its saturated vapor. Surprisingly, gels with any solvent contents, which fall into the broad range between the vapor-equilibrated and liquid-equilibrated extreme contents, retain their volumes constant in the saturated vapor atmosphere. This paradox of a wide range of gels swollen to a different extent and, nevertheless, standing in equilibrium with saturated vapor is explained by the specificity of the network polymers, namely, that the energy of the solvent-polymer interactions is easily compensated by the energy of remaining between-chain interactions at any solvent content in the above range. Therefore, the strain-free swollen gels do not generate enhanced vapor pressure, but neither display the ability to take up more sorbate from its vapor. © 2011 American Chemical Society

Vapor-liquid equilibria for difluoromethane + dichloromethane at 303.2 and 313.2 K and 1,1-difluoroethane + vinyl chloride at 303.2 and 323.2 K

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

Lim, J.S.; Lee, Y.W.; Lee, Y.Y.

1997-05-01

Isothermal vapor-liquid equilibria for difluoromethane (HFC-32) + dichloromethane at 303.2 K and 313.2 K and 1,1-difluoroethane (HFC-152a) + vinyl chloride at 303.2 K and 323.2 K were measured in a circulation-type apparatus. The experimental data were correlated with the Peng-Robinson equation of state using the Wong and Sandler mixing rule, and the relevant parameters are presented.

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.

Vapor-liquid equilibria for 1,1,1,2-tetrafluoroethane + 1-chloro-1,2,2,2-tetrafluoroethane and 1-chloro-1,2,2,2-tetrafluoroethane + 1-chloro-1,1-difluoroethane systems

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

Lee, J.; Lee, J.; Kim, H.

1996-07-01

Isothermal vapor-liquid equilibria were determined for two binary mixtures of refrigerants with a circulation type apparatus. The 1,1,1,2-tetrafluoroethane (HFC-134a) + 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124) system was studied at 296.45, 302.25, and 307.25 K. The 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124) + 1-chloro-1,1-difluoroethane (HCFC-142b) system was studied at 298.15 and 312.15 K. At each temperature, the pressure and vapor and liquid compositions were measured. Results were correlated with the Peng-Robinson equation of state.

The influence of liquid/vapor phase change onto the Nusselt number

NASA Astrophysics Data System (ADS)

Popescu, Elena-Roxana; Colin, Catherine; Tanguy, Sebastien

2017-11-01

In spite of its significant interest in various fields, there is currently a very few information on how an external flow will modify the evaporation or the condensation of a liquid surface. Although most applications involve turbulent flows, the simpler configuration where a laminar superheated or subcooled vapor flow is shearing a saturated liquid interface has still never been solved. Based on a numerical approach, we propose to characterize the interaction between a laminar boundary layer of a superheated or subcooled vapor flow and a static liquid pool at saturation temperature. By performing a full set of simulations sweeping the parameters space, correlations are proposed for the first time on the Nusselt number depending on the dimensionless numbers that characterize both vaporization and condensation. As attended, the Nusselt number decreases or increases in the configurations involving respectively vaporization or condensation. More unexpected is the behaviour of the friction of the vapor flow on the liquid pool, for which we report that it is weakly affected by the phase change, despite the important variation of the local flow structure due to evaporation or condensation.

Improved thermal lattice Boltzmann model for simulation of liquid-vapor phase change

NASA Astrophysics Data System (ADS)

Li, Qing; Zhou, P.; Yan, H. J.

2017-12-01

In this paper, an improved thermal lattice Boltzmann (LB) model is proposed for simulating liquid-vapor phase change, which is aimed at improving an existing thermal LB model for liquid-vapor phase change [S. Gong and P. Cheng, Int. J. Heat Mass Transfer 55, 4923 (2012), 10.1016/j.ijheatmasstransfer.2012.04.037]. First, we emphasize that the replacement of ∇ .(λ ∇ T ) /∇.(λ ∇ T ) ρ cV ρ cV with ∇ .(χ ∇ T ) is an inappropriate treatment for diffuse interface modeling of liquid-vapor phase change. Furthermore, the error terms ∂t 0(T v ) +∇ .(T vv ) , which exist in the macroscopic temperature equation recovered from the previous model, are eliminated in the present model through a way that is consistent with the philosophy of the LB method. Moreover, the discrete effect of the source term is also eliminated in the present model. Numerical simulations are performed for droplet evaporation and bubble nucleation to validate the capability of the model for simulating liquid-vapor phase change. It is shown that the numerical results of the improved model agree well with those of a finite-difference scheme. Meanwhile, it is found that the replacement of ∇ .(λ ∇ T ) /∇ .(λ ∇ T ) ρ cV ρ cV with ∇ .(χ ∇ T ) leads to significant numerical errors and the error terms in the recovered macroscopic temperature equation also result in considerable errors.

Phase Equilibria Diagrams Database

National Institute of Standards and Technology Data Gateway

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

Wetting phenomenon in the liquid-vapor phase coexistence of a partially miscible Lennard-Jones binary mixture

NASA Astrophysics Data System (ADS)

Ramírez-Santiago, Guillermo; Díaz-Herrera, Enrique; Moreno Razo, José A.

2004-03-01

We have carried out extensive equilibrium MD simulations to study wetting phenomena in the liquid-vapor phase coexistence of a partially miscible binary LJ mixture. We find that in the temperature range 0.60 ≤ T^* < 0.80, the system separates forming a liquid A-liquid B interface in coexistence with the vapor phase. At higher temperatures, 0.80 ≤ T^* < 1.25 the liquid phases are wet by the vapor phase. By studying the behavior of the surface tension as a function of temperature we estimate the wetting transition temperature (WTT) to be T^*_w≃ 0.80. The adsorption of molecules at the liquid-liquid interface shows a discontinuity at about T^*≃ 0.79 suggesting that the wetting transition is a first order phase transition. These results are in agreement with some experiments carried out in fluid binary mixtures. In addition, we estimated the consolute temperature to be T^* _cons≃ 1.25. The calculated phase diagram of the mixture suggest the existence of a tricritical point.

Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-08-01

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

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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.

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.

Experimental study of flash boiling spray vaporization through quantitative vapor concentration and liquid temperature measurements

NASA Astrophysics Data System (ADS)

Zhang, Gaoming; Hung, David L. S.; Xu, Min

2014-08-01

Flash boiling sprays of liquid injection under superheated conditions provide the novel solutions of fast vaporization and better air-fuel mixture formation for internal combustion engines. However, the physical mechanisms of flash boiling spray vaporization are more complicated than the droplet surface vaporization due to the unique bubble generation and boiling process inside a superheated bulk liquid, which are not well understood. In this study, the vaporization of flash boiling sprays was investigated experimentally through the quantitative measurements of vapor concentration and liquid temperature. Specifically, the laser-induced exciplex fluorescence technique was applied to distinguish the liquid and vapor distributions. Quantitative vapor concentration was obtained by correlating the intensity of vapor-phase fluorescence with vapor concentration through systematic corrections and calibrations. The intensities of two wavelengths were captured simultaneously from the liquid-phase fluorescence spectra, and their intensity ratios were correlated with liquid temperature. The results show that both liquid and vapor phase of multi-hole sprays collapse toward the centerline of the spray with different mass distributions under the flash boiling conditions. Large amount of vapor aggregates along the centerline of the spray to form a "gas jet" structure, whereas the liquid distributes more uniformly with large vortexes formed in the vicinity of the spray tip. The vaporization process under the flash boiling condition is greatly enhanced due to the intense bubble generation and burst. The liquid temperature measurements show strong temperature variations inside the flash boiling sprays with hot zones present in the "gas jet" structure and vortex region. In addition, high vapor concentration and closed vortex motion seem to have inhibited the heat and mass transfer in these regions. In summary, the vapor concentration and liquid temperature provide detailed information

Mid-infrared laser-absorption diagnostic for vapor-phase fuel mole fraction and liquid fuel film thickness

NASA Astrophysics Data System (ADS)

Porter, J. M.; Jeffries, J. B.; Hanson, R. K.

2011-02-01

A novel two-wavelength mid-infrared laser-absorption diagnostic has been developed for simultaneous measurements of vapor-phase fuel mole fraction and liquid fuel film thickness. The diagnostic was demonstrated for time-resolved measurements of n-dodecane liquid films in the absence and presence of n-decane vapor at 25°C and 1 atm. Laser wavelengths were selected from FTIR measurements of the C-H stretching band of vapor n-decane and liquid n-dodecane near 3.4 μm (3000 cm-1). n-Dodecane film thicknesses <20 μm were accurately measured in the absence of vapor, and simultaneous measurements of n-dodecane liquid film thickness and n-decane vapor mole fraction (300 ppm) were measured with <10% uncertainty for film thicknesses <10 μm. A potential application of the measurement technique is to provide accurate values of vapor mole fraction in combustion environments where strong absorption by liquid fuel or oil films on windows make conventional direct absorption measurements of the gas problematic.

Melting and Vaporization of the 1223 Phase in the System (Tl-Pb-Ba-Sr-Ca-Cu-O)

PubMed Central

Cook, L. P.; Wong-Ng, W.; Paranthaman, P.

1996-01-01

The melting and vaporization of the 1223 [(Tl,Pb):(Ba,Sr):Ca:Cu] oxide phase in the system (Tl-Pb-Ba-Sr-Ca-Cu-O) have been investigated using a combination of dynamic methods (differential thermal analysis, thermogravimetry, effusion) and post-quenching characterization techniques (powder x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectrometry). Vaporization rates, thermal events, and melt compositions were followed as a function of thallia loss from a 1223 stoichiometry. Melting and vaporization equilibria of the 1223 phase are complex, with as many as seven phases participating simultaneously. At a total pressure of 0.1 MPa the 1223 phase was found to melt completely at (980 ± 5) °C in oxygen, at a thallia partial pressure (pTl2O) of (4.6 ± 0.5) kPa, where the quoted uncertainties are standard uncertainties, i.e., 1 estimated standard deviation. The melting reaction involves five other solids and a liquid, nominally as follows: 1223→1212+(Ca,Sr)2CuO3+(Sr,Ca)CuO2+BaPbO3+(Ca,Sr)O+Liquid Stoichiometries of the participating phases have been determined from microchemical analysis, and substantial elemental substitution on the 1212 and 1223 crystallographic sites is indicated. The 1223 phase occurs in equilibrium with liquids from its melting point down to at least 935 °C. The composition of the lowest melting liquid detected for the bulk compositions of this study has been measured using microchemical analysis. Applications to the processing of superconducting wires and tapes are discussed. PMID:27805086

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.

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

PubMed

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

2009-04-23

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

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Feasibility Study of Vapor-Mist Phase Reaction Lubrication Using a Thioether Liquid

NASA Technical Reports Server (NTRS)

Morales, Wilfredo; Handschuh, Robert F.; Krantz, Timothy L.

2007-01-01

A primary technology barrier preventing the operation of gas turbine engines and aircraft gearboxes at higher temperatures is the inability of currently used liquid lubricants to survive at the desired operating conditions over an extended time period. Current state-of-the-art organic liquid lubricants rapidly degrade at temperatures above 300 C; hence, another form of lubrication is necessary. Vapor or mist phase reaction lubrication is a unique, alternative technology for high temperature lubrication. The majority of past studies have employed a liquid phosphate ester that was vaporized or misted, and delivered to bearings or gears where the phosphate ester reacted with the metal surfaces generating a solid lubricious film. This method resulted in acceptable operating temperatures suggesting some good lubrication properties, but the continuous reaction between the phosphate ester and the iron surfaces led to wear rates unacceptable for gas turbine engine or aircraft gearbox applications. In this study, an alternative non-phosphate liquid was used to mist phase lubricate a spur gearbox rig operating at 10,000 rpm under highly loaded conditions. After 21 million shaft revolutions of operation the gears exhibited only minor wear.

Interfacial tension and vapor-liquid equilibria in the critical region of mixtures

NASA Technical Reports Server (NTRS)

Moldover, Michael R.; Rainwater, James C.

1988-01-01

In the critical region, the concept of two-scale-factor universality can be used to accurately predict the surface tension between near-critical vapor and liquid phases from the singularity in the thermodynamic properties of the bulk fluid. In the present work, this idea is generalized to binary mixtures and is illustrated using the data of Hsu et al. (1985) for CO2 + n-butane. The pressure-temperature-composition-density data for coexisting, near-critical phases of the mixtures are fitted with a thermodynamic potential comprised of a sum of a singular term and nonsingular terms. The nonuniversal amplitudes characterizing the singular term for the mixtures are obtained from the amplitudes for the pure components by interpolation in a space of thermodynamic 'field' variables. The interfacial tensions predicted for the mixtures from the singular term are within 10 percent of the data on three isotherms in the pressure range (Pc - P)/Pc of less than 0.5. This difference is comparable to the combined experimental and model errors.

Space cryogenics components based on the thermomechanical effect - Vapor-liquid phase separation

NASA Technical Reports Server (NTRS)

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

1989-01-01

Applications of the thermomechanical effect has been qualified including incorporation in large-scale space systems in the area of vapor-liquid phase separation (VLPS). The theory of the porous-plug phase separator is developed for the limit of a high thermal impedance of the solid-state grains. Extensions of the theory of nonlinear turbulent flow are presented based on experimental results.

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

PubMed

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

2017-10-19

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

Superfluid helium 2 liquid-vapor phase separation: Technology assessment

NASA Technical Reports Server (NTRS)

Lee, J. M.

1984-01-01

A literature survey of helium 2 liquid vapor phase separation is presented. Currently, two types of He 2 phase separators are being investigated: porous, sintered metal plugs and the active phase separator. The permeability K(P) shows consistency in porous plug geometric characterization. Both the heat and mass fluxes increase with K(P). Downstream pressure regulation to adjust for varying heat loads and both temperatures is possible. For large dynamic heat loads, the active phase separator shows a maximum heat rejection rate of up to 2 W and bath temperature stability of 0.1 mK. Porous plug phase separation performance should be investigated for application to SIRTF and, in particular, that plugs of from 10 to the minus ninth square centimeters to 10 to the minus eighth square centimeters in conjunction with downstream pressure regulation be studied.

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

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

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.

Stability limit of liquid water in metastable equilibrium with subsaturated vapors.

PubMed

Wheeler, Tobias D; Stroock, Abraham D

2009-07-07

A pure liquid can reach metastable equilibrium with its subsaturated vapor across an appropriate membrane. This situation is analogous to osmotic equilibrium: the reduced chemical potential of the dilute phase (the subsaturated vapor) is compensated by a difference in pressure between the phases. To equilibrate with subsaturated vapor, the liquid phase assumes a pressure that is lower than its standard vapor pressure, such that the liquid phase is metastable with respect to the vapor phase. For sufficiently subsaturated vapors, the liquid phase can even assume negative pressures. The appropriate membrane for this metastable equilibrium must provide the necessary mechanical support to sustain the difference in pressure between the two phases, limit nonhomogeneous mechanisms of cavitation, and resist the entry of the dilutant (gases) into the pure phase (liquid). In this article, we present a study of the limit of stability of liquid water--the degree of subsaturation at which the liquid cavitates--in this metastable state within microscale voids embedded in hydrogel membranes. We refer to these structures as vapor-coupled voids (VCVs). In these VCVs, we observed that liquid water cavitated when placed in equilibrium with vapors of activity aw,vapairliquid based on thermodynamic calculations, the liquid cavitated at pressures Pvapor nuclei, and (iv

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.

Simplified thermodynamic functions for vapor-liquid phase separation and fountain effect pumps

NASA Technical Reports Server (NTRS)

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

1984-01-01

He-4 fluid handling devices near 2 K require novel components for non-Newtonian fluid transport in He II. Related sizing of devices has to be based on appropriate thermophysical property functions. The present paper presents simplified equilibrium state functions for porous media components which serve as vapor-liquid phase separators and fountain effect pumps.

Vapor-liquid nucleation: the solid touch.

PubMed

Yarom, Michal; Marmur, Abraham

2015-08-01

Vapor-liquid nucleation is a ubiquitous process that has been widely researched in many disciplines. Yet, case studies are quite scattered in the literature, and the implications of some of its basic concepts are not always clearly stated. This is especially noticeable for heterogeneous nucleation, which involves a solid surface in touch with the liquid and vapor. The current review attempts to offer a comprehensive, though concise, thermodynamic discussion of homogeneous and heterogeneous nucleation in vapor-liquid systems. The fundamental concepts of nucleation are detailed, with emphasis on the role of the chemical potential, and on intuitive explanations whenever possible. We review various types of nucleating systems and discuss the effect of the solid geometry on the characteristics of the new phase formation. In addition, we consider the effect of mixing on the vapor-liquid equilibrium. An interesting sub-case is that of a non-volatile solute that modifies the chemical potential of the liquid, but not of the vapor. Finally, we point out topics that need either further research or more exact, accurate presentation. Copyright © 2014 Elsevier B.V. All rights reserved.

Gas-liquid chromatography with a volatile "stationary" liquid phase.

PubMed

Wells, P S; Zhou, S; Parcher, J F

2002-05-01

A unique type of gas-liquid chromatography is described in which both mobile and "stationary" phases are composed of synthetic mixtures of helium and carbon dioxide. At temperatures below the critical point of the binary mixture and pressures above the vapor pressure of pure liquid carbon dioxide, helium and carbon dioxide can form two immiscible phases over extended composition ranges. A binary vapor phase enriched in helium can act as the mobile phase for chromatographic separations, whereas a CO2-rich liquid in equilibrium with the vapor phase, but condensed on the column wall, can act as a pseudostationary phase. Several examples of chromatographic separations obtained in "empty" capillary columns with no ordinary stationary liquid phase illustrate the range of conditions that produce such separations. In addition, several experiments are reported that confirm the proposed two-phase hypothesis. The possible consequences of the observed chromatographic phenomenon in the field of supercritical fluid chromatography with helium headspace carbon dioxide are discussed.

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

NASA Astrophysics Data System (ADS)

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

2009-04-01

The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part

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.; 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.

Phase equilibria in fullerene-containing systems as a basis for development of manufacture and application processes for nanocarbon materials

NASA Astrophysics Data System (ADS)

Semenov, K. N.; Charykov, N. A.; Postnov, V. N.; Sharoyko, V. V.; Murin, I. V.

2016-01-01

This review is the first attempt to integrate the available data on all types of phase equilibria (solubility, extraction and sorption) in systems containing light fullerenes (C60 and C70). In the case of solubility diagrams, the following types of phase equilibria are considered: individual fullerene (C60 or C70)-solvent under polythermal and polybaric conditions; C60-C70-solvent, individual fullerene-solvent(1)-solvent(2), as well as multicomponent systems comprising a single fullerene or an industrial mixture of fullerenes and vegetable oils, animal fats or essential oils under polythermal conditions. All published experimental data on the extraction equilibria in C60-C70-liquid phase(1)-liquid phase(2) systems are described systematically and the sorption characteristics of various materials towards light fullerenes are estimated. The possibility of application of these experimental data for development of pre-chromatographic and chromatographic methods for separation of fullerene mixtures and application of fullerenes as nanomodifiers are described. The bibliography includes 87 references.

On the critical temperature, normal boiling point, and vapor pressure of ionic liquids.

PubMed

Rebelo, Luis P N; Canongia Lopes, José N; Esperança, José M S S; Filipe, Eduardo

2005-04-07

One-stage, reduced-pressure distillations at moderate temperature of 1-decyl- and 1-dodecyl-3-methylimidazolium bistriflilamide ([Ntf(2)](-)) ionic liquids (ILs) have been performed. These liquid-vapor equilibria can be understood in light of predictions for normal boiling points of ILs. The predictions are based on experimental surface tension and density data, which are used to estimate the critical points of several ILs and their corresponding normal boiling temperatures. In contrast to the situation found for relatively unstable ILs at high-temperature such as those containing [BF(4)](-) or [PF(6)](-) anions, [Ntf(2)](-)-based ILs constitute a promising class in which reliable, accurate vapor pressure measurements can in principle be performed. This property is paramount for assisting in the development and testing of accurate molecular models.

Phase Equilibria and Crystallography of Ceramic Oxides

PubMed Central

Wong-Ng, W.; Roth, R. S.; Vanderah, T. A.; McMurdie, H. F.

2001-01-01

Research in phase equilibria and crystallography has been a tradition in the Ceramics Division at National Bureau of Standards/National Institute of Standatrds and Technology (NBS/NIST) since the early thirties. In the early years, effort was concentrated in areas of Portland cement, ceramic glazes and glasses, instrument bearings, and battery materials. In the past 40 years, a large portion of the work was related to electronic materials, including ferroelectrics, piezoelectrics, ionic conductors, dielectrics, microwave dielectrics, and high-temperature superconductors. As a result of the phase equilibria studies, many new compounds have been discovered. Some of these discoveries have had a significant impact on US industry. Structure determinations of these new phases have often been carried out as a joint effort among NBS/NIST colleagues and also with outside collaborators using both single crystal and neutron and x-ray powder diffraction techniques. All phase equilibria diagrams were included in Phase Diagrams for Ceramists, which are collaborative publications between The American Ceramic Society (ACerS) and NBS/NIST. All x-ray powder diffraction patterns have been included in the Powder Diffraction File (PDF). This article gives a brief account of the history of the development of the phase equilibria and crystallographic research on ceramic oxides in the Ceramics Division. Represented systems, particularly electronic materials, are highlighted. PMID:27500068

Student Understanding of Liquid-Vapor Phase Equilibrium

ERIC Educational Resources Information Center

Boudreaux, Andrew; Campbell, Craig

2012-01-01

Student understanding of the equilibrium coexistence of a liquid and its vapor was the subject of an extended investigation. Written assessment questions were administered to undergraduates enrolled in introductory physics and chemistry courses. Responses have been analyzed to document conceptual and reasoning difficulties in sufficient detail to…

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

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

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

1994-10-01

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

Vapor-liquid equilibria for R-22, R-134a, R-125, and R-32/125 with a polyol ester lubricant: Measurements and departure from ideality

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

Martz, W.L.; Burton, C.M.; Jacobi, A.M.

1996-11-01

The effect of a polyol ester lubricant on equilibrium pressure, liquid density, and viscosity is presented for R-22, R-125, and R-134a at varying temperatures and concentrations. Preliminary vapor-liquid equilibrium (VLE) data and miscibility observations are also presented for an R-32/R-125 blend (50%/50%) with the ISO 68 polyol ester (POE). Real-gas behavior is modeled using the vapor-phase fugacity, and vapor pressure effects on liquid fugacities are taken into account with the Poynting effect. Positive, negative, and mixed deviations form the Lewis-Randall rule are observed in the activity coefficient behavior. Departures from ideality are related to molecular size differences, intermolecular forces inmore » the mixture, and other factors. The data are discussed in the context of previous results for other refrigerants and thermodynamic modeling of refrigerant and oil mixtures.« less

Study of the liquid vapor equilibrium in the bromine-hydrobromic acid-water system

NASA Technical Reports Server (NTRS)

Benizri, R.; Lessart, P.; Courvoisier, P.

1984-01-01

A glass ebullioscope was built and at atmospheric pressure, liquid-vapor equilibria relative to the Br2-HBr-H2O system, in the concentration range of interest for evaluation of the Mark 13 cycle was studied. Measurements were performed for the brome-azeotrope (HBr-H2O) pseudo-binary system and for the ternary system at temperatures lower than 125 C and in the bromine concentration range up to 13% wt.

A search for the prewetting line. [in binary liquid system at vapor-liquid interface

NASA Technical Reports Server (NTRS)

Schmidt, J. W.; Moldover, M. R.

1986-01-01

This paper describes efforts to locate the prewetting line in a binary liquid system (isopropanol-perfluoromethylcyclohexane) at the vapor-liquid interface. Tight upper bounds were placed on the temperature separation (0.2 K) between the prewetting line and the line of bulk liquid phase separation. The prewetting line in systems at equilibrium was not detected. Experimental signatures indicative of the prewetting line occurred only in nonequilibrium situations. Several theories predict that the adsorption of one of the components (the fluorocarbon, in this case) at the liquid-vapor interface should increase abruptly, at a temperature sightly above the temperature at which the mixture separates into two liquid phases. A regular solution calculation indicates that this prewetting line should have been easily detectable with the instruments used in this experiment. Significant features of the experiment are: (1) low-gradient thermostatting, (2) in situ stirring, (3) precision ellipsometry from the vapor-liquid interface, (4) high resolution differential index of refraction measurements using a novel cell design, and (5) computer control.

Influence of phase transition on the instability of a liquid-vapor interface in a gravitational field

NASA Astrophysics Data System (ADS)

Konovalov, V. V.; Lyubimov, D. V.; Lyubimova, T. P.

2017-06-01

This study is concerned with the linear stability of the horizontal interface between thick layers of a viscous heat-conducting liquid and its vapor in a gravitational field subject to phase transition. We consider the case when the hydrostatic base state is consistent with a balanced heat flux at the liquid-vapor interface. The corrections to the growth rate of the most dangerous perturbations and cutoff wave number, characterizing the influence of phase transition on the Rayleigh-Taylor instability, are found to be different from the data in the literature. Most of the previous results were obtained in the framework of a quasiequilibrium approximation, which had been shown to conform to the limit of thin media layers under equality of the interface temperature to a saturation temperature. The main difference from the results obtained with the quasiequilibrium approach is new values of the proportionality coefficients that correlate our corrections with the intensity of weak heating. Moreover, at large values of the heat flux rate, when deviations from the approximate linear law are important, the effect of phase transition is limited and does not exceed the size of the vapor viscosity effect.

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

PubMed

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

2016-01-28

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

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

PubMed

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

2018-07-20

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

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

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

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

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 formore » 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.« less

Numerical simulation of superheated vapor bubble rising in stagnant liquid

NASA Astrophysics Data System (ADS)

Samkhaniani, N.; Ansari, M. R.

2017-09-01

In present study, the rising of superheated vapor bubble in saturated liquid is simulated using volume of fluid method in OpenFOAM cfd package. The surface tension between vapor-liquid phases is considered using continuous surface force method. In order to reduce spurious current near interface, Lafaurie smoothing filter is applied to improve curvature calculation. Phase change is considered using Tanasawa mass transfer model. The variation of saturation temperature in vapor bubble with local pressure is considered with simplified Clausius-Clapeyron relation. The couple velocity-pressure equation is solved using PISO algorithm. The numerical model is validated with: (1) isothermal bubble rising and (2) one-dimensional horizontal film condensation. Then, the shape and life time history of single superheated vapor bubble are investigated. The present numerical study shows vapor bubble in saturated liquid undergoes boiling and condensation. It indicates bubble life time is nearly linear proportional with bubble size and superheat temperature.

Floating liquid phase in sedimenting colloid-polymer mixtures.

PubMed

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

2004-08-20

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

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.

First-order wetting transition at a liquid-vapor interface

NASA Technical Reports Server (NTRS)

Schmidt, J. W.; Moldover, M. R.

1983-01-01

Evidence from reflectance and contact angle measurements is presented that three-phase mixtures of i-C3H7OH-C7F14 exhibit a first-order wetting phase transition at the liquid-vapor interface at 38 C. Equilibration phenomena support this interpretation. Ellipsometry was used to measure the apparent thickness of the intruding layer in the three-phase mixture. At temperatures slightly above the wetting temperature T(w), the intruding layer's thickness is several hundred angstroms and its variation with temperature is extremely weak. Below T(w), three-phase contact can occur between the vapor and both the upper and lower liquid phases; one of the angles which characterizes this contact has a very simple temperature dependence. The thickness of the intruding layer, monitored as the solutions approached equilibrium, is found to depend quite weakly on the height spanned by the upper liquid phase in the vicinity of a first-order wetting transition.

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

NASA Astrophysics Data System (ADS)

Narayanan, Vineed; Venkatarathnam, G.

2018-03-01

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

Non-aqueous phase liquid spreading during soil vapor extraction

PubMed Central

Kneafsey, Timothy J.; Hunt, James R.

2010-01-01

Many non-aqueous phase liquids (NAPLs) are expected to spread at the air – water interface, particularly under non-equilibrium conditions. In the vadose zone, this spreading should increase the surface area for mass transfer and the efficiency of volatile NAPL recovery by soil vapor extraction (SVE). Observations of spreading on water wet surfaces led to a conceptual model of oil spreading vertically above a NAPL pool in the vadose zone. Analysis of this model predicts that spreading can enhance the SVE contaminant recovery compared to conditions where the liquid does not spread. Experiments were conducted with spreading volatile oils hexane and heptane in wet porous media and capillary tubes, where spreading was observed at the scale of centimeters. Within porous medium columns up to a meter in height containing stagnant gas, spreading was less than ten centimeters and did not contribute significantly to hexane volatilization. Water film thinning and oil film pinning may have prevented significant oil film spreading, and thus did not enhance SVE at the scale of a meter. The experiments performed indicate that volatile oil spreading at the field scale is unlikely to contribute significantly to the efficiency of SVE. PMID:14734243

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

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

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

1995-03-01

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

Migration of carbon nanotubes from liquid phase to vapor phase in the refrigerant-based nanofluid pool boiling

PubMed Central

2011-01-01

The migration characteristics of carbon nanotubes from liquid phase to vapor phase in the refrigerant-based nanofluid pool boiling were investigated experimentally. Four types of carbon nanotubes with the outside diameters from 15 to 80 nm and the lengths from 1.5 to 10 μm were used in the experiments. The refrigerants include R113, R141b and n-pentane. The oil concentration is from 0 to 10 wt.%, the heat flux is from 10 to 100 kW·m-2, and the initial liquid-level height is from 1.3 to 3.4 cm. The experimental results indicate that the migration ratio of carbon nanotube increases with the increase of the outside diameter or the length of carbon nanotube. For the fixed type of carbon nanotube, the migration ratio decreases with the increase of the oil concentration or the heat flux, and increases with the increase of the initial liquid-level height. The migration ratio of carbon nanotube increases with the decrease of dynamic viscosity of refrigerant or the increase of liquid phase density of refrigerant. A model for predicting the migration ratio of carbon nanotubes in the refrigerant-based nanofluid pool boiling is proposed, and the predictions agree with 92% of the experimental data within a deviation of ±20%. PMID:21711730

The liquid-vapor equilibria of TIP4P/2005 and BLYPSP-4F water models determined through direct simulations of the liquid-vapor interface.

PubMed

Hu, Hongyi; Wang, Feng

2015-06-07

In this paper, the surface tension and critical properties for the TIP4P/2005 and BLYPSP-4F models are reported. A clear dependence of surface tension on the van der Waals cutoff radius (rvdw) is shown when van der Waals interactions are modeled with a simple cutoff scheme. A linear extrapolation formula is proposed that can be used to determine the infinite rvdw surface tension through a few simulations with finite rvdw. A procedure for determining liquid and vapor densities is proposed that does not require fitting to a profile function. Although the critical temperature of water is also found to depend on the choice of rvdw, the dependence is weaker. We argue that a rvdw of 1.75 nm is a good compromise for water simulations when long-range van der Waals correction is not applied. Since the majority of computational programs do not support rigorous treatment of long-range dispersion, the establishment of a minimal acceptable rvdw is important for the simulation of a variety of inhomogeneous systems, such as water bubbles, and water in confined environments. The BLYPSP-4F model predicts room temperature surface tension marginally better than TIP4P/2005 but overestimates the critical temperature. This is expected since only liquid configurations were fit during the development of the BLYPSP-4F potential. The potential is expected to underestimate the stability of vapor and thus overestimate the region of stability for the liquid.

New Density Functional Approach for Solid-Liquid-Vapor Transitions in Pure Materials

NASA Astrophysics Data System (ADS)

Kocher, Gabriel; Provatas, Nikolas

2015-04-01

A new phase field crystal (PFC) type theory is presented, which accounts for the full spectrum of solid-liquid-vapor phase transitions within the framework of a single density order parameter. Its equilibrium properties show the most quantitative features to date in PFC modeling of pure substances, and full consistency with thermodynamics in pressure-volume-temperature space is demonstrated. A method to control either the volume or the pressure of the system is also introduced. Nonequilibrium simulations show that 2- and 3-phase growth of solid, vapor, and liquid can be achieved, while our formalism also allows for a full range of pressure-induced transformations. This model opens up a new window for the study of pressure driven interactions of condensed phases with vapor, an experimentally relevant paradigm previously missing from phase field crystal theories.

