Surfactant-enhanced remediation of a trichloroethene-contaminated aquifer. 1. Transport of triton X-100

USGS Publications Warehouse

Smith, J.A.; Sahoo, D.; Mclellan, H.M.; Imbrigiotta, T.E.

1997-01-01

Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer at Picatinny Arsenal, NJ, has been studied through a series of laboratory and field experiments. In the laboratory, batch and column experiments were conducted to quantify the rate and amount of Triton X-100 sorption to the aquifer sediments. In the field, a 400 mg/L aqueous Triton X-100 solution was injected into the aquifer at a rate of 26.5 L/min for a 35-d period. The transport of Triton X-100 was monitored by sampling and analysis of groundwater at six locations surrounding the injection well. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two- dimensional (respectively) transient solute transport models with either equilibrium or rate-limited sorption. These analyses reveal that Triton X- 100 sorption to the aquifer solids is slow relative to advective and dispersive transport and that an equilibrium sorption model cannot simulate accurately the observed soil column and field data. Comparison of kinetic sorption parameters from batch, column, and field transport data indicate that both physical heterogeneities and Triton X-100 mass transfer between water and soil contribute to the kinetic transport effects.Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer was studied. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two-dimensional transient solute transport models with either equilibrium or rate-limited sorption. These analyses revealed that Triton X-100 sorption to the aquifer solids was slow relative to advective and dispersive transport.

The assumption of equilibrium in models of migration.

PubMed

Schachter, J; Althaus, P G

1993-02-01

In recent articles Evans (1990) and Harrigan and McGregor (1993) (hereafter HM) scrutinized the equilibrium model of migration presented in a 1989 paper by Schachter and Althaus. This model used standard microeconomics to analyze gross interregional migration flows based on the assumption that gross flows are in approximate equilibrium. HM criticized the model as theoretically untenable, while Evans summoned empirical as well as theoretical objections. HM claimed that equilibrium of gross migration flows could be ruled out on theoretical grounds. They argued that the absence of net migration requires that either all regions have equal populations or that unsustainable regional migration propensities must obtain. In fact some moves are inter- and other are intraregional. It does not follow, however, that the number of interregional migrants will be larger for the more populous region. Alternatively, a country could be divided into a large number of small regions that have equal populations. With uniform propensities to move, each of these analytical regions would experience in equilibrium zero net migration. Hence, the condition that net migration equal zero is entirely consistent with unequal distributions of population across regions. The criticisms of Evans were based both on flawed reasoning and on misinterpretation of the results of a number of econometric studies. His reasoning assumed that the existence of demand shifts as found by Goldfarb and Yezer (1987) and Topel (1986) invalidated the equilibrium model. The equilibrium never really obtains exactly, but economic modeling of migration properly begins with a simple equilibrium model of the system. A careful reading of the papers Evans cited in support of his position showed that in fact they affirmed rather than denied the appropriateness of equilibrium modeling. Zero net migration together with nonzero gross migration are not theoretically incompatible with regional heterogeneity of population, wages, or amenities.

Instantaneous charge state of uranium projectiles in fully ionized plasmas from energy loss experiments

NASA Astrophysics Data System (ADS)

Morales, Roberto; Barriga-Carrasco, Manuel D.; Casas, David

2017-04-01

The instantaneous charge state of uranium ions traveling through a fully ionized hydrogen plasma has been theoretically studied and compared with one of the first energy loss experiments in plasmas, carried out at GSI-Darmstadt by Hoffmann et al. in the 1990s. For this purpose, two different methods to estimate the instantaneous charge state of the projectile have been employed: (1) rate equations using ionization and recombination cross sections and (2) equilibrium charge state formulas for plasmas. Also, the equilibrium charge state has been obtained using these ionization and recombination cross sections and compared with the former equilibrium formulas. The equilibrium charge state of projectiles in plasmas is not always reached, and it depends mainly on the projectile velocity and the plasma density. Therefore, a non-equilibrium or an instantaneous description of the projectile charge is necessary. The charge state of projectile ions cannot be measured, except after exiting the target, and experimental data remain very scarce. Thus, the validity of our charge state model is checked by comparing the theoretical predictions with an energy loss experiment, as the energy loss has a generally quadratic dependence on the projectile charge state. The dielectric formalism has been used to calculate the plasma stopping power including the Brandt-Kitagawa (BK) model to describe the charge distribution of the projectile. In this charge distribution, the instantaneous number of bound electrons instead of the equilibrium number has been taken into account. Comparing our theoretical predictions with experiments, it is shown the necessity of including the instantaneous charge state and the BK charge distribution for a correct energy loss estimation. The results also show that the initial charge state has a strong influence in order to estimate the energy loss of the uranium ions.

Identifiability of sorption parameters in stirred flow-through reactor experiments and their identification with a Bayesian approach.

PubMed

Nicoulaud-Gouin, V; Garcia-Sanchez, L; Giacalone, M; Attard, J C; Martin-Garin, A; Bois, F Y

2016-10-01

This paper addresses the methodological conditions -particularly experimental design and statistical inference- ensuring the identifiability of sorption parameters from breakthrough curves measured during stirred flow-through reactor experiments also known as continuous flow stirred-tank reactor (CSTR) experiments. The equilibrium-kinetic (EK) sorption model was selected as nonequilibrium parameterization embedding the K d approach. Parameter identifiability was studied formally on the equations governing outlet concentrations. It was also studied numerically on 6 simulated CSTR experiments on a soil with known equilibrium-kinetic sorption parameters. EK sorption parameters can not be identified from a single breakthrough curve of a CSTR experiment, because K d,1 and k - were diagnosed collinear. For pairs of CSTR experiments, Bayesian inference allowed to select the correct models of sorption and error among sorption alternatives. Bayesian inference was conducted with SAMCAT software (Sensitivity Analysis and Markov Chain simulations Applied to Transfer models) which launched the simulations through the embedded simulation engine GNU-MCSim, and automated their configuration and post-processing. Experimental designs consisting in varying flow rates between experiments reaching equilibrium at contamination stage were found optimal, because they simultaneously gave accurate sorption parameters and predictions. Bayesian results were comparable to maximum likehood method but they avoided convergence problems, the marginal likelihood allowed to compare all models, and credible interval gave directly the uncertainty of sorption parameters θ. Although these findings are limited to the specific conditions studied here, in particular the considered sorption model, the chosen parameter values and error structure, they help in the conception and analysis of future CSTR experiments with radionuclides whose kinetic behaviour is suspected. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mathematical model for HIV spreads control program with ART treatment

NASA Astrophysics Data System (ADS)

Maimunah; Aldila, Dipo

2018-03-01

In this article, using a deterministic approach in a seven-dimensional nonlinear ordinary differential equation, we establish a mathematical model for the spread of HIV with an ART treatment intervention. In a simplified model, when no ART treatment is implemented, disease-free and the endemic equilibrium points were established analytically along with the basic reproduction number. The local stability criteria of disease-free equilibrium and the existing criteria of endemic equilibrium were analyzed. We find that endemic equilibrium exists when the basic reproduction number is larger than one. From the sensitivity analysis of the basic reproduction number of the complete model (with ART treatment), we find that the increased number of infected humans who follow the ART treatment program will reduce the basic reproduction number. We simulate this result also in the numerical experiment of the autonomous system to show how treatment intervention impacts the reduction of the infected population during the intervention time period.

Bounded energy states in homogeneous turbulent shear flow: An alternative view

NASA Technical Reports Server (NTRS)

Bernard, Peter S.; Speziale, Charles G.