Interfacial nonequilibrium and Bénard-Marangoni instability of a liquid-vapor system

NASA Astrophysics Data System (ADS)

Margerit, J.; Colinet, P.; Lebon, G.; Iorio, C. S.; Legros, J. C.

2003-10-01

We study Bénard-Marangoni instability in a system formed by a horizontal liquid layer and its overlying vapor. The liquid is lying on a hot rigid plate and the vapor is bounded by a cold parallel plate. A pump maintains a reduced pressure in the vapor layer and evacuates the vapor. This investigation is undertaken within the classical quasisteady approximation for both the vapor and the liquid phases. The two layers are separated by a deformable interface. Temporarily frozen temperature and velocity distributions are employed at each instant for the stability analysis, limited to infinitesimal disturbances (linear regime). We use irreversible thermodynamics to model the phase change under interfacial nonequilibrium. Within this description, the interface appears as a barrier for transport of both heat and mass. Hence, in contrast with previous studies, we consider the possibility of a temperature jump across the interface, as recently measured experimentally. The stability analysis shows that the interfacial resistances to heat and mass transfer have a destabilizing influence compared to an interface that is in thermodynamic equilibrium. The role of the fluctuations in the vapor phase on the onset of instability is discussed. The conditions to reduce the system to a one phase model are also established. Finally, the influence of the evaporation parameters and of the presence of an inert gas on the marginal stability curves is discussed.

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

PubMed

Sun, Lixin; Zhao, Honggang; Kiselev, Sergei B; McCabe, Clare

2005-05-12

The SAFT-VRX equation of state combines the SAFT-VR equation with a crossover function that smoothly transforms the classical equation into a nonanalytical form close to the critical point. By a combinination of the accuracy of the SAFT-VR approach away from the critical region with the asymptotic scaling behavior seen at the critical point of real fluids, the SAFT-VRX equation can accurately describe the global fluid phase diagram. In previous work, we demonstrated that the SAFT-VRX equation very accurately describes the pvT and phase behavior of both nonassociating and associating pure fluids, with a minimum of fitting to experimental data. Here, we present a generalized SAFT-VRX equation of state for binary mixtures that is found to accurately predict the vapor-liquid equilibrium and pvT behavior of the systems studied. In particular, we examine binary mixtures of n-alkanes and carbon dioxide + n-alkanes. The SAFT-VRX equation accurately describes not only the gas-liquid critical locus for these systems but also the vapor-liquid equilibrium phase diagrams and thermal properties in single-phase regions.

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

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

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

1999-12-01

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

Infrared spectroscopic studies of the conformation in ethyl alpha-haloacetates in the vapor, liquid and solid phases.

PubMed

Jassem, Naserallah A; El-Bermani, Muhsin F

2010-07-01

Infrared spectra of ethyl alpha-fluoroacetate, ethyl alpha-chloroacetate, ethyl alpha-bromoacetate and ethyl alpha-iodoacetate have been measured in the solid, liquid and vapor phases in the region 4000-200 cm(-1). Vibrational frequency assignment of the observed bands to the appropriate modes of vibration was made. Calculations at DFT B3LYP/6-311+G** level, Job: conformer distribution, using Spartan program '08, release 132 was made to determine which conformers exist in which molecule. The results indicated that the first compound exists as an equilibrium mixture of cis and trans conformers and the other three compounds exist as equilibrium mixtures of cis and gauche conformers. Enthalpy differences between the conformers have been determined experimentally for each compound and for every phase. The values indicated that the trans of the first compound is more stable in the vapor phase, while the cis is the more stable in both the liquid and solid phases. In the other three compounds the gauche is more stable in the vapor and liquid phases, while the cis conformer is the more stable in the solid phase for each of the second and third compound, except for ethyl alpha-iodoacetate, the gauche conformer is the more stable over the three phases. Molar energy of activation Ea and the pseudo-thermodynamic parameters of activation DeltaH(double dagger), DeltaS(double dagger) and DeltaG(double dagger) were determined in the solid phase by applying Arrhenius equation; using bands arising from single conformers. The respective E(a) values of these compounds are 5.1+/-0.4, 6.7+/-0.1, 7.5+/-1.3 and 12.0+/-0.6 kJ mol(-1). Potential energy surface calculations were made at two levels; for ethyl alpha-fluoroacetate and ethyl alpha-chloroacetate; the calculations were established at DFT B3LYP/6-311+G** level and for ethyl alpha-bromoacetate and ethyl alpha-iodoacetate at DFT B3LYP/6-311G* level. The results showed no potential energy minimum exists for the gauche conformer in

Empirical model for calculating vapor-liquid equilibrium and associated phase enthalpy for the CO$sub 2$--O$sub 2$--Kr--Xe system for application to the KALC process

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

Glass, R. W.; Gilliam, T. M.; Fowler, V. L.

An empirical model is presented for vapor-liquid equilibria and enthalpy for the CO$sub 2$-O$sub 2$ system. In the model, krypton and xenon in very low concentrations are combined with the CO$sub 2$-O$sub 2$ system, thereby representing the total system of primary interest in the High-Temperature Gas- Cooled Reactor program for removing krypton from off-gas generated during the reprocessing of spent fuel. Selected properties of the individual and combined components being considered are presented in the form of tables and empirical equations. (auth)

Evaluation of the Antibacterial Potential of Liquid and Vapor Phase Phenolic Essential Oil Compounds against Oral Microorganisms

PubMed Central

Wu, Chi-Hao; Ko, Shun-Yao; Chen, Michael Yuanchien; Shih, Yin-Hua; Shieh, Tzong-Ming; Chuang, Li-Chuan; Wu, Ching-Yi

2016-01-01

The aim of the present study was to determine the antibacterial activities of the phenolic essential oil (EO) compounds hinokitiol, carvacrol, thymol, and menthol against oral pathogens. Aggregatibacter actinomycetemcomitans, Streptococcus mutans, Methicillin-resistant Staphylococcus aureus (MRSA), and Escherichia. coli were used in this study. The minimum inhibitory concentrations (MICs), minimum bactericidal concentrations (MBCs), bacterial growth curves, temperature and pH stabilities, and synergistic effects of the liquid and vapor EO compounds were tested. The MIC/MBC of the EO compounds, ranging from the strongest to weakest, were hinokitiol (40–60 μg/mL/40-100 μg/mL), thymol (100–200 μg/mL/200-400 μg/mL), carvacrol (200–400 μg/mL/200-600 μg/mL), and menthol (500-more than 2500 μg/mL/1000-more than 2500 μg/mL). The antibacterial activities of the four EO phenolic compound based on the agar diffusion test and bacterial growth curves showed that the four EO phenolic compounds were stable under different temperatures for 24 h, but the thymol activity decreased when the temperature was higher than 80°C. The combination of liquid carvacrol with thymol did not show any synergistic effects. The activities of the vaporous carvacrol and thymol were inhibited by the presence of water. Continual violent shaking during culture enhanced the activity of menthol. Both liquid and vaporous hinokitiol were stable at different temperatures and pH conditions. The combination of vaporous hinokitiol with zinc oxide did not show synergistic effects. These results showed that the liquid and vapor phases of hinokitiol have strong anti-oral bacteria abilities. Hinokitiol has the potential to be applied in oral health care products, dental materials, and infection controls to exert antimicrobial activity. PMID:27681039

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)

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

PubMed

Kalampounias, Angelos G; Boghosian, Soghomon

2009-09-01

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

Vapor ingestion in Centaur liquid-hydrogen tank

NASA Technical Reports Server (NTRS)

Symons, E. P.

1977-01-01

Vapor ingestion phenomena were investigated using scale models of the Centaur liquid hydrogen tank to determine the height of the free surface of the liquid when vapor is intially ingested into the tank outlet. Data are compared with an analysin and, is general the agreement is very good. Predictions are presented for minimum liquid levels required in the Centaur liquid hydrogen tank in order to prevent vapor ingestion when restarting the engines in space and the quantities of liquid remaining in the tank at vapor ingestion during main engine firing.

Vapor-liquid coexistence of the Stockmayer fluid in nonuniform external fields.

PubMed

Samin, Sela; Tsori, Yoav; Holm, Christian

2013-05-01

We investigate the structure and phase behavior of the Stockmayer fluid in the presence of nonuniform electric fields using molecular simulation. We find that an initially homogeneous vapor phase undergoes a local phase separation in a nonuniform field due to the combined effect of the field gradient and the fluid vapor-liquid equilibrium. This results in a high-density fluid condensing in the strong field region. The system polarization exhibits a strong field dependence due to the fluid condensation.

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

PubMed

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

2011-02-01

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

Melt-Vapor Phase Diagram of the Te-S System

NASA Astrophysics Data System (ADS)

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

2018-03-01

The values of partial pressure of saturated vapor of the constituents of the Te-S system are determined from boiling points. The boundaries of the melt-vapor phase transition at atmospheric pressure and in vacuum of 2000 and 100 Pa are calculated on the basis of partial pressures. A phase diagram that includes vapor-liquid equilibrium fields whose boundaries allow us to assess the behavior of elements upon distillation fractioning is plotted. It is established that the separation of elements is possible at the first evaporation-condensation cycle. Complications can be caused by crystallization of a sulfur solid solution in tellurium.

Pressurization of a Flightweight, Liquid Hydrogen Tank: Evaporation & Condensation at a Liquid/Vapor Interface

NASA Technical Reports Server (NTRS)

Stewart, Mark E. M.

2017-01-01

This paper presents an analysis and simulation of evaporation and condensation at a motionless liquid/vapor interface. A 1-D model equation, emphasizing heat and mass transfer at the interface, is solved in two ways, and incorporated into a subgrid interface model within a CFD simulation. Simulation predictions are compared with experimental data from the CPST Engineering Design Unit tank, a cryogenic fluid management test tank in 1-g. The numerical challenge here is the physics of the liquid/vapor interface; pressurizing the ullage heats it by several degrees, and sets up an interfacial temperature gradient that transfers heat to the liquid phase-the rate limiting step of condensation is heat conducted through the liquid and vapor. This physics occurs in thin thermal layers O(1 mm) on either side of the interface which is resolved by the subgrid interface model. An accommodation coefficient of 1.0 is used in the simulations which is consistent with theory and measurements. This model is predictive of evaporation/condensation rates, that is, there is no parameter tuning.

Phase Equilibria of the Brine Systems Containing Strontium and Calcium Ions

NASA Astrophysics Data System (ADS)

Wang, Xia; Zhao, Kaiyu; Li, Long; Guo, Yafei; Meng, Lingzong; Deng, Tianlong

2017-12-01

It is well known that the comprehensive utilization of the Salt Lake resources successfully must be guided corresponding to the aqueous phase equilibria and phase diagrams. Researches on the phase relationships of brine systems containing calcium and strontium ions are essential to promote the development for the relative resources discovered in China at recent years. In this paper, the phase equilibria of calcium-containing systems, strontium-containing systems and calcium-strontium coexisted brine systems around the world were reviewed. The problems existed recently and new trends in future were point out.

Investigation of local evaporation flux and vapor-phase pressure at an evaporative droplet interface.

PubMed

Duan, Fei; Ward, C A

2009-07-07

In the steady-state experiments of water droplet evaporation, when the throat was heating at a stainless steel conical funnel, the interfacial liquid temperature was found to increase parabolically from the center line to the rim of the funnel with the global vapor-phase pressure at around 600 Pa. The energy conservation analysis at the interface indicates that the energy required for evaporation is maintained by thermal conduction to the interface from the liquid and vapor phases, thermocapillary convection at interface, and the viscous dissipation globally and locally. The local evaporation flux increases from the center line to the periphery as a result of multiple effects of energy transport at the interface. The local vapor-phase pressure predicted from statistical rate theory (SRT) is also found to increase monotonically toward the interface edge from the center line. However, the average value of the local vapor-phase pressures is in agreement with the measured global vapor-phase pressure within the measured error bar.

Notes on Vapor Pressure Equilibria Measurements

NASA Astrophysics Data System (ADS)

Krieger, Albert G.; Henderson, John W.

1996-11-01

After reading the article in this Journal (1), we would like to share our experience with a similar experiment based on an earlier article in this Journal (2). Freshman students at our institution use manometers and 24/40 ground-glass distillation apparatus (abandoned by our organic chemistry classes) to measure boiling points at reduced pressures. Distilled water and 2-methyl-1-propanol are typical liquids of interest. Students enter their collected data into an Excel template which generates graphs of P vs. T and log P vs 1/T to demonstrate the nonlinear and linear relationships that exist between vapor pressures and temperatures. The templates use the Clausius-Clapeyron equation to determine the normal boiling point and the enthalpy of vaporization of the liquid studies. The boiling point determined for water is 100 oC and for 2-methyl-1-propanol is 106 oC, within 2 o of the CRC Handbook data. We have found that the availability of state-of-the-art equipment need not limit the ability to teach and demonstrate fundamental principles. The Excel template (Macintosh) is available upon request domestically and for the cost of international postage for others. Literature Cited 1. Kidahl, N.; Berka, L. H. J. Chem. Educ. 1995, 72, 258. 2. Schaber, P. M. J. Chem. Educ. 1985, 62, 345.

Thermodynamic Properties of Nitrogen Including Liquid and Vapor Phases from 63K to 2000K with Pressures to 10,000 Bar

NASA Technical Reports Server (NTRS)

Jacobsen, Richard T.; Stewart, Richard B.

1973-01-01

Tables of thermodynamic properties of nitrogen are presented for the liquid and vapor phases for temperatures from the freezing line to 2000K and pressures to 10,000 bar. The tables include values of density, internal energy, enthalpy, entropy, isochoric heat capacity, isobaric heat capacity velocity of sound, the isotherm derivative, and the isochor derivative. The thermodynamic property tables are based on an equation of state, P=P (p,T), which accurately represents liquid and gaseous nitrogen for the range of pressures and temperatures covered by the tables. Comparisons of property values calculated from the equation of state with measured values for P-p-T, heat capacity, enthalpy, latent heat, and velocity of sound are included to illustrate the agreement between the experimental data and the tables of properties presented here. The coefficients of the equation of state were determined by a weighted least squares fit to selected P-p-T data and, simultaneously, to isochoric heat capacity data determined by corresponding states analysis from oxygen data, and to data which define the phase equilibrium criteria for the saturated liquid and the saturated vapor. The vapor pressure equation, melting curve equation, and an equation to represent the ideal gas heat capacity are also presented. Estimates of the accuracy of the equation of state, the vapor pressure equation, and the ideal gas heat capacity equation are given. The equation of state, derivatives of the equation, and the integral functions for calculating derived thermodynamic properties are included.

Numerical Modeling of Liquid-Vapor Phase Change

NASA Technical Reports Server (NTRS)

Esmaeeli, Asghar; Arpaci, Vedat S.

2001-01-01

We implemented a two- and three-dimensional finite difference/front tracking technique to solve liquid-vapor phase change problems. The mathematical and the numerical features of the method were explained in great detail in our previous reports, Briefly, we used a single formula representation which incorporated jump conditions into the governing equations. The interfacial terms were distributed as singular terms using delta functions so that the governing equations would be the same as conventional conservation equations away from the interface and in the vicinity of the interface they would provide correct jump conditions. We used a fixed staggered grid to discretize these equations and an unstructured grid to explicitly track the front. While in two dimensions the front was simply a connection of small line segments, in three dimensions it was represented by a connection of small triangular elements. The equations were written in conservative forms and during the course of computations we used regriding to control the size of the elements of the unstructured grid. Moreover, we implemented a coalescence in two dimensions which allowed the merging of different fronts or two segments of the same front when they were sufficiently close. We used our code to study thermocapillary migration of bubbles, burst of bubbles at a free surface, buoyancy-driven interactions of bubbles, evaporation of drops, rapid evaporation of an interface, planar solidification of an undercooled melt, dendritic solidification, and a host of other problems cited in the reference.

Kinetic and Mechanistic Study of Vapor-Phase Free Radical Polymerization onto Liquid Surfaces

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

Gupta, Malancha

The primary objective of this proposal was to study vapor deposition of polymers onto liquid surfaces. Deposition onto liquid surfaces is a relatively new area of research because the past few decades have focused on deposition onto solid materials. We used initiated chemical vapor deposition to deposit polymers onto the liquid surfaces. The process is a one-step, solventless, free-radical polymerization process in which monomer and initiator molecules are flowed into a vacuum chamber. We found that the surface tension interaction between the polymer and the liquid determines whether a film or nanoparticles are formed. We also found that we couldmore » form gels by using soluble monomers. We found that we could tune the size of the nanoparticles by varying the viscosity of the liquid and the process parameters including pressure and time. These insights allow scalable synthesis of polymer materials for a variety of separation and catalysis applications.« less

Vapor Phase Deposition Using Plasma Spray-PVD™

NASA Astrophysics Data System (ADS)

von Niessen, K.; Gindrat, M.; Refke, A.

2010-01-01

Plasma spray—physical vapor deposition (PS-PVD) is a low pressure plasma spray technology to deposit coatings out of the vapor phase. PS-PVD is a part of the family of new hybrid processes recently developed by Sulzer Metco AG (Switzerland) on the basis of the well-established low pressure plasma spraying (LPPS) technology. Included in this new process family are plasma spray—chemical vapor deposition (PS-CVD) and plasma spray—thin film (PS-TF) processes. In comparison to conventional vacuum plasma spraying and LPPS, these new processes use a high energy plasma gun operated at a work pressure below 2 mbar. This leads to unconventional plasma jet characteristics which can be used to obtain specific and unique coatings. An important new feature of PS-PVD is the possibility to deposit a coating not only by melting the feed stock material which builds up a layer from liquid splats, but also by vaporizing the injected material. Therefore, the PS-PVD process fills the gap between the conventional PVD technologies and standard thermal spray processes. The possibility to vaporize feedstock material and to produce layers out of the vapor phase results in new and unique coating microstructures. The properties of such coatings are superior to those of thermal spray and EB-PVD coatings. This paper reports on the progress made at Sulzer Metco to develop functional coatings build up from vapor phase of oxide ceramics and metals.

Application of ionic liquid in liquid phase microextraction technology.

PubMed

Han, Dandan; Tang, Baokun; Lee, Yu Ri; Row, Kyung Ho

2012-11-01

Ionic liquids (ILs) are novel nonmolecular solvents. Their unique properties, such as high thermal stability, tunable viscosity, negligible vapor pressure, nonflammability, and good solubility for inorganic and organic compounds, make them excellent candidates as extraction media for a range of microextraction techniques. Many physical properties of ILs can be varied, and the structural design can be tuned to impart the desired functionality and enhance the analyte extraction selectivity, efficiency, and sensitivity. This paper provides an overview of the applications of ILs in liquid phase microextraction technology, such as single-drop microextraction, hollow fiber based liquid phase microextraction, and dispersive liquid-liquid microextraction. The sensitivity, linear calibration range, and detection limits for a range of target analytes in the methods were analyzed to determine the advantages of ILs in liquid phase microextraction. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase transformations and phase equilibria in the Co–Sn–Ti system in the crystallization interval

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

Fartushna, Iu.; Bulanova, M.; National Technical University of Ukraine, Kiev Polytechnical Institute, Kiev

2016-12-15

The Co–Sn–Ti system was studied in the crystallization interval (below ~50 at% Sn) by the methods of Scanning Electron Microscopy, microprobe analysis, Differential Thermal Analysis, X-ray diffraction. The liquidus and solidus projections and the melting diagram were constructed. Only Co{sub 2}TiSn(τ1) ternary compound (Heusler phase-L1{sub 2}) was found in equilibria with the liquid in the concentration interval studied. Taking into account our recent data, the liquidus projection is characterized by the fields of primary crystallization of (βTi), (Co), binary-based phases Ti{sub 3}Sn, Ti{sub 2}Sn, Ti{sub 5}Sn{sub 3}, Ti{sub 6}Sn{sub 5}, Ti{sub 2}Co, TiCo, TiCo{sub 2} (c), TiCo{sub 2} (h), TiCo{submore » 3}, βCo{sub 3}Sn{sub 2}, CoSn and ternary τ1. The solidus projection is characterized by thirteen three-phase fields, which result from invariant four-phase equilibria, five are of eutectic type (E) and eight of transition type (U) and the existence of one more region Ti{sub 2}Sn{sub 3}+βCoSn{sub 3}+(Sn) in the solidus projection is discussed. - Graphical abstract: Liquidus projection of the Ti–РЎРѕ –Sn system. Fields of crystallization, isotherms and monovariant lines. - Highlights: • The Ti–Co–Sn system is first studied in the composition range up to 50% of Sn. • Liquidus and solidus projections, melting diagram and reaction scheme are constructed. • One ternary compound form in the studied temperature interval: (Co{sub 2}TiSn(τ1)).« less

Prediction of the vapor pressure and vaporization enthalpy of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids.

PubMed

Diedenhofen, Michael; Klamt, Andreas; Marsh, Kenneth; Schäfer, Ansgar

2007-09-07

The vapor pressures and vaporization enthalpies of a series of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids have been predicted with two different approaches using the COSMO-RS method and quantum chemical gas phase calculations. While the calculated enthalpies are in good agreement with the experimental data, COSMO-RS seems to underestimate the vapor pressures by roughly 0.5-4 log units dependent on the IL and approach used.

Solid-phase equilibria on Pluto's surface

NASA Astrophysics Data System (ADS)

Tan, Sugata P.; Kargel, Jeffrey S.

2018-03-01

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

Process for vaporizing a liquid hydrocarbon fuel

DOEpatents

Szydlowski, Donald F.; Kuzminskas, Vaidotas; Bittner, Joseph E.

1981-01-01

The object of the invention is to provide a process for vaporizing liquid hydrocarbon fuels efficiently and without the formation of carbon residue on the apparatus used. The process includes simultaneously passing the liquid fuel and an inert hot gas downwardly through a plurality of vertically spaed apart regions of high surface area packing material. The liquid thinly coats the packing surface, and the sensible heat of the hot gas vaporizes this coating of liquid. Unvaporized liquid passing through one region of packing is uniformly redistributed over the top surface of the next region until all fuel has been vaporized using only the sensible heat of the hot gas stream.

Liquid-vapor phase relations in the Si-O system: A calorically constrained van der Waals-type model

NASA Astrophysics Data System (ADS)

Connolly, James A. D.

2016-09-01

This work explores the use of several van der Waals (vW)-type equations of state (EoS) for predicting vaporous phase relations and speciation in the Si-O system, with emphasis on the azeotropic boiling curve of SiO2-rich liquid. Comparison with the observed Rb and Hg boiling curves demonstrates that prediction accuracy is improved if the a-parameter of the EoS, which characterizes vW forces, is constrained by ambient pressure heat capacities. All EoS considered accurately reproduce metal boiling curve trajectories, but absent knowledge of the true critical compressibility factor, critical temperatures remain uncertain by ~500 K. The EoS plausibly represent the termination of the azeotropic boiling curve of silica-rich liquid by a critical point across which the dominant Si oxidation state changes abruptly from the tetravalent state characteristic of the liquid to the divalent state characteristic of the vapor. The azeotropic composition diverges from silica toward metal-rich compositions with increasing temperature. Consequently, silica boiling is divariant and atmospheric loss after a giant impact would enrich residual silicate liquids in reduced silicon. Two major sources of uncertainty in the boiling curve prediction are the heat capacity of silica liquid, which may decay during depolymerization from the near-Dulong-Petit limit heat capacity of the ionic liquid to value characteristic of the molecular liquid, and the unknown liquid affinity of silicon monoxide. Extremal scenarios for these uncertainties yield critical temperatures and compositions of 5200-6200 K and Si1.1O2-Si1.4O2. The lowest critical temperatures are marginally consistent with shock experiments and are therefore considered more probable.

Phase equilibria of chlorofluorocarbon alternative refrigerant mixtures

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

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

1999-03-01

Isothermal vapor-liquid equilibrium data were determined for binary systems of difluoromethane/1,1,1,2-tetrafluoroethane (HFC-32/HFC-134a), difluoromethane/pentafluoroethane (HFC-32/HFC-125), difluoromethane/1,1,1-trifluoroethane (HFC-32/HFC-143A), and difluoromethane/1,1-difluoroethane (HFC-32/HFC-152a). The vapor and liquid compositions and pressures were measured in a circulation-type apparatus at 303.15 K and 323.15 K. The experimental data were compared with literature results and correlated with the Canahan-Starling-De Santis equation of state within the uncertainty of {+-}1.0%.

Incorporating Phase-Dependent Polarizability in Non-Additive Electrostatic Models for Molecular Dynamics Simulations of the Aqueous Liquid-Vapor Interface.

PubMed

Bauer, Brad A; Warren, G Lee; Patel, Sandeep

2009-02-10

We discuss a new classical water force field that explicitly accounts for differences in polarizability between liquid and vapor phases. The TIP4P-QDP (4-point transferable intermolecular potential with charge dependent-polarizability) force field is a modification of the original TIP4P-FQ fluctuating charge water force field of Rick et al.(1) that self-consistently adjusts its atomic hardness parameters via a scaling function dependent on the M-site charge. The electronegativity (χ) parameters are also scaled in order to reproduce condensed-phase dipole moments of comparable magnitude to TIP4P-FQ. TIP4P-QDP is parameterized to reproduce experimental gas-phase and select condensed-phase properties. The TIP4P-QDP water model possesses a gas phase polarizability of 1.40 Å(3) and gas-phase dipole moment of 1.85 Debye, in excellent agreement with experiment and high-level ab initio predictions. The liquid density of TIP4P-QDP is 0.9954(±0.0002) g/cm(3) at 298 K and 1 atmosphere, and the enthalpy of vaporization is 10.55(±0.12) kcal/mol. Other condensed-phase properties such as the isobaric heat capacity, isothermal compressibility, and diffusion constant are also calculated within reasonable accuracy of experiment and consistent with predictions of other current state-of-the-art water force fields. The average molecular dipole moment of TIP4P-QDP in the condensed phase is 2.641(±0.001) Debye, approximately 0.02 Debye higher than TIP4P-FQ and within the range of values currently surmised for the bulk liquid. The dielectric constant, ε = 85.8 ± 1.0, is 10% higher than experiment. This is reasoned to be due to the increase in the condensed phase dipole moment over TIP4P-FQ, which estimates ε remarkably well. Radial distribution functions for TIP4P-QDP and TIP4P-FQ show similar features, with TIP4P-QDP showing slightly reduced peak heights and subtle shifts towards larger distance interactions. Since the greatest effects of the phase-dependent polarizability are

Incorporating Phase-Dependent Polarizability in Non-Additive Electrostatic Models for Molecular Dynamics Simulations of the Aqueous Liquid-Vapor Interface

PubMed Central

Bauer, Brad A.; Warren, G. Lee; Patel, Sandeep

2012-01-01

We discuss a new classical water force field that explicitly accounts for differences in polarizability between liquid and vapor phases. The TIP4P-QDP (4-point transferable intermolecular potential with charge dependent-polarizability) force field is a modification of the original TIP4P-FQ fluctuating charge water force field of Rick et al.1 that self-consistently adjusts its atomic hardness parameters via a scaling function dependent on the M-site charge. The electronegativity (χ) parameters are also scaled in order to reproduce condensed-phase dipole moments of comparable magnitude to TIP4P-FQ. TIP4P-QDP is parameterized to reproduce experimental gas-phase and select condensed-phase properties. The TIP4P-QDP water model possesses a gas phase polarizability of 1.40 Å3 and gas-phase dipole moment of 1.85 Debye, in excellent agreement with experiment and high-level ab initio predictions. The liquid density of TIP4P-QDP is 0.9954(±0.0002) g/cm3 at 298 K and 1 atmosphere, and the enthalpy of vaporization is 10.55(±0.12) kcal/mol. Other condensed-phase properties such as the isobaric heat capacity, isothermal compressibility, and diffusion constant are also calculated within reasonable accuracy of experiment and consistent with predictions of other current state-of-the-art water force fields. The average molecular dipole moment of TIP4P-QDP in the condensed phase is 2.641(±0.001) Debye, approximately 0.02 Debye higher than TIP4P-FQ and within the range of values currently surmised for the bulk liquid. The dielectric constant, ε = 85.8 ± 1.0, is 10% higher than experiment. This is reasoned to be due to the increase in the condensed phase dipole moment over TIP4P-FQ, which estimates ε remarkably well. Radial distribution functions for TIP4P-QDP and TIP4P-FQ show similar features, with TIP4P-QDP showing slightly reduced peak heights and subtle shifts towards larger distance interactions. Since the greatest effects of the phase-dependent polarizability are

Effects of capillary heterogeneity on vapor-liquid counterflow in porous media

NASA Astrophysics Data System (ADS)

Stubos, A. K.; Satik, C.; Yortsos, Y. C.

1992-06-01

Based on a continuum description, the effect of capillary heterogeneity, induced by variation in permeability, on the steady state, countercurrent, vapor-liquid flow in porous media is analyzed. It is shown that the heterogeneity acts as a body force that may enhance or diminish gravity effects on heat pipes. Selection rules that determine the steady states reached in homogeneous, gravity-driven heat pipes are also formulated. It is shown that the 'infinite' two-phase zone may terminate by a substantial change in the permeability somewhere in the medium. The two possible sequences, liquid-liquid dominated-dry, or liquid-vapor dominated-dry find applications in geothermal systems. Finally, it is shown that although weak heterogeneity affects only gravity controlled flows, stronger variations in permeability can give rise to significant capillary effects.

Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

DOE PAGES

Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.; ...

2017-11-24

Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

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

Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.

Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

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

USGS Publications Warehouse

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

1996-01-01

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

Compatibility testing of spacecraft materials and spacestorable liquid propellants. [liquid and vapor fluorine and FLOX

NASA Technical Reports Server (NTRS)

Denson, J. R.; Toy, A.

1974-01-01

Compatibility data for aluminum alloy 2219-T87 and titanium alloy Ti-6Al-4V were obtained while these alloys were exposed to both liquid and vapor fluorine and FLOX at -320 F + or -10 F. These data were obtained using a new low cost compatibility method which incorporates totally sealed containers and double dogbone test specimens and propellants in the simultaneous exposure to vapor and liquid phases. The compatibility investigation covered a storage period in excess of one year. Pitting was more severe in the 2219-T87 aluminum alloy than in the Ti-6Al-4V titanium alloy for both fluorine and FLOX exposure. The degree of chemical attack is more severe in the presence of FLOX than in fluorine and phase. The mechanical properties of the two alloys were not affected by storage in either of the two propellants.

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

NASA Astrophysics Data System (ADS)

Sowers, Susanne Lynn

1997-11-01

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

Curvature induced phase stability of an intensely heated liquid

NASA Astrophysics Data System (ADS)

Sasikumar, Kiran; Liang, Zhi; Cahill, David G.; Keblinski, Pawel

2014-06-01

We use non-equilibrium molecular dynamics simulations to study the heat transfer around intensely heated solid nanoparticles immersed in a model Lennard-Jones fluid. We focus our studies on the role of the nanoparticle curvature on the liquid phase stability under steady-state heating. For small nanoparticles we observe a stable liquid phase near the nanoparticle surface, which can be at a temperature well above the boiling point. Furthermore, for particles with radius smaller than a critical radius of 2 nm we do not observe formation of vapor even above the critical temperature. Instead, we report the existence of a stable fluid region with a density much larger than that of the vapor phase. We explain the stability in terms of the Laplace pressure associated with the formation of a vapor nanocavity and the associated effect on the Gibbs free energy.

Liquid-vapor phase equilibria of three-component systems of propanol-2-propanoic acid esters

NASA Astrophysics Data System (ADS)

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

2017-12-01

The boiling points of solutions of three-component systems formed by propanol-2 and propanoic acid esters are measured at different pressures by means of ebulliometry. The coefficients of the activity of the solutions' components are measured using Wilson and nonrandom two-liquid (NRTL) equations. The results from calculations are in line with the experimental data.

Liquid phase stabilization versus bubble formation at a nanoscale curved interface

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Luo, Tengfei

2018-03-01

We investigate the nature of vapor bubble formation near a nanoscale-curved convex liquid-solid interface using two models: an equilibrium Gibbs model for homogenous nucleation, and a nonequilibrium dynamic van der Waals-diffuse-interface model for phase change in an initially cool liquid. Vapor bubble formation is shown to occur for sufficiently large radius of curvature and is suppressed for smaller radii. Solid-fluid interactions are accounted for and it is shown that liquid-vapor interfacial energy, and hence Laplace pressure, has limited influence over bubble formation. The dominant factor is the energetic cost of creating the solid-vapor interface from the existing solid-liquid interface, as demonstrated via both equilibrium and nonequilibrium arguments.

Estimating vapor pressures of pure liquids

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

Haraburda, S.S.

1996-03-01

Calculating the vapor pressures for pure liquid chemicals is a key step in designing equipment for separation of liquid mixtures. Here is a useful way to develop an equation for predicting vapor pressures over a range of temperatures. The technique uses known vapor pressure points for different temperatures. Although a vapor-pressure equation is being showcased in this article, the basic method has much broader applicability -- in fact, users can apply it to develop equations for any temperature-dependent model. The method can be easily adapted for use in software programs for mathematics evaluation, minimizing the need for any programming. Themore » model used is the Antoine equation, which typically provides a good correlation with experimental or measured data.« less

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

NASA Astrophysics Data System (ADS)

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

2002-06-01

The concentrations and ratios of the major elements determine the physical properties and the phase equilibria behavior of peridotites and basalts in response to the changing energy contents of the systems. The behavior of the trace elements and isotopic features are influenced in their turn by the phase equilibria, by the physical character of the partial melting and partial crystallization processes, and by the way in which a magma interacts with its wall rocks. Concentrating on the trace element and isotope contents of basalts to the exclusion of the field relations, petrology, major element data, and phase equilibria is as improvident as slaughtering the buffalo for the sake of its tongue. The crust is a cool boundary layer and a density filter, which impedes the upward transfer of hot, dense "primary" picritic and komatiitic liquids. Planetary crusts are sites of large-scale contamination and extensive partial crystallization of primitive melts striving to escape to the surface. Escape of truly unmodified primitive melts to the surface is a rare event, requiring the resolution of daunting problems in chemical and mechanical engineering. Primary status for volumetrically abundant basalts such as mid-ocean ridge basalt, ocean island basalt, and continental flood basalts is denied by their low-pressure cotectic character, first remarked upon on petrological grounds in 1928 and on experimental grounds in 1962. These basalt liquids are products of crystal-liquid separation at low pressure. Primary status for these common basalts is further denied by the phase equilibria of such compositions at elevated pressures, when the required residual mantle mineralogy (magnesian olivine and orthopyroxene) is not stable at the liquidus. It is also denied by the picritic or komatiitic nature of partial melts of candidate upper-mantle compositions at high pressures - a conclusion supported by calculation of the melt composition, which would need to be extracted in order to

Order parameter free enhanced sampling of the vapor-liquid transition using the generalized replica exchange method.

PubMed

Lu, Qing; Kim, Jaegil; Straub, John E

2013-03-14

The generalized Replica Exchange Method (gREM) is extended into the isobaric-isothermal ensemble, and applied to simulate a vapor-liquid phase transition in Lennard-Jones fluids. Merging an optimally designed generalized ensemble sampling with replica exchange, gREM is particularly well suited for the effective simulation of first-order phase transitions characterized by "backbending" in the statistical temperature. While the metastable and unstable states in the vicinity of the first-order phase transition are masked by the enthalpy gap in temperature replica exchange method simulations, they are transformed into stable states through the parameterized effective sampling weights in gREM simulations, and join vapor and liquid phases with a succession of unimodal enthalpy distributions. The enhanced sampling across metastable and unstable states is achieved without the need to identify a "good" order parameter for biased sampling. We performed gREM simulations at various pressures below and near the critical pressure to examine the change in behavior of the vapor-liquid phase transition at different pressures. We observed a crossover from the first-order phase transition at low pressure, characterized by the backbending in the statistical temperature and the "kink" in the Gibbs free energy, to a continuous second-order phase transition near the critical pressure. The controlling mechanisms of nucleation and continuous phase transition are evident and the coexistence properties and phase diagram are found in agreement with literature results.

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

NASA Astrophysics Data System (ADS)

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

2001-08-01

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

The application of the high-speed photography in the experiments of boiling liquid expanding vapor explosions

NASA Astrophysics Data System (ADS)

Chen, Sining; Sun, Jinhua; Chen, Dongliang

2007-01-01

The liquefied-petroleum gas tank in some failure situations may release its contents, and then a series of hazards with different degrees of severity may occur. The most dangerous accident is the boiling liquid expanding vapor explosion (BLEVE). In this paper, a small-scale experiment was established to experimentally investigate the possible processes that could lead to a BLEVE. As there is some danger in using LPG in the experiments, water was used as the test fluid. The change of pressure and temperature was measured during the experiment. The ejection of the vapor and the sequent two-phase flow were recorded by a high-speed video camera. It was observed that two pressure peaks result after the pressure is released. The vapor was first ejected at a high speed; there was a sudden pressure drop which made the liquid superheated. The superheated liquid then boiled violently causing the liquid contents to swell, and also, the vapor pressure in the tank increased rapidly. The second pressure peak was possibly due to the swell of this two-phase flow which was likely to violently impact the wall of the tank with high speed. The whole evolution of the two-phase flow was recorded through photos captured by the high-speed video camera, and the "two step" BLEVE process was confirmed.

An Indirect Method for Vapor Pressure and Phase Change Enthalpy Determination by Thermogravimetry

NASA Astrophysics Data System (ADS)

Giani, Samuele; Riesen, Rudolf; Schawe, Jürgen E. K.

2018-07-01

Vapor pressure is a fundamental property of a pure substance. This property is the pressure of a compound's vapor in thermodynamic equilibrium with its condensed phase (solid or liquid). When phase equilibrium condition is met, phase coexistence of a pure substance involves a continuum interplay of vaporization or sublimation to gas and condensation back to their liquid or solid form, respectively. Thermogravimetric analysis (TGA) techniques are based on mass loss determination and are well suited for the study of such phenomena. In this work, it is shown that TGA method using a reference substance is a suitable technique for vapor pressure determination. This method is easy and fast because it involves a series of isothermal segments. In contrast to original Knudsen's approach, where the use of high vacuum is mandatory, adopting the proposed method a given experimental setup is calibrated under ambient pressure conditions. The theoretical framework of this method is based on a generalization of Langmuir equation of free evaporation: The real strength of the proposed method is the ability to determine the vapor pressure independently of the molecular mass of the vapor. A demonstration of this method has been performed using the Clausius-Clapeyron equation of state to derive the working equation. This algorithm, however, is adaptive and admits the use of other equations of state. The results of a series of experiments with organic molecules indicate that the average difference of the measured and the literature vapor pressure amounts to about 5 %. Vapor pressure determined in this study spans from few mPa up to several kPa. Once the p versus T diagram is obtained, phase transition enthalpy can additionally be calculated from the data.

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

PubMed

Céolin, R; Rietveld, I B

2017-03-01

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

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

NASA Astrophysics Data System (ADS)

Ghasemi, Masoomeh; Johansson, Jonas

2017-04-01

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

Sporicidal Activity of the KMT reagent in its vapor phase against Geobacillus stearothermophilus Spores.

PubMed

Kida, Nori; Mochizuki, Yasushi; Taguchi, Fumiaki

2007-01-01

In an investigation of the sporicidal activity of the KMT reagent, a vapor phase study was performed using five kinds of carriers contaminated with Geobacillus stearothermophilus spores. When 25 ml of the KMT reagent was vaporized in a chamber (capacity; approximately 95 liters), the 2-step heating method (vaporization by a combination of low temperature and high temperature) showed the most effective sporicidal activity in comparison with the 1-step heating method (rapid vaporization). The 2-step heating method appeared to be related to the sporicidal activity of vaporized KMT reagent, i.e., ethanol and iodine, which vaporized mainly when heated at a low temperature such as 55 C, and acidic water, which vaporized mainly when heated at a high temperature such as 300 C. We proposed that the KMT reagent can be used as a new disinfectant not only in the liquid phase but also in the vapor phase in the same way as peracetic acid and hydrogen peroxide.

Nonequilibrium kinetic boundary condition at the vapor-liquid interface of argon

NASA Astrophysics Data System (ADS)

Ishiyama, Tatsuya; Fujikawa, Shigeo; Kurz, Thomas; Lauterborn, Werner

2013-10-01

A boundary condition for the Boltzmann equation (kinetic boundary condition, KBC) at the vapor-liquid interface of argon is constructed with the help of molecular dynamics (MD) simulations. The KBC is examined at a constant liquid temperature of 85 K in a wide range of nonequilibrium states of vapor. The present investigation is an extension of a previous one by Ishiyama, Yano, and Fujikawa [Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.95.084504 95, 084504 (2005)] and provides a more complete form of the KBC. The present KBC includes a thermal accommodation coefficient in addition to evaporation and condensation coefficients, and these coefficients are determined in MD simulations uniquely. The thermal accommodation coefficient shows an anisotropic behavior at the interface for molecular velocities normal versus tangential to the interface. It is also found that the evaporation and condensation coefficients are almost constant in a fairly wide range of nonequilibrium states. The thermal accommodation coefficient of the normal velocity component is almost unity, while that of the tangential component shows a decreasing function of the density of vapor incident on the interface, indicating that the tangential velocity distribution of molecules leaving the interface into the vapor phase may deviate from the tangential parts of the Maxwell velocity distribution at the liquid temperature. A mechanism for the deviation of the KBC from the isotropic Maxwell KBC at the liquid temperature is discussed in terms of anisotropic energy relaxation at the interface. The liquid-temperature dependence of the present KBC is also discussed.

Large-capacity pump vaporizer for liquid hydrogen and nitrogen

NASA Technical Reports Server (NTRS)

Hauser, J. A.

1970-01-01

Pump vaporizer system delivers 500 standard cubic feet per minute of hydrogen or nitrogen, one system delivers both gases. Vacuum-jacketed pump discharges liquid hydrogen or liquid nitrogen into vaporizing system heated by ambient air. Principal characteristics of the flow and discharge system, pump, and vaporizer are given.

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

PubMed

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

2005-05-01

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.

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.

Shock-and-Release to the Liquid-Vapor Phase Boundary: Experiments and Applications to Planetary Science

NASA Astrophysics Data System (ADS)

Stewart, Sarah

2017-06-01

Shock-induced vaporization was a common process during the end stages of terrestrial planet formation and transient features in extra-solar systems are attributed to recent giant impacts. At the Sandia Z Machine, my collaborators and I are conducting experiments to study the shock Hugoniot and release to the liquid-vapor phase boundary of major minerals in rocky planets. Current work on forsterite, enstatite and bronzite and previous results on silica, iron and periclase demonstrate that shock-induced vaporization played a larger role during planet formation than previously thought. I will provide an overview of the experimental results and describe how the data have changed our views of planetary impact events in our solar system and beyond. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. This work is supported by the Z Fundamental Science Program at Sandia National Laboratories, DOE-NNSA Grant DE- NA0002937, NASA Grant # NNX15AH54G, and UC Multicampus-National Lab Collaborative Research and Training Grant #LFR-17-449059.

Temperature-difference-driven mass transfer through the vapor from a cold to a warm liquid.

PubMed

Struchtrup, Henning; Kjelstrup, Signe; Bedeaux, Dick

2012-06-01

Irreversible thermodynamics provides interface conditions that yield temperature and chemical potential jumps at phase boundaries. The interfacial jumps allow unexpected transport phenomena, such as the inverted temperature profile [Pao, Phys. Fluids 14, 306 (1971)] and mass transfer from a cold to a warm liquid driven by a temperature difference across the vapor phase [Mills and Phillips, Chem. Phys. Lett. 372, 615 (2002)]. Careful evaluation of the thermodynamic laws has shown [Bedeaux et al., Physica A 169, 263 (1990)] that the inverted temperature profile is observed for processes with a high heat of vaporization. In this paper, we show that cold to warm mass transfer through the vapor from a cold to a warm liquid is only possible when the heat of evaporation is sufficiently small. A necessary criterium for the size of the mass transfer coefficient is given.

The competition between liquid and vapor transport in transpiring leaves.

PubMed

Rockwell, Fulton Ewing; Holbrook, N Michele; Stroock, Abraham Duncan

2014-04-01

In leaves, the transpirational flux of water exits the veins as liquid and travels toward the stomata in both the vapor and liquid phases before exiting the leaf as vapor. Yet, whether most of the evaporation occurs from the vascular bundles (perivascular), from the photosynthetic mesophyll cells, or within the vicinity of the stomatal pore (peristomatal) remains in dispute. Here, a one-dimensional model of the competition between liquid and vapor transport is developed from the perspective of nonisothermal coupled heat and water molecule transport in a composite medium of airspace and cells. An analytical solution to the model is found in terms of the energy and transpirational fluxes from the leaf surfaces and the absorbed solar energy load, leading to mathematical expressions for the proportions of evaporation accounted for by the vascular, mesophyll, and epidermal regions. The distribution of evaporation in a given leaf is predicted to be variable, changing with the local environment, and to range from dominantly perivascular to dominantly peristomatal depending on internal leaf architecture, with mesophyll evaporation a subordinate component. Using mature red oak (Quercus rubra) trees, we show that the model can be solved for a specific instance of a transpiring leaf by combining gas-exchange data, anatomical measurements, and hydraulic experiments. We also investigate the effect of radiation load on the control of transpiration, the potential for condensation on the inside of an epidermis, and the impact of vapor transport on the hydraulic efficiency of leaf tissue outside the xylem.

Interaction of a sodium ion with the water liquid-vapor interface

NASA Technical Reports Server (NTRS)

Wilson, M. A.; Pohorille, A.; Pratt, L. R.; MacElroy, R. D. (Principal Investigator)

1989-01-01

Molecular dynamics results are presented for the density profile of a sodium ion near the water liquid-vapor interface at 320 K. These results are compared with the predictions of a simple dielectric model for the interaction of a monovalent ion with this interface. The interfacial region described by the model profile is too narrow and the profile decreases too abruptly near the solution interface. Thus, the simple model does not provide a satisfactory description of the molecular dynamics results for ion positions within two molecular diameters from the solution interface where appreciable ion concentrations are observed. These results suggest that surfaces associated with dielectric models of ionic processes at aqueous solution interfaces should be located at least two molecular diameters inside the liquid phase. A free energy expense of about 2 kcal/mol is required to move the ion within two molecular layers of the free water liquid-vapor interface.

Methods for calculation of engineering parameters for gas separation. [vapor pressure and solubility of gases in organic liquids

NASA Technical Reports Server (NTRS)

Lawson, D. D.

1979-01-01

A group additivity method is generated which allows estimation, from the structural formulas alone, of the energy of vaporization and the molar volume at 25 C of many nonpolar organic liquids. Using these two parameters and appropriate thermodynamic relations, the vapor pressure of the liquid phase and the solubility of various gases in nonpolar organic liquids are predicted. It is also possible to use the data to evaluate organic and some inorganic liquids for use in gas separation stages or liquids as heat exchange fluids in prospective thermochemical cycles for hydrogen production.

Predicting the growth of S i3N4 nanowires by phase-equilibrium-dominated vapor-liquid-solid mechanism

NASA Astrophysics Data System (ADS)

Zhang, Yongliang; Cai, Jing; Yang, Lijun; Wu, Qiang; Wang, Xizhang; Hu, Zheng

2017-09-01

Nanomaterial synthesis is experiencing a profound evolution from empirical science ("cook-and-look") to prediction and design, which depends on the deep insight into the growth mechanism. Herein, we report a generalized prediction of the growth of S i3N4 nanowires by nitriding F e28S i72 alloy particles across different phase regions based on our finding of the phase-equilibrium-dominated vapor-liquid-solid (PED-VLS) mechanism. All the predictions about the growth of S i3N4 nanowires, and the associated evolutions of lattice parameters and geometries of the coexisting Fe -Si alloy phases, are experimentally confirmed quantitatively. This progress corroborates the general validity of the PED-VLS mechanism, which could be applied to the design and controllable synthesis of various one-dimensional nanomaterials.

Vapor phase pyrolysis

NASA Technical Reports Server (NTRS)

Steurer, Wolfgang

1992-01-01

The vapor phase pyrolysis process is designed exclusively for the lunar production of oxygen. In this concept, granulated raw material (soil) that consists almost entirely of metal oxides is vaporized and the vapor is raised to a temperature where it dissociates into suboxides and free oxygen. Rapid cooling of the dissociated vapor to a discrete temperature causes condensation of the suboxides, while the oxygen remains essentially intact and can be collected downstream. The gas flow path and flow rate are maintained at an optimum level by control of the pressure differential between the vaporization region and the oxygen collection system with the aid of the environmental vacuum.

The Relation between Vaporization Enthalpies and Viscosities: Eyring's Theory Applied to Selected Ionic Liquids.

PubMed

Bonsa, Anne-Marie; Paschek, Dietmar; Zaitsau, Dzmitry H; Emel'yanenko, Vladimir N; Verevkin, Sergey P; Ludwig, Ralf

2017-05-19

Key properties for the use of ionic liquids as electrolytes in batteries are low viscosities, low vapor pressure and high vaporization enthalpies. Whereas the measurement of transport properties is well established, the determination of vaporization enthalpies of these extremely low volatile compounds is still a challenge. At a first glance both properties seem to describe different thermophysical phenomena. However, eighty years ago Eyring suggested a theory which related viscosities and vaporization enthalpies to each other. The model is based on Eyring's theory of absolute reaction rates. Recent attempts to apply Eyring's theory to ionic liquids failed. The motivation of our study is to show that Eyring's theory works, if the assumptions specific for ionic liquids are fulfilled. For that purpose we measured the viscosities of three well selected protic ionic liquids (PILs) at different temperatures. The temperature dependences of viscosities were approximated by the Vogel-Fulcher-Tamann (VFT) relation and extrapolated to the high-temperature regime up to 600 K. Then the VFT-data could be fitted to the Eyring-model. The values of vaporization enthalpies for the three selected PILs predicted by the Eyring model have been very close to the experimental values measured by well-established techniques. We conclude that the Eyring theory can be successfully applied to the chosen set of PILs, if the assumption that ionic pairs of the viscous flow in the liquid and the ionic pairs in the gas phase are similar is fulfilled. It was also noticed that proper transfer of energies can be only derived if the viscosities and the vaporization energies are known for temperatures close to the liquid-gas transition temperature. The idea to correlate easy measurable viscosities of ionic liquids with their vaporization enthalpies opens a new way for a reliable assessment of these thermodynamic properties for a broad range of ionic liquids. © 2017 Wiley-VCH Verlag GmbH & Co. KGa

Multiphase, multicomponent parameter estimation for liquid and vapor fluxes in deep arid systems using hydrologic data and natural environmental tracers

USGS Publications Warehouse

Kwicklis, Edward M.; Wolfsberg, Andrew V.; Stauffer, Philip H.; Walvoord, Michelle Ann; Sully, Michael J.

2006-01-01

Multiphase, multicomponent numerical models of long-term unsaturated-zone liquid and vapor movement were created for a thick alluvial basin at the Nevada Test Site to predict present-day liquid and vapor fluxes. The numerical models are based on recently developed conceptual models of unsaturated-zone moisture movement in thick alluvium that explain present-day water potential and tracer profiles in terms of major climate and vegetation transitions that have occurred during the past 10 000 yr or more. The numerical models were calibrated using borehole hydrologic and environmental tracer data available from a low-level radioactive waste management site located in a former nuclear weapons testing area. The environmental tracer data used in the model calibration includes tracers that migrate in both the liquid and vapor phases (??D, ??18O) and tracers that migrate solely as dissolved solutes (Cl), thus enabling the estimation of some gas-phase as well as liquid-phase transport parameters. Parameter uncertainties and correlations identified during model calibration were used to generate parameter combinations for a set of Monte Carlo simulations to more fully characterize the uncertainty in liquid and vapor fluxes. The calculated background liquid and vapor fluxes decrease as the estimated time since the transition to the present-day arid climate increases. However, on the whole, the estimated fluxes display relatively little variability because correlations among parameters tend to create parameter sets for which changes in some parameters offset the effects of others in the set. Independent estimates on the timing since the climate transition established from packrat midden data were essential for constraining the model calibration results. The study demonstrates the utility of environmental tracer data in developing numerical models of liquid- and gas-phase moisture movement and the importance of considering parameter correlations when using Monte Carlo analysis to

Vapor-Liquid Partitioning of Iron and Manganese in Hydrothermal Fluids: An Experimental Investigation with Application to the Integrated Study of Basalt-hosted Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Pester, N. J.; Seyfried, W. E.

2010-12-01

The chemistry of deep-sea hydrothermal vent fluids, expressed at the seafloor, reflects a complex history of physicochemical reactions. After three decades of field and experimental investigations, the processes of fluid-mineral equilibria that transform seawater into that of a typical “black smoker” are generally well described in the literature. Deep crustal fluids, when encountering a given heat source that ultimately drives hydrothermal circulation, routinely intersect the two-phase boundary. This process results in the nearly ubiquitous observations of variable salinity in vent fluids and is often a secondary driver of circulation via the evolution of a more buoyant (i.e. less saline) phase. Phase separation in chemically complex fluids results in the partitioning of dissolved species between the two evolved phases that deviates from simple charge balance calculations and these effects become more prominent with increasing temperature and/or decreasing pressure along the two-phase envelope. This process of partitioning has not been extensively studied and the interplay between the effects of phase separation and fluid-mineral equilibrium are not well understood. Most basalt-hosted hydrothermal systems appear to enter a steady state mode wherein fluids approach the heat source at depth and rise immediately once the two-phase boundary is met. Thus, venting fluids exhibit only modest deviations from seawater bulk salinity and the effects of partitioning are likely minor for all but the most volatile elements. Time series observations at integrated study sites, however, demonstrate dynamic changes in fluid chemistry following eruptions/magmatic events, including order of magnitude increases in gas concentrations and unexpectedly high Fe/Cl ratios. In this case, the time dependence of vapor-liquid partitioning relative to fluid-mineral equilibrium must be considered when attempting to interpret changes in subsurface reaction conditions. The two-phase region of

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

NASA Astrophysics Data System (ADS)

Acree, William; Chickos, James S.

2017-03-01

The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

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

NASA Astrophysics Data System (ADS)

Shevchenko, M.; Jak, E.

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

Anisimov, M. P.

2016-12-01

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

Phase equilibria constraints on models of subduction zone magmatism

NASA Astrophysics Data System (ADS)

Myers, James D.; Johnston, Dana A.

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

Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

NASA Astrophysics Data System (ADS)

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

This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

Modeling the Capillary Pressure for the Migration of the Liquid Phase in Granular Solid-Liquid-Vapor Systems: Application to the Control of the Composition Profile in W-Cu FGM Materials

NASA Astrophysics Data System (ADS)

Missiaen, Jean-Michel; Raharijaona, Jean-Joël; Delannay, Francis

2016-11-01

A model is developed to compute the capillary pressure for the migration of the liquid phase out or into a uniform solid-liquid-vapor system. The capillary pressure is defined as the reduction of the overall interface energy per volume increment of the transferred fluid phase. The model takes into account the particle size of the solid particle aggregate, the packing configuration (coordination number, porosity), the volume fractions of the different phases, and the values of the interface energies in the system. The model is used for analyzing the stability of the composition profile during processing of W-Cu functionally graded materials combining a composition gradient with a particle size gradient. The migration pressure is computed with the model in two stages: (1) just after the melting of copper, i.e., when sintering and shape accommodation of the W particle aggregate can still be neglected and (2) at high temperature, when the system is close to full density with equilibrium particle shape. The model predicts well the different stages of liquid-phase migration observed experimentally.

Compressed liquid densities, saturated liquid densities, and vapor pressures of 1,1-difluoroethane

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

Defibaugh, D.R.; Morrison, G.

1996-05-01

The compressed liquid densities and vapor pressures of 1,1-difluoroethane (HFC-152a) have been measured, correlated, and compared with other data. The liquid densities were measured with a combined standard uncertainty of {+-}0.05% using a vibrating tube densimeter over a temperature range of 243 K to 371 K and at pressures from near the saturated vapor pressure to 6,500 kPa; thus the data extend nearly to the critical point ({Tc} = 386.41 K and P{sub c} = 4514.7 kPa). The vapor pressures were measured with a combined standard uncertainty of {+-}0.02% using a stainless steel ebulliometer in the temperature range from 280more » K to 335 K. Saturated liquid densities were calculated by extrapolating the compressed liquid isotherms to the saturation pressure.« less

Irradiation of fish fillets: Relation of vapor phase reactions to storage quality

USGS Publications Warehouse

Spinelli, J.; Dollar, A.M.; Wedemeyer, G.A.; Gallagher, E.C.

1969-01-01

Fish fillets irradiated under air, nitrogen, oxygen, or carbon dioxide atmospheres developed rancidlike flavors when they were stored at refrigerated temperatures. Packing and irradiating under vacuum or helium prevented development of off-flavors during storage.Significant quantities of nitrate and oxidizing substances were formed when oxygen, nitrogen, or air were present in the vapor or liquid phases contained in a Pyrex glass model system exposed to ionizing radiation supplied by a 60Co source. It was demonstrated that the delayed flavor changes that occur in stored fish fillets result from the reaction of vapor phase radiolysis products and the fish tissue substrates.

Liquid-vapor equilibrium and interfacial properties of square wells in two dimensions

NASA Astrophysics Data System (ADS)

Armas-Pérez, Julio C.; Quintana-H, Jacqueline; Chapela, Gustavo A.

2013-01-01

Liquid-vapor coexistence and interfacial properties of square wells in two dimensions are calculated. Orthobaric densities, vapor pressures, surface tensions, and interfacial thicknesses are reported. Results are presented for a series of potential widths λ* = 1.4, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, and 5, where λ* is given in units of the hard core diameter σ. Critical and triple points are explored. No critical point was found for λ* < 1.4. Corresponding states principle analysis is performed for the whole series. For λ* = 1.4 and 1.5 evidence is presented that at an intermediate temperature between the critical and the triple point temperatures the liquid branch becomes an amorphous solid. This point is recognized in Armas-Pérez et al. [unpublished] as a hexatic phase transition. It is located at reduced temperatures T* = 0.47 and 0.35 for λ* = 1.4 and 1.5, respectively. Properties such as the surface tension, vapor pressure, and interfacial thickness do not present any discontinuity at these points. This amorphous solid branch does not follow the corresponding state principle, which is only applied to liquids and gases.

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

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.

Numerical modelling of multiphase liquid-vapor-gas flows with interfaces and cavitation

NASA Astrophysics Data System (ADS)

Pelanti, Marica

2017-11-01

We are interested in the simulation of multiphase flows where the dynamical appearance of vapor cavities and evaporation fronts in a liquid is coupled to the dynamics of a third non-condensable gaseous phase. We describe these flows by a single-velocity three-phase compressible flow model composed of the phasic mass and total energy equations, the volume fraction equations, and the mixture momentum equation. The model includes stiff mechanical and thermal relaxation source terms for all the phases, and chemical relaxation terms to describe mass transfer between the liquid and vapor phases of the species that may undergo transition. The flow equations are solved by a mixture-energy-consistent finite volume wave propagation scheme, combined with simple and robust procedures for the treatment of the stiff relaxation terms. An analytical study of the characteristic wave speeds of the hierarchy of relaxed models associated to the parent model system is also presented. We show several numerical experiments, including two-dimensional simulations of underwater explosive phenomena where highly pressurized gases trigger cavitation processes close to a rigid surface or to a free surface. This work was supported by the French Government Grant DGA N. 2012.60.0011.00.470.75.01, and partially by the Norwegian Grant RCN N. 234126/E30.

Towards Cryogenic Liquid-Vapor Energy Storage Units for space applications

NASA Astrophysics Data System (ADS)

Afonso, Josiana Prado

With the development of mechanical coolers and very sensitive cryogenic sensors, it could be interesting to use Energy Storage Units (ESU) and turn off the cryocooler to operate in a free micro vibration environment. An ESU would also avoid cryogenic systems oversized to attenuate temperature fluctuations due to thermal load variations which is useful particularly for space applications. In both cases, the temperature drift must remain limited to keep good detector performances. In this thesis, ESUs based on the high latent heat associated to liquid-vapor phase change to store energy have been studied. To limit temperature drifts while keeping small size cell at low temperature, a potential solution consists in splitting the ESU in two volumes: a low temperature cell coupled to a cryocooler cold finger through a thermal heat switch and an expansion volume at room temperature to reduce the temperature increase occurring during liquid evaporation. To obtain a vanishing temperature drift, a new improvement has been tested using two-phase nitrogen: a controlled valve was inserted between the two volumes in order to control the cold cell pressure. In addition, a porous material was used inside the cell to turn the ESU gravity independent and suitable for space applications. In this case, experiments reveal not fully understood results concerning both energy storage and liquid-wall temperature difference. To capture the thermal influence of the porous media, a dedicated cell with poorly conductive lateral wall was built and operated with two-phase helium. After its characterization outside the saturation conditions (conduction, convection), experiments were performed, with and without porous media, heating at the top or the bottom of the cell with various heat fluxes and for different saturation temperatures. In parallel, a model describing the thermal response for a cell containing liquid and vapor with a porous medium heated at the top ("against gravity") was developed

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

PubMed

Pino, Verónica; Afonso, Ana M

2012-02-10

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

Determination of Methane Hydrate Solubility in the Absence of Vapor Phase by in-situ Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Lu, W.; Chou, I.; Burruss, R.

2006-12-01

Prediction of the occurrence, distribution, and evolution of methane hydrate in porous marine sediments requires information on solubilities of methane hydrate in water. Solubilities of methane hydrate in the presence of a vapor phase are well established, but those in the absence of a vapor phase are not well defined with differences up to 30%. We have measured methane concentrations in pure water in equilibrium with sI methane hydrate, in the absence of vapor phase, by in-situ Raman spectroscopy at temperatures (T) from 2 to 20 (± 0.3) °C and pressures (P) at 10, 20, 30, and 40 (± 0.4%) MPa. Methane hydrate was synthesized in a high-pressure capillary optical cell (Chou et al., 2005; Advances in High-Pressure Technology for Geophysical Applications. Ed. J. Chen et al., Chapter 24, p. 475, Elsevier). A small quantity of methane was first loaded in an evacuated cell and then pressurized by water. Hydrate crystals were formed near the liquid-vapor interface near the enclosed end of the optical tube at room T, and were then placed at the center of a USGS-type heating-cooling stage. By adjusting sample P and T, the crystals went through dissolution-formation cycles three to four times in three days until the vapor phase was completely consumed and several crystals (typically 40 x 40 x 10 μm) were formed. These crystals were located at about 200 μm from the enclosed end and were about 20 to 40 μm from each other. Raman spectra were collected for the liquid phase adjacent to hydrate crystals near the enclosed end of the tube. A volumetric decrease in crystal size was observed away from the sampling spot; however, no such volumetric decrease was observed in or near the sampling spot. Therefore, equilibrium was likely established locally within the sampling area. The results are represented by the following linear isobaric equations: 10 MPa: ln [X(CH4)] = 0.06175 T - 6.79507; r2 = 0.9991 (n = 6) 20 MPa: ln [X(CH4)] = 0.06170 T - 6.82816; r2 = 0.9985 (n = 6) 30 MPa

Analytical study of the liquid phase transient behavior of a high temperature heat pipe. M.S. Thesis

NASA Technical Reports Server (NTRS)

Roche, Gregory Lawrence

1988-01-01

The transient operation of the liquid phase of a high temperature heat pipe is studied. The study was conducted in support of advanced heat pipe applications that require reliable transport of high temperature drops and significant distances under a broad spectrum of operating conditions. The heat pipe configuration studied consists of a sealed cylindrical enclosure containing a capillary wick structure and sodium working fluid. The wick is an annular flow channel configuration formed between the enclosure interior wall and a concentric cylindrical tube of fine pore screen. The study approach is analytical through the solution of the governing equations. The energy equation is solved over the pipe wall and liquid region using the finite difference Peaceman-Rachford alternating direction implicit numerical method. The continuity and momentum equations are solved over the liquid region by the integral method. The energy equation and liquid dynamics equation are tightly coupled due to the phase change process at the liquid-vapor interface. A kinetic theory model is used to define the phase change process in terms of the temperature jump between the liquid-vapor surface and the bulk vapor. Extensive auxiliary relations, including sodium properties as functions of temperature, are used to close the analytical system. The solution procedure is implemented in a FORTRAN algorithm with some optimization features to take advantage of the IBM System/370 Model 3090 vectorization facility. The code was intended for coupling to a vapor phase algorithm so that the entire heat pipe problem could be solved. As a test of code capabilities, the vapor phase was approximated in a simple manner.