1990-01-01

The equilibrium structure of homogeneous turbulent shear flow is investigated from a theoretical standpoint. Existing turbulence models, in apparent agreement with physical and numerical experiments, predict an unbounded exponential time growth of the turbulent kinetic energy and dissipation rate; only the anisotropy tensor and turbulent time scale reach a structural equilibrium. It is shown that if vortex stretching is accounted for in the dissipation rate transport equation, then there can exist equilibrium solutions, with bounded energy states, where the turbulence production is balanced by its dissipation. Illustrative calculations are present for a k-epsilon model modified to account for vortex stretching. The calculations indicate an initial exponential time growth of the turbulent kinetic energy and dissipation rate for elapsed times that are as large as those considered in any of the previously conducted physical or numerical experiments on homogeneous shear flow. However, vortex stretching eventually takes over and forces a production-equals-dissipation equilibrium with bounded energy states. The validity of this result is further supported by an independent theoretical argument. It is concluded that the generally accepted structural equilibrium for homogeneous shear flow with unbounded component energies is in need of re-examination.

Maintenance of equilibrium point control during an unexpectedly loaded rapid limb movement.

PubMed

Simmons, R W; Richardson, C

1984-06-08

Two experiments investigated whether the equilibrium point hypothesis or the mass-spring model of motor control subserves positioning accuracy during spring loaded, rapid, bi-articulated movement. For intact preparations, the equilibrium point hypothesis predicts response accuracy to be determined by a mixture of afferent and efferent information, whereas the mass-spring model predicts positioning to be under a direct control system. Subjects completed a series of load-resisted training trials to a spatial target. The magnitude of a sustained spring load was unexpectedly increased on selected trials. Results indicated positioning accuracy and applied force varied with increases in load, which suggests that the original efferent commands are modified by afferent information during the movement as predicted by the equilibrium point hypothesis.

Ion exchange of several radionuclides on the hydrous crystalline silicotitanate, UOP IONSIV IE-911

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

Huckman, M.E.; Latheef, I.M.; Anthony, R.G.

1999-04-01

The crystalline silicotitanate, UOP IONSIV IE-911, is a proven material for removing radionuclides from a wide variety of waste streams. It is superior for removing several radionuclides from the highly alkaline solutions typical of DOE wastes. This laboratory previously developed an equilibrium model applicable to complex solutions for IE-910 (the power form of the granular IE-911), and more recently, the authors have developed several single component ion-exchange kinetic models for predicting column breakthrough curves and batch reactor concentration histories. In this paper, the authors model ion-exchange column performance using effective diffusivities determined from batch kinetic experiments. This technique is preferablemore » because the batch experiments are easier, faster, and cheaper to perform than column experiments. They also extend these ideas to multicomponent systems. Finally, they evaluate the ability of the equilibrium model to predict data for IE-911.« less

Pair potentials for warm dense matter and their application to x-ray Thomson scattering in aluminum and beryllium.

PubMed

Harbour, L; Dharma-Wardana, M W C; Klug, D D; Lewis, L J

2016-11-01

Ultrafast laser experiments yield increasingly reliable data on warm dense matter, but their interpretation requires theoretical models. We employ an efficient density functional neutral-pseudoatom hypernetted-chain (NPA-HNC) model with accuracy comparable to ab initio simulations and which provides first-principles pseudopotentials and pair potentials for warm-dense matter. It avoids the use of (i) ad hoc core-repulsion models and (ii) "Yukawa screening" and (iii) need not assume ion-electron thermal equilibrium. Computations of the x-ray Thomson scattering (XRTS) spectra of aluminum and beryllium are compared with recent experiments and with density-functional-theory molecular-dynamics (DFT-MD) simulations. The NPA-HNC structure factors, compressibilities, phonons, and conductivities agree closely with DFT-MD results, while Yukawa screening gives misleading results. The analysis of the XRTS data for two of the experiments, using two-temperature quasi-equilibrium models, is supported by calculations of their temperature relaxation times.

Non-equilibrium thermodynamical description of rhythmic motion patterns of active systems: a canonical-dissipative approach.

PubMed

Dotov, D G; Kim, S; Frank, T D

2015-02-01

We derive explicit expressions for the non-equilibrium thermodynamical variables of a canonical-dissipative limit cycle oscillator describing rhythmic motion patterns of active systems. These variables are statistical entropy, non-equilibrium internal energy, and non-equilibrium free energy. In particular, the expression for the non-equilibrium free energy is derived as a function of a suitable control parameter. The control parameter determines the Hopf bifurcation point of the deterministic active system and describes the effective pumping of the oscillator. In analogy to the equilibrium free energy of the Landau theory, it is shown that the non-equilibrium free energy decays as a function of the control parameter. In doing so, a similarity between certain equilibrium and non-equilibrium phase transitions is pointed out. Data from an experiment on human rhythmic movements is presented. Estimates for pumping intensity as well as the thermodynamical variables are reported. It is shown that in the experiment the non-equilibrium free energy decayed when pumping intensity was increased, which is consistent with the theory. Moreover, pumping intensities close to zero could be observed at relatively slow intended rhythmic movements. In view of the Hopf bifurcation underlying the limit cycle oscillator model, this observation suggests that the intended limit cycle movements were actually more similar to trajectories of a randomly perturbed stable focus. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Modeling multicomponent ion exchange equilibrium utilizing hydrous crystalline silicotitanates by a multiple interactive ion exchange site model

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

Zheng, Z.; Anthony, R.G.; Miller, J.E.

1997-06-01

An equilibrium multicomponent ion exchange model is presented for the ion exchange of group I metals by TAM-5, a hydrous crystalline silicotitanate. On the basis of the data from ion exchange and structure studies, the solid phase is represented as Na{sub 3}X instead of the usual form of NaX. By using this solid phase representation, the solid can be considered as an ideal phase. A set of model ion exchange reactions is proposed for ion exchange between H{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, and Cs{sup +}. The equilibrium constants for these reactions were estimated from experiments with simplemore » ion exchange systems. Bromley`s model for activity coefficients of electrolytic solutions was used to account for liquid phase nonideality. Bromley`s model parameters for CsOH at high ionic strength and for NO{sub 2}{sup {minus}} and Al(OH){sub 4}{sup {minus}} were estimated in order to apply the model for complex waste simulants. The equilibrium compositions and distribution coefficients of counterions were calculated for complex simulants typical of DOE wastes by solving the equilibrium equations for the model reactions and material balance equations. The predictions match the experimental results within 10% for all of these solutions.« less

Adsorption of anionic and cationic dyes on activated carbon from aqueous solutions: equilibrium and kinetics.

PubMed

Rodríguez, Araceli; García, Juan; Ovejero, Gabriel; Mestanza, María

2009-12-30

Activated carbon was utilized as adsorbent to remove anionic dye, Orange II (OII), and cationic dye, Methylene blue (MB), from aqueous solutions by adsorption. Batch experiments were conducted to study the effects of temperature (30-65 degrees C), initial concentration of adsorbate (300-500 mg L(-1)) and pH (3.0-9.0) on dyes adsorption. Equilibrium adsorption isotherms and kinetics were investigated. The equilibrium experimental data were analyzed by the Langmuir, Freundlich, Toth and Redlich-Peterson models. The kinetic data obtained with different carbon mass were analyzed using a pseudo-first order, pseudo-second order, intraparticle diffusion, Bangham and Chien-Clayton equations. The best results were achieved with the Langmuir isotherm equilibrium model and with the pseudo-second order kinetic model. The activated carbon was found to be very effective as adsorbent for MB and OII from aqueous solutions.

Laboratory Scale Experiments and Numerical Modeling of Cosolvent flushing of NAPL Mixtures in Saturated Porous Media

NASA Astrophysics Data System (ADS)

Agaoglu, B.; Scheytt, T. J.; Copty, N. K.