"Pressure Blocking" Effect in the Growing Vapor Bubble in a Highly Superheated Liquid

NASA Astrophysics Data System (ADS)

Zudin, Yu. B.; Zenin, V. V.

2016-09-01

The problem on the growth of a vapor bubble in a liquid whose superheating enthalpy exceeds the phase transition heat has been considered. A physical model of the "pressure blocking" in the bubble is presented. The problem for the conditions of the experiment on the effervescence of a butane drop has been solved numerically. An algorithm for constructing an analytical solution of the problem on the bubble growth in a highly superheated liquid is proposed.

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

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas; Jayaraman, Arthi

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

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Metal-organic vapor phase epitaxy of (GaAl)As for 0.85-μm laser diodes

NASA Astrophysics Data System (ADS)

Jacobs, K.; Bugge, F.; Butzke, G.; Lehmann, L.; Schimko, R.

1988-11-01

Metal-organic vapor phase epitaxy was used to grow stripe heterolaser diodes that were hitherto fabricated by liquid phase epitaxy. The main relationships between the growth parameters (partial input pressures, temperatures) and the properties of materials (thicknesses, solid-solution compositions, carrier densities) were investigated. The results were in full agreement with the mechanism of growth controlled by a vapor-phase diffusion. The results achieved routinely in the growth of GaAs are reported. It is shown that double heterostructure laser diodes fabricated by metal-organic vapor phase epitaxy compete favorably with those grown so far by liquid phase epitaxy, including their degradation and reliability.

Acoustically-Enhanced Direct Contact Vapor Bubble Condensation

NASA Astrophysics Data System (ADS)

Boziuk, Thomas; Smith, Marc; Glezer, Ari

2017-11-01

Rate-limited, direct contact vapor condensation of vapor bubbles that are formed by direct steam injection through a nozzle in a quiescent subcooled liquid bath is accelerated using ultrasonic (MHz-range) actuation. A submerged, low power actuator produces an acoustic beam whose radiation pressure deforms the liquid-vapor interface, leading to the formation of a liquid spear that penetrates the vapor bubble to form a vapor torus with a significantly larger surface area and condensation rate. Ultrasonic focusing along the spear leads to the ejection of small, subcooled droplets through the vapor volume that impact the vapor-liquid interface and further enhance the condensation. High-speed Schlieren imaging of the formation and collapse of the vapor bubbles in the absence and presence of actuation shows that the impulse associated with the collapse of the toroidal volume leads to the formation of a turbulent vortex ring in the liquid phase. Liquid motions near the condensing vapor volume are investigated in the absence and presence of acoustic actuation using high-magnification PIV and show the evolution of a liquid jet through the center of the condensing toroidal volume and the formation and advection of vortex ring structures whose impulse appear to increase with temperature difference between the liquid and vapor phases. High-speed image processing is used to assess the effect of the actuation on the temporal and spatial variations in the characteristic scales and condensation rates of the vapor bubbles.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

The effect of heated vapor-phase acidification on organic carbon concentrations and isotopic values in geologic rock samples

NASA Astrophysics Data System (ADS)

Wang, R. Z.; West, A. J.; Yager, J. A.; Rollins, N.; Li, G.; Berelson, W.

2016-12-01

Carbon signatures recorded in the modern and geologic rock record can give insight on the Earth's carbon cycle through time. This is especially true for organic carbon (OC), which can help us understand how the biosphere has evolved over Earth's history. However, carbon recorded in rocks is a combination of OC and inorganic carbon (IC) mostly in the form of carbonate minerals. To measure OC, IC must therefore first be removed through a process called "decarbonation." This is often done through a leaching process with hydrochloric acid (HCl). However, three well known problems exist for the decarbonation process: 1) Incomplete removal of IC, 2) Unintentional removal of OC, and 3) Addition of false carbon blank. Currently, vapor (gas) phase removal of OC is preferred to liquid phase treatment because it has been shown that OC is lost to solubilization during liquid phase acidification. Vapor phase treatment is largely thought to avoid the problem of OC loss, but this has not yet been rigorously investigated. This study investigates that assumption and shows that vapor phase treatment can cause unintentional OC loss. We show that vapor phase treatment must be sensitive to rock type and treatment length to produce robust OC isotopic measurements and concentrations.

Phase equilibria and crystal chemistry of rubidium niobates and rubidium tantalates

NASA Technical Reports Server (NTRS)

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

1977-01-01

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

Phase-transitional Fe3O4/perfluorohexane Microspheres for Magnetic Droplet Vaporization.

PubMed

Wang, Ronghui; Zhou, Yang; Zhang, Ping; Chen, Yu; Gao, Wei; Xu, Jinshun; Chen, Hangrong; Cai, Xiaojun; Zhang, Kun; Li, Pan; Wang, Zhigang; Hu, Bing; Ying, Tao; Zheng, Yuanyi

2017-01-01

Activating droplets vaporization has become an attractive strategy for ultrasound imaging and physical therapy due to the significant increase in ultrasound backscatter signals and its ability to physically damage the tumor cells. However, the current two types of transitional droplets named after their activation methods have their respective limitations. To circumvent the limitations of these activation methods, here we report the concept of magnetic droplet vaporization (MDV) for stimuli-responsive cancer theranostics by a magnetic-responsive phase-transitional agent. This magnetic-sensitive phase-transitional agent-perfluorohexane (PFH)-loaded porous magnetic microspheres (PFH-PMMs), with high magnetic-thermal energy-transfer capability, could quickly respond to external alternating current (AC) magnetic fields to produce thermal energy and trigger the vaporization of the liquid PFH. We systematically demonstrated MDV both in vitro and in vivo. This novel trigger method with deep penetration can penetrate the air-filled viscera and trigger the vaporization of the phase-transitional agent without the need of pre-focusing lesion. This unique MDV strategy is expected to substantially broaden the biomedical applications of nanotechnology and promote the clinical treatment of tumors that are not responsive to chemical therapies.

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

PubMed Central

Domańska, Urszula

2010-01-01

A review of the relevant literature on 1-alkyl-1-methylpyrrolidinium-based ionic liquids has been presented. The phase diagrams for the binary systems of {1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [EMPYR][CF3SO3] + water, or + 1-butanol} and for the binary systems of {1-propyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [PMPYR][CF3SO3] + water, or + an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol)} have been determined at atmospheric pressure using a dynamic method. The influence of alcohol chain length was discussed for the [PMPYR][CF3SO3]. A systematic decrease in the solubility was observed with an increase of the alkyl chain length of an alcohol. (Solid + liquid) phase equilibria with complete miscibility in the liquid phase region were observed for the systems involving water and alcohols. The solubility of the ionic liquid increases as the alkyl chain length on the pyrrolidinium cation increases. The correlation of the experimental data has been carried out using the Wilson, UNIQUAC and the NRTL equations. The phase diagrams reported here have been compared to the systems published earlier with the 1-alkyl-1-methylpyrrolidinium-based ionic liquids. The influence of the cation and anion on the phase behaviour has been discussed. The basic thermal properties of pure ILs, i.e., melting temperature and the enthalpy of fusion, the solid-solid phase transition temperature and enthalpy have been measured using a differential scanning microcalorimetry technique. PMID:20480044

Empty liquid phase of colloidal ellipsoids: the role of shape and interaction anisotropy.

PubMed

Varga, Szabolcs; Meneses-Júarez, Efrain; Odriozola, Gerardo

2014-04-07

We study the effect of anisotropic excluded volume and attractive interactions on the vapor-liquid phase transition of colloidal ellipsoids. In our model, the hard ellipsoid is embedded into an ellipsoidal well, where both the shape of the hard ellipsoid and that of the added enclosing ellipsoidal well can be varied independently. The bulk properties of these particles are examined by means of a van der Waals type perturbation theory and validated with replica exchange Monte Carlo simulations. It is shown that both the critical volume fraction (ηc) and the critical temperature (Tc) of the vapor-liquid phase transition vanish with increasing shape anisotropy for oblate shapes, while ηc → 0 and Tc ≠ 0 are obtained for very elongated prolate shapes. These results suggest that the chance to stabilize empty liquids (a liquid phase with vanishing density) is higher in suspensions of rod-like colloidal ellipsoids than in those of plate-like ones.

Vapor-phase infrared laser spectroscopy: from gas sensing to forensic urinalysis.

PubMed

Bartlome, Richard; Rey, Julien M; Sigrist, Markus W

2008-07-15

Numerous gas-sensing devices are based on infrared laser spectroscopy. In this paper, the technique is further developed and, for the first time, applied to forensic urinalysis. For this purpose, a difference frequency generation laser was coupled to an in-house-built, high-temperature multipass cell (HTMC). The continuous tuning range of the laser was extended to 329 cm(-1) in the fingerprint C-H stretching region between 3 and 4 microm. The HTMC is a long-path absorption cell designed to withstand organic samples in the vapor phase (Bartlome, R.; Baer, M.; Sigrist, M. W. Rev. Sci. Instrum. 2007, 78, 013110). Quantitative measurements were taken on pure ephedrine and pseudoephedrine vapors. Despite featuring similarities, the vapor-phase infrared spectra of these diastereoisomers are clearly distinguishable with respect to a vibrational band centered at 2970.5 and 2980.1 cm(-1), respectively. Ephedrine-positive and pseudoephedrine-positive urine samples were prepared by means of liquid-liquid extraction and directly evaporated in the HTMC without any preliminary chromatographic separation. When 10 or 20 mL of ephedrine-positive human urine is prepared, the detection limit of ephedrine, prohibited in sports as of 10 microg/mL, is 50 or 25 microg/mL, respectively. The laser spectrometer has room for much improvement; its potential is discussed with respect to doping agents detection.

A Generalized Eulerian-Lagrangian Analysis, with Application to Liquid Flows with Vapor Bubbles

NASA Technical Reports Server (NTRS)

Dejong, Frederik J.; Meyyappan, Meyya

1993-01-01

Under a NASA MSFC SBIR Phase 2 effort an analysis has been developed for liquid flows with vapor bubbles such as those in liquid rocket engine components. The analysis is based on a combined Eulerian-Lagrangian technique, in which Eulerian conservation equations are solved for the liquid phase, while Lagrangian equations of motion are integrated in computational coordinates for the vapor phase. The novel aspect of the Lagrangian analysis developed under this effort is that it combines features of the so-called particle distribution approach with those of the so-called particle trajectory approach and can, in fact, be considered as a generalization of both of those traditional methods. The result of this generalization is a reduction in CPU time and memory requirements. Particle time step (stability) limitations have been eliminated by semi-implicit integration of the particle equations of motion (and, for certain applications, the particle temperature equation), although practical limitations remain in effect for reasons of accuracy. The analysis has been applied to the simulation of cavitating flow through a single-bladed section of a labyrinth seal. Models for the simulation of bubble formation and growth have been included, as well as models for bubble drag and heat transfer. The results indicate that bubble formation is more or less 'explosive'. for a given flow field, the number density of bubble nucleation sites is very sensitive to the vapor properties and the surface tension. The bubble motion, on the other hand, is much less sensitive to the properties, but is affected strongly by the local pressure gradients in the flow field. In situations where either the material properties or the flow field are not known with sufficient accuracy, parametric studies can be carried out rapidly to assess the effect of the important variables. Future work will include application of the analysis to cavitation in inducer flow fields.

Development of a wet vapor homogeneous liquid metal MHD power system

NASA Astrophysics Data System (ADS)

1989-04-01

During the period covered by this report (October 1988 to March 1989), the following work was done: the mixing stream condensation process was analyzed, and a theoretical model for simulating this process was modified. A parametric study is being conducted at the present time; the separation processes were analyzed; and the experimental system was specified and its design is at present in an advanced stage. The mixing stream condensation process was analyzed. For the parameters defined in the SOW of this project the process was found to be a mist flow direct contact condensation, where the hot gas mixture consisting of inert gas and vapor is the continuous phase, and the subcooled liquid on which the vapor is condensed if the droplets dispersed phase. Two possibilities of creating the mist flow were considered. The first, injecting the cold Liquid Metal (LM) into the Mixing Streams Condenser (MSC) entrance as a jet and breaking it into LM fragments and the fragments into droplets by momentum transfer breakup mechanism. The second, atomizing the cooled LM stream into little droplets (approximately 100 micrometers in diameter) and accelerating them by the gas. The second possibility was preferred due to its much higher heat and mass transfer surface and coefficients relative to the first one.

Vapor-Enabled Propulsion for Plasmonic Photothermal Motor at the Liquid/Air Interface.

PubMed

Meng, Fanchen; Hao, Wei; Yu, Shengtao; Feng, Rui; Liu, Yanming; Yu, Fan; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

2017-09-13

This paper explores a new propulsion mechanism that is based on the ejection of hot vapor jet to propel the motor at the liquid/air interface. For conventional photothermal motors, which mostly are driven by Marangoni effect, it is challenging to propel those motors at the surfaces of liquids with low surface tension due to the reduced Marangoni effect. With this new vapor-enabled propulsion mechanism, the motors can move rapidly at the liquid/air interface of liquids with a broad range of surface tensions. A design that can accumulate the hot vapor is further demonstrated to enhance both the propulsion force as well as the applicable range of liquids for such motors. This new propulsion mechanism will help open up new opportunities for the photothermal motors with desired motion controls at a wide range of liquid/air interfaces where hot vapor can be generated.

Phase behavior of metastable liquid silicon at negative pressure: Ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Zhao, G.; Yu, Y. J.; Yan, J. L.; Ding, M. C.; Zhao, X. G.; Wang, H. Y.

2016-04-01

Extensive first-principle molecular dynamics simulations are performed to study the phase behavior of metastable liquid Si at negative pressure. Our results show that the high-density liquid (HDL) and HDL-vapor spinodals indeed form a continuous reentrant curve and the liquid-liquid critical point seems to just coincide with its minimum. The line of density maxima also has a strong tendency to pass through this minimum. The phase behaviour of metastable liquid Si therefore tends to be a critical-point-free scenario rather than a second-critical-point one based on SW potential.

Simulation of water vapor condensation on LOX droplet surface using liquid nitrogen

NASA Technical Reports Server (NTRS)

Powell, Eugene A.

1988-01-01

The formation of ice or water layers on liquid oxygen (LOX) droplets in the Space Shuttle Main Engine (SSME) environment was investigated. Formulation of such ice/water layers is indicated by phase-equilibrium considerations under conditions of high partial pressure of water vapor (steam) and low LOX droplet temperature prevailing in the SSME preburner or main chamber. An experimental investigation was begun using liquid nitrogen as a LOX simulant. A monodisperse liquid nitrogen droplet generator was developed which uses an acoustic driver to force the stream of liquid emerging from a capillary tube to break up into a stream of regularly space uniformly sized spherical droplets. The atmospheric pressure liquid nitrogen in the droplet generator reservoir was cooled below its boiling point to prevent two phase flow from occurring in the capillary tube. An existing steam chamber was modified for injection of liquid nitrogen droplets into atmospheric pressure superheated steam. The droplets were imaged using a stroboscopic video system and a laser shadowgraphy system. Several tests were conducted in which liquid nitrogen droplets were injected into the steam chamber. Under conditions of periodic droplet formation, images of 600 micron diameter liquid nitrogen droplets were obtained with the stroboscopic video systems.

Vaporization of the prototypical ionic liquid BMImNTf₂ under equilibrium conditions: a multitechnique study.

PubMed

Brunetti, Bruno; Ciccioli, Andrea; Gigli, Guido; Lapi, Andrea; Misceo, Nicolaemanuele; Tanzi, Luana; Vecchio Ciprioti, Stefano

2014-08-07

The vaporization behaviour and thermodynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf2) were studied by combining the Knudsen Effusion Mass Loss (KEML) and Knudsen Effusion Mass Spectrometry (KEMS) techniques. KEML studies were carried out in a large temperature range (398-567) K by using effusion orifices with 0.3, 1, and 3 mm diameters. The vapor pressures so measured revealed no kinetically hindered vaporization effects and provided second-law vaporization enthalpies at the mean experimental temperatures in close agreement with literature. By exploiting the large temperature range covered, the heat capacity change associated with vaporization was estimated, resulting in a value of -66.8 J K(-1) mol(-1), much lower than that predicted from calorimetric measurements on the liquid phase and theoretical calculations on the gas phase. The conversion of the high temperature vaporization enthalpy to 298 K was discussed and the value Δ(l)(g)H(m)(298 K) = (128.6 ± 1.3) kJ mol(-1) assessed on the basis of data from literature and present work. Vapor pressure data were also processed by the third-law procedure using different estimations for the auxiliary thermal functions, and a Δ(l)(g)H(m)(298 K) consistent with the assessed value was obtained, although the overall agreement is sensitive to the accuracy of heat capacity data. KEMS measurements were carried out in the lower temperature range (393-467) K and showed that the largely prevailing ion species is BMIm(+), supporting the common view of BMImNTf2 vaporizing as individual, neutral ion pairs also under equilibrium conditions. By monitoring the mass spectrometric signal of this ion as a function of temperature, a second-law Δ(l)(g)H(m)(298 K) of 129.4 ± 7.3 kJ mol(-1) was obtained, well consistent with KEML and literature results. Finally, by combining KEML and KEMS measurements, the electron impact ionization cross section of BMIm(+) was estimated.

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Liquid-vapor rectilinear diameter revisited

NASA Astrophysics Data System (ADS)

Garrabos, Y.; Lecoutre, C.; Marre, S.; Beysens, D.; Hahn, I.

2018-02-01

In the modern theory of critical phenomena, the liquid-vapor density diameter in simple fluids is generally expected to deviate from a rectilinear law approaching the critical point. However, by performing precise scannerlike optical measurements of the position of the SF6 liquid-vapor meniscus, in an approach much closer to criticality in temperature and density than earlier measurements, no deviation from a rectilinear diameter can be detected. The observed meniscus position from far (10 K ) to extremely close (1 mK ) to the critical temperature is analyzed using recent theoretical models to predict the complete scaling consequences of a fluid asymmetry. The temperature dependence of the meniscus position appears consistent with the law of rectilinear diameter. The apparent absence of the critical hook in SF6 therefore seemingly rules out the need for the pressure scaling field contribution in the complete scaling theoretical framework in this SF6 analysis. More generally, this work suggests a way to clarify the experimental ambiguities in the simple fluids for the near-critical singularities in the density diameter.

Mid-infrared laser-absorption diagnostic for vapor-phase measurements in an evaporating n-decane aerosol

NASA Astrophysics Data System (ADS)

Porter, J. M.; Jeffries, J. B.; Hanson, R. K.

2009-09-01

A novel three-wavelength mid-infrared laser-based absorption/extinction diagnostic has been developed for simultaneous measurement of temperature and vapor-phase mole fraction in an evaporating hydrocarbon fuel aerosol (vapor and liquid droplets). The measurement technique was demonstrated for an n-decane aerosol with D 50˜3 μ m in steady and shock-heated flows with a measurement bandwidth of 125 kHz. Laser wavelengths were selected from FTIR measurements of the C-H stretching band of vapor and liquid n-decane near 3.4 μm (3000 cm -1), and from modeled light scattering from droplets. Measurements were made for vapor mole fractions below 2.3 percent with errors less than 10 percent, and simultaneous temperature measurements over the range 300 K< T<900 K were made with errors less than 3 percent. The measurement technique is designed to provide accurate values of temperature and vapor mole fraction in evaporating polydispersed aerosols with small mean diameters ( D 50<10 μ m), where near-infrared laser-based scattering corrections are prone to error.

Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: The collective-variables-based approach

NASA Astrophysics Data System (ADS)

Patsahan, O. V.; Patsahan, T. M.; Holovko, M. F.

2018-02-01

We develop a theory based on the method of collective variables to study the vapor-liquid equilibrium of asymmetric ionic fluids confined in a disordered porous matrix. The approach allows us to formulate the perturbation theory using an extension of the scaled particle theory for a description of a reference system presented as a two-component hard-sphere fluid confined in a hard-sphere matrix. Treating an ionic fluid as a size- and charge-asymmetric primitive model (PM) we derive an explicit expression for the relevant chemical potential of a confined ionic system which takes into account the third-order correlations between ions. Using this expression, the phase diagrams for a size-asymmetric PM are calculated for different matrix porosities as well as for different sizes of matrix and fluid particles. It is observed that general trends of the coexistence curves with the matrix porosity are similar to those of simple fluids under disordered confinement, i.e., the coexistence region gets narrower with a decrease of porosity and, simultaneously, the reduced critical temperature Tc* and the critical density ρi,c * become lower. At the same time, our results suggest that an increase in size asymmetry of oppositely charged ions considerably affects the vapor-liquid diagrams leading to a faster decrease of Tc* and ρi,c * and even to a disappearance of the phase transition, especially for the case of small matrix particles.

Multiphase, multicomponent phase behavior prediction

NASA Astrophysics Data System (ADS)

Dadmohammadi, Younas

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

Liquid fuel vaporizer and combustion chamber having an adjustable thermal conductor

DOEpatents

Powell, Michael R; Whyatt, Greg A; Howe, Daniel T; Fountain, Matthew S

2014-03-04

The efficiency and effectiveness of apparatuses for vaporizing and combusting liquid fuel can be improved using thermal conductors. For example, an apparatus having a liquid fuel vaporizer and a combustion chamber can be characterized by a thermal conductor that conducts heat from the combustion chamber to the vaporizer. The thermal conductor can be a movable member positioned at an insertion depth within the combustion chamber that corresponds to a rate of heat conduction from the combustion chamber to the vaporizer. The rate of heat conduction can, therefore, be adjusted by positioning the movable member at a different insertion depth.

The Competition between Liquid and Vapor Transport in Transpiring Leaves1[W][OPEN

PubMed Central

Rockwell, Fulton Ewing; Holbrook, N. Michele; Stroock, Abraham Duncan

2014-01-01

In leaves, the transpirational flux of water exits the veins as liquid and travels toward the stomata in both the vapor and liquid phases before exiting the leaf as vapor. Yet, whether most of the evaporation occurs from the vascular bundles (perivascular), from the photosynthetic mesophyll cells, or within the vicinity of the stomatal pore (peristomatal) remains in dispute. Here, a one-dimensional model of the competition between liquid and vapor transport is developed from the perspective of nonisothermal coupled heat and water molecule transport in a composite medium of airspace and cells. An analytical solution to the model is found in terms of the energy and transpirational fluxes from the leaf surfaces and the absorbed solar energy load, leading to mathematical expressions for the proportions of evaporation accounted for by the vascular, mesophyll, and epidermal regions. The distribution of evaporation in a given leaf is predicted to be variable, changing with the local environment, and to range from dominantly perivascular to dominantly peristomatal depending on internal leaf architecture, with mesophyll evaporation a subordinate component. Using mature red oak (Quercus rubra) trees, we show that the model can be solved for a specific instance of a transpiring leaf by combining gas-exchange data, anatomical measurements, and hydraulic experiments. We also investigate the effect of radiation load on the control of transpiration, the potential for condensation on the inside of an epidermis, and the impact of vapor transport on the hydraulic efficiency of leaf tissue outside the xylem. PMID:24572172

Modélisation et simulation numérique du changement de phase liquide vapeur en cavité

NASA Astrophysics Data System (ADS)

Daru, Virginie; Duluc, Marie-Christine; Le Maître, Olivier; Juric, Damir; Le Quéré, Patrick

2006-01-01

A model for the simulation of boiling flow with phase change in a closed cavity is presented. A front-tracking method is used to deal with the liquid-vapor interface. The liquid phase is incompressible while the vapor phase is weakly compressible and obeys to the perfect gas law. This model can deal with large density ratio ( ρ/ρ≃1000) flows while accounting for the saturation curve. Computations are performed on a 1D validation case, idealizing a pressure cooker. Results are compared with a low Mach number approximation. To cite this article: V. Daru et al., C. R. Mecanique 334 (2006).

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

USGS Publications Warehouse

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

2006-01-01

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

Phase Equilibria of Sn-Co-Cu Ternary System

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

Liquid-vapor transition on patterned solid surfaces in a shear flow

NASA Astrophysics Data System (ADS)

Yao, Wenqi; Ren, Weiqing

2015-12-01

Liquids on a solid surface patterned with microstructures can exhibit the Cassie-Baxter (Cassie) state and the wetted Wenzel state. The transitions between the two states and the effects of surface topography, surface chemistry as well as the geometry of the microstructures on the transitions have been extensively studied in earlier work. However, most of these work focused on the study of the free energy landscape and the energy barriers. In the current work, we consider the transitions in the presence of a shear flow. We compute the minimum action path between the Wenzel and Cassie states using the minimum action method [W. E, W. Ren, and E. Vanden-Eijnden, Commun. Pure Appl. Math. 57, 637 (2004)]. Numerical results are obtained for transitions on a surface patterned with straight pillars. It is found that the shear flow facilitates the transition from the Wenzel state to the Cassie state, while it inhibits the transition backwards. The Wenzel state becomes unstable when the shear rate reaches a certain critical value. Two different scenarios for the Wenzel-Cassie transition are observed. At low shear rate, the transition happens via nucleation of the vapor phase at the bottom of the groove followed by its growth. At high shear rate, in contrary, the nucleation of the vapor phase occurs at the top corner of a pillar. The vapor phase grows in the direction of the flow, and the system goes through an intermediate metastable state before reaching the Cassie state.

Phase transition thermodynamics of bisphenols.

PubMed

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

2014-10-16

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

Extended vapor-liquid-solid growth of silicon carbide nanowires.

PubMed

Rajesh, John Anthuvan; Pandurangan, Arumugam

2014-04-01

We developed an alloy catalytic method to explain extended vapor-liquid-solid (VLS) growth of silicon carbide nanowires (SiC NWs) by a simple thermal evaporation of silicon and activated carbon mixture using lanthanum nickel (LaNi5) alloy as catalyst in a chemical vapor deposition process. The LaNi5 alloy binary phase diagram and the phase relationships in the La-Ni-Si ternary system were play a key role to determine the growth parameters in this VLS mechanism. Different reaction temperatures (1300, 1350 and 1400 degrees C) were applied to prove the established growth process by experimentally. Scanning electron microscopy and transmission electron microscopy studies show that the crystalline quality of the SiC NWs increases with the temperature at which they have been synthesized. La-Ni alloyed catalyst particles observed on the top of the SiC NWs confirms that the growth process follows this extended VLS mechanism. The X-ray diffraction and confocal Raman spectroscopy analyses demonstrate that the crystalline structure of the SiC NWs was zinc blende 3C-SiC. Optical property of the SiC NWs was investigated by photoluminescence technique at room temperature. Such a new alloy catalytic method may be extended to synthesis other one-dimensional nanostructures.

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

PubMed

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

2016-03-01

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

Thermodynamic curvature for attractive and repulsive intermolecular forces

NASA Astrophysics Data System (ADS)

May, Helge-Otmar; Mausbach, Peter; Ruppeiner, George

2013-09-01

The thermodynamic curvature scalar R for the Lennard-Jones system is evaluated in phase space, including vapor, liquid, and solid state. We paid special attention to the investigation of R along vapor-liquid, liquid-solid, and vapor-solid equilibria. Because R is a measure of interaction strength, we traced out the line R=0 dividing the phase space into regions with effectively attractive (R<0) or repulsive (R>0) interactions. Furthermore, we analyzed the dependence of R on the strength of attraction applying a perturbation ansatz proposed by Weeks-Chandler-Anderson. Our results show clearly a transition from R>0 (for poorly repulsive interaction) to R<0 when loading attraction in the intermolecular potential.

Liquid-Phase Circulation and Mixing in Multicomponent Droplets Vaporizing in a Laminar Convective Environment

DTIC Science & Technology

1993-10-15

included an f/2.8 dual port long-distance microscope coupled to a black d•rl white CCD video camera. A long-pass filter (with a cut-off at 530 nm) was...evaporation rates of multicomponent droplets is needed for the calibration of exciplex -based vapor/liquid visualization techniques that are employed today in...Publishing Co., Houston. Texas. Hanlon. T. R.. and Melton. L. A. (1992). Exciplex fluorescence thermometry of falling hexadecane droplets. Journal of Heat

Semiempirical self-consistent polarization description of bulk water, the liquid-vapor interface, and cubic ice.

PubMed

Murdachaew, Garold; Mundy, Christopher J; Schenter, Gregory K; Laino, Teodoro; Hutter, Jürg

2011-06-16

We have applied an efficient electronic structure approach, the semiempirical self-consistent polarization neglect of diatomic differential overlap (SCP-NDDO) method, previously parametrized to reproduce properties of water clusters by Chang, Schenter, and Garrett [ J. Chem. Phys. 2008 , 128 , 164111 ] and now implemented in the CP2K package, to model ambient liquid water at 300 K (both the bulk and the liquid-vapor interface) and cubic ice at 15 and 250 K. The SCP-NDDO potential retains its transferability and good performance across the full range of conditions encountered in the clusters and the bulk phases of water. In particular, we obtain good results for the density, radial distribution functions, enthalpy of vaporization, self-diffusion coefficient, molecular dipole moment distribution, and hydrogen bond populations, in comparison to experimental measurements. © 2011 American Chemical Society

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

PubMed

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

2012-05-14

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

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

DOE PAGES

Gujral, Ankit; Gomez, Jaritza; Ruan, Shigang; ...

2017-10-04

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition.more » As a result, the structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.« less

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

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

Gujral, Ankit; Gomez, Jaritza; Ruan, Shigang

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition.more » As a result, the structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.« less

Computer simulation of liquid-vapor coexistence of confined quantum fluids

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

Trejos, Víctor M.; Gil-Villegas, Alejandro, E-mail: gil@fisica.ugto.mx; Martinez, Alejandro

2013-11-14

The liquid-vapor coexistence (LV) of bulk and confined quantum fluids has been studied by Monte Carlo computer simulation for particles interacting via a semiclassical effective pair potential V{sub eff}(r) = V{sub LJ} + V{sub Q}, where V{sub LJ} is the Lennard-Jones 12-6 potential (LJ) and V{sub Q} is the first-order Wigner-Kirkwood (WK-1) quantum potential, that depends on β = 1/kT and de Boer's quantumness parameter Λ=h/σ√(mε), where k and h are the Boltzmann's and Planck's constants, respectively, m is the particle's mass, T is the temperature of the system, and σ and ε are the LJ potential parameters. The non-conformalmore » properties of the system of particles interacting via the effective pair potential V{sub eff}(r) are due to Λ, since the LV phase diagram is modified by varying Λ. We found that the WK-1 system gives an accurate description of the LV coexistence for bulk phases of several quantum fluids, obtained by the Gibbs Ensemble Monte Carlo method (GEMC). Confinement effects were introduced using the Canonical Ensemble (NVT) to simulate quantum fluids contained within parallel hard walls separated by a distance L{sub p}, within the range 2σ ⩽ L{sub p} ⩽ 6σ. The critical temperature of the system is reduced by decreasing L{sub p} and increasing Λ, and the liquid-vapor transition is not longer observed for L{sub p}/σ < 2, in contrast to what has been observed for the classical system.« less

40 CFR 264.1057 - Standards: Valves in gas/vapor service or in light liquid -service.

Code of Federal Regulations, 2014 CFR

2014-07-01

...: Valves in gas/vapor service or in light liquid -service. (a) Each valve in gas/vapor or light liquid... 40 Protection of Environment 26 2014-07-01 2014-07-01 false Standards: Valves in gas/vapor service or in light liquid -service. 264.1057 Section 264.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 264.1057 - Standards: Valves in gas/vapor service or in light liquid -service.

Code of Federal Regulations, 2011 CFR

2011-07-01

...: Valves in gas/vapor service or in light liquid -service. (a) Each valve in gas/vapor or light liquid... 40 Protection of Environment 26 2011-07-01 2011-07-01 false Standards: Valves in gas/vapor service or in light liquid -service. 264.1057 Section 264.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 264.1057 - Standards: Valves in gas/vapor service or in light liquid -service.

Code of Federal Regulations, 2010 CFR

2010-07-01

...: Valves in gas/vapor service or in light liquid -service. (a) Each valve in gas/vapor or light liquid... 40 Protection of Environment 25 2010-07-01 2010-07-01 false Standards: Valves in gas/vapor service or in light liquid -service. 264.1057 Section 264.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 264.1057 - Standards: Valves in gas/vapor service or in light liquid -service.

Code of Federal Regulations, 2012 CFR

2012-07-01

...: Valves in gas/vapor service or in light liquid -service. (a) Each valve in gas/vapor or light liquid... 40 Protection of Environment 27 2012-07-01 2012-07-01 false Standards: Valves in gas/vapor service or in light liquid -service. 264.1057 Section 264.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 264.1057 - Standards: Valves in gas/vapor service or in light liquid -service.

Code of Federal Regulations, 2013 CFR

2013-07-01

...: Valves in gas/vapor service or in light liquid -service. (a) Each valve in gas/vapor or light liquid... 40 Protection of Environment 27 2013-07-01 2013-07-01 false Standards: Valves in gas/vapor service or in light liquid -service. 264.1057 Section 264.1057 Protection of Environment ENVIRONMENTAL...

Implementation of perturbed-chain statistical associating fluid theory (PC-SAFT), generalized (G)SAFT+cubic, and cubic-plus-association (CPA) for modeling thermophysical properties of selected 1-alkyl-3-methylimidazolium ionic liquids in a wide pressure range.

PubMed

Polishuk, Ilya

2013-03-14

This study is the first comparative investigation of predicting the isochoric and the isobaric heat capacities, the isothermal and the isentropic compressibilities, the isobaric thermal expansibilities, the thermal pressure coefficients, and the sound velocities of ionic liquids by statistical associating fluid theory (SAFT) equation of state (EoS) models and cubic-plus-association (CPA). It is demonstrated that, taking into account the high uncertainty of the literature data (excluding sound velocities), the generalized for heavy compounds version of SAFT+Cubic (GSAFT+Cubic) appears as a robust estimator of the auxiliary thermodynamic properties under consideration. In the case of the ionic liquids the performance of PC-SAFT seems to be less accurate in comparison to ordinary compounds. In particular, PC-SAFT substantially overestimates heat capacities and underestimates the temperature and pressure dependencies of sound velocities and compressibilities. An undesired phenomenon of predicting high fictitious critical temperatures of ionic liquids by PC-SAFT should be noticed as well. CPA is the less accurate estimator of the liquid phase properties, but it is advantageous in modeling vapor pressures and vaporization enthalpies of ionic liquids. At the same time, the preliminary results indicate that the inaccuracies in predicting the deep vacuum vapor pressures of ionic liquids do not influence modeling of phase equilibria in their mixtures at much higher pressures.

Vapor and liquid optical monitoring with sculptured Bragg microcavities

NASA Astrophysics Data System (ADS)

Oliva-Ramirez, Manuel; Gil-Rostra, Jorge; López-Santos, Maria C.; González-Elipe, Agustín. R.; Yubero, Francisco

2017-08-01

Sculptured porous Bragg Microcavities (BMs) formed by the successive stacking of columnar SiO2 and TiO2 thin films with zig-zag columnar microstructure are prepared by glancing angle deposition. These BMs act as wavelength dependent optical retarders. This optical behavior is attributed to a self-structuration mechanism involving a fence-bundling association of nanocolumns as observed by Focused Ion Beam Scanning Electron Microscopy. The retardance of these optically active BMs can be modulated by dynamic infiltration of their open porosity with vapors, liquids or solutions with different refractive indices. The tunable birefringence of these nanostructured photonic systems have been successfully simulated with a simple model that assumes that each layer within the BMs stack has uniaxial birefringence. This type of self-associated nanostructures has been incorporated to microfluidic chips for free label vapor and liquid sensing. Several examples of the detection performance of these chips, working either in reflection or transmission configuration, for the optical characterization of vapor and liquids of different refractive index and aqueous solutions of glucose flowing through the microfluidic chips are described.

Calculating the enthalpy of vaporization for ionic liquid clusters.

PubMed

Kelkar, Manish S; Maginn, Edward J

2007-08-16

Classical atomistic simulations are used to compute the enthalpy of vaporization of a series of ionic liquids composed of 1-alkyl-3-methylimidazolium cations paired with the bis(trifluoromethylsulfonyl)imide anion. The calculations show that the enthalpy of vaporization is lowest for neutral ion pairs. The enthalpy of vaporization increases by about 40 kJ/mol with the addition of each ion pair to the vaporizing cluster. Non-neutral clusters have much higher vaporization enthalpies than their neutral counterparts and thus are not expected to make up a significant fraction of volatile species. The enthalpy of vaporization increases slightly as the cation alkyl chain length increases and as temperature decreases. The calculated vaporization enthalpies are consistent with two sets of recent experimental measurements as well as with previous atomistic simulations.

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

USGS Publications Warehouse

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

2007-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

Liquid-phase and vapor-phase dehydration of organic/water solutions

DOEpatents

Huang, Yu [Palo Alto, CA; Ly, Jennifer [San Jose, CA; Aldajani, Tiem [San Jose, CA; Baker, Richard W [Palo Alto, CA

2011-08-23

Processes for dehydrating an organic/water solution by pervaporation or vapor separation using fluorinated membranes. The processes are particularly useful for treating mixtures containing light organic components, such as ethanol, isopropanol or acetic acid.

Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

PubMed

Poole, Colin F; Lenca, Nicole

2014-08-29

Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present. Copyright © 2014 Elsevier B.V. All rights reserved.

CFD analysis of laboratory scale phase equilibrium cell operation

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

CFD analysis of laboratory scale phase equilibrium cell operation.

PubMed

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

2017-10-01

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

Combination downflow-upflow vapor-liquid separator

DOEpatents

Kidwell, John H.; Prueter, William P.; Eaton, Andrew M.

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.

An Experimental Visualization and Image Analysis of Electrohydrodynamically Induced Vapor-Phase Silicon Oil Flow under DC Corona Discharge

NASA Astrophysics Data System (ADS)

Ohyama, Ryu-Ichiro; Fukumoto, Masaru

A DC corona discharge induced electrohydrodynamic (EHD) flow phenomenon for a multi-phase fluid containing a vapor-phase dielectric liquid in the fresh air was investigated. The experimental electrode system was a simple arrangement of needle-plate electrodes for the corona discharges and high-resistivity silicon oil was used as the vapor-phase liquid enclosure. The qualitative observation of EHD flow patterns was conducted by an optical processing on computer tomography and the time-series of discharge current pulse generations at corona discharge electrode were measured simultaneously. These experimental results were analyzed in relationship between the EHD flow motions and the current pulse generations in synchronization. The current pulses and the EHD flow motions from the corona discharge electrode presented a continuous mode similar to the ionic wind in the fresh air and an intermittent mode. In the intermittent mode, the observed EHD flow motion was synchronized with the separated discharge pulse generations. From these experimental results, it was expected that the existence of silicon oil vapor trapped charges gave an occasion to the intermittent generations of the discharge pulses and the secondary EHD flow.

Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid-vapor interface

NASA Astrophysics Data System (ADS)

Nagayama, Gyoko; Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

2015-07-01

The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid-vapor interface.

PubMed

Nagayama, Gyoko; Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

2015-07-07

The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

Intermolecular network analysis of the liquid and vapor interfaces of pentane and water: microsolvation does not trend with interfacial properties.

PubMed

Ghadar, Yasaman; Clark, Aurora E

2014-06-28

Liquid:vapor and liquid:liquid interfaces exhibit complex organizational structure and dynamics at the molecular level. In the case of water and organic solvents, the hydrophobicity of the organic, its conformational flexibility, and compressibility, all influence interfacial properties. This work compares the interfacial tension, width, molecular conformations and orientations at the vapor and aqueous liquid interfaces of two solvents, n-pentane and neopentane, whose varying molecular shapes can lead to significantly different interfacial behavior. Particular emphasis has been dedicated toward understanding how the hydrogen bond network of water responds to the pentane relative to the vapor interface and the sensitivity of the network to the individual pentane isomer and system temperature. Interfacial microsolvation of the immiscible solvents has been examined using graph theoretical methods that quantify the structure and dynamics of microsolvated species (both H2O in C5H12 and C5H12 in H2O). At room temperature, interfacial water at the pentane phase boundary is found to have markedly different organization and dynamics than at the vapor interface (as indicated by the hydrogen bond distributions and hydrogen bond persistence in solution). While the mesoscale interfacial properties (e.g. interfacial tension) are sensitive to the specific pentane isomer, the distribution and persistence of microsolvated species at the interface is nearly identical for both systems, irrespective of temperature (between 273 K and 298 K). This has important implications for understanding how properties defined by the interfacial organization are related to the underlying solvation reactions that drive formation of the phase boundary.

Vapor condensation onto a non-volatile liquid drop

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

Inci, Levent; Bowles, Richard K., E-mail: richard.bowles@usask.ca

2013-12-07

Molecular dynamics simulations of miscible and partially miscible binary Lennard–Jones mixtures are used to study the dynamics and thermodynamics of vapor condensation onto a non-volatile liquid drop in the canonical ensemble. When the system volume is large, the driving force for condensation is low and only a submonolayer of the solvent is adsorbed onto the liquid drop. A small degree of mixing of the solvent phase into the core of the particles occurs for the miscible system. At smaller volumes, complete film formation is observed and the dynamics of film growth are dominated by cluster-cluster coalescence. Mixing into the coremore » of the droplet is also observed for partially miscible systems below an onset volume suggesting the presence of a solubility transition. We also develop a non-volatile liquid drop model, based on the capillarity approximations, that exhibits a solubility transition between small and large drops for partially miscible mixtures and has a hysteresis loop similar to the one observed in the deliquescence of small soluble salt particles. The properties of the model are compared to our simulation results and the model is used to study the formulation of classical nucleation theory for systems with low free energy barriers.« less

Effects of gravity reduction on phase equilibria. Part 1: Unary and binary isostructural solids

NASA Technical Reports Server (NTRS)

Larson, D. J., Jr.

1975-01-01

Analysis of the Skylab II M553 Experiment samples resulted in the hypothesis that the reduced gravity environment was altering the melting and solidification reactions. A theoretical study was conducted to define the conditions under which such alteration of phase relations is feasible, determine whether it is restricted to space processing, and, if so, ascertain which alloy systems or phase reactions are most likely to demonstrate such effects. Phase equilibria of unary and binary systems with a single solid phase (unary and isomorphous) were considered.

Phase transformations during the growth of paracetamol crystals from the vapor phase

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.; Bordei, N. S.

2014-07-01

Phase transformations during the growth of paracetamol crystals from the vapor phase are studied by differential scanning calorimetry. It is found that the vapor-crystal phase transition is actually a superposition of two phase transitions: a first-order phase transition with variable density and a second-order phase transition with variable ordering. The latter, being a diffuse phase transition, results in the formation of a new, "pretransition," phase irreversibly spent in the course of the transition, which ends in the appearance of orthorhombic crystals. X-ray diffraction data and micrograph are presented.

Experimental technique for studying high-temperature phase equilibria in reactive molten metal based systems

NASA Astrophysics Data System (ADS)

Ermoline, Alexandre

The general objective of this work is to develop an experimental technique for studying the high-temperature phase compositions and phase equilibria in molten metal-based binary and ternary systems, such as Zr-O-N, B-N-O, Al-O, and others. A specific material system of Zr-O-N was selected for studying and testing this technique. The information about the high-temperature phase equilibria in reactive metal-based systems is scarce and their studying is difficult because of chemical reactions occurring between samples and essentially any container materials, and causing contamination of the system. Containerless microgravity experiments for studying equilibria in molten metal-gas systems were designed to be conducted onboard of a NASA KC-135 aircraft flying parabolic trajectories. A uniaxial apparatus suitable for acoustic levitation, laser heating, and splat quenching of small samples was developed and equipped with computer-based controller and optical diagnostics. Normal-gravity tests were conducted to determine the most suitable operating parameters of the levitator by direct observations of the levitated samples, as opposed to more traditional pressure mapping of the acoustic field. The size range of samples that could be reliably heated and quenched in this setup was determined to be on the order of 1--3 mm. In microgravity experiments, small spherical specimens (1--2 mm diameter), prepared as pressed, premixed solid components, ZrO2, ZrN, and Zr powders, were acoustically levitated inside an argon-filled chamber at one atmosphere and heated by a CO2 laser. The levitating samples could be continuously laser heated for about 1 sec, resulting in local sample melting. The sample stability in the vertical direction was undisturbed by simultaneous laser heating. Oscillations of the levitating sample in the horizontal direction increased while it was heated, which eventually resulted in the movement of the sample away from its stable levitation position and the laser

Numerical investigation of the pseudopotential lattice Boltzmann modeling of liquid-vapor for multi-phase flows

NASA Astrophysics Data System (ADS)

Nemati, Maedeh; Shateri Najaf Abady, Ali Reza; Toghraie, Davood; Karimipour, Arash

2018-01-01

The incorporation of different equations of state into single-component multiphase lattice Boltzmann model is considered in this paper. The original pseudopotential model is first detailed, and several cubic equations of state, the Redlich-Kwong, Redlich-Kwong-Soave, and Peng-Robinson are then incorporated into the lattice Boltzmann model. A comparison of the numerical simulation achievements on the basis of density ratios and spurious currents is used for presentation of the details of phase separation in these non-ideal single-component systems. The paper demonstrates that the scheme for the inter-particle interaction force term as well as the force term incorporation method matters to achieve more accurate and stable results. The velocity shifting method is demonstrated as the force term incorporation method, among many, with accuracy and stability results. Kupershtokh scheme also makes it possible to achieve large density ratio (up to 104) and to reproduce the coexistence curve with high accuracy. Significant reduction of the spurious currents at vapor-liquid interface is another observation. High-density ratio and spurious current reduction resulted from the Redlich-Kwong-Soave and Peng-Robinson EOSs, in higher accordance with the Maxwell construction results.

Vapor and liquid optical monitoring with sculptured Bragg microcavities

NASA Astrophysics Data System (ADS)

Oliva-Ramirez, Manuel; Gil-Rostra, Jorge; López-Santos, Maria Carmen; González-Elipe, Agustín R.; Yubero, Francisco

2017-10-01

Sculptured porous Bragg microcavities (BMs) formed by the successive stacking of columnar SiO2 and TiO2 thin films with a zig-zag columnar microstructure are prepared by glancing angle deposition. These BMs act as wavelength-dependent optical retarders. This optical behavior is attributed to a self-structuration of the stacked layers involving the lateral association of nanocolumns in the direction perpendicular to the main flux of particles during the multilayer film growth, as observed by focused ion beam scanning electron microscopy. The retardance of these optically active BMs can be modulated by dynamic infiltration of their open porosity with vapors, liquids, or solutions with different refractive indices. The tunable birefringence of these nanostructured photonic systems has been successfully simulated with a simple model that assumes that each layer within the BMs stack has uniaxial birefringence. The sculptured BMs have been incorporated as microfluidic chips for optical transduction for label-free vapor and liquid sensing. Several examples of the detection performance of these chips, working either in reflection or transmission configuration, for the optical monitoring of vapor and liquids of different refractive indices and aqueous solutions of glucose flowing through the microfluidic chips are described.

Condensation on a noncollapsing vapor bubble in a subcooled liquid

NASA Technical Reports Server (NTRS)

Baumeister, K. J.; Simoneau, R. J.

1979-01-01

An experimental procedure is presented by which an estimate can be made of the condensation coefficient on a noncollapsing stationary vapor bubble in subcooled liquid nitrogen. Film boiling from a thin wire was used to generate vapor bubbles which remain fixed to the wire at their base. A balance was established between the evaporation in the thin annular region along the wire and the condensation in the vapor bubbles.

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

ERIC Educational Resources Information Center

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

2011-01-01

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

Phase equilibrium measurements on nine binary mixtures

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

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 existsmore » 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.« less

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

NASA Technical Reports Server (NTRS)

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

1987-01-01

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

Liquid-vapor relations for the system NaCl-H2O: summary of the P-T- x surface from 300° to 500°C

USGS Publications Warehouse

Bischoff, J.L.; Pitzer, Kenneth S.

1989-01-01

Experimental data on the vapor-liquid equilibrium relations for the system NaCl-H2O were compiled and compared in order to provide an improved estimate of the P-T-x surface between 300° to 500°C, a range for which the system changes from subcritical to critical behavior. Data for the three-phase curve (halite + liquid + vapor) and the NaCl-H2O critical curve were evaluated, and the best fits for these extrema then were used to guide selection of best fit for isothermal plots for the vapor-liquid region in-between. Smoothing was carried out in an iterative procedure by replotting the best-fit data as isobars and then as isopleths, until an internally consistent set of data was obtained. The results are presented in table form that will have application to theoretical modelling and to the understanding of two-phase behavior in saline geothermal systems.

Effect of core twisting on self-assembly and optical properties of perylene bisimide dyes in solution and columnar liquid crystalline phases.

PubMed

Chen, Zhijian; Baumeister, Ute; Tschierske, Carsten; Würthner, Frank

2007-01-01

A series of highly soluble and fluorescent core-twisted perylene bisimide dyes (PBIs) 3 a-f with different substituents at the bay area (1,6,7,12 positions of the perylene core) were synthesized and fully characterized by (1)H NMR, UV/Vis spectroscopy, MS spectrometry, and elemental analysis. The pi-pi aggregation properties of these new functional dyes were investigated in detail both in solution and in condensed phase by UV/Vis and fluorescence spectroscopy, vapor pressure osmometry (VPO), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. Concentration-dependent UV/Vis measurements and VPO analysis revealed that these core-twisted pi-conjugated systems show distinct self-dimerization equilibria in apolar solvent methylcyclohexane (MCH) with dimerization constants between 1.3x10(4) and 30 M(-1). The photoluminescence spectra of the dimers of PBIs 3 a-f exhibit bathochromic shifts of quite different magnitude which could be attributed to different longitudinal or rotational offsets between the dyes as well as differences in the respective pi-pi stacking distance. In condensed state, quite a few of these PBIs form luminescent rectangular or hexagonal columnar liquid crystalline phases with low isotropization temperatures. The effects of the distortion of the pi systems on their pi-pi stacking and the optical properties of the resultant stacks in solution and in LC phases have been explored in detail. In one case (3 a) a particularly interesting phase change from crystalline into liquid crystalline could be observed upon annealing that was accompanied by a transformation from non-fluorescent H-type into strongly fluorescent J-type packing of the dyes.

Constructing a superhydrophobic surface on polydimethylsiloxane via spin coating and vapor-liquid sol-gel process.

PubMed

Peng, Yu-Ting; Lo, Kuo-Feng; Juang, Yi-Je

2010-04-06

In this study, a superhydrophobic surface on polydimethylsiloxane (PDMS) substrate was constructed via the proposed vapor-liquid sol-gel process in conjunction with spin coating of dodecyltrichlorosilane (DTS). Unlike the conventional sol-gel process where the reaction takes place in the liquid phase, layers of silica (SiO(2)) particles were formed through the reaction between the reactant spin-coated on the PDMS surface and vapor of the acid solution. This led to the SiO(2) particles inlaid on the PDMS surface. Followed by subsequent spin coating of DTS solution, the wrinkle-like structure was formed, and the static contact angle of the water droplet on the surface could reach 162 degrees with 2 degrees sliding angle and less than 5 degrees contact angle hysteresis. The effect of layers of SiO(2) particles, concentrations of DTS solution and surface topography on superhydrophobicity of the surface is discussed.

Small-scale experimental study of vaporization flux of liquid nitrogen released on water.

PubMed

Gopalaswami, Nirupama; Olewski, Tomasz; Véchot, Luc N; Mannan, M Sam

2015-10-30

A small-scale experimental study was conducted using liquid nitrogen to investigate the convective heat transfer behavior of cryogenic liquids released on water. The experiment was performed by spilling five different amounts of liquid nitrogen at different release rates and initial water temperatures. The vaporization mass fluxes of liquid nitrogen were determined directly from the mass loss measured during the experiment. A variation of initial vaporization fluxes and a subsequent shift in heat transfer mechanism were observed with changes in initial water temperature. The initial vaporization fluxes were directly dependent on the liquid nitrogen spill rate. The heat flux from water to liquid nitrogen determined from experimental data was validated with two theoretical correlations for convective boiling. It was also observed from validation with correlations that liquid nitrogen was found to be predominantly in the film boiling regime. The substantial results provide a suitable procedure for predicting the heat flux from water to cryogenic liquids that is required for source term modeling. Copyright © 2015 Elsevier B.V. All rights reserved.

Condensation of acetol and acetic acid vapor with sprayed liquid

USDA-ARS?s Scientific Manuscript database

A cellulose-derived fraction of biomass pyrolysis vapor was simulated by evaporating acetol and acetic acid (AA) from flasks on a hot plate. The liquid in the flasks was infused with heated nitrogen. The vapor/nitrogen stream was superheated in a tube oven and condensed by contact with a cloud of ...

40 CFR 265.1057 - Standards: Valves in gas/vapor service or in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

....1057 Standards: Valves in gas/vapor service or in light liquid service. (a) Each valve in gas/vapor or... 40 Protection of Environment 26 2011-07-01 2011-07-01 false Standards: Valves in gas/vapor service or in light liquid service. 265.1057 Section 265.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 265.1057 - Standards: Valves in gas/vapor service or in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

....1057 Standards: Valves in gas/vapor service or in light liquid service. (a) Each valve in gas/vapor or... 40 Protection of Environment 25 2010-07-01 2010-07-01 false Standards: Valves in gas/vapor service or in light liquid service. 265.1057 Section 265.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 265.1057 - Standards: Valves in gas/vapor service or in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

....1057 Standards: Valves in gas/vapor service or in light liquid service. (a) Each valve in gas/vapor or... 40 Protection of Environment 27 2012-07-01 2012-07-01 false Standards: Valves in gas/vapor service or in light liquid service. 265.1057 Section 265.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 265.1057 - Standards: Valves in gas/vapor service or in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

....1057 Standards: Valves in gas/vapor service or in light liquid service. (a) Each valve in gas/vapor or... 40 Protection of Environment 27 2013-07-01 2013-07-01 false Standards: Valves in gas/vapor service or in light liquid service. 265.1057 Section 265.1057 Protection of Environment ENVIRONMENTAL...

40 CFR 265.1057 - Standards: Valves in gas/vapor service or in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

....1057 Standards: Valves in gas/vapor service or in light liquid service. (a) Each valve in gas/vapor or... 40 Protection of Environment 26 2014-07-01 2014-07-01 false Standards: Valves in gas/vapor service or in light liquid service. 265.1057 Section 265.1057 Protection of Environment ENVIRONMENTAL...

Liquid phase evaporation on the normal shock wave in moist air transonic flows in nozzles

NASA Astrophysics Data System (ADS)

Dykas, Sławomir; Szymański, Artur; Majkut, Mirosław

2017-06-01

This paper presents a numerical analysis of the atmospheric air transonic flow through de Laval nozzles. By nature, atmospheric air always contains a certain amount of water vapor. The calculations were made using a Laval nozzle with a high expansion rate and a convergent-divergent (CD) "half-nozzle", referred to as a transonic diffuser, with a much slower expansion rate. The calculations were performed using an in-house CFD code. The computational model made it possible to simulate the formation of the liquid phase due to spontaneous condensation of water vapor contained in moist air. The transonic flow calculations also take account of the presence of a normal shock wave in the nozzle supersonic part to analyze the effect of the liquid phase evaporation.

Dispersive micro-solid phase extraction combined with dispersive liquid-liquid microextraction for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Chen, Shizhong; Zhu, Shengping; Lu, Dengbo

2018-01-01

A method was developed for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after preconcentration/separation using dispersive micro-solid phase extraction (DMSPE) and dispersive liquid-liquid micro-extraction (DLLME). In DMSPE, titanium dioxide nanofibers were used for preconcentration and separation of analytes. The upper aqueous phase and elution solution from DMSPE were used for further preconcentration and separation of Sb(III) and Sb(V) by DLLME without any pre-oxidation or pre-reduction operation, respectively. The extracts from DLLME were used for ETV-ICP-MS determination with APDC as a chemical modifier. Under optimal conditions, the detection limits of this method were 0.019 and 0.025 pg mL- 1 with relative standard deviations of 5.7% and 6.9% for Sb(III) and Sb(V) (c = 1.0 ng mL- 1, n = 9), respectively. This method was applied for speciation analysis of Sb and its distribution in the tea leaves and the tea infusion, including total, suspended, soluble, organic and inorganic Sb as well as Sb(III) and Sb(V). The results showed that the contents of Sb are 62.7, 12.9 and 47.3 ng g- 1 in the tea leaves, tea residue and tea soup, respectively; those of soluble, organic, inorganic, Sb(III) and Sb(V) are 0.41, 0.11, 0.29, 0.21 and 0.07 ng mL- 1 in the tea soup, respectively. A certified reference material of tea leaves (GBW 07605) was analyzed by this method with satisfactory results.

n-Type Doping of Vapor-Liquid-Solid Grown GaAs Nanowires.

PubMed

Gutsche, Christoph; Lysov, Andrey; Regolin, Ingo; Blekker, Kai; Prost, Werner; Tegude, Franz-Josef

2011-12-01

In this letter, n-type doping of GaAs nanowires grown by metal-organic vapor phase epitaxy in the vapor-liquid-solid growth mode on (111)B GaAs substrates is reported. A low growth temperature of 400°C is adjusted in order to exclude shell growth. The impact of doping precursors on the morphology of GaAs nanowires was investigated. Tetraethyl tin as doping precursor enables heavily n-type doped GaAs nanowires in a relatively small process window while no doping effect could be found for ditertiarybutylsilane. Electrical measurements carried out on single nanowires reveal an axially non-uniform doping profile. Within a number of wires from the same run, the donor concentrations ND of GaAs nanowires are found to vary from 7 × 10(17) cm(-3) to 2 × 10(18) cm(-3). The n-type conductivity is proven by the transfer characteristics of fabricated nanowire metal-insulator-semiconductor field-effect transistor devices.

IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively.

PubMed

Ni, Yicun; Skinner, J L

2015-07-07

Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm(-1) and a positive band centered at 1670 cm(-1). We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.

IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

NASA Astrophysics Data System (ADS)

Ni, Yicun; Skinner, J. L.

2015-07-01

Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm-1 and a positive band centered at 1670 cm-1. We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.

IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

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

Ni, Yicun; Skinner, J. L.

Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFGmore » spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm{sup −1} and a positive band centered at 1670 cm{sup −1}. We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.« less

Semi-empirical correlation for binary interaction parameters of the Peng-Robinson equation of state with the van der Waals mixing rules for the prediction of high-pressure vapor-liquid equilibrium.

PubMed

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

2013-03-01

Peng-Robinson 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 Huron-Vidal 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.

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

An assessment of the liquid-gas partitioning behavior of major wastewater odorants using two comparative experimental approaches: liquid sample-based vaporization vs. impinger-based dynamic headspace extraction into sorbent tubes.

PubMed

Iqbal, Mohammad Asif; Kim, Ki-Hyun; Szulejko, Jan E; Cho, Jinwoo

2014-01-01

The gas-liquid partitioning behavior of major odorants (acetic acid, propionic acid, isobutyric acid, n-butyric acid, i-valeric acid, n-valeric acid, hexanoic acid, phenol, p-cresol, indole, skatole, and toluene (as a reference)) commonly found in microbially digested wastewaters was investigated by two experimental approaches. Firstly, a simple vaporization method was applied to measure the target odorants dissolved in liquid samples with the aid of sorbent tube/thermal desorption/gas chromatography/mass spectrometry. As an alternative method, an impinger-based dynamic headspace sampling method was also explored to measure the partitioning of target odorants between the gas and liquid phases with the same detection system. The relative extraction efficiency (in percent) of the odorants by dynamic headspace sampling was estimated against the calibration results derived by the vaporization method. Finally, the concentrations of the major odorants in real digested wastewater samples were also analyzed using both analytical approaches. Through a parallel application of the two experimental methods, we intended to develop an experimental approach to be able to assess the liquid-to-gas phase partitioning behavior of major odorants in a complex wastewater system. The relative sensitivity of the two methods expressed in terms of response factor ratios (RFvap/RFimp) of liquid standard calibration between vaporization and impinger-based calibrations varied widely from 981 (skatole) to 6,022 (acetic acid). Comparison of this relative sensitivity thus highlights the rather low extraction efficiency of the highly soluble and more acidic odorants from wastewater samples in dynamic headspace sampling.

Adsorptive Water Removal from Dichloromethane and Vapor-Phase Regeneration of a Molecular Sieve 3A Packed Bed

PubMed Central

2017-01-01

The drying of dichloromethane with a molecular sieve 3A packed bed process is modeled and experimentally verified. In the process, the dichloromethane is dried in the liquid phase and the adsorbent is regenerated by water desorption with dried dichloromethane product in the vapor phase. Adsorption equilibrium experiments show that dichloromethane does not compete with water adsorption, because of size exclusion; the pure water vapor isotherm from literature provides an accurate representation of the experiments. The breakthrough curves are adequately described by a mathematical model that includes external mass transfer, pore diffusion, and surface diffusion. During the desorption step, the main heat transfer mechanism is the condensation of the superheated dichloromethane vapor. The regeneration time is shortened significantly by external bed heating. Cyclic steady-state experiments demonstrate the feasibility of this novel, zero-emission drying process. PMID:28539701

Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system

NASA Technical Reports Server (NTRS)

Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.

1989-01-01

Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.

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

PubMed

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

2017-11-08

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

A nonadditive methanol force field: Bulk liquid and liquid-vapor interfacial properties via molecular dynamics simulations using a fluctuating charge model

NASA Astrophysics Data System (ADS)

Patel, Sandeep; Brooks, Charles L.

2005-01-01

We study the bulk and interfacial properties of methanol via molecular dynamics simulations using a CHARMM (Chemistry at HARvard Molecular Mechanics) fluctuating charge force field. We discuss the parametrization of the electrostatic model as part of the ongoing CHARMM development for polarizable protein force fields. The bulk liquid properties are in agreement with available experimental data and competitive with existing fixed-charge and polarizable force fields. The liquid density and vaporization enthalpy are determined to be 0.809 g/cm3 and 8.9 kcal/mol compared to the experimental values of 0.787 g/cm3 and 8.94 kcal/mol, respectively. The liquid structure as indicated by radial distribution functions is in keeping with the most recent neutron diffraction results; the force field shows a slightly more ordered liquid, necessarily arising from the enhanced condensed phase electrostatics (as evidenced by an induced liquid phase dipole moment of 0.7 D), although the average coordination with two neighboring molecules is consistent with the experimental diffraction study as well as with recent density functional molecular dynamics calculations. The predicted surface tension of 19.66±1.03 dyn/cm is slightly lower than the experimental value of 22.6 dyn/cm, but still competitive with classical force fields. The interface demonstrates the preferential molecular orientation of molecules as observed via nonlinear optical spectroscopic methods. Finally, via canonical molecular dynamics simulations, we assess the model's ability to reproduce the vapor-liquid equilibrium from 298 to 423 K, the simulation data then used to obtain estimates of the model's critical temperature and density. The model predicts a critical temperature of 470.1 K and critical density of 0.312 g/cm3 compared to the experimental values of 512.65 K and 0.279 g/cm3, respectively. The model underestimates the critical temperature by 8% and overestimates the critical density by 10%, and in this sense

Surface vibrational structure at alkane liquid/vapor interfaces

NASA Astrophysics Data System (ADS)

Esenturk, Okan; Walker, Robert A.