2011-12-01

This study examines the mechanistic processes governing multiphase flow of a water-cosolvent-NAPL system in saturated porous media. Laboratory batch and column flushing experiments were conducted to determine the equilibrium properties of pure NAPL and synthetically prepared NAPL mixtures as well as NAPL recovery mechanisms for different water-ethanol contents. The effect of contact time was investigated by considering different steady and intermittent flow velocities. A modified version of multiphase flow simulator (UTCHEM) was used to compare the multiphase model simulations with the column experiment results. The effect of employing different grid geometries (1D, 2D, 3D), heterogeneity and different initial NAPL saturation configurations were also examined in the model. It is shown that the change in velocity affects the mass transfer rate between phases as well as the ultimate NAPL recovery percentage. The experiments with slow flow rate flushing of pure NAPL and the 3D UTCHEM simulations gave similar effluent concentrations and NAPL cumulative recoveries. The results were less consistent for fast non-equilibrium flow conditions. The dissolution process from the NAPL mixture into the water-ethanol flushing solutions was found to be more complex than dissolution expressions incorporated in the numerical model. The dissolution rate of individual organic compounds (namely Toluene and Benzene) from a mixture NAPL into the ethanol-water flushing solution is found not to correlate with their equilibrium solubility values.The implications of this controlled experimental and modeling study on field cosolvent remediation applications are discussed.

Bounded energy states in homogeneous turbulent shear flow - An alternative view

NASA Technical Reports Server (NTRS)

Bernard, P. S.; Speziale, C. G.

1992-01-01

The equilibrium structure of homogeneous turbulent shear flow is investigated from a theoretical standpoint. Existing turbulence models, in apparent agreement with physical and numerical experiments, predict an unbounded exponential time growth of the turbulent kinetic energy and dissipation rate; only the anisotropy tensor and turbulent time scale reach a structural equilibrium. It is shown that if a residual vortex stretching term is maintained in the dissipation rate transport equation, then there can exist equilibrium solutions, with bounded energy states, where the turbulence production is balanced by its dissipation. Illustrative calculations are presented for a k-epsilon model modified to account for net vortex stretching.

Saturated and unsaturated salt transport in peat from a constructed fen

NASA Astrophysics Data System (ADS)

Simhayov, Reuven B.; Weber, Tobias K. D.; Price, Jonathan S.

2018-02-01

The underlying processes governing solute transport in peat from an experimentally constructed fen peatland were analyzed by performing saturated and unsaturated solute breakthrough experiments using Na+ and Cl- as reactive and non-reactive solutes, respectively. We tested the performance of three solute transport models, including the classical equilibrium convection-dispersion equation (CDE), a chemical non-equilibrium one-site adsorption model (OSA) and a model to account for physical non-equilibrium, the mobile-immobile (MIM) phases. The selection was motivated by the fact that the applicability of the MIM in peat soils finds a wide consensus. However, results from inverse modeling and a robust statistical evaluation of this peat provide evidence that the measured breakthrough of the conservative tracer, Cl-, could be simulated well using the CDE. Furthermore, the very high Damköhler number (which approaches infinity) suggests instantaneous equilibration between the mobile and immobile phases underscoring the redundancy of the MIM approach for this particular peat. Scanning electron microscope images of the peat show the typical multi-pore size distribution structures have been homogenized sufficiently by decomposition, such that physical non-equilibrium solute transport no longer governs the transport process. This result is corroborated by the fact the soil hydraulic properties were adequately described using a unimodal van Genuchten-Mualem model between saturation and a pressure head of ˜ -1000 cm of water. Hence, MIM was not the most suitable choice, and the long tailing of the Na+ breakthrough curve was caused by chemical non-equilibrium. Successful description was possible using the OSA model. To test our results for the unsaturated case, we conducted an unsaturated steady-state evaporation experiment to drive Na+ and Cl- transport. Using the parameterized transport models from the saturated experiments, we could numerically simulate the unsaturated transport using Hydrus-1-D. The simulation showed a good prediction of observed values, confirming the suitability of the parameters for use in a slightly unsaturated transport simulation. The findings improve the understanding of solute redistribution in the constructed fen and imply that MIM should not be automatically assumed for solute transport in peat but rather should be evidence based.

An experiment on radioactive equilibrium and its modelling using the ‘radioactive dice’ approach

NASA Astrophysics Data System (ADS)

Santostasi, Davide; Malgieri, Massimiliano; Montagna, Paolo; Vitulo, Paolo

2017-07-01

In this article we describe an educational activity on radioactive equilibrium we performed with secondary school students (17-18 years old) in the context of a vocational guidance stage for talented students at the Department of Physics of the University of Pavia. Radioactive equilibrium is investigated experimentally by having students measure the activity of 214Bi from two different samples, obtained using different preparation procedures from an uraniferous rock. Students are guided in understanding the mathematical structure of radioactive equilibrium through a modelling activity in two parts. Before the lab measurements, a dice game, which extends the traditional ‘radioactive dice’ activity to the case of a chain of two decaying nuclides, is performed by students divided into small groups. At the end of the laboratory work, students design and run a simple spreadsheet simulation modelling the same basic radioactive chain with user defined decay constants. By setting the constants to realistic values corresponding to nuclides of the uranium decay chain, students can deepen their understanding of the meaning of the experimental data, and also explore the difference between cases of non-equilibrium, transient and secular equilibrium.

Physico-chemical processes for landfill leachate treatment: Experiments and mathematical models

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

Xing, W.; Ngo, H.H.; Kim, S.H.

2008-07-01

In this study, the adsorption of synthetic landfill leachate onto four kinds of activated carbon has been investigated. From the equilibrium and kinetics experiments, it was observed that coal based PAC presented the highest organic pollutants removal efficiency (54%), followed by coal based GAC (50%), wood based GAC (33%) and wood based PAC (14%). The adsorption equilibrium of PAC and GAC was successfully predicted by Henry-Freundlich adsorption model whilst LDFA + Dual isotherm Kinetics model could describe well the batch adsorption kinetics. The flocculation and flocculation-adsorption experiments were also conducted. The results indicated that flocculation did not perform well onmore » organics removal because of the dominance of low molecular weight organic compounds in synthetic landfill leachate. Consequently, flocculation as pretreatment to adsorption and a combination of flocculation-adsorption could not improve much the organic removal efficiency for the single adsorption process.« less

Sorption equilibrium, thermodynamics and pH-indicator properties of cresyl violet dye/bentonite composite system.

PubMed

Georgieva, Nedyalka; Yaneva, Zvezdelina; Dermendzhieva, Diyana

2017-09-01

The aim of the present study was to develop cresyl violet (CV)/bentonite composite system, to investigate the equilibrium sorption of the fluorescent dye on bentonite, to determine the characteristic equilibrium and thermodynamic parameters of the system by appropriate empirical isotherm models and to assess its pH-indicator properties. The absorption characteristics of CV solutions were investigated by UV/VIS spectrophotometer. Equilibrium experiments were conducted and the experimental data were modelled by six mathematical isotherm models. The analyses of the experimental data showed that bentonite exhibited significantly high capacity - 169.92 mg/g, towards CV. The encapsulation efficiency was 85%. The Langmuir, Flory-Huggins and El-Awady models best represented the experimental results. The free Gibbs energy of adsorption (ΔG o ) was calculated on the basis of the values of the equilibrium coefficients determined by the proposed models. The values of ΔG determined by the Langmuir, Temkin and Flory-Huggins models are within the range -20 to -40 kJ/mol, which indicates that the adsorption process is spontaneous and chemisorption takes place due to charge sharing or transfer from the dye molecules to the sorbent surface as a coordinate type of bond. The investigations of the obtained CV/bentonite hybrid systems for application as pH-markers showed satisfactory results.

Ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure

NASA Astrophysics Data System (ADS)

Sucipto, Retno Kumala Hesti; Kuswandi, Wibawa, Gede

2017-05-01

The objective of this study was to determine ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure. Using 25 mL equilibrium cell equipped jacketted water connected to water bath to maintain equilibrium temperature constant. The procedure of this experiment was conducted by inserting mixture of eugenol + tert-butanol + water system at certain composition into equilibrium cell. The solution was stirred for 4 hours and then was allowed for 20 hours in order to separate aqueous and organic phases completely. The temperature equilibrium cell of and the atmosphere pressure were recorded as equilibrium temperature and pressure for each measurenment. The equilibrium compositions of each phase were analyzed using Gas Chromatography. The experimental data obtained in this work were correlated with NRTL and UNIQUAC models with root mean square deviation between esperimental and calculated equilibrium compositions of 0.03% and 0.04% respectively.

Phase Equilibrium, Chemical Equilibrium, and a Test of the Third Law: Experiments for Physical Chemistry.

ERIC Educational Resources Information Center

Dannhauser, Walter

1980-01-01

Described is an experiment designed to provide an experimental basis for a unifying point of view (utilizing theoretical framework and chemistry laboratory experiments) for physical chemistry students. Three experiments are described: phase equilibrium, chemical equilibrium, and a test of the third law of thermodynamics. (Author/DS)

Imbalance detection in a manufacturing system: An agent-based model usage

NASA Astrophysics Data System (ADS)

Shevchuk, G. K.; Zvereva, O. M.; Medvedev, M. A.

2017-11-01

This paper delivers the results of the research work targeted at communications in a manufacturing system. A computer agent-based model which simulates manufacturing system functioning has been engineered. The system lifecycle consists of two recursively repeated stages: a communication stage and a production stage. Model data sets were estimated with the static Leontief's equilibrium equation usage. In experiments relationships between the manufacturing system lifecycle time and conditions of equilibrium violations have been identified. The research results are to be used to propose violation negative influence compensation methods.

Enhanced picture of protein-folding intermediates using organic solvents in H/D exchange and quench-flow experiments

PubMed Central

Nishimura, Chiaki; Dyson, H. Jane; Wright, Peter E.

2005-01-01

Hydrogen/deuterium exchange followed by trapping of the labeled species in the aprotic solvent DMSO has been used to elucidate structure in both the burst-phase molten globule-folding intermediate of apomyoglobin and in an equilibrium intermediate that models the kinetic intermediate. Precise estimates can be made of exchange times in an interrupted exchange-out experiment at pH 4 followed by analysis in DMSO solution, giving extensive sequence-specific information about the structure of the equilibrium intermediate. In addition, the use of DMSO as a solvent for NMR measurements after quench-flow pH-pulse labeling experiments gives a greatly increased data set for the elucidation of the kinetic folding pathway. Interestingly, differences are observed in some regions of apomyoglobin between the equilibrium and kinetic intermediates. These differences are quantitative rather than qualitative; that is, the overall patterns of labeling and secondary structure formation remain similar between the two species. However, local differences are observed, which probably reflect the difference in the solution conditions for the equilibrium experiment (pH 4) vs. the kinetic experiment (pH 6) and the change in the status of the stabilizing hydrogen bond between the side chains of His-24 and His-119. PMID:15769860

Multi-scale modelling of supercapacitors: From molecular simulations to a transmission line model

NASA Astrophysics Data System (ADS)

Pean, C.; Rotenberg, B.; Simon, P.; Salanne, M.

2016-09-01

We perform molecular dynamics simulations of a typical nanoporous-carbon based supercapacitor. The organic electrolyte consists in 1-ethyl-3-methylimidazolium and hexafluorophosphate ions dissolved in acetonitrile. We simulate systems at equilibrium, for various applied voltages. This allows us to determine the relevant thermodynamic (capacitance) and transport (in-pore resistivities) properties. These quantities are then injected in a transmission line model for testing its ability to predict the charging properties of the device. The results from this macroscopic model are in good agreement with non-equilibrium molecular dynamics simulations, which validates its use for interpreting electrochemical impedance experiments.

Equivalences between refractive index and equilibrium water content of conventional and silicone hydrogel soft contact lenses from automated and manual refractometry.

PubMed

González-Méijome, José M; López-Alemany, Antonio; Lira, Madalena; Almeida, José B; Oliveira, M Elisabete C D Real; Parafita, Manuel A

2007-01-01

The purpose of the present study was to develop mathematical relationships that allow obtaining equilibrium water content and refractive index of conventional and silicone hydrogel soft contact lenses from refractive index measures obtained with automated refractometry or equilibrium water content measures derived from manual refractometry, respectively. Twelve HEMA-based hydrogels of different hydration and four siloxane-based polymers were assayed. A manual refractometer and a digital refractometer were used. Polynomial models obtained from the sucrose curves of equilibrium water content against refractive index and vice-versa were used either considering the whole range of sucrose concentrations (16-100% equilibrium water content) or a range confined to the equilibrium water content of current soft contact lenses (approximately 20-80% equilibrium water content). Values of equilibrium water content measured with the Atago N-2E and those derived from the refractive index measurement with CLR 12-70 by the applications of sucrose-based models displayed a strong linear correlation (r2 = 0.978). The same correlations were obtained when the models are applied to obtain refractive index values from the Atago N-2E and compared with those (values) given by the CLR 12-70 (r2 = 0.978). No significantly different results are obtained between models derived from the whole range of the sucrose solution or the model limited to the normal range of soft contact lens hydration. Present results will have implications for future experimental and clinical research regarding normal hydration and dehydration experiments with hydrogel polymers, and particularly in the field of contact lenses. 2006 Wiley Periodicals, Inc.

Xcas as a Programming Environment for Stability Conditions for a Class of Differential Equation Models in Economics

NASA Astrophysics Data System (ADS)

Halkos, George E.; Tsilika, Kyriaki D.

2011-09-01

In this paper we examine the property of asymptotic stability in several dynamic economic systems, modeled in ordinary differential equation formulations of time parameter t. Asymptotic stability ensures intertemporal equilibrium for the economic quantity the solution stands for, regardless of what the initial conditions happen to be. Existence of economic equilibrium in continuous time models is checked via a Symbolic language, the Xcas program editor. Using stability theorems of differential equations as background a brief overview of symbolic capabilities of free software Xcas is given. We present computational experience with a programming style for stability results of ordinary linear and nonlinear differential equations. Numerical experiments on traditional applications of economic dynamics exhibit the simplicity clarity and brevity of input and output of our computer codes.

Using Electrophoretic Mobility Shift Assays to Measure Equilibrium Dissociation Constants: GAL4-p53 Binding DNA as a Model System

ERIC Educational Resources Information Center

Heffler, Michael A.; Walters, Ryan D.; Kugel, Jennifer F.

2012-01-01

An undergraduate biochemistry laboratory experiment is described that will teach students the practical and theoretical considerations for measuring the equilibrium dissociation constant (K[subscript D]) for a protein/DNA interaction using electrophoretic mobility shift assays (EMSAs). An EMSA monitors the migration of DNA through a native gel;…

Tightly Coupled Mechanistic Study of Materials in the Extreme Space Environment

DTIC Science & Technology

2016-10-11

to examine spacecraft contamination issues from the perspective of non- equilibrium gas dynamics (Levin), material response at the atomistic level...Space Environment Group has worked to examine spacecraft contamination issues from the perspective of non- equilibrium gas dynamics (Levin...material response at the atomistic level (Rajan), high fidelity gas -surface chemistry models (van Duin), and experiments to characterize and test

Optimal control of a coupled partial and ordinary differential equations system for the assimilation of polarimetry Stokes vector measurements in tokamak free-boundary equilibrium reconstruction with application to ITER

NASA Astrophysics Data System (ADS)

Faugeras, Blaise; Blum, Jacques; Heumann, Holger; Boulbe, Cédric

2017-08-01

The modelization of polarimetry Faraday rotation measurements commonly used in tokamak plasma equilibrium reconstruction codes is an approximation to the Stokes model. This approximation is not valid for the foreseen ITER scenarios where high current and electron density plasma regimes are expected. In this work a method enabling the consistent resolution of the inverse equilibrium reconstruction problem in the framework of non-linear free-boundary equilibrium coupled to the Stokes model equation for polarimetry is provided. Using optimal control theory we derive the optimality system for this inverse problem. A sequential quadratic programming (SQP) method is proposed for its numerical resolution. Numerical experiments with noisy synthetic measurements in the ITER tokamak configuration for two test cases, the second of which is an H-mode plasma, show that the method is efficient and that the accuracy of the identification of the unknown profile functions is improved compared to the use of classical Faraday measurements.