2006-11-01

Broadband vibrational sum frequency spectroscopy (VSFS) has been used to examine the surface structure of alkane liquid/vapor interfaces. The alkanes range in length from n-nonane (C9H20) to n-heptadecane (C17H36), and all liquids except heptadecane are studied at temperatures well above their bulk (and surface) freezing temperatures. Intensities of vibrational bands in the CH stretching region acquired under different polarization conditions show systematic, chain length dependent changes. Data provide clear evidence of methyl group segregation at the liquid/vapor interface, but two different models of alkane chain structure can predict chain length dependent changes in band intensities. Each model leads to a different interpretation of the extent to which different chain segments contribute to the anisotropic interfacial region. One model postulates that changes in vibrational band intensities arise solely from a reduced surface coverage of methyl groups as alkane chain length increases. The additional methylene groups at the surface must be randomly distributed and make no net contribution to the observed VSF spectra. The second model considers a simple statistical distribution of methyl and methylene groups populating a three dimensional, interfacial lattice. This statistical picture implies that the VSF signal arises from a region extending several functional groups into the bulk liquid, and that the growing fraction of methylene groups in longer chain alkanes bears responsibility for the observed spectral changes. The data and resulting interpretations provide clear benchmarks for emerging theories of molecular structure and organization at liquid surfaces, especially for liquids lacking strong polar ordering.

Saturated liquid density of 1,1-difluoroethane(R 152a) and thermodynamic properties along the vapor-liquid coexistence curve

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

Sato, H.; Okada, M.; Uematsu, M.

1987-01-01

Saturated liquid densities of 1,1-difluoroethane (CH/sub 3/CHF/sub 2/) are measured at temperatures from 223 K to 363 K with the estimated uncertainty of +-0.2% by a magnetic densimetry. The experimental results are compared with the available experimental data and some correlations and equations of state. A simple correlation for the saturated liquid density is developed as a function of temperature. This correlation covers the temperature range up to the critical point which reproduces the present experimental results with the percent means deviation of 0.11%. Adding the available experimental data with respect to the vapor pressure, critical parameters, saturated vapor density,more » and the second virial coefficient to the present saturated liquid density data, the parameters of the Redlich-Kwong-Soave equation of state are determined and the thermodynamic properties along the vapor-liquid coexistence curve are derived.« less

Buoyancy effects on the vapor condensation rate on a horizontal liquid surface

NASA Technical Reports Server (NTRS)

Hasan, Mohammad M.; Lin, Chin-Shun

1989-01-01

The results are presented of a numerical study of the effects of buoyancy on the direct condensation of saturated or nearly saturated vapor on a horizontal liquid surface in a cylindrical tank. The liquid motion beneath the liquid-vapor interface is induced by an axisymmetric laminar jet of subcooled liquid. Analysis and numerical results show that the dominant parameter which determines the influence of buoyancy on the condensation rate is the Richardson number. However, the effect of buoyancy on the condensation rate cannot be quantified in terms of the Richardson number alone. The critical value of the Richardson number below which the condensation rate is not significantly reduced depends on the Reynolds number as well as the Prandtl number.

Investigating Vaporization of Silica through Laser Driven Shock Wave Experiments

NASA Astrophysics Data System (ADS)

Kraus, R. G.; Swift, D. C.; Stewart, S. T.; Smith, R.; Bolme, C. A.; Spaulding, D. K.; Hicks, D.; Eggert, J.; Collins, G.

2010-12-01

Giant impacts melt and vaporize a significant amount of the bolide and target body. However, our ability to determine how much melt or vapor a given impact creates depends strongly on our understanding of the liquid-vapor phase boundary of geologic materials. Our current knowledge of the liquid-vapor equilibrium for one of the most important minerals, SiO2, is rather limited due to the difficulty of performing experiments in this area of phase space. In this study, we investigate the liquid-vapor coexistence region by shocking quartz into a supercritical fluid state and allowing it to adiabatically expand to a state on the liquid-vapor phase boundary. Although shock compression and release has been used to study the liquid-vapor equilibrium of metals [1], few attempts have been made at studying geologic materials by this method [2]. Shock waves were produced by direct ablation of the quartz sample using the Jupiter Laser Facility of Lawrence Livermore National Laboratory. Steady shock pressures of 120-360 GPa were produced in the quartz samples: high enough to force the quartz into a supercritical fluid state. As the shock wave propagates through the sample, we measure the shock velocity using a line imaging velocity interferometer system for any reflector (VISAR) and shock temperature using a streaked optical pyrometer (SOP). When the shock wave reaches the free surface of the sample, the material adiabatically expands. Upon breakout of the shock at the free surface, the SOP records a distinct drop in radiance due to the lower temperature of the expanded material. For a subset of experiments, a LiF window is positioned downrange of the expanding silica. When the expanding silica impacts the LiF window, the velocity at the interface between the expanding silica and LiF window is measured using the VISAR. From the shock velocity measurements, we accurately determine the shocked state in the quartz. The post-shock radiance measurements are used to constrain the

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Passive Vaporizing Heat Sink

NASA Technical Reports Server (NTRS)

Knowles, TImothy R.; Ashford, Victor A.; Carpenter, Michael G.; Bier, Thomas M.

2011-01-01

A passive vaporizing heat sink has been developed as a relatively lightweight, compact alternative to related prior heat sinks based, variously, on evaporation of sprayed liquids or on sublimation of solids. This heat sink is designed for short-term dissipation of a large amount of heat and was originally intended for use in regulating the temperature of spacecraft equipment during launch or re-entry. It could also be useful in a terrestrial setting in which there is a requirement for a lightweight, compact means of short-term cooling. This heat sink includes a hermetic package closed with a pressure-relief valve and containing an expendable and rechargeable coolant liquid (e.g., water) and a conductive carbon-fiber wick. The vapor of the liquid escapes when the temperature exceeds the boiling point corresponding to the vapor pressure determined by the setting of the pressure-relief valve. The great advantage of this heat sink over a melting-paraffin or similar phase-change heat sink of equal capacity is that by virtue of the =10x greater latent heat of vaporization, a coolant-liquid volume equal to =1/10 of the paraffin volume can suffice.

Optimization of the freezing process for hematopoietic progenitor cells: effect of precooling, initial dimethyl sulfoxide concentration, freezing program, and storage in vapor-phase or liquid nitrogen on in vitro white blood cell quality.

PubMed

Dijkstra-Tiekstra, Margriet J; Setroikromo, Airies C; Kraan, Marcha; Gkoumassi, Effimia; de Wildt-Eggen, Janny

2014-12-01

Adding dimethyl sulfoxide (DMSO) to hematopoietic progenitor cells (HPCs) causes an exothermic reaction, potentially affecting their viability. The freezing method might also influence this. The aim was to investigate the effect of 1) precooling of DMSO and plasma (D/P) and white blood cell (WBC)-enriched product, 2) DMSO concentration of D/P, 3) freezing program, and 4) storage method on WBC quality. WBC-enriched product without CD34+ cells was used instead of HPCs. This was divided into six or eight portions. D/P (20 or 50%; precooled or room temperature [RT]) was added to the WBC-enriched product (precooled or RT), resulting in 10% DMSO, while monitoring temperature. The product was frozen using controlled-rate freezing ("fast-rate" or "slow-rate") and placed in vapor-phase or liquid nitrogen. After thawing, WBC recovery and viability were determined. Temperature increased most for precooled D/P to precooled WBC-enriched product, without influence of 20 or 50% D/P, but remained for all variations below 30°C. WBC recovery for both freezing programs was more than 95%. Recovery of WBC viability was higher for slow-rate freezing compared to fast-rate freezing (74% vs. 61%; p < 0.05) and also for 50% compared to 20% D/P (two test variations). Effect of precooling D/P or WBC-enriched product and of storage in vapor-phase or liquid nitrogen was marginal. Based on these results, precooling is not necessary. Fifty percent D/P is preferred over 20% D/P. Slow-rate freezing is preferred over fast-rate freezing. For safety reasons storage in vapor-phase nitrogen is preferred over storage in liquid nitrogen. Additional testing using real HPCs might be necessary. © 2014 AABB.

Composition, diffusion, and antifungal activity of black mustard (Brassica nigra) essential oil when applied by direct addition or vapor phase contact.

PubMed

Mejía-Garibay, Beatriz; Palou, Enrique; López-Malo, Aurelio

2015-04-01

In this study, we characterized the essential oil (EO) of black mustard (Brassica nigra) and quantified its antimicrobial activity, when applied by direct contact into the liquid medium or by exposure in the vapor phase (in laboratory media or in a bread-type product), against the growth of Aspergillus niger, Aspergillus ochraceus, or Penicillium citrinum. Allyl-isothiocyanate (AITC) was identified as the major component of B. nigra EO with a concentration of 378.35 mg/ml. When B. nigra EO was applied by direct contact into the liquid medium, it inhibited the growth of A. ochraceus and P. citrinum when the concentration was 2 μl/ml of liquid medium (MIC), while for A. niger, a MIC of B. nigra EO was 4 μl/ml of liquid medium. Exposure of molds to B. nigra EO in vapor phase showed that 41.1 μl of B. nigra EO per liter of air delayed the growth of P. citrinum and A. niger by 10 days, while A. ochraceus growth was delayed for 20 days. Exposure to concentrations ≥ 47 μl of B. nigra EO per liter of air (MIC) inhibited the growth of tested molds by 30 days, and they were not able to recover after further incubation into an environment free of EO (fungicidal effect). Adsorbed AITC was quantified by exposing potato dextrose agar to B. nigra EO in a vapor phase, exhibiting that AITC was retained at least 5 days when testing EO at its MIC or with higher concentrations. Mustard EO MIC was also effective against the evaluated molds inhibiting their growth for 30 days in a bread-type product when exposed to EO by vapor contact, demonstrating its antifungal activity.

Motion of liquid plugs between vapor bubbles in capillary tubes: a comparison between fluids

NASA Astrophysics Data System (ADS)

Bertossi, Rémi; Ayel, Vincent; Mehta, Balkrishna; Romestant, Cyril; Bertin, Yves; Khandekar, Sameer

2017-11-01

Pulsating heat pipes (PHP) are now well-known devices in which liquid/vapor slug flow oscillates in a capillary tube wound between hot and cold sources. In this context, this paper focuses on the motion of the liquid plug, trapped between vapor bubbles, moving in capillary tubes, to try to better understand the thermo-physical phenomena involved in such devices. This study is divided into three parts. In the first part, an experimental study presents the evolution of the vapor pressure during the evaporation process of a liquid thin film deposited from a liquid plug flowing in a heated capillary tube: it is found that the behavior of the generated and removed vapor can be very different, according to the thermophysical properties of the fluids. In the second part, a transient model allows to compare, in terms of pressure and duration, the motion of a constant-length liquid plug trapped between two bubbles subjected to a constant difference of vapor pressure: the results highlight that the performances of the four fluids are also very different. Finally, a third model that can be considered as an improvement of the second one, is also presented: here, the liquid slug is surrounded by two vapor bubbles, one subjected to evaporation, the pressure in both bubbles is now a result of the calculation. This model still allows comparing the behaviors of the fluid. Even if our models are quite far from a complete model of a real PHP, results do indicate towards the applicability of different fluids as suitable working fluids for PHPs, particularly in terms of the flow instabilities which they generate.

Formation, structure, and evolution of boiling nucleus and interfacial tension between bulk liquid phase and nucleus

NASA Astrophysics Data System (ADS)

Wang, Xiao-Dong; Peng, Xiao-Feng; Tian, Yong; Wang, Bu-Xuan

2005-05-01

In this paper, the concept of the molecular free path is introduced to derive a criterion distinguishing active molecules from inactive molecules in liquid phase. A concept of the critical aggregation concentration (CAC) of active molecules is proposed to describe the physical configuration before the formation of a nucleus during vapor-liquid phase transition. All active molecules exist as monomers when the concentration of active molecules is lower than CAC, while the active molecules will generate aggregation once the concentration of the active molecules reaches CAC. However, these aggregates with aggregation number, N, smaller than five can steadily exist in bulk phase. The other excess active molecules can only produce infinite aggregation and form a critical nucleus of vapor-liquid phase transition. Without any outer perturbation the state point of CAC corresponds to the critical superheated or supercooled state. Meanwhile, a model of two-region structure of a nucleus is proposed to describe nucleus evolution. The interfacial tension between bulk liquid phase and nucleus is dependent of the density gradient in the transition region and varies with the structure change of the transition region. With the interfacial tension calculated using this model, the predicted nucleation rate is very close to the experimental measurement. Furthermore, this model and associated analysis provides solid theoretical evidences to clarify the definition of nucleation rate and understand nucleation phenomenon with the insight into the physical nature.

Structure, Hydrodynamics, and Phase Transition of Freely Suspended Liquid Crystals

NASA Technical Reports Server (NTRS)

Clark, Noel A.

2000-01-01

Smectic liquid crystals are phases of rod shaped molecules organized into one dimensionally (1D) periodic arrays of layers, each layer being between one and two molecular lengths thick. In the least ordered smectic phases, the smectics A and C, each layer is a two dimensional (2D) liquid. Additionally there are a variety of more ordered smectic phases having hexatic short range translational order or 2D crystalline quasi long range translational order within the layers. The inherent fluid-layer structure and low vapor pressure of smectic liquid crystals enable the long term stabilization of freely suspended, single component, layered fluid films as thin as 30A, a single molecular layer. The layering forces the films to be an integral number of smectic layers thick, quantizing their thickness in layer units and forcing a film of a particular number of layers to be physically homogeneous with respect to its layer structure over its entire area. Optical reflectivity enables the precise determination of the number of layers. These ultrathin freely suspended liquid crystal films are structures of fundamental interest in condensed matter and fluid physics. They are the thinnest known stable condensed phase fluid structures and have the largest surface-to-volume ratio of any stable fluid preparation, making them ideal for the study of the effects of reduced dimensionality on phase behavior and on fluctuation and interface phenomena. Their low vapor pressure and quantized thickness enable the effective use of microgravity to extend the study of basic capillary phenomena to ultrathin fluid films. Freely suspended films have been a wellspring of new liquid crystal physics. They have been used to provide unique experimental conditions for the study of condensed phase transitions in two dimensions. They are the only system in which the hexatic has been unambiguously identified as a phase of matter, and the only physical system in which fluctuations of a 2D XY system and

Molecular dynamics of the water liquid-vapor interface

NASA Technical Reports Server (NTRS)

Wilson, M. A.; Pohorille, A.; Pratt, L. R.; MacElroy, R. D. (Principal Investigator)

1987-01-01

The results of molecular dynamics calculations on the equilibrium interface between liquid water and its vapor at 325 K are presented. For the TIP4P model of water intermolecular pair potentials, the average surface dipole density points from the vapor to the liquid. The most common orientations of water molecules have the C2 nu molecular axis roughly parallel to the interface. The distributions are quite broad and therefore compatible with the intermolecular correlations characteristic of bulk liquid water. All near-neighbor pairs in the outermost interfacial layers are hydrogen bonded according to the common definition adopted here. The orientational preferences of water molecules near a free surface differ from those near rigidly planar walls which can be interpreted in terms of patterns found in hexagonal ice 1. The mean electric field in the interfacial region is parallel to the mean polarization which indicates that attention cannot be limited to dipolar charge distributions in macroscopic descriptions of the electrical properties of this interface. The value of the surface tension obtained is 132 +/- 46 dyn/cm, significantly different from the value for experimental water of 68 dyn/cm at 325 K.

Characterization of van der Waals type bimodal,- lambda,- meta- and spinodal phase transitions in liquid mixtures, solid suspensions and thin films.

PubMed

Rosenholm, Jarl B

2018-03-01

The perfect gas law is used as a reference when selecting state variables (P, V, T, n) needed to characterize ideal gases (vapors), liquids and solids. Van der Waals equation of state is used as a reference for models characterizing interactions in liquids, solids and their mixtures. Van der Waals loop introduces meta- and unstable states between the observed gas (vapor)-liquid P-V transitions at low T. These intermediate states are shown to appear also between liquid-liquid, liquid-solid and solid-solid phase transitions. First-order phase transitions are characterized by a sharp discontinuity of first-order partial derivatives (P, S, V) of Helmholtz and Gibbs free energies. Second-order partial derivatives (K T , B, C V , C P , E) consist of a static contribution relating to second-order phase transitions and a relaxation contribution representing the degree of first-order phase transitions. Bimodal (first-order) and spinodal (second-order) phase boundaries are used to separate stable phases from metastable and unstable phases. The boundaries are identified and quantified by partial derivatives of molar Gibbs free energy or chemical potentials with respect to P, S, V and composition (mole fractions). Molecules confined to spread Langmuir monolayers or adsorbed Gibbs monolayers are characterized by equation of state and adsorption isotherms relating to a two-dimensional van der Waals equation of state. The basic work of two-dimensional wetting (cohesion, adsorption, spreading, immersion), have to be adjusted by a horizontal surface pressure in the presence of adsorbed vapor layers. If the adsorption is extended to liquid films a vertical surface pressure (Π) may be added to account for the lateral interaction, thus restoring PV = ΠAh dependence of thin films. Van der Waals attraction, Coulomb repulsion and structural hydration forces contribute to the vertical surface pressure. A van der Waals type coexistence of ordered (dispersed) and disordered

Using Dalton's Law of Partial Pressures to Determine the Vapor Pressure of a Volatile Liquid

ERIC Educational Resources Information Center

Hilgeman, Fred R.; Bertrand, Gary; Wilson, Brent

2007-01-01

This experiment, designed for a general chemistry laboratory, illustrates the use of Dalton's law of partial pressures to determine the vapor pressure of a volatile liquid. A predetermined volume of air is injected into a calibrated tube filled with a liquid whose vapor pressure is to be measured. The volume of the liquid displaced is greater than…

On The Validity of the Assumed PDF Method for Modeling Binary Mixing/Reaction of Evaporated Vapor in GAS/Liquid-Droplet Turbulent Shear Flow

NASA Technical Reports Server (NTRS)

Miller, R. S.; Bellan, J.

1997-01-01

An Investigation of the statistical description of binary mixing and/or reaction between a carrier gas and an evaporated vapor species in two-phase gas-liquid turbulent flows is perfomed through both theroetical analysis and comparisons with results from direct numerical simulations (DNS) of a two-phase mixing layer.

Liquid-vapor interface locations in a spheroidal container under low gravity

NASA Technical Reports Server (NTRS)

Carney, M. J.

1986-01-01

As a part of the general study of liquid behavior in low gravity environments, an experimental investigation was conducted to determine if there are equilibrium liquid-vapor interface configurations that can exist at more than one location in oblate spheroidal containers under reduced gravity conditions. Static contact angles of the test liquids on the spheroid surface were restricted to near 0 deg. The experiments were conducted in a low gravity environment. An oblate spheroidal tank was tested with an eccentricity of 0.68 and a semimajor axis of 2.0 cm. Both quantitative and qualitative data were obtained on the liquid-vapor interface configuration and position inside the container. The results of these data, and their impat on previous work in this area, are discussed. Of particular interest are those equilibrium interface configurations that can exist at multiple locations in the container.

40 CFR 63.1027 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Standards § 63.1027 Connectors in gas and vapor service and in light liquid service standards. (a..., the owner or operator shall monitor all connectors in gas and vapor and light liquid service as... 40 Protection of Environment 10 2011-07-01 2011-07-01 false Connectors in gas and vapor service...

40 CFR 63.1027 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards § 63.1027 Connectors in gas and vapor service and in light liquid service standards. (a..., the owner or operator shall monitor all connectors in gas and vapor and light liquid service as... 40 Protection of Environment 10 2010-07-01 2010-07-01 false Connectors in gas and vapor service...

40 CFR 63.1027 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Standards § 63.1027 Connectors in gas and vapor service and in light liquid service standards. (a..., the owner or operator shall monitor all connectors in gas and vapor and light liquid service as... 40 Protection of Environment 11 2014-07-01 2014-07-01 false Connectors in gas and vapor service...

40 CFR 63.1027 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Standards § 63.1027 Connectors in gas and vapor service and in light liquid service standards. (a..., the owner or operator shall monitor all connectors in gas and vapor and light liquid service as... 40 Protection of Environment 11 2012-07-01 2012-07-01 false Connectors in gas and vapor service...

40 CFR 63.1027 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Standards § 63.1027 Connectors in gas and vapor service and in light liquid service standards. (a..., the owner or operator shall monitor all connectors in gas and vapor and light liquid service as... 40 Protection of Environment 11 2013-07-01 2013-07-01 false Connectors in gas and vapor service...

Pressurization of a Flightweight, Liquid Hydrogen Tank: Evaporation and Condensation at a Liquid Vapor Interface

NASA Technical Reports Server (NTRS)

Stewart, Mark

2017-01-01

Evaporation and condensation at a liquid-vapor interface is important for long-term, in-space cryogenic propellant storage. Yet the current understanding of inter-facial physics does not consistently predict behavior of evaporation or condensation rates. The proposed paper will present a physical model, based on the 1-D Heat equation and Schrage's equation, which demonstrates thin thermal layers at the fluid vapor interface.

Plasma Spray-PVD: A New Thermal Spray Process to Deposit Out of the Vapor Phase

NASA Astrophysics Data System (ADS)

von Niessen, Konstantin; Gindrat, Malko

2011-06-01

Plasma spray-physical vapor deposition (PS-PVD) is a low pressure plasma spray technology recently developed by Sulzer Metco AG (Switzerland). Even though it is a thermal spray process, it can deposit coatings out of the vapor phase. The basis of PS-PVD is the low pressure plasma spraying (LPPS) technology that has been well established in industry for several years. In comparison to conventional vacuum plasma spraying (VPS) or low pressure plasma spraying (LPPS), the new proposed process uses a high energy plasma gun operated at a reduced work pressure of 0.1 kPa (1 mbar). Owing to the high energy plasma and further reduced work pressure, PS-PVD is able to deposit a coating not only by melting the feed stock material which builds up a layer from liquid splats but also by vaporizing the injected material. Therefore, the PS-PVD process fills the gap between the conventional physical vapor deposition (PVD) technologies and standard thermal spray processes. The possibility to vaporize feedstock material and to produce layers out of the vapor phase results in new and unique coating microstructures. The properties of such coatings are superior to those of thermal spray and electron beam-physical vapor deposition (EB-PVD) coatings. In contrast to EB-PVD, PS-PVD incorporates the vaporized coating material into a supersonic plasma plume. Owing to the forced gas stream of the plasma jet, complex shaped parts such as multi-airfoil turbine vanes can be coated with columnar thermal barrier coatings using PS-PVD. Even shadowed areas and areas which are not in the line of sight of the coating source can be coated homogeneously. This article reports on the progress made by Sulzer Metco in developing a thermal spray process to produce coatings out of the vapor phase. Columnar thermal barrier coatings made of Yttria-stabilized Zircona (YSZ) are optimized to serve in a turbine engine. This process includes not only preferable coating properties such as strain tolerance and erosion

Thermal-hydraulic behaviors of vapor-liquid interface due to arrival of a pressure wave

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

Inoue, Akira; Fujii, Yoshifumi; Matsuzaki, Mitsuo

In the vapor explosion, a pressure wave (shock wave) plays a fundamental role for triggering, propagation and enhancement of the explosion. Energy of the explosion is related to the magnitude of heat transfer rate from hot liquid to cold volatile one. This is related to an increasing rate of interface area and to an amount of transient heat flux between the liquids. In this study, the characteristics of transient heat transfer and behaviors of vapor film both on the platinum tube and on the hot melt tin drop, under same boundary conditions have been investigated. It is considered that theremore » exists a fundamental mechanism of the explosion in the initial expansion process of the hot liquid drop immediately after arrival of pressure wave. The growth rate of the vapor film is much faster on the hot liquid than that on the solid surface. Two kinds of roughness were observed, one due to the Taylor instability, by rapid growth of the explosion bubble, and another, nucleation sites were observed at the vapor-liquid interface. Based on detailed observation of early stage interface behaviors after arrival of a pressure wave, the thermal fragmentation mechanism is proposed.« less

Properties of water along the liquid-vapor coexistence curve via molecular dynamics simulations using the polarizable TIP4P-QDP-LJ water model

PubMed Central

Bauer, Brad A.; Patel, Sandeep

2009-01-01

We present an extension of the TIP4P-QDP model, TIP4P-QDP-LJ, that is designed to couple changes in repulsive and dispersive nonbond interactions to changes in polarizability. Polarizability is intimately related to the dispersion component of classical force field models of interactions, and we explore the effect of incorporating this connection explicitly on properties along the liquid-vapor coexistence curve of pure water. Parametrized to reproduce condensed-phase liquid water properties at 298 K, the TIP4P-QDP-LJ model predicts density, enthalpy of vaporization, self-diffusion constant, and the dielectric constant at ambient conditions to about the same accuracy as TIP4P-QDP but shows remarkable improvement in reproducing the liquid-vapor coexistence curve. TIP4P-QDP-LJ predicts critical constants of Tc=623 K, ρc=0.351 g∕cm3, and Pc=250.9 atm, which are in good agreement with experimental values of Tc=647.1 K, ρc=0.322 g∕cm3, and Pc=218 atm, respectively. Applying a scaling factor correction (obtained by fitting the experimental vapor-liquid equilibrium data to the law of rectilinear diameters using a three-term Wegner expansion) the model predicts critical constants (Tc=631 K and ρc=0.308 g∕cm3). Dependence of enthalpy of vaporization, self-diffusion constant, surface tension, and dielectric constant on temperature are shown to reproduce experimental trends. We also explore the interfacial potential drop across the liquid-vapor interface for the temperatures studied. The interfacial potential demonstrates little temperature dependence at lower temperatures (300–450 K) and significantly enhanced (exponential) dependence at elevated temperatures. Terms arising from the decomposition of the interfacial potential into dipole and quadrupole contributions are shown to monotonically approach zero as the temperature approaches the critical temperature. Results of this study suggest that self-consistently treating the coupling of phase

Properties of water along the liquid-vapor coexistence curve via molecular dynamics simulations using the polarizable TIP4P-QDP-LJ water model.

PubMed

Bauer, Brad A; Patel, Sandeep

2009-08-28

We present an extension of the TIP4P-QDP model, TIP4P-QDP-LJ, that is designed to couple changes in repulsive and dispersive nonbond interactions to changes in polarizability. Polarizability is intimately related to the dispersion component of classical force field models of interactions, and we explore the effect of incorporating this connection explicitly on properties along the liquid-vapor coexistence curve of pure water. Parametrized to reproduce condensed-phase liquid water properties at 298 K, the TIP4P-QDP-LJ model predicts density, enthalpy of vaporization, self-diffusion constant, and the dielectric constant at ambient conditions to about the same accuracy as TIP4P-QDP but shows remarkable improvement in reproducing the liquid-vapor coexistence curve. TIP4P-QDP-LJ predicts critical constants of T(c)=623 K, rho(c)=0.351 g/cm(3), and P(c)=250.9 atm, which are in good agreement with experimental values of T(c)=647.1 K, rho(c)=0.322 g/cm(3), and P(c)=218 atm, respectively. Applying a scaling factor correction (obtained by fitting the experimental vapor-liquid equilibrium data to the law of rectilinear diameters using a three-term Wegner expansion) the model predicts critical constants (T(c)=631 K and rho(c)=0.308 g/cm(3)). Dependence of enthalpy of vaporization, self-diffusion constant, surface tension, and dielectric constant on temperature are shown to reproduce experimental trends. We also explore the interfacial potential drop across the liquid-vapor interface for the temperatures studied. The interfacial potential demonstrates little temperature dependence at lower temperatures (300-450 K) and significantly enhanced (exponential) dependence at elevated temperatures. Terms arising from the decomposition of the interfacial potential into dipole and quadrupole contributions are shown to monotonically approach zero as the temperature approaches the critical temperature. Results of this study suggest that self-consistently treating the coupling of phase

40 CFR 63.1006 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... § 63.1006 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... requested by the Administrator. For each such demonstration, all valves in gas and vapor and light liquid... 40 Protection of Environment 10 2011-07-01 2011-07-01 false Valves in gas and vapor service and in...

40 CFR 63.1006 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2014 CFR

2014-07-01

... § 63.1006 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... requested by the Administrator. For each such demonstration, all valves in gas and vapor and light liquid... 40 Protection of Environment 11 2014-07-01 2014-07-01 false Valves in gas and vapor service and in...

40 CFR 63.1006 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2013 CFR

2013-07-01

... § 63.1006 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... requested by the Administrator. For each such demonstration, all valves in gas and vapor and light liquid... 40 Protection of Environment 11 2013-07-01 2013-07-01 false Valves in gas and vapor service and in...

40 CFR 63.1006 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2012 CFR

2012-07-01

... § 63.1006 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... requested by the Administrator. For each such demonstration, all valves in gas and vapor and light liquid... 40 Protection of Environment 11 2012-07-01 2012-07-01 false Valves in gas and vapor service and in...

40 CFR 63.1006 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... § 63.1006 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... requested by the Administrator. For each such demonstration, all valves in gas and vapor and light liquid... 40 Protection of Environment 10 2010-07-01 2010-07-01 false Valves in gas and vapor service and in...

40 CFR 63.649 - Alternative means of emission limitation: Connectors in gas/vapor service and light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... limitation: Connectors in gas/vapor service and light liquid service. 63.649 Section 63.649 Protection of...: Connectors in gas/vapor service and light liquid service. (a) If an owner or operator elects to monitor... gas/vapor service and for connectors in light liquid service. The data for the two groups of...

40 CFR 63.649 - Alternative means of emission limitation: Connectors in gas/vapor service and light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... limitation: Connectors in gas/vapor service and light liquid service. 63.649 Section 63.649 Protection of...: Connectors in gas/vapor service and light liquid service. (a) If an owner or operator elects to monitor... gas/vapor service and for connectors in light liquid service. The data for the two groups of...

40 CFR 63.649 - Alternative means of emission limitation: Connectors in gas/vapor service and light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... limitation: Connectors in gas/vapor service and light liquid service. 63.649 Section 63.649 Protection of...: Connectors in gas/vapor service and light liquid service. (a) If an owner or operator elects to monitor... gas/vapor service and for connectors in light liquid service. The data for the two groups of...

40 CFR 63.649 - Alternative means of emission limitation: Connectors in gas/vapor service and light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... limitation: Connectors in gas/vapor service and light liquid service. 63.649 Section 63.649 Protection of...: Connectors in gas/vapor service and light liquid service. (a) If an owner or operator elects to monitor... gas/vapor service and for connectors in light liquid service. The data for the two groups of...

40 CFR 63.649 - Alternative means of emission limitation: Connectors in gas/vapor service and light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... limitation: Connectors in gas/vapor service and light liquid service. 63.649 Section 63.649 Protection of...: Connectors in gas/vapor service and light liquid service. (a) If an owner or operator elects to monitor... gas/vapor service and for connectors in light liquid service. The data for the two groups of...

Leveraging Gibbs Ensemble Molecular Dynamics and Hybrid Monte Carlo/Molecular Dynamics for Efficient Study of Phase Equilibria.

PubMed

Gartner, Thomas E; Epps, Thomas H; Jayaraman, Arthi

2016-11-08

We describe an extension of the Gibbs ensemble molecular dynamics (GEMD) method for studying phase equilibria. Our modifications to GEMD allow for direct control over particle transfer between phases and improve the method's numerical stability. Additionally, we found that the modified GEMD approach had advantages in computational efficiency in comparison to a hybrid Monte Carlo (MC)/MD Gibbs ensemble scheme in the context of the single component Lennard-Jones fluid. We note that this increase in computational efficiency does not compromise the close agreement of phase equilibrium results between the two methods. However, numerical instabilities in the GEMD scheme hamper GEMD's use near the critical point. We propose that the computationally efficient GEMD simulations can be used to map out the majority of the phase window, with hybrid MC/MD used as a follow up for conditions under which GEMD may be unstable (e.g., near-critical behavior). In this manner, we can capitalize on the contrasting strengths of these two methods to enable the efficient study of phase equilibria for systems that present challenges for a purely stochastic GEMC method, such as dense or low temperature systems, and/or those with complex molecular topologies.

An accurate density functional theory for the vapor-liquid interface of associating chain molecules based on the statistical associating fluid theory for potentials of variable range

NASA Astrophysics Data System (ADS)

Gloor, Guy J.; Jackson, George; Blas, Felipe J.; del Río, Elvira Martín; de Miguel, Enrique

2004-12-01

A Helmholtz free energy density functional is developed to describe the vapor-liquid interface of associating chain molecules. The functional is based on the statistical associating fluid theory with attractive potentials of variable range (SAFT-VR) for the homogenous fluid [A. Gil-Villegas, A. Galindo, P. J. Whitehead, S. J. Mills, G. Jackson, and A. N. Burgess, J. Chem. Phys. 106, 4168 (1997)]. A standard perturbative density functional theory (DFT) is constructed by partitioning the free energy density into a reference term (which incorporates all of the short-range interactions, and is treated locally) and an attractive perturbation (which incorporates the long-range dispersion interactions). In our previous work [F. J. Blas, E. Martín del Río, E. de Miguel, and G. Jackson, Mol. Phys. 99, 1851 (2001); G. J. Gloor, F. J. Blas, E. Martín del Río, E. de Miguel, and G. Jackson, Fluid Phase Equil. 194, 521 (2002)] we used a mean-field version of the theory (SAFT-HS) in which the pair correlations were neglected in the attractive term. This provides only a qualitative description of the vapor-liquid interface, due to the inadequate mean-field treatment of the vapor-liquid equilibria. Two different approaches are used to include the correlations in the attractive term: in the first, the free energy of the homogeneous fluid is partitioned such that the effect of correlations are incorporated in the local reference term; in the second, a density averaged correlation function is incorporated into the perturbative term in a similar way to that proposed by Toxvaerd [S. Toxvaerd, J. Chem. Phys. 64, 2863 (1976)]. The latter is found to provide the most accurate description of the vapor-liquid surface tension on comparison with new simulation data for a square-well fluid of variable range. The SAFT-VR DFT is used to examine the effect of molecular chain length and association on the surface tension. Different association schemes (dimerization, straight and branched chain

40 CFR 60.482-7 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Before November 7, 2006 § 60.482-7 Standards: Valves in gas/vapor service and in light liquid service. (a... operation in gas/vapor service or light liquid service after the initial startup date for the process unit... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standards: Valves in gas/vapor service...

40 CFR 60.482-7 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Before November 7, 2006 § 60.482-7 Standards: Valves in gas/vapor service and in light liquid service. (a... operation in gas/vapor service or light liquid service after the initial startup date for the process unit... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standards: Valves in gas/vapor service...

40 CFR 60.482-7 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Before November 7, 2006 § 60.482-7 Standards: Valves in gas/vapor service and in light liquid service. (a... operation in gas/vapor service or light liquid service after the initial startup date for the process unit... 40 Protection of Environment 7 2013-07-01 2013-07-01 false Standards: Valves in gas/vapor service...

40 CFR 60.482-7 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Before November 7, 2006 § 60.482-7 Standards: Valves in gas/vapor service and in light liquid service. (a... operation in gas/vapor service or light liquid service after the initial startup date for the process unit... 40 Protection of Environment 7 2014-07-01 2014-07-01 false Standards: Valves in gas/vapor service...

40 CFR 60.482-7 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Before November 7, 2006 § 60.482-7 Standards: Valves in gas/vapor service and in light liquid service. (a... operation in gas/vapor service or light liquid service after the initial startup date for the process unit... 40 Protection of Environment 7 2012-07-01 2012-07-01 false Standards: Valves in gas/vapor service...

Electrical impedance imaging in two-phase, gas-liquid flows: 1. Initial investigation

NASA Technical Reports Server (NTRS)

Lin, J. T.; Ovacik, L.; Jones, O. C.

1991-01-01

The determination of interfacial area density in two-phase, gas-liquid flows is one of the major elements impeding significant development of predictive tools based on the two-fluid model. Currently, these models require coupling of liquid and vapor at interfaces using constitutive equations which do not exist in any but the most rudimentary form. Work described herein represents the first step towards the development of Electrical Impedance Computed Tomography (EICT) for nonintrusive determination of interfacial structure and evolution in such flows.

Metamorphism and partial melting of ordinary chondrites: Calculated phase equilibria

NASA Astrophysics Data System (ADS)

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

2016-01-01

Constraining the metamorphic pressures (P) and temperatures (T) recorded by meteorites is key to understanding the size and thermal history of their asteroid parent bodies. New thermodynamic models calibrated to very low P for minerals and melt in terrestrial mantle peridotite permit quantitative investigation of high-T metamorphism in ordinary chondrites using phase equilibria modelling. Isochemical P-T phase diagrams based on the average composition of H, L and LL chondrite falls and contoured for the composition and abundance of olivine, ortho- and clinopyroxene, plagioclase and chromite provide a good match with values measured in so-called equilibrated (petrologic type 4-6) samples. Some compositional variables, in particular Al in orthopyroxene and Na in clinopyroxene, exhibit a strong pressure dependence when considered over a range of several kilobars, providing a means of recognising meteorites derived from the cores of asteroids with radii of several hundred kilometres, if such bodies existed at that time. At the low pressures (<1 kbar) that typify thermal metamorphism, several compositional variables are good thermometers. Although those based on Fe-Mg exchange are likely to have been reset during slow cooling, those based on coupled substitution, in particular Ca and Al in orthopyroxene and Na in clinopyroxene, are less susceptible to retrograde diffusion and are potentially more faithful recorders of peak conditions. The intersection of isopleths of these variables may allow pressures to be quantified, even at low P, permitting constraints on the minimum size of parent asteroid bodies. The phase diagrams predict the onset of partial melting at 1050-1100 °C by incongruent reactions consuming plagioclase, clinopyroxene and orthopyroxene, whose compositions change abruptly as melting proceeds. These predictions match natural observations well and support the view that type 7 chondrites represent a suprasolidus continuation of the established petrologic

Enthalpy and phase behavior of coal derived liquid mixtures. Technical progress report, April-June 1986

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

Yesavage, V.F.; Kidnay, A.J.

Enthalpy measurements for the m-cresol/tetralin binary system, and the quinoline/tertralin binary system have been completed and are included. A calibration check on the calorimeter was performed and is presented in Appendix C. Vapor liquid equilibria measurements for the quinoline/tetralin system have been completed for four isotherms; 250, 275, 300, and 325/sup 0/C. These results and a summary of progress to date for the VLE apparatus are in the appendix at the end of this report. Also, preliminary work has begun on the quinoline/m-cresol/tetralin ternary system. Correlational work has consisted of the development of mathematical expressions for fugacity and enthalpy usingmore » various combinations of mixing rules and equations of state discussed in earlier reports. Also maximum likelihood routines has been written to determine the necessary parameters for binary data obtained in this investigation.« less

Thermodynamic and structure-property study of liquid-vapor equilibrium for aroma compounds.

PubMed

Tromelin, Anne; Andriot, Isabelle; Kopjar, Mirela; Guichard, Elisabeth

2010-04-14

Thermodynamic parameters (T, DeltaH degrees , DeltaS degrees , K) were collected from the literature and/or calculated for five esters, four ketones, two aldehydes, and three alcohols, pure compounds and compounds in aqueous solution. Examination of correlations between these parameters and the range values of DeltaH degrees and DeltaS degrees puts forward the key roles of enthalpy for vaporization of pure compounds and of entropy in liquid-vapor equilibrium of compounds in aqueous solution. A structure-property relationship (SPR) study was performed using molecular descriptors on aroma compounds to better understand their vaporization behavior. In addition to the role of polarity for vapor-liquid equilibrium of compounds in aqueous solution, the structure-property study points out the role of chain length and branching, illustrated by the correlation between the connectivity index CHI-V-1 and the difference between T and log K for vaporization of pure compounds and compounds in aqueous solution. Moreover, examination of the esters' enthalpy values allowed a probable conformation adopted by ethyl octanoate in aqueous solution to be proposed.

Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

40 CFR 65.108 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Standards: Connectors in gas/vapor service and in light liquid service. (a) Compliance schedule. Except as... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 65.108 Section 65.108 Protection of Environment ENVIRONMENTAL...

40 CFR 65.109 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Standards: Agitators in gas/vapor service and in light liquid service. (a) Compliance schedule. The owner or... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 65.109 Section 65.109 Protection of Environment ENVIRONMENTAL...

40 CFR 65.109 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Standards: Agitators in gas/vapor service and in light liquid service. (a) Compliance schedule. The owner or... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 65.109 Section 65.109 Protection of Environment ENVIRONMENTAL...

40 CFR 65.108 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Standards: Connectors in gas/vapor service and in light liquid service. (a) Compliance schedule. Except as... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 65.108 Section 65.108 Protection of Environment ENVIRONMENTAL...

40 CFR 65.109 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards: Agitators in gas/vapor service and in light liquid service. (a) Compliance schedule. The owner or... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 65.109 Section 65.109 Protection of Environment ENVIRONMENTAL...

40 CFR 65.108 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards: Connectors in gas/vapor service and in light liquid service. (a) Compliance schedule. Except as... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 65.108 Section 65.108 Protection of Environment ENVIRONMENTAL...

40 CFR 65.108 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Standards: Connectors in gas/vapor service and in light liquid service. (a) Compliance schedule. Except as... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 65.108 Section 65.108 Protection of Environment ENVIRONMENTAL...

40 CFR 65.108 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Standards: Connectors in gas/vapor service and in light liquid service. (a) Compliance schedule. Except as... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 65.108 Section 65.108 Protection of Environment ENVIRONMENTAL...

40 CFR 65.109 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Standards: Agitators in gas/vapor service and in light liquid service. (a) Compliance schedule. The owner or... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 65.109 Section 65.109 Protection of Environment ENVIRONMENTAL...

40 CFR 65.109 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Standards: Agitators in gas/vapor service and in light liquid service. (a) Compliance schedule. The owner or... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 65.109 Section 65.109 Protection of Environment ENVIRONMENTAL...

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Influence of liquid water and water vapor on antimisting kerosene (AMK)

NASA Technical Reports Server (NTRS)

Yavrouian, A. H.; Sarolouki, M.; Sarohia, V.

1983-01-01

Experiments have been performed to evaluate the compatibility of liquid water and water vapor with antimisting kerosenes (AMK) containing polymer additive FM-9 developed by Imperial Chemical Industries. This effort consists of the determination of water solubility in AMK, influence of water on restoration (degradation) of AMK, and effect of water on standard AMK quality control methods. The principal conclusions of this investigation are: (1) the uptake of water in AMK critically depends upon the degree of agitation and can be as high as 1300 ppm at 20 C, (2) more than 250 to 300 ppm of water in AMK causes an insoluble second phase to form. The amount of this second phase depends on fuel temperature, agitation, degree of restoration (degradation) and the water content of the fuel, (3) laboratory scale experiments indicate precipitate formation when water vapor comes in contact with cold fuel surfaces at a much lower level of water (125 to 150 ppm), (4) precipitate formation is very pronounced in these experiments where humid air is percolated through a cold fuel (-20 C), (5) laboratory tests further indicate that water droplet settling time is markedly reduced in AMK as compared to jet A, (6) limited low temperature testing down to -30 C under laboratory conditions indicates the formation of stable, transparent gels.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Structure and phase behavior of a confined nanodroplet composed of the flexible chain molecules.

PubMed

Kim, Soon-Chul; Kim, Eun-Young; Seong, Baek-Seok

2011-04-28

A polymer density functional theory has been employed for investigating the structure and phase behaviors of the chain polymer, which is modelled as the tangentially connected sphere chain with an attractive interaction, inside the nanosized pores. The excess free energy of the chain polymer has been approximated as the modified fundamental measure-theory for the hard spheres, the Wertheim's first-order perturbation for the chain connectivity, and the mean-field approximation for the van der Waals contribution. For the value of the chemical potential corresponding to a stable liquid phase in the bulk system and a metastable vapor phase, the flexible chain molecules undergo the liquid-vapor transition as the pore size is reduced; the vapor is the stable phase at small volume, whereas the liquid is the stable phase at large volume. The wide liquid-vapor coexistence curve, which explains the wide range of metastable liquid-vapor states, is observed at low temperature. The increase of temperature and decrease of pore size result in a narrowing of liquid-vapor coexistence curves. The increase of chain length leads to a shift of the liquid-vapor coexistence curve towards lower values of chemical potential. The coexistence curves for the confined phase diagram are contained within the corresponding bulk liquid-vapor coexistence curve. The equilibrium capillary phase transition occurs at a higher chemical potential than in the bulk phase.

Thermodynamic considerations of the vapor phase reactions in III-nitride metal organic vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

2017-04-01

We analyzed the metal organic vapor phase epitaxial growth mechanism of the III-nitride semiconductors GaN, AlN, and InN by first-principles calculations and thermodynamic analyses. In these analyses, we investigated the decomposition processes of the group III source gases X(CH3)3 (X = Ga, Al, In) at finite temperatures and determined whether the (CH3)2GaNH2 adduct can be formed or not. The results of our calculations show that the (CH3)2GaNH2 adduct cannot be formed in the gas phase in GaN metal organic vapor phase epitaxy (MOVPE), whereas, in AlN MOVPE, the formation of the (CH3)2AlNH2 adduct in the gas phase is exclusive. In the case of GaN MOVPE, trimethylgallium (TMG, [Ga(CH3)3]) decomposition into Ga gas on the growth surface with the assistance of H2 carrier gas, instead of the formation of the (CH3)2GaNH2 adduct, occurs almost exclusively. Moreover, in the case of InN MOVPE, the formation of the (CH3)2InNH2 adduct does not occur and it is relatively easy to produce In gas even without H2 in the carrier gas.

40 CFR 63.173 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Equipment Leaks § 63.173 Standards: Agitators in gas/vapor service and in light liquid service. (a)(1) Each... 40 Protection of Environment 9 2011-07-01 2011-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 63.173 Section 63.173 Protection of Environment ENVIRONMENTAL...

40 CFR 63.173 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Equipment Leaks § 63.173 Standards: Agitators in gas/vapor service and in light liquid service. (a)(1) Each... 40 Protection of Environment 10 2012-07-01 2012-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 63.173 Section 63.173 Protection of Environment ENVIRONMENTAL...

40 CFR 65.106 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards: Valves in gas/vapor service and in light liquid service. (a) Compliance schedule. (1) The owner... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Standards: Valves in gas/vapor service and in light liquid service. 65.106 Section 65.106 Protection of Environment ENVIRONMENTAL PROTECTION...

40 CFR 63.173 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Equipment Leaks § 63.173 Standards: Agitators in gas/vapor service and in light liquid service. (a)(1) Each... 40 Protection of Environment 10 2014-07-01 2014-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 63.173 Section 63.173 Protection of Environment ENVIRONMENTAL...

40 CFR 63.173 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Equipment Leaks § 63.173 Standards: Agitators in gas/vapor service and in light liquid service. (a)(1) Each... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 63.173 Section 63.173 Protection of Environment ENVIRONMENTAL...

40 CFR 63.174 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Equipment Leaks § 63.174 Standards: Connectors in gas/vapor service and in light liquid service. (a) The... 40 Protection of Environment 10 2013-07-01 2013-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 63.174 Section 63.174 Protection of Environment ENVIRONMENTAL...

40 CFR 65.106 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Standards: Valves in gas/vapor service and in light liquid service. (a) Compliance schedule. (1) The owner... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Standards: Valves in gas/vapor service and in light liquid service. 65.106 Section 65.106 Protection of Environment ENVIRONMENTAL PROTECTION...

40 CFR 63.174 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Equipment Leaks § 63.174 Standards: Connectors in gas/vapor service and in light liquid service. (a) The... 40 Protection of Environment 10 2012-07-01 2012-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 63.174 Section 63.174 Protection of Environment ENVIRONMENTAL...

40 CFR 65.106 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Standards: Valves in gas/vapor service and in light liquid service. (a) Compliance schedule. (1) The owner... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Standards: Valves in gas/vapor service and in light liquid service. 65.106 Section 65.106 Protection of Environment ENVIRONMENTAL PROTECTION...

40 CFR 65.106 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Standards: Valves in gas/vapor service and in light liquid service. (a) Compliance schedule. (1) The owner... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Standards: Valves in gas/vapor service and in light liquid service. 65.106 Section 65.106 Protection of Environment ENVIRONMENTAL PROTECTION...

40 CFR 63.174 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Equipment Leaks § 63.174 Standards: Connectors in gas/vapor service and in light liquid service. (a) The... 40 Protection of Environment 10 2014-07-01 2014-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 63.174 Section 63.174 Protection of Environment ENVIRONMENTAL...

40 CFR 63.174 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Equipment Leaks § 63.174 Standards: Connectors in gas/vapor service and in light liquid service. (a) The... 40 Protection of Environment 9 2011-07-01 2011-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 63.174 Section 63.174 Protection of Environment ENVIRONMENTAL...

40 CFR 63.174 - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Equipment Leaks § 63.174 Standards: Connectors in gas/vapor service and in light liquid service. (a) The... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Standards: Connectors in gas/vapor service and in light liquid service. 63.174 Section 63.174 Protection of Environment ENVIRONMENTAL...

40 CFR 63.173 - Standards: Agitators in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Equipment Leaks § 63.173 Standards: Agitators in gas/vapor service and in light liquid service. (a)(1) Each... 40 Protection of Environment 10 2013-07-01 2013-07-01 false Standards: Agitators in gas/vapor service and in light liquid service. 63.173 Section 63.173 Protection of Environment ENVIRONMENTAL...

40 CFR 65.106 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Standards: Valves in gas/vapor service and in light liquid service. (a) Compliance schedule. (1) The owner... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Standards: Valves in gas/vapor service and in light liquid service. 65.106 Section 65.106 Protection of Environment ENVIRONMENTAL PROTECTION...

Water vapor radiometry research and development phase

NASA Technical Reports Server (NTRS)

Resch, G. M.; Chavez, M. C.; Yamane, N. L.; Barbier, K. M.; Chandlee, R. C.

1985-01-01

This report describes the research and development phase for eight dual-channel water vapor radiometers constructed for the Crustal Dynamics Project at the Goddard Space Flight Center, Greenbelt, Maryland, and for the NASA Deep Space Network. These instruments were developed to demonstrate that the variable path delay imposed on microwave radio transmissions by atmospheric water vapor can be calibrated, particularly as this phenomenon affects very long baseline interferometry measurement systems. Water vapor radiometry technology can also be used in systems that involve moist air meteorology and propagation studies.

Ionic liquids. Combination of combustion calorimetry with high-level quantum chemical calculations for deriving vaporization enthalpies.

PubMed

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas; Schick, Christoph

2008-07-10

In this work, the molar enthalpies of formation of the ionic liquids [C2MIM][NO3] and [C4MIM][NO3] were measured by means of combustion calorimetry. The molar enthalpy of fusion of [C2MIM][NO3] was measured using differential scanning calorimetry. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the G3MP2 theory. We have used a combination of traditional combustion calorimetry with modern high-level ab initio calculations in order to obtain the molar enthalpies of vaporization of a series of the ionic liquids under study.

40 CFR 60.482-11a - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

...-11a Standards: Connectors in gas/vapor service and in light liquid service. (a) The owner or operator... connectors in gas and vapor and light liquid service as specified in paragraphs (a) and (b)(3) of this... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standards: Connectors in gas/vapor...

40 CFR 60.482-11a - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

...-11a Standards: Connectors in gas/vapor service and in light liquid service. (a) The owner or operator... connectors in gas and vapor and light liquid service as specified in paragraphs (a) and (b)(3) of this... 40 Protection of Environment 7 2013-07-01 2013-07-01 false Standards: Connectors in gas/vapor...

40 CFR 60.482-11a - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-11a Standards: Connectors in gas/vapor service and in light liquid service. (a) The owner or operator... connectors in gas and vapor and light liquid service as specified in paragraphs (a) and (b)(3) of this... 40 Protection of Environment 7 2012-07-01 2012-07-01 false Standards: Connectors in gas/vapor...

40 CFR 60.482-11a - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

...-11a Standards: Connectors in gas/vapor service and in light liquid service. (a) The owner or operator... connectors in gas and vapor and light liquid service as specified in paragraphs (a) and (b)(3) of this... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standards: Connectors in gas/vapor...

40 CFR 60.482-11a - Standards: Connectors in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-11a Standards: Connectors in gas/vapor service and in light liquid service. (a) The owner or operator... connectors in gas and vapor and light liquid service as specified in paragraphs (a) and (b)(3) of this... 40 Protection of Environment 7 2014-07-01 2014-07-01 false Standards: Connectors in gas/vapor...

Local mass and energy transports in evaporation processes from a vapor-liquid interface in a slit pore based on molecular dynamics

NASA Astrophysics Data System (ADS)

Fujiwara, K.; Shibahara, M.

2018-02-01

Molecular evaporation processes from a vapor-liquid interface formed in a slit-like pore were examined based on the classical molecular dynamics method, in order to elucidate a molecular mechanism of local mass and energy transports in a slit. The calculation system consisted of monatomic molecules and atoms which interact through the 12-6 Lennard-Jones potential. At first, a liquid was situated in a slit with a vapor-liquid interface, and instantaneous amounts of the mass and energy fluxes defined locally in the slit were obtained in two dimensions to reveal local fluctuation properties of the fluid in equilibrium states. Then, imposing a temperature gradient in the calculation system, non-equilibrium evaporation processes in the slit were investigated in details based on the local mass and energy fluxes. In this study, we focused on the fluid which is in the vicinity of the solid surface and in contact with the vapor phase. In the non-equilibrium evaporation processes, the results revealed that the local energy transport mechanism in the vicinity of the solid surface is different from that of the vapor phase, especially in the case of the relatively strong fluid-solid interaction. The results also revealed that the local mass transport in the vicinity of the solid surface can be interpreted based on the mechanism of the local energy transport, and the mechanism provides valuable information about pictures of the evaporation phenomena especially in the vicinity of the hydrophilic surfaces. It suggests that evaluating and changing this mechanism of the local energy transport are necessary to control the local mass flux more precisely in the vicinity of the solid surface.

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

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

Miyabe, Kanji; Guiochon, Georges A

2005-09-01

The retention behavior on silica gels bonded to C{sub 18} and C{sub 1} alkyl ligands of different densities was studied in reversed-phase liquid chromatography (RPLC) from the viewpoints of two extrathermodynamic relationships, enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, the four tests proposed by Krug et al. were applied to the values of the retention equilibrium constants (K) normalized by the alkyl ligand density. These tests showed that a real EEC of the retention equilibrium originates from substantial physico-chemical effects. Second, we derived a new model based on the EEC to explain the LFER between the retentionmore » equilibria under different RPLC conditions. The new model indicates how the slope and intercept of the LFER are correlated to the compensation temperatures derived from the EEC analyses and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy. Finally, we calculated K under various RPLC conditions from only one original experimental K datum by assuming that the contributions of the C{sub 18} and C{sub 1} ligands to K are additive and that their contributions are proportional to the density of each ligand. The estimated K values are in agreement with the corresponding experimental data, demonstrating that our model is useful to explain the variations of K due to changes in the RPLC conditions.« less

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

PubMed Central

Wang, Tian; Kevorkov, Dmytro; Medraj, Mamoun

2016-01-01

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

Effect of Liquid Surface Turbulent Motion on the Vapor Condensation in a Mixing Tank

NASA Technical Reports Server (NTRS)

Lin, C. S.; Hasan, M. M.

1991-01-01

The effect of liquid surface motion on the vapor condensation in a tank mixed by an axial turbulent jet is numerically investigated. The average value (over the interface area) of the root-mean-squared (rms) turbulent velocity at the interface is shown to be linearly increasing with decreasing liquid height and increasing jet diameter for a given tank size. The average rms turbulent velocity is incorporated in Brown et al. (1990) condensation correlation to predict the condensation of vapor on a liquid surface. The results are in good agreement with available condensation data.

Predicting the Fluid-Phase Behavior of Aqueous Solutions of ELP (VPGVG) Sequences Using SAFT-VR.

PubMed

Zhao, Binwu; Lindeboom, Tom; Benner, Steven; Jackson, George; Galindo, Amparo; Hall, Carol K

2017-10-24

The statistical associating fluid theory for potentials of variable range (SAFT-VR) is used to predict the fluid phase behavior of elastin-like polypeptide (ELP) sequences in aqueous solution with special focus on the loci of lower critical solution temperatures (LCSTs). A SAFT-VR model for these solutions is developed following a coarse-graining approach combining information from atomistic simulations and from previous SAFT models for previously reported relevant systems. Constant-pressure temperature-composition phase diagrams are determined for solutions of (VPGVG) n sequences + water with n = 1 to 300. The SAFT-VR equation of state lends itself to the straightforward calculation of phase boundaries so that complete fluid-phase equilibria can be calculated efficiently. A broad range of thermodynamic conditions of temperature and pressure are considered, and regions of vapor-liquid and liquid-liquid coexistence, including LCSTs, are found. The calculated phase boundaries at low concentrations match those measured experimentally. The temperature-composition phase diagrams of the aqueous ELP solutions at low pressure (0.1 MPa) are similar to those of types V and VI phase behavior in the classification of Scott and van Konynenburg. An analysis of the high-pressure phase behavior confirms, however, that a closed-loop liquid-liquid immiscibility region, separate from the gas-liquid envelope, is present for aqueous solutions of (VPGVG) 30 ; such a phase diagram is typical of type VI phase behavior. ELPs with shorter lengths exhibit both liquid-liquid and gas-liquid regions, both of which become less extensive as the chain length of the ELP is decreased. The strength of the hydrogen-bonding interaction is also found to affect the phase diagram of the (VPGVG) 30 system in that the liquid-liquid and gas-liquid regions expand as the hydrogen-bonding strength is decreased and shrink as it is increased. The LCSTs of the mixtures are seen to decrease as the ELP chain length

Application of Thioether for Vapor Phase Lubrication

NASA Technical Reports Server (NTRS)

Graham, E. Earl

1997-01-01

The objective of these studies was to identify the optimal conditions for vapor phase lubrication using Thioether for both sliding and rolling wear. The important variable include; (1) The component materials including M50 steel, monel and silicon nitride. (2) The vapor concentration and flow rate. (3) The temperature in the range of 600 F to 1500 F. (4) The loads and rolling and/or sliding speeds.

Ionic liquids: differential scanning calorimetry as a new indirect method for determination of vaporization enthalpies.

PubMed

Verevkin, Sergey P; Emel'yanenko, Vladimir N; Zaitsau, Dzmitry H; Ralys, Ricardas V; Schick, Christoph

2012-04-12

Differential scanning calorimetry (DSC) has been used to measure enthalpies of synthesis reactions of the 1-alkyl-3-methylimidazolium bromide [C(n)mim][Br] ionic liquids from 1-methylimidazole and n-alkyl bromides (with n = 4, 5, 6, 7, and 8). The optimal experimental conditions have been elaborated. Enthalpies of formation of these ionic liquids in the liquid state have been determined using the DSC results according to the Hess Law. The ideal-gas enthalpies of formation of [C(n)mim][Br] were calculated using the methods of quantum chemistry. They were used together with the DSC results to derive indirectly the enthalpies of vaporization of the ionic liquids under study. In order to validate the indirect determination, the experimental vaporization enthalpy of [C(4)mim][Br] was measured by using a quartz crystal microbalance (QCM). The combination of reaction enthalpy measurements by DSC with modern high-level first-principles calculations opens valuable indirect thermochemical options to obtain values of vaporization enthalpies of ionic liquids.

Self-diffusion Coefficient and Structure of Binary n-Alkane Mixtures at the Liquid-Vapor Interfaces.

PubMed

Chilukoti, Hari Krishna; Kikugawa, Gota; Ohara, Taku

2015-10-15

The self-diffusion coefficient and molecular-scale structure of several binary n-alkane liquid mixtures in the liquid-vapor interface regions have been examined using molecular dynamics simulations. It was observed that in hexane-tetracosane mixture hexane molecules are accumulated in the liquid-vapor interface region and the accumulation intensity decreases with increase in a molar fraction of hexane in the examined range. Molecular alignment and configuration in the interface region of the liquid mixture change with a molar fraction of hexane. The self-diffusion coefficient in the direction parallel to the interface of both tetracosane and hexane in their binary mixture increases in the interface region. It was found that the self-diffusion coefficient of both tetracosane and hexane in their binary mixture is considerably higher in the vapor side of the interface region as the molar fraction of hexane goes lower, which is mostly due to the increase in local free volume caused by the local structure of the liquid in the interface region.

40 CFR 63.168 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... § 63.168 Standards: Valves in gas/vapor service and in light liquid service. (a) The provisions of this section apply to valves that are either in gas service or in light liquid service. (1) The provisions are... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Standards: Valves in gas/vapor service...

40 CFR 63.168 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2011 CFR

2011-07-01

... § 63.168 Standards: Valves in gas/vapor service and in light liquid service. (a) The provisions of this section apply to valves that are either in gas service or in light liquid service. (1) The provisions are... 40 Protection of Environment 9 2011-07-01 2011-07-01 false Standards: Valves in gas/vapor service...

40 CFR 63.168 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2013 CFR

2013-07-01

... § 63.168 Standards: Valves in gas/vapor service and in light liquid service. (a) The provisions of this section apply to valves that are either in gas service or in light liquid service. (1) The provisions are... 40 Protection of Environment 10 2013-07-01 2013-07-01 false Standards: Valves in gas/vapor service...

40 CFR 63.168 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

... § 63.168 Standards: Valves in gas/vapor service and in light liquid service. (a) The provisions of this section apply to valves that are either in gas service or in light liquid service. (1) The provisions are... 40 Protection of Environment 10 2014-07-01 2014-07-01 false Standards: Valves in gas/vapor service...

40 CFR 63.168 - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2012 CFR

2012-07-01

... § 63.168 Standards: Valves in gas/vapor service and in light liquid service. (a) The provisions of this section apply to valves that are either in gas service or in light liquid service. (1) The provisions are... 40 Protection of Environment 10 2012-07-01 2012-07-01 false Standards: Valves in gas/vapor service...

Liquid-Vapor Interface Configurations Investigated in Low Gravity

NASA Technical Reports Server (NTRS)

Concus, Paul; Finn, Robert; Weislogel, Mark M.

1998-01-01

The Interface Configuration Experiment (ICE) is part of a multifaceted study that is exploring the often striking behavior of liquid-vapor interfaces in low-gravity environments. Although the experiment was posed largely as a test of current mathematical theory, applications of the results should be manifold. In space almost every fluid system is affected, if not dominated, by capillarity (the effects of surface tension). As a result, knowledge of fluid interface behavior, in particular an equilibrium interface shape from which any analysis must begin, is fundamental--from the control of liquid fuels and oxygen in storage tanks to the design and development of inspace thermal systems, such as heat pipes and capillary pumped loops. ICE has increased, and should continue to increase, such knowledge as it probes the specific peculiarities of current theory upon which our present understanding rests. Several versions of ICE have been conducted in the drop towers at the NASA Lewis Research Center, on the space shuttles during the first and second United States Microgravity Laboratory missions (USML-1 and USML-2), and most recently aboard the Russian Mir space station. These studies focused on interfacial problems concerning the existence, uniqueness, configuration, stability, and flow characteristics of liquid-vapor interfaces. Results to date have clearly demonstrated the value of the present theory and the extent to which it can predict the behavior of capillary systems.

Preparing highly ordered glasses of discotic liquid crystalline systems by vapor deposition

NASA Astrophysics Data System (ADS)

Gujral, Ankit; Gomez, Jaritza; Bishop, Camille E.; Toney, Michael F.; Ediger, M. D.

Anisotropic molecular packing, particularly in highly ordered liquid-crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized out-of-equilibrium (glassy) solids of discotic liquid-crystalline (LC) systems. Using grazing incidence x-ray scattering, we compare 3 systems: a rectangular columnar LC, a hexagonal columnar LC and a non-liquid crystal former. The packing motifs accessible by vapor deposition are highly organized and vary from face-on to edge-on columnar arrangements depending upon substrate temperature. A subset of these structures cannot be accessed under equilibrium conditions. The structures formed at a given substrate temperature can be understood as the result of the system partially equilibrating toward the structure of the free surface of the equilibrium liquid crystal. Consistent with this view, the structures formed are independent of the substrate material.

The partitioning of Cu, Au and Mo between liquid and vapor at magmatic temperatures and its implications for the genesis of magmatic-hydrothermal ore deposits

NASA Astrophysics Data System (ADS)

Zajacz, Zoltán; Candela, Philip A.; Piccoli, Philip M.