Reactive solute transport in streams: 2. Simulation of a pH modification experiment

USGS Publications Warehouse

Runkel, Robert L.; McKnight, Diane M.; Bencala, Kenneth E.; Chapra, Steven C.

1996-01-01

We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pKsp from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pKsp from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and pH profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH-dependent processes within the context of hydrologic transport.

Reactive Solute Transport in Streams: 2. Simulation of a pH Modification Experiment

NASA Astrophysics Data System (ADS)

Runkel, Robert L.; McKnight, Diane M.; Bencala, Kenneth E.; Chapra, Steven C.

1996-02-01

We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pKsp from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pKsp from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and pH profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH-dependent processes within the context of hydrologic transport.

Lysozyme

NASA Technical Reports Server (NTRS)

2004-01-01

Protein isolated from hen egg-white and functions as a bacteriostatic enzyme by degrading bacterial cell walls. First enzyme ever characterized by protein crystallography. It is used as an excellent model system for better understanding parameters involved in microgravity experiments with data from laboratory experiments to study the equilibrium rate of hanging drop experiments in microgravity.

Microgravity

NASA Image and Video Library

2004-04-15

Protein isolated from hen egg-white and functions as a bacteriostatic enzyme by degrading bacterial cell walls. First enzyme ever characterized by protein crystallography. It is used as an excellent model system for better understanding parameters involved in microgravity experiments with data from laboratory experiments to study the equilibrium rate of hanging drop experiments in microgravity.

Chemical reactions simulated by ground-water-quality models

USGS Publications Warehouse

Grove, David B.; Stollenwerk, Kenneth G.

1987-01-01

Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

Potential adsorption of methylene blue from aqueous solution using green macroalgaePosidonia oceanica.

NASA Astrophysics Data System (ADS)

Allouche, F.-N.; Yassaa, N.

2018-03-01

The use of inexpensive biological materials, such as marine algae for removing dyes from contaminated industrial effluents appears as a potential alternative method. The aim of this study is to investigate the aptitude of marine macroalgae Posidonia Oceanica local biomass abundant on the coasts of Algeria for selective sorption of methylene blue (MB) from an aqueous solution in batch experiments at 20 °C. A maximum percentage removal of Posidonia oceanica occurs at pH 5. Equilibrium isotherm data were analyzed using the Langmuir and the Freundlich isotherms. The adsorption equilibrium of methylene blue was best describe by Langmuir model than the Freundlich model. The maximum sorption capacity was 357 mgg-1at pH 5. The sorption data were very well described by the pseudo-second-order model. Keywords: Posidonia oceanica, Methylene blue (MB), Biosorption, Isotherm Equilibrium, Kinetics; Modelling.

Validation of extended magnetohydrodynamic simulations of the HIT-SI3 experiment using the NIMROD code

NASA Astrophysics Data System (ADS)

Morgan, K. D.; Jarboe, T. R.; Hossack, A. C.; Chandra, R. N.; Everson, C. J.

2017-12-01

The HIT-SI3 experiment uses a set of inductively driven helicity injectors to apply a non-axisymmetric current drive on the edge of the plasma, driving an axisymmetric spheromak equilibrium in a central confinement volume. These helicity injectors drive a non-axisymmetric perturbation that oscillates in time, with relative temporal phasing of the injectors modifying the mode structure of the applied perturbation. A set of three experimental discharges with different perturbation spectra are modelled using the NIMROD extended magnetohydrodynamics code, and comparisons are made to both magnetic and fluid measurements. These models successfully capture the bulk dynamics of both the perturbation and the equilibrium, though disagreements related to the pressure gradients experimentally measured exist.

One-dimensional thermohydraulic code THESEUS and its application to chilldown process simulation in two-phase hydrogen flows

NASA Astrophysics Data System (ADS)

Papadimitriou, P.; Skorek, T.

THESUS is a thermohydraulic code for the calculation of steady state and transient processes of two-phase cryogenic flows. The physical model is based on four conservation equations with separate liquid and gas phase mass conservation equations. The thermohydraulic non-equilibrium is calculated by means of evaporation and condensation models. The mechanical non-equilibrium is modeled by a full-range drift-flux model. Also heat conduction in solid structures and heat exchange for the full spectrum of heat transfer regimes can be simulated. Test analyses of two-channel chilldown experiments and comparisons with the measured data have been performed.

Practical Approaches to Protein Folding and Assembly

PubMed Central

Walters, Jad; Milam, Sara L.; Clark, A. Clay

2009-01-01

We describe here the use of several spectroscopies, such as fluorescence emission, circular dichroism, and differential quenching by acrylamide, in examining the equilibrium and kinetic folding of proteins. The first section regarding equilibrium techniques provides practical information for determining the conformational stability of a protein. In addition, several equilibrium-folding models are discussed, from two-state monomer to four-state homodimer, providing a comprehensive protocol for interpretation of folding curves. The second section focuses on the experimental design and interpretation of kinetic data, such as burst-phase analysis and exponential fits, used in elucidating kinetic folding pathways. In addition, simulation programs are used routinely to support folding models generated by kinetic experiments, and the fundamentals of simulations are covered. PMID:19289201

Competitive adsorption of furfural and phenolic compounds onto activated carbon in fixed bed column.

PubMed

Sulaymon, Abbas H; Ahmed, Kawther W

2008-01-15

For a multicomponent competitive adsorption of furfural and phenolic compounds, a mathematical model was builtto describe the mass transfer kinetics in a fixed bed column with activated carbon. The effects of competitive adsorption equilibrium constant, axial dispersion, external mass transfer, and intraparticle diffusion resistance on the breakthrough curve were studied for weakly adsorbed compound (furfural) and strongly adsorbed compounds (parachlorophenol and phenol). Experiments were carried out to remove the furfural and phenolic compound from aqueous solution. The equilibrium data and intraparticle diffusion coefficients obtained from separate experiments in a batch adsorber, by fitting the experimental data with theoretical model. The results show that the mathematical model includes external mass transfer and pore diffusion using nonlinear isotherms and provides a good description of the adsorption process for furfural and phenolic compounds in a fixed bed adsorber.

Solution properties of almandine-pyrope garnet as determined by phase equilibrium experiments

USGS Publications Warehouse

Koziol, A.M.; Bohlen, S.R.

1992-01-01

The thermodynamic mixing properties of almandine-pyrope garnet were derived from phase equilibrium experiments at temperatures of 900 and 1000??C and pressures from 8 to 14 kbar. Almandine has essentially ideal behavior in almandine-pyrope garnet over the composition range Alm89-Alm61 at the above experimental conditions. In all experimental products a systematic partitioning of Fe and Mg between garnet and ilmenite was seen with ln Kd ??? 1.59 which was not temperature sensitive. The results support the use of garnet mixing models that incorporate ideal or nearly ideal Fe-Mg parameters. -from Authors

Theory for rates, equilibrium constants, and Brønsted slopes in F1-ATPase single molecule imaging experiments

PubMed Central

Volkán-Kacsó, Sándor; Marcus, Rudolph A.

2015-01-01

A theoretical model of elastically coupled reactions is proposed for single molecule imaging and rotor manipulation experiments on F1-ATPase. Stalling experiments are considered in which rates of individual ligand binding, ligand release, and chemical reaction steps have an exponential dependence on rotor angle. These data are treated in terms of the effect of thermodynamic driving forces on reaction rates, and lead to equations relating rate constants and free energies to the stalling angle. These relations, in turn, are modeled using a formalism originally developed to treat electron and other transfer reactions. During stalling the free energy profile of the enzymatic steps is altered by a work term due to elastic structural twisting. Using biochemical and single molecule data, the dependence of the rate constant and equilibrium constant on the stall angle, as well as the Børnsted slope are predicted and compared with experiment. Reasonable agreement is found with stalling experiments for ATP and GTP binding. The model can be applied to other torque-generating steps of reversible ligand binding, such as ADP and Pi release, when sufficient data become available. PMID:26483483

Emergence of currents as a transient quantum effect in nonequilibrium systems

NASA Astrophysics Data System (ADS)

Granot, Er'El; Marchewka, Avi

2011-09-01

Most current calculations are based on equilibrium or semi-equilibrium models. However, except for very special scenarios (like ring configuration), the current cannot exist in equilibrium. Moreover, unlike with equilibrium scenarios, there is no generic approach to confront out-of-equilibrium currents. In this paper we used recent studies on transient quantum mechanics to solve the current, which appears in the presence of very high density gradients and fast transients. It shows that the emerging current appears instantaneously, and although the density beyond the discontinuity is initially negligible the currents there have a finite value, and remain constant for a finite period. It is shown that this nonequilibrium effect can be measured in real experiments (such as cooled rubidium atoms), where the discontinuity is replaced with a finite width (hundreds of nanometers) gradient.

Selfish routing equilibrium in stochastic traffic network: A probability-dominant description.

PubMed

Zhang, Wenyi; He, Zhengbing; Guan, Wei; Ma, Rui

2017-01-01

This paper suggests a probability-dominant user equilibrium (PdUE) model to describe the selfish routing equilibrium in a stochastic traffic network. At PdUE, travel demands are only assigned to the most dominant routes in the same origin-destination pair. A probability-dominant rerouting dynamic model is proposed to explain the behavioral mechanism of PdUE. To facilitate applications, the logit formula of PdUE is developed, of which a well-designed route set is not indispensable and the equivalent varitional inequality formation is simple. Two routing strategies, i.e., the probability-dominant strategy (PDS) and the dominant probability strategy (DPS), are discussed through a hypothetical experiment. It is found that, whether out of insurance or striving for perfection, PDS is a better choice than DPS. For more general cases, the conducted numerical tests lead to the same conclusion. These imply that PdUE (rather than the conventional stochastic user equilibrium) is a desirable selfish routing equilibrium for a stochastic network, given that the probability distributions of travel time are available to travelers.

Selfish routing equilibrium in stochastic traffic network: A probability-dominant description

PubMed Central

Zhang, Wenyi; Guan, Wei; Ma, Rui

2017-01-01

This paper suggests a probability-dominant user equilibrium (PdUE) model to describe the selfish routing equilibrium in a stochastic traffic network. At PdUE, travel demands are only assigned to the most dominant routes in the same origin-destination pair. A probability-dominant rerouting dynamic model is proposed to explain the behavioral mechanism of PdUE. To facilitate applications, the logit formula of PdUE is developed, of which a well-designed route set is not indispensable and the equivalent varitional inequality formation is simple. Two routing strategies, i.e., the probability-dominant strategy (PDS) and the dominant probability strategy (DPS), are discussed through a hypothetical experiment. It is found that, whether out of insurance or striving for perfection, PDS is a better choice than DPS. For more general cases, the conducted numerical tests lead to the same conclusion. These imply that PdUE (rather than the conventional stochastic user equilibrium) is a desirable selfish routing equilibrium for a stochastic network, given that the probability distributions of travel time are available to travelers. PMID:28829834

Investigation of Non-Equilibrium Radiation for Earth Entry

NASA Technical Reports Server (NTRS)

Brandis, A. M.; Johnston, C. O.; Cruden, B. A.

2016-01-01

For Earth re-entry at velocities between 8 and 11.5 km/s, the accuracy of NASA's computational uid dynamic and radiative simulations of non-equilibrium shock layer radiation is assessed through comparisons with measurements. These measurements were obtained in the NASA Ames Research Center's Electric Arc Shock Tube (EAST) facility. The experiments were aimed at measuring the spatially and spectrally resolved radiance at relevant entry conditions for both an approximate Earth atmosphere (79% N2 : 21% O2 by mole) as well as a more accurate composition featuring the trace species Ar and CO2 (78.08% N2 : 20.95% O2 : 0.04% CO2 : 0.93% Ar by mole). The experiments were configured to target a wide range of conditions, of which shots from 8 to 11.5 km/s at 0.2 Torr (26.7 Pa) are examined in this paper. The non-equilibrium component was chosen to be the focus of this study as it can account for a significant percentage of the emitted radiation for Earth re-entry, and more importantly, non-equilibrium has traditionally been assigned a large uncertainty for vehicle design. The main goals of this study are to present the shock tube data in the form of a non-equilibrium metric, evaluate the level of agreement between the experiment and simulations, identify key discrepancies and to examine critical aspects of modeling non-equilibrium radiating flows. Radiance pro les integrated over discreet wavelength regions, ranging from the Vacuum Ultra Violet (VUV) through to the Near Infra-Red (NIR), were compared in order to maximize both the spectral coverage and the number of experiments that could be used in the analysis. A previously defined non-equilibrium metric has been used to allow comparisons with several shots and reveal trends in the data. Overall, LAURA/HARA is shown to under-predict EAST by as much as 40% and over-predict by as much as 12% depending on the shock speed. DPLR/NEQAIR is shown to under-predict EAST by as much as 50% and over-predict by as much as 20% depending on the shock speed. The one standard deviation scatter in the EAST results was calculated to be 31%. An estimate for the upper bound of the absolute error in wall-directed heat flux was calculated. Below 9 km/s, where the relative difference is large, the absolute error in radiative heat flux due to non-equilibrium models is estimated to be less then 1 W/sq cm. At the highest shock speed of 11 km/s, the error in non-equilibrium is estimated to be less than 20 W/sq cm.

Reflective equilibrium and empirical data: third person moral experiences in empirical medical ethics.

PubMed

De Vries, Martine; Van Leeuwen, Evert

2010-11-01

In ethics, the use of empirical data has become more and more popular, leading to a distinct form of applied ethics, namely empirical ethics. This 'empirical turn' is especially visible in bioethics. There are various ways of combining empirical research and ethical reflection. In this paper we discuss the use of empirical data in a special form of Reflective Equilibrium (RE), namely the Network Model with Third Person Moral Experiences. In this model, the empirical data consist of the moral experiences of people in a practice. Although inclusion of these moral experiences in this specific model of RE can be well defended, their use in the application of the model still raises important questions. What precisely are moral experiences? How to determine relevance of experiences, in other words: should there be a selection of the moral experiences that are eventually used in the RE? How much weight should the empirical data have in the RE? And the key question: can the use of RE by empirical ethicists really produce answers to practical moral questions? In this paper we start to answer the above questions by giving examples taken from our research project on understanding the norm of informed consent in the field of pediatric oncology. We especially emphasize that incorporation of empirical data in a network model can reduce the risk of self-justification and bias and can increase the credibility of the RE reached. © 2009 Blackwell Publishing Ltd.

Kinetics and equilibrium modelling of lead uptake by algae Gelidium and algal waste from agar extraction industry.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2007-05-08

Pb(II) biosorption onto algae Gelidium, algal waste from agar extraction industry and a composite material was studied. Discrete and continuous site distribution models were used to describe the biosorption equilibrium at different pH (5.3, 4 and 3), considering competition among Pb(II) ions and protons. The affinity distribution function of Pb(II) on the active sites was calculated by the Sips distribution. The Langmuir equilibrium constant was compared with the apparent affinity calculated by the discrete model, showing higher affinity for lead ions at higher pH values. Kinetic experiments were conducted at initial Pb(II) concentrations of 29-104 mgl(-1) and data fitted to pseudo-first Lagergren and second-order models. The adsorptive behaviour of biosorbent particles was modelled using a batch mass transfer kinetic model, which successfully predicts Pb(II) concentration profiles at different initial lead concentration and pH, and provides significant insights on the biosorbents performance. Average values of homogeneous diffusivity, D(h), are 3.6 x 10(-8); 6.1 x 10(-8) and 2.4 x 10(-8)cm(2)s(-1), respectively, for Gelidium, algal waste and composite material. The concentration of lead inside biosorbent particles follows a parabolic profile that becomes linear near equilibrium.

Multigroup SIR epidemic model with stochastic perturbation

NASA Astrophysics Data System (ADS)

Ji, Chunyan; Jiang, Daqing; Shi, Ningzhong

2011-05-01

In this paper, we discuss a multigroup SIR model with stochastic perturbation. We deduce the globally asymptotic stability of the disease-free equilibrium when R0≤1, which means the disease will die out. On the other hand, when R0>1, we derive the disease will prevail, which is measured through the difference between the solution and the endemic equilibrium of the deterministic model in time average. Furthermore, we prove the system is persistent in the mean which also reflects the disease will prevail. The key to our analysis is choosing appropriate Lyapunov functions. Finally, we illustrate the dynamic behavior of the model with n=2 and their approximations via a range of numerical experiments.

Final Scientific Report: Experimental Investigation of Reconnection in a Line-tied Plasma

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

Forest, Cary

This grant used funding from the NSF/DoE Partnership on Plasma Science to investigate magnetic reconnection phenomena in a line-tied pinch experiment. The experiment was upgraded from a previous device intended to study fusion plasma-related instabilities to a new configuration capable of studying a number of new, previously unstudied configurations. A high spatial and time resolution array of magnetic probes was constructed to measure time evolving structures present as instability and turbulence developed. The most important new equilibrium made possible by this grant was a Zero-Net-Current equilibrium that models the footpoint twisting of solar flux tubes that occurs prior to solarmore » eruptions (flares and coronal mass ejections). This new equilibrium was successfully created in the lab, and it exhibited a host of instabilities. In particular, at low current when the equilibrium was not overly stressed, a saturated internal kink mode oscillation was observed. At high current, 2 D magnetic turbulence developed which we attribute to the lack of a equilibrium brought about by a subcritical transition to turbulence. A second set of experiments involved the turbulent interactions of a collection of flux tubes all being twisted independently, a problem known as the Parker Problem. Current profiles consisting of 2, 3 and 4 guns were used to impose a fine scale drive, and resulted in a new experimental platform in which the injection scale of the magnetic turbulence could be controlled. First experiments in this configuration support the conclusion that an inverse cascade of magnetic energy occurred which self-organized the plasma into a nearly axisymmetric current distribution.« less

Plastic flow modeling in glassy polymers

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

Clements, Brad

2010-12-13

Glassy amorphous and semi-crystalline polymers exhibit strong rate, temperature, and pressure dependent polymeric yield. As a rule of thumb, in uniaxial compression experiments the yield stress increases with the loading rate and applied pressure, and decreases as the temperature increases. Moreover, by varying the loading state itself complex yield behavior can be observed. One example that illustrates this complexity is that most polymers in their glassy regimes (i.e., when the temperature is below their characteristic glass transition temperature) exhibit very pronounced yield in their uniaxial stress stress-strain response but very nebulous yield in their uniaxial strain response. In uniaxial compression,more » a prototypical glassy-polymer stress-strain curve has a stress plateau, often followed by softening, and upon further straining, a hardening response. Uniaxial compression experiments of this type are typically done from rates of 10{sup -5} s{sup -1} up to about 1 s{sup -1}. At still higher rates, say at several thousands per second as determined from Split Hopkinson Pressure Bar experiments, the yield can again be measured and is consistent with the above rule of thumb. One might expect that that these two sets of experiments should allow for a successful extrapolation to yet higher rates. A standard means to probe high rates (on the order of 105-107 S-I) is to use a uniaxial strain plate impact experiment. It is well known that in plate impact experiments on metals that the yield stress is manifested in a well-defined Hugoniot Elastic Limit (HEL). In contrast however, when plate impact experiments are done on glassy polymers, the HEL is arguably not observed, let alone observed at the stress estimated by extrapolating from the lower strain rate experiments. One might argue that polymer yield is still active but somehow masked by the experiment. After reviewing relevant experiments, we attempt to address this issue. We begin by first presenting our recently developed glassy polymer model. While polymers are well known for their non-equilibrium deviatoric behavior we have found the need for incorporating both equilibrium and non-equilibrium volumetric behavior into our theory. Experimental evidence supporting the notion of non-equilibrium volumetric behavior will be summarized. Our polymer yield model accurately captures the stress plateau, softening and hardening and its yield stress predictions agree well with measured values for several glassy polymers including PMMA, PC, and an epoxy resin. We then apply our theory to plate impact experiments in an attempt to address the questions associated with high rate polymer yield in uniaxial strain configurations.« less

Combined Homogeneous Surface Diffusion Model - Design of experiments approach to optimize dye adsorption considering both equilibrium and kinetic aspects.

PubMed

Muthukkumaran, A; Aravamudan, K

2017-12-15

Adsorption, a popular technique for removing azo dyes from aqueous streams, is influenced by several factors such as pH, initial dye concentration, temperature and adsorbent dosage. Any strategy that seeks to identify optimal conditions involving these factors, should take into account both kinetic and equilibrium aspects since they influence rate and extent of removal by adsorption. Hence rigorous kinetics and accurate equilibrium models are required. In this work, the experimental investigations pertaining to adsorption of acid orange 10 dye (AO10) on activated carbon were carried out using Central Composite Design (CCD) strategy. The significant factors that affected adsorption were identified to be solution temperature, solution pH, adsorbent dosage and initial solution concentration. Thermodynamic analysis showed the endothermic nature of the dye adsorption process. The kinetics of adsorption has been rigorously modeled using the Homogeneous Surface Diffusion Model (HSDM) after incorporating the non-linear Freundlich adsorption isotherm. Optimization was performed for kinetic parameters (color removal time and surface diffusion coefficient) as well as the equilibrium affected response viz. percentage removal. Finally, the optimum conditions predicted were experimentally validated. Copyright © 2017 Elsevier Ltd. All rights reserved.

The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

PubMed

Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

2016-07-27

An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

Biosorption and desorption of Cd2+ from wastewater by dehydrated shreds of Cladophora fascicularis

NASA Astrophysics Data System (ADS)

Deng, Liping; Zhu, Xiaobin; Su, Yingying; Su, Hua; Wang, Xinting

2008-02-01

The adsorption and desorption of algae Cladophora fascicularis and their relation with initial Cd2+ concentration, initial pH, and co-existing ions were studied. Adsorption equilibrium and biosorption kinetics were established from batch experiments. The adsorption equilibrium was adequately described by the Langmuir isotherm, and biosorption kinetics was in pseudo-second order model. The experiment on co-existing ions showed that the biosorption capacity of biomass decreased with an increasing concentration of competing ions. Desorption experiments indicated that EDTA was efficient desorbent for recovery from Cd2+. With high capacities of metal biosorption and desorption, the biomass of Cladophora fascicularis is promising as a cost-effective biosorbent for the removal of Cd2+ from wastewater.

Characterization and Computational Modeling of Minor Phases in Alloy LSHR

NASA Technical Reports Server (NTRS)

Jou, Herng-Jeng; Olson, Gregory; Gabb, Timothy; Garg, Anita; Miller, Derek

2012-01-01

The minor phases of powder metallurgy disk superalloy LSHR were studied. Samples were consistently heat treated at three different temperatures for long times to approach equilibrium. Additional heat treatments were also performed for shorter times, to assess minor phase kinetics in non-equilibrium conditions. Minor phases including MC carbides, M23C6 carbides, M3B2 borides, and sigma were identified. Their average sizes and total area fractions were determined. CALPHAD thermodynamics databases and PrecipiCalc(TradeMark), a computational precipitation modeling tool, were employed with Ni-base thermodynamics and diffusion databases to model and simulate the phase microstructural evolution observed in the experiments with an objective to identify the model limitations and the directions of model enhancement.

Dynamic and static equilibrium sea level effects of Greenland Ice Sheet melt: An assessment of partially-coupled idealized water hosing experiments (Invited)

NASA Astrophysics Data System (ADS)

Kopp, R. E.; Mitrovica, J. X.; Griffies, S. M.; Yin, J.; Hay, C. C.; Stouffer, R. J.

2010-12-01

Regional sea level can deviate from mean global sea level because of both dynamic sea level (DSL) effects, resulting from oceanic and atmospheric circulation and temperature and salinity distributions, and changes in the static equilibrium (SE) sea level configuration, produced by the gravitational, elastic, and rotational effects of mass redistribution. Both effects will contribute to future sea level change, but because they are studied by two different subdisciplines -- climate modeling and glacial rebound modeling -- projections that attempt to combine both have to date been scarce. To compare their magnitude, we simulated the effects of Greenland Ice Sheet (GIS) melt by conducting idealized North Atlantic "water-hosing" experiments in a climate model unidirectionally coupled to a SE sea level model. At current rates of GIS melt, freshwater hosing experiments in fully coupled atmosphere-ocean general circulation models (AOGCMs) do not yield clear DSL trends but do generate DSL variability; comparing that variability to expected static equilibrium "fingerprints" suggests that at least about 40 years of observations are needed to detect the "fingerprints" of ice sheet melt at current Greenland melt rates of about 0.3 mm equivalent sea level (esl)/year. Accelerated melt rates of about 2--6 mm esl/y, as may occur later in the century, should be detectable above background DSL variability within less than a decade of their onset. At these higher melt rates, AOGCMs do yield clear DSL trends. In the GFDL CM 2.1 model, DSL trends are strongest in the western North Atlantic, while SE effects come to dominate in most of the ocean when melt exceeds about 20 cm esl.

Phase Transitions and Scaling in Systems Far from Equilibrium

NASA Astrophysics Data System (ADS)

Täuber, Uwe C.

2017-03-01

Scaling ideas and renormalization group approaches proved crucial for a deep understanding and classification of critical phenomena in thermal equilibrium. Over the past decades, these powerful conceptual and mathematical tools were extended to continuous phase transitions separating distinct nonequilibrium stationary states in driven classical and quantum systems. In concordance with detailed numerical simulations and laboratory experiments, several prominent dynamical universality classes have emerged that govern large-scale, long-time scaling properties both near and far from thermal equilibrium. These pertain to genuine specific critical points as well as entire parameter space regions for steady states that display generic scale invariance. The exploration of nonstationary relaxation properties and associated physical aging scaling constitutes a complementary potent means to characterize cooperative dynamics in complex out-of-equilibrium systems. This review describes dynamic scaling features through paradigmatic examples that include near-equilibrium critical dynamics, driven lattice gases and growing interfaces, correlation-dominated reaction-diffusion systems, and basic epidemic models.

An equilibrium model for the coupled ocean-atmosphere boundary layer in the tropics

NASA Technical Reports Server (NTRS)

Sui, C.-H.; Lau, K.-M.; Betts, Alan K.

1991-01-01

An atmospheric convective boundary layer (CBL) model is coupled to an ocean mixed-layer (OML) model in order to study the equilibrium state of the coupled system in the tropics, particularly in the Pacific region. The equilibrium state of the coupled system is solved as a function of sea-surface temperature (SST) for a given surface wind and as a function of surface wind for a given SST. It is noted that in both cases, the depth of the CBL and OML increases and the upwelling below the OML decreases, corresponding to either increasing SST or increasing surface wind. The coupled ocean-atmosphere model is solved iteratively as a function of surface wind for a fixed upwelling and a fixed OML depth, and it is observed that SST falls with increasing wind in both cases. Realistic gradients of mixed-layer depth and upwelling are observed in experiments with surface wind and SST prescribed as a function of longitude.

The Dependence of Tropical Cyclone Count and Size on Rotation Rate

NASA Astrophysics Data System (ADS)

Chavas, D. R.; Reed, K. A.

2017-12-01

Both theory and idealized equilibrium modeling studies indicate that tropical cyclone size decreases with background rotation rate. In contrast, in real-world observations size tends to increase with latitude. Here we seek to resolve this apparent contradiction via a set of reduced-complexity global aquaplanet simulations with varying planetary rotation rates using the NCAR Community Atmosphere Model 5. The latitudinal distribution of both storm count and size are found to vary markedly with rotation rate, yielding insight into the dynamical constraints on tropical cyclone activity on a rotating planet. Moreover, storm size is found to vary non-monotonically with latitude, indicating that non-equilibrium effects are crucial to the life-cycle evolution of size in nature. Results are then compared to experiments in idealized, time-dependent limited-area modeling simulations using CM1 in axisymmetric and three-dimensional geometry. Taken together, this hierarchy of models is used to quantify the role of equilibrium versus transient controls on storm size and the relevance of each to real storms in nature.

Thermal Behavior of Cd During Sludge Incineration: Experiments and Thermodynamic Equilibrium Model.

PubMed

Liu, Jingyong; Zhuo, Zhongxu; Sun, Shuiyu; Xie, Wuming; Lu, Shaoyou; Sun, Jian; Kuo, Jiahong; Yujie, Wang

2016-12-01

  Experiments and thermodynamic equilibrium calculations were performed to investigate the behavior of Cd during sewage sludge incineration. The chemical equilibrium calculations indicated that chlorine significantly increased the volatilization of Cd in the form of CdCl2. In addition, SiO2-containing materials can function as sorbents for stabilizing Cd. The effect of PVC added to the sludge on the migration of Cd in the sludge was greater than that of NaCl. As the temperature increased, both organic and inorganic chlorides reduced the Cd distribution in the bottom ash. The chloride concentration, and the incineration time exhibited insignificant changes in Cd emission. With the addition of either NaCl or PVC into the sludge, the phases of Cd present in the bottom slag were primarily present in the form of silica-alumina oxides or multi-metal oxide, which could inhabit the Cd volatilization.

Mesoscale Modeling of LX-17 Under Isentropic Compression

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

Springer, H K; Willey, T M; Friedman, G

Mesoscale simulations of LX-17 incorporating different equilibrium mixture models were used to investigate the unreacted equation-of-state (UEOS) of TATB. Candidate TATB UEOS were calculated using the equilibrium mixture models and benchmarked with mesoscale simulations of isentropic compression experiments (ICE). X-ray computed tomography (XRCT) data provided the basis for initializing the simulations with realistic microstructural