2017-06-01

The partition coefficients of Cu, Au and Mo between liquid and vapor were determined at P = 130 MPa and T = 900 °C, and P = 90 MPa and T = 650 °C and redox conditions favoring the dominance of reduced S species in the fluid. The experiments at 900 °C were conducted in rapid-quench Molybdenum-Hafnium Carbide externally-heated pressure vessel assemblies, whereas those at 650 °C were run in René41 pressure vessels. The fluids were sampled at run conditions using the synthetic fluid inclusion technique. The host quartz was fractured in situ during the experiments ensuring the entrapment of equilibrium fluids. A new method was developed to quantify the composition of the vapor inclusions from LA-ICPMS analyses relying on the use of boron as an internal standard, an element that fractionates between vapor and liquid to a very small degree. The bulk starting fluid compositions closely represented those expected to exsolve from felsic silicate melts in upper crustal magma reservoirs (0.64 m NaCl, 0.32 m KCl, ±0.2 m HCl and/or 4 wt% S). The experiments were conducted in Au97Cu3 alloy capsules allowing the simultaneous determination of apparent Au and Cu solubilities in the liquid and the vapor phase. Though the apparent metal solubilities were strongly affected by the addition of HCl and S in both phases, all three elements were found to preferentially partition to a liquid phase at all studied conditions with an increasing degree of preference for the liquid in the following order Au < Cu < Mo. The presence of HCl and S did not have a significant effect on the liquid/vapor partition coefficients of either Au or Cu, whereas the presence of HCl slightly shifted the partitioning of Mo in favor of the vapor. Ore metal partition coefficients normalized to that of Na (Ki-Naliq/ vap =Diliq/vap /DNaliq/vap) fall in the following ranges respectively for each studied metal: KAu-Naliq / vap = 0.20 ± 0.07-0.50 ± 0.19 (1σ); KCu-Naliq / vap = 0.36 ± 0.12-0.76 ± 0.22; KMo

Formation of the racemic compound of ephedrine base from a physical mixture of its enantiomers in the solid, liquid, solution, or vapor state.

PubMed

Duddu, S P; Grant, D J

1992-08-01

Physical mixtures (conglomerates) of the two enantiomers of ephedrine base, each containing 0.5% (w/w) of water, were observed to be converted to the 1:1 racemic compound in the solid, liquid, solution, or vapor state. From a geometrically mixed racemic conglomerate of particle size 250-300 microns (50-60 mesh), the formation of the racemic compound follows second-order kinetics (first order with respect to each enantiomer), with a rate constant of 392 mol-1 hr-1 at 22 degrees C. The reaction appears to proceed via the vapor phase as indicated by the growth of the crystals of the racemic compound between diametrically separated crystals of the two enantiomers in a glass petri dish. The observed kinetics of conversion in the solid state are explained by a homogeneous reaction model via the vapor and/or liquid states. Formation of the racemic compound from the crystals of ephedrine enantiomers in the solution state may explain why Schmidt et al. (Pharm. Res. 5:391-395, 1988) observed a consistently lower aqueous solubility of the mixture than of the pure enantiomers. The solid phase in equilibrium with the solution at the end of the experiment was found to be the racemic compound, whose melting point and heat of fusion are higher than those of the enantiomers. An association reaction, of measurable rate, between the opposite enantiomers in a binary mixture in the solid, liquid, solution, or vapor state to form the racemic compound may be more common than is generally realized.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A.; Simonetti, Dante A.; Kunkes, Edward L.

2015-12-08

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A [Verona, WI; Simonetti, Dante A [Middleton, WI; Kunkes, Edward L [Madison, WI

2011-12-13

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Methodology for Assessing a Boiling Liquid Expanding Vapor Explosion (BLEVE) Blast Potential

NASA Technical Reports Server (NTRS)

Keddy, Chris P.

2012-01-01

Composite Vessels are now used to store a variety of fluids or gases including cryogenic fluids under pressure. Sudden failure of these vessels under certain conditions can lead to a potentially catastrophic vapor expansion if thermal control is not maintained prior to failure. This can lead to a "Boiling Liquid Expanding Vapor Explosion" or BLEVE.

Dense Non Aqueous Phase Liquid (DNAPL) Removal from Fractured Rock using Thermal Conductive Heating (TCH)

DTIC Science & Technology

2013-01-01

of 95% or greater in parent compounds . The data also show that most rock concentrations were lowered to around 0-5...INTRODUCTION 1.1 BACKGROUND The removal of dense non-aqueous phase liquids (DNAPL) and associated dissolved phase compounds is challenging in ...trend as presented in Figure 10. Figure 10. Vapor stream VOC concentrations for the dominant compounds . The more or less consistent level of

40 CFR 63.1028 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Standards § 63.1028 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2013-07-01 2013-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1028 Section 63.1028 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1028 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Standards § 63.1028 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2014-07-01 2014-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1028 Section 63.1028 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1008 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2013 CFR

2013-07-01

... § 63.1008 Connectors in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2013-07-01 2013-07-01 false Connectors in gas and vapor service and in light liquid service standards. 63.1008 Section 63.1008 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1025 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Standards § 63.1025 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2014-07-01 2014-07-01 false Valves in gas and vapor service and in light liquid service standards. 63.1025 Section 63.1025 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1028 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Standards § 63.1028 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2011-07-01 2011-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1028 Section 63.1028 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1008 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2014 CFR

2014-07-01

... § 63.1008 Connectors in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2014-07-01 2014-07-01 false Connectors in gas and vapor service and in light liquid service standards. 63.1008 Section 63.1008 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1025 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards § 63.1025 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2010-07-01 2010-07-01 false Valves in gas and vapor service and in light liquid service standards. 63.1025 Section 63.1025 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1009 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2014 CFR

2014-07-01

... § 63.1009 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2014-07-01 2014-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1009 Section 63.1009 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1009 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... § 63.1009 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2011-07-01 2011-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1009 Section 63.1009 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1025 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Standards § 63.1025 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2011-07-01 2011-07-01 false Valves in gas and vapor service and in light liquid service standards. 63.1025 Section 63.1025 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1008 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... § 63.1008 Connectors in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2010-07-01 2010-07-01 false Connectors in gas and vapor service and in light liquid service standards. 63.1008 Section 63.1008 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1028 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Standards § 63.1028 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2012-07-01 2012-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1028 Section 63.1028 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1008 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2012 CFR

2012-07-01

... § 63.1008 Connectors in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2012-07-01 2012-07-01 false Connectors in gas and vapor service and in light liquid service standards. 63.1008 Section 63.1008 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1009 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... § 63.1009 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2010-07-01 2010-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1009 Section 63.1009 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1009 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2012 CFR

2012-07-01

... § 63.1009 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2012-07-01 2012-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1009 Section 63.1009 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1028 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards § 63.1028 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2010-07-01 2010-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1028 Section 63.1028 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1025 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Standards § 63.1025 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2013-07-01 2013-07-01 false Valves in gas and vapor service and in light liquid service standards. 63.1025 Section 63.1025 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1009 - Agitators in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2013 CFR

2013-07-01

... § 63.1009 Agitators in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2013-07-01 2013-07-01 false Agitators in gas and vapor service and in light liquid service standards. 63.1009 Section 63.1009 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1008 - Connectors in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... § 63.1008 Connectors in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 10 2011-07-01 2011-07-01 false Connectors in gas and vapor service and in light liquid service standards. 63.1008 Section 63.1008 Protection of Environment ENVIRONMENTAL...

40 CFR 63.1025 - Valves in gas and vapor service and in light liquid service standards.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Standards § 63.1025 Valves in gas and vapor service and in light liquid service standards. (a) Compliance... 40 Protection of Environment 11 2012-07-01 2012-07-01 false Valves in gas and vapor service and in light liquid service standards. 63.1025 Section 63.1025 Protection of Environment ENVIRONMENTAL...

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

NASA Astrophysics Data System (ADS)

Fang, Gu; Chen, Chih-chi

2015-07-01

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

Interfacial condensation induced by sub-cooled liquid jet

NASA Astrophysics Data System (ADS)

Rame, Enrique; Balasubramaniam, R.

2016-11-01

When a sub-cooled liquid jet impinges on the free surface between a liquid and its vapor, vapor will condense at a rate dependent on the sub-cooling, the jet strength and fluid properties. In 1966 and during the examination of a different type of condensation flow, Shekriladeze found an approximate result, valid at large condensation rates, that decouples the flow in the liquid phase from that of the vapor, without putting it in the context of a formal asymptotic approximation. In this talk we will develop an asymptotic approximation that contains Shekriladze's result, and extend the calculations to the case when a non-condensable gas is present in the vapor phase.

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

PubMed

Li, Jianguo; Rajagopalan, Raj; Jiang, Jianwen

2008-05-28

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

Pressure control in interfacial systems: Atomistic simulations of vapor nucleation

NASA Astrophysics Data System (ADS)

Marchio, S.; Meloni, S.; Giacomello, A.; Valeriani, C.; Casciola, C. M.

2018-02-01

A large number of phenomena of scientific and technological interest involve multiple phases and occur at constant pressure of one of the two phases, e.g., the liquid phase in vapor nucleation. It is therefore of great interest to be able to reproduce such conditions in atomistic simulations. Here we study how popular barostats, originally devised for homogeneous systems, behave when applied straightforwardly to heterogeneous systems. We focus on vapor nucleation from a super-heated Lennard-Jones liquid, studied via hybrid restrained Monte Carlo simulations. The results show a departure from the trends predicted for the case of constant liquid pressure, i.e., from the conditions of classical nucleation theory. Artifacts deriving from standard (global) barostats are shown to depend on the size of the simulation box. In particular, for Lennard-Jones liquid systems of 7000 and 13 500 atoms, at conditions typically found in the literature, we have estimated an error of 10-15 kBT on the free-energy barrier, corresponding to an error of 104-106 s-1σ-3 on the nucleation rate. A mechanical (local) barostat is proposed which heals the artifacts for the considered case of vapor nucleation.

The gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide from combustion calorimetry, vapor pressure measurements, and ab initio calculations.

PubMed

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas

2007-04-04

Ionic liquids are attracting growing interest as alternatives to conventional molecular solvents. Experimental values of vapor pressure, enthalpy of vaporization, and enthalpy of formation of ionic liquids are the key thermodynamic quantities, which are required for the validation and development of the molecular modeling and ab initio methods toward this new class of solvents. In this work, the molar enthalpy of formation of the liquid 1-butyl-3-methylimidazolium dicyanamide, 206.2 +/- 2.5 kJ.mol-1, was measured by means of combustion calorimetry. The molar enthalpy of vaporization of 1-butyl-3-methylimidazolium dicyanamide, 157.2 +/- 1.1 kJ.mol-1, was obtained from the temperature dependence of the vapor pressure measured using the transpiration method. The latter method has been checked with measurements of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, where data are available from the effusion technique. The first experimental determination of the gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide, 363.4 +/- 2.7 kJ.mol-1, from thermochemical measurements (combustion and transpiration) is presented. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for 1-butyl-3-methylimidazolium dicyanamide using the G3MP2 theory. Excellent agreement with experimental results has been observed. The method developed opens a new way to obtain thermodynamic properties of ionic liquids which have not been available so far.

Nematic-like stable glasses without equilibrium liquid crystal phases

DOE Data Explorer

Gomez, Jaritza [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Gujral, Ankit [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Huang, Chengbin [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Bishop, Camille [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Yu, Lian [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Ediger, Mark [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA

2017-02-01

We report the thermal and structural properties of glasses of posaconazole, a rod-like molecule, prepared using physical vapor deposition (PVD). PVD glasses of posaconazole can show substantial molecular orientation depending upon the choice of substrate temperature, Tsubstrate, during deposition.Ellipsometry and IR measurements indicate that glasses prepared at Tsubstrate very near the glass transition temperature (Tg) are highly ordered. For these posaconazole glasses, the orientation order parameter is similar to that observed in macroscopically aligned nematic liquid crystals, indicating that the molecules are mostly parallel to one another and perpendicular to the interface. To our knowledge, these are the most anisotropic glasses ever prepared by PVD from a molecule that does not form equilibrium liquid crystal phases. These results are consistent with a previously proposed mechanism in which molecular orientation in PVD glasses is inherited from the orientation present at the free surface of the equilibrium liquid. This mechanism suggests that molecular orientation at the surface of the equilibrium liquid of posaconazole is nematic-like. Posaconazole glasses can show very high kinetic stability; the isothermal transformation of a 400 nm glass into the supercooled liquid occurs via a propagating front that originates at the free surface and requires ~105 times the structural relaxation time of the liquid (τα). We also studied the kinetic stability of PVD glasses of itraconazole, which is a structurally similar molecule with equilibrium liquid crystal phases. While itraconazole glasses can be even more anisotropic than posaconazole glasses, they exhibit lower kinetic stability.

Theory and computer simulation of hard-core Yukawa mixtures: thermodynamical, structural and phase coexistence properties.

PubMed

Mkanya, Anele; Pellicane, Giuseppe; Pini, Davide; Caccamo, Carlo

2017-09-13

We report extensive calculations, based on the modified hypernetted chain (MHNC) theory, on the hierarchical reference theory (HRT), and on Monte Carlo simulations, of thermodynamical, structural and phase coexistence properties of symmetric binary hard-core Yukawa mixtures (HCYM) with attractive interactions at equal species concentration. The obtained results are throughout compared with those available in the literature for the same systems. It turns out that the MHNC predictions for thermodynamic and structural quantities are quite accurate in comparison with the MC data. The HRT is equally accurate for thermodynamics, and slightly less accurate for structure. Liquid-vapor (LV) and liquid-liquid (LL) consolute coexistence conditions as emerging from simulations, are also highly satisfactorily reproduced by both the MHNC and HRT for relatively long ranged potentials. When the potential range reduces, the MHNC faces problems in determining the LV binodal line; however, the LL consolute line and the critical end point (CEP) temperature and density turn out to be still satisfactorily predicted within this theory. The HRT also predicts with good accuracy the CEP position. The possibility of employing liquid state theories HCYM for the purpose of reliably determining phase equilibria in multicomponent colloidal fluids of current technological interest, is discussed.

Theory and computer simulation of hard-core Yukawa mixtures: thermodynamical, structural and phase coexistence properties

NASA Astrophysics Data System (ADS)

Mkanya, Anele; Pellicane, Giuseppe; Pini, Davide; Caccamo, Carlo

2017-09-01

We report extensive calculations, based on the modified hypernetted chain (MHNC) theory, on the hierarchical reference theory (HRT), and on Monte Carlo simulations, of thermodynamical, structural and phase coexistence properties of symmetric binary hard-core Yukawa mixtures (HCYM) with attractive interactions at equal species concentration. The obtained results are throughout compared with those available in the literature for the same systems. It turns out that the MHNC predictions for thermodynamic and structural quantities are quite accurate in comparison with the MC data. The HRT is equally accurate for thermodynamics, and slightly less accurate for structure. Liquid-vapor (LV) and liquid-liquid (LL) consolute coexistence conditions as emerging from simulations, are also highly satisfactorily reproduced by both the MHNC and HRT for relatively long ranged potentials. When the potential range reduces, the MHNC faces problems in determining the LV binodal line; however, the LL consolute line and the critical end point (CEP) temperature and density turn out to be still satisfactorily predicted within this theory. The HRT also predicts with good accuracy the CEP position. The possibility of employing liquid state theories HCYM for the purpose of reliably determining phase equilibria in multicomponent colloidal fluids of current technological interest, is discussed.

Effect of the Thermocouple on Measuring the Temperature Discontinuity at a Liquid-Vapor Interface.

PubMed

Kazemi, Mohammad Amin; Nobes, David S; Elliott, Janet A W

2017-07-18

The coupled heat and mass transfer that occurs in evaporation is of interest in a large number of fields such as evaporative cooling, distillation, drying, coating, printing, crystallization, welding, atmospheric processes, and pool fires. The temperature jump that occurs at an evaporating interface is of central importance to understanding this complex process. Over the past three decades, thermocouples have been widely used to measure the interfacial temperature jumps at a liquid-vapor interface during evaporation. However, the reliability of these measurements has not been investigated so far. In this study, a numerical simulation of a thermocouple when it measures the interfacial temperatures at a liquid-vapor interface is conducted to understand the possible effects of the thermocouple on the measured temperature and features in the temperature profile. The differential equations of heat transfer in the solid and fluids as well as the momentum transfer in the fluids are coupled together and solved numerically subject to appropriate boundary conditions between the solid and fluids. The results of the numerical simulation showed that while thermocouples can measure the interfacial temperatures in the liquid correctly, they fail to read the actual interfacial temperatures in the vapor. As the results of our numerical study suggest, the temperature jumps at a liquid-vapor interface measured experimentally by using a thermocouple are larger than what really exists at the interface. For a typical experimental study of evaporation of water at low pressure, it was found that the temperature jumps measured by a thermocouple are overestimated by almost 50%. However, the revised temperature jumps are still in agreement with the statistical rate theory of interfacial transport. As well as addressing the specific application of the liquid-vapor temperature jump, this paper provides significant insight into the role that heat transfer plays in the operation of thermocouples

Re-entrant phase behavior for systems with competition between phase separation and self-assembly

NASA Astrophysics Data System (ADS)

Reinhardt, Aleks; Williamson, Alexander J.; Doye, Jonathan P. K.; Carrete, Jesús; Varela, Luis M.; Louis, Ard A.

2011-03-01

In patchy particle systems where there is a competition between the self-assembly of finite clusters and liquid-vapor phase separation, re-entrant phase behavior can be observed, with the system passing from a monomeric vapor phase to a region of liquid-vapor phase coexistence and then to a vapor phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse clusters that have no attractive interactions with any of the other species. The resulting phase diagrams show a clear region of re-entrance. However, for the most physically reasonable parameter values of the model, this behavior is restricted to a certain range of density, with phase separation still persisting at high densities.

Evaporative mass transfer behavior of a complex immiscible liquid.

PubMed

McColl, Colleen M; Johnson, Gwynn R; Brusseau, Mark L

2008-09-01

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult's law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.

Evaporative Mass Transfer Behavior of a Complex Immiscible Liquid

PubMed Central

McColl, Colleen M.; Johnson, Gwynn R.; Brusseau, Mark L.

2010-01-01

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult’s law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium. PMID:18614196

Semiphenomenological model for gas-liquid phase transitions.

PubMed

Benilov, E S; Benilov, M S

2016-03-01

We examine a rarefied gas with inter-molecular attraction. It is argued that the attraction force amplifies random density fluctuations by pulling molecules from lower-density regions into high-density regions and thus may give rise to an instability. To describe this effect, we use a kinetic equation where the attraction force is taken into account in a way similar to how electromagnetic forces in plasma are treated in the Vlasov model. It is demonstrated that the instability occurs when the temperature T is lower than a certain threshold value T(s) depending on the gas density. It is further shown that, even if T is only marginally lower than T(s), the instability generates clusters with density much higher than that of the gas. These results suggest that the instability should be interpreted as a gas-liquid phase transition, with T(s) being the temperature of saturated vapor and the high-density clusters representing liquid droplets.

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.

Bacterial chemotaxis along vapor-phase gradients of naphthalene.

PubMed

Hanzel, Joanna; Harms, Hauke; Wick, Lukas Y

2010-12-15

The role of bacterial growth and translocation for the bioremediation of organic contaminants in the vadose zone is poorly understood. Whereas air-filled pores restrict the mobility of bacteria, diffusion of volatile organic compounds in air is more efficient than in water. Past research, however, has focused on chemotactic swimming of bacteria along gradients of water-dissolved chemicals. In this study we tested if and to what extent Pseudomonas putida PpG7 (NAH7) chemotactically reacts to vapor-phase gradients forming above their swimming medium by the volatilization from a spot source of solid naphthalene. The development of an aqueous naphthalene gradient by air-water partitioning was largely suppressed by means of activated carbon in the agar. Surprisingly, strain PpG7 was repelled by vapor-phase naphthalene although the steady state gaseous concentrations were 50-100 times lower than the aqueous concentrations that result in positive chemotaxis of the same strain. It is thus assumed that the efficient gas-phase diffusion resulting in a steady, and possibly toxic, naphthalene flux to the cells controlled the chemotactic reaction rather than the concentration to which the cells were exposed. To our knowledge this is the first demonstration of apparent chemotactic behavior of bacteria in response to vapor-phase effector gradients.

Vapor-phase exchange of perchloroethene between soil and plants

USGS Publications Warehouse

Struckhoff, G.C.; Burken, J.G.; Schumacher, J.G.

2005-01-01

Tree core concentrations of tetrachloroethylene (perchloroethene, PCE) at the Riverfront Superfund Site in New Haven, MO, were found to mimic the profile of soil phase concentrations. The observed soil-tree core relationship was stronger than that of groundwater PCE to tree core concentrations at the same site. Earlier research has shown a direct, linear relationship between tree core and groundwater concentrations of chlorinated solvents and other organics. Laboratory-scale experiments were performed to elucidate this phenomenon, including determining partitioning coefficients of PCE between plant tissues and air and between plant tissues and water, measured to be 8.1 and 49 L/kg, respectively. The direct relationship of soil to tree core PCE concentrations was hypothesized to be caused by diffusion between tree roots and the soil vapor phase in the subsurface. The central findings of this research are discovering the importance of subsurface vapor-phase transfer for VOCs and uncovering a direct relationship between soil vapor-phase chlorinated solvents and uptake rates that impact contaminant translocation from the subsurface and transfer into the atmosphere. ?? 2005 American Chemical Society.

Vaporization of protic ionic liquids derived from organic superbases and short carboxylic acids.

PubMed

Ribeiro, Filipe M S; Lima, Carlos F R A C; Vaz, Inês C M; Rodrigues, Ana S M C; Sapei, Erlin; Melo, André; Silva, Artur M S; Santos, Luís M N B F

2017-06-28

This work presents a comprehensive evaluation of the phase behaviour and cohesive enthalpy of protic ionic liquids (PILs) composed of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) organic superbases with short-chain length (acetic, propionic and butyric) carboxylic acids. Glass transition temperatures, T g , and enthalpies of vaporization, ΔH vap , were measured for six [BH][A] (1 : 1) PILs (B = DBN, DBU; A = MeCOO, EtCOO, nPrCOO), revealing more significant changes upon increasing the number of -CH 2 - groups in the base than in the acid. The magnitude of ΔH vap evidences that liquid PILs have a high proportion of ions, although the results also indicate that in DBN PILs the concentration of neutral species is not negligible. In the gas phase, these PILs exist as a distribution of ion pairs and isolated neutral species, with speciation being dependent on the temperature and pressure conditions - at high temperatures and low pressures the separated neutral species dominate. The higher T g and ΔH vap of the DBU PILs are explained by the stronger basicity of DBU (as supported by NMR and computational calculations), which increases the extent of proton exchange and the ionic character of the corresponding PILs, resulting in stronger intermolecular interactions in condensed phases.

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.

Interfacial Properties and Mechanisms Dominating Gas Hydrate Cohesion and Adhesion in Liquid and Vapor Hydrocarbon Phases.

PubMed

Hu, Sijia; Koh, Carolyn A

2017-10-24

The interfacial properties and mechanisms of gas hydrate systems play a major role in controlling their interparticle and surface interactions, which is desirable for nearly all energy applications of clathrate hydrates. In particular, preventing gas hydrate interparticle agglomeration and/or particle-surface deposition is critical to the prevention of gas hydrate blockages during the exploration and transportation of oil and gas subsea flow lines. These agglomeration and deposition processes are dominated by particle-particle cohesive forces and particle-surface adhesive force. In this study, we present the first direct measurements on the cohesive and adhesive forces studies of the CH 4 /C 2 H 6 gas hydrate in a liquid hydrocarbon-dominated system utilizing a high-pressure micromechanical force (HP-MMF) apparatus. A CH 4 /C 2 H 6 gas mixture was used as the gas hydrate former in the model liquid hydrocarbon phase. For the cohesive force baseline test, it was found that the addition of liquid hydrocarbon changed the interfacial tension and contact angle of water in the liquid hydrocarbon compared to water in the gas phase, resulting in a force of 23.5 ± 2.5 mN m -1 at 3.45 MPa and 274 K for a 2 h annealing time period in which hydrate shell growth occurs. It was observed that the cohesive force was inversely proportional to the annealing time, whereas the force increased with increasing contact time. For a longer contact time (>12 h), the force could not be measured because the two hydrate particles adhered permanently to form one large particle. The particle-surface adhesive force in the model liquid hydrocarbon was measured to be 5.3 ± 1.1 mN m -1 under the same experimental condition. Finally, with a 1 h contact time, the hydrate particle and the carbon steel (CS) surface were sintered together and the force was higher than what could be measured by the current apparatus. A possible mechanism is presented in this article to describe the effect of contact time

Evaluation of Vapor Pressure and Ultra-High Vacuum Tribological Properties of Ionic Liquids (2) Mixtures and Additives

NASA Technical Reports Server (NTRS)

Morales, Wilfredo; Koch, Victor R.; Street, Kenneth W., Jr.; Richard, Ryan M.

2008-01-01

Ionic liquids are salts, many of which are typically viscous fluids at room temperature. The fluids are characterized by negligible vapor pressures under ambient conditions. These properties have led us to study the effectiveness of ionic liquids containing both organic cations and anions for use as space lubricants. In the previous paper we have measured the vapor pressure and some tribological properties of two distinct ionic liquids under simulated space conditions. In this paper we will present vapor pressure measurements for two new ionic liquids and friction coefficient data for boundary lubrication conditions in a spiral orbit tribometer using stainless steel tribocouples. In addition we present the first tribological data on mixed ionic liquids and an ionic liquid additive. Post mortem infrared and Raman analysis of the balls and races indicates the major degradation pathway for these two organic ionic liquids is similar to those of other carbon based lubricants, i.e. deterioration of the organic structure into amorphous graphitic carbon. The coefficients of friction and lifetimes of these lubricants are comparable to or exceed these properties for several commonly used space oils.

Fluid inclusions in vadose cement with consistent vapor to liquid ratios, Pleistocene Miami Limestone, southeastern Florida

USGS Publications Warehouse

Barker, C.E.; Halley, R.B.

1988-01-01

Vadose cements in the Late Pleistocene Miami Limestone contain regions with two-phase aqueous fluid inclusions that have consistent vapor to liquid (V-L) ratios. When heated, these seemingly primary inclusions homogenize to a liquid phase in a range between 75??C and 130??C (mean = 100??C) and have final melting temperatures between -0.3?? and 0.0??C. The original distribution of Th was broadened during measurements because of fluid inclusion reequilibration. The narrow range of Th in these fluid inclusions suggest unusually consistent V-L ratios. They occur with small, obscure, single phase liquid-filled inclusions, which infer a low temperature origin (less than 60??C), and contradict the higher temperature origin implied by the two phase inclusions. The diagenetic environment producing these seemingly primary fluid inclusions can be inferred from the origin of the host calcite enclosing them. The ??18O composition of these cements (-4 to-5.5%., PDB) and the fresh water in the fluid inclusions are consistent with precipitation from low-temperature meteoric water. The carbon-isotope composition of the vadose cements that contain only rare two-phase fluid inclusions are comparable to the host rock matrix (??13C between 0 and +4%., PDB). Cements that contain common two-phase fluid-inclusions have a distinctly lighter carbon isotopic composition of -3 to -5%.. The carbon isotope composition of cements that contain common two-phase inclusions are about 6%. lighter than those of other vadose cements; models of early meteoric diagenesis indicate that this is the result of precipitation from water that has been influenced by soil gas CO2. Our hypothesis is that the primary fluid inclusions, those with consistent V-L ratios and the single-phase liquid inclusions, form at near-surface temperature (25??C) and pressure when consistent proportions of soil gas and meteoric water percolating through the vadose zone are trapped within elongate vacuoles. This study corroborates

Method and turbine for extracting kinetic energy from a stream of two-phase fluid

NASA Technical Reports Server (NTRS)

Elliott, D. G. (Inventor)

1979-01-01

An axial flow separator turbine is described which includes a number of nozzles for delivering streams of a two-phase fluid along linear paths. A phase separator which responsively separates the vapor and liquid is characterized by concentrically related annuli supported for rotation within the paths. The separator has endless channels for confining the liquid under the influence of centrifugal forces. A vapor turbine fan extracts kinetic energy from the liquid. Angular momentum of both the liquid phase and the vapor phase of the fluid is converted to torque.

Stand-off detection of vapor phase explosives by resonance enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ehlerding, Anneli; Johansson, Ida; Wallin, Sara; Östmark, Henric

2010-10-01

Stand-off measurements on nitromethane (NM), 2,4-DNT and 2,4,6-TNT in vapor phase using resonance Raman spectroscopy have been performed. The Raman cross sections for NM, DNT and TNT in vapor phase have been measured in the wavelength range 210-300 nm under laboratory conditions, in order to estimate how large resonance enhancement factors can be achieved for these explosives. The measurements show that the signal is greatly enhanced, up to 250.000 times for 2,4-DNT and 60.000 times for 2,4,6-TNT compared to the non-resonant signal at 532 nm. For NM the resonance enhancement enabled realistic outdoor measurements in vapor phase at 13 m distance. This all indicate a potential for resonance Raman spectroscopy as a stand-off technique for detection of vapor phase explosives.

Vapor Bubbles

NASA Astrophysics Data System (ADS)

Prosperetti, Andrea

2017-01-01

This article reviews the fundamental physics of vapor bubbles in liquids. Work on bubble growth and condensation for stationary and translating bubbles is summarized and the differences with bubbles containing a permanent gas stressed. In particular, it is shown that the natural frequency of a vapor bubble is proportional not to the inverse radius, as for a gas bubble, but to the inverse radius raised to the power 2/3. Permanent gas dissolved in the liquid diffuses into the bubble with strong effects on its dynamics. The effects of the diffusion of heat and mass on the propagation of pressure waves in a vaporous bubbly liquid are discussed. Other topics briefly touched on include thermocapillary flow, plasmonic nanobubbles, and vapor bubbles in an immiscible liquid.

Critical points of metal vapors

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

Khomkin, A. L., E-mail: alhomkin@mail.ru; Shumikhin, A. S.

2015-09-15

A new method is proposed for calculating the parameters of critical points and binodals for the vapor–liquid (insulator–metal) phase transition in vapors of metals with multielectron valence shells. The method is based on a model developed earlier for the vapors of alkali metals, atomic hydrogen, and exciton gas, proceeding from the assumption that the cohesion determining the basic characteristics of metals under normal conditions is also responsible for their properties in the vicinity of the critical point. It is proposed to calculate the cohesion of multielectron atoms using well-known scaling relations for the binding energy, which are constructed for mostmore » metals in the periodic table by processing the results of many numerical calculations. The adopted model allows the parameters of critical points and binodals for the vapor–liquid phase transition in metal vapors to be calculated using published data on the properties of metals under normal conditions. The parameters of critical points have been calculated for a large number of metals and show satisfactory agreement with experimental data for alkali metals and with available estimates for all other metals. Binodals of metals have been calculated for the first time.« less

VAPOR PRESSURES, LIQUID MOLAR VOLUMES, VAPOR NON- IDEALITIES, AND CRITICAL PROPERTIES OF SOME FLUORINATED ETHERS: CF3OCF2OCF3, CF3OCF2 CF2H, c-CF2CF2CF2O, CF3OCF2H, AND CF3OCH3; AND OF CCl3F AND CF2ClH

EPA Science Inventory

Vapor pressures, compressibilities, expansivities, and molar volumes of the liquid phase have been measured between room temperature and the critical temperature for a series of fluorinated ethers: CF3OCF2OCF3, CF3OCF2CF2H, c-CF2CF2CF2O, CF3OCF2H, and CF3OCH3. Vapor-phase non-ide...

40 CFR 60.482-7a - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

...-7a Standards: Valves in gas/vapor service and in light liquid service. (a)(1) Each valve shall be... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standards: Valves in gas/vapor service and in light liquid service. 60.482-7a Section 60.482-7a Protection of Environment ENVIRONMENTAL...

40 CFR 60.482-7a - Standards: Valves in gas/vapor service and in light liquid service.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-7a Standards: Valves in gas/vapor service and in light liquid service. (a)(1) Each valve shall be... 40 Protection of Environment 7 2014-07-01 2014-07-01 false Standards: Valves in gas/vapor service and in light liquid service. 60.482-7a Section 60.482-7a Protection of Environment ENVIRONMENTAL...

40 CFR 60.482-7a - Standards: Valves in gas/vapor service and in light liquid service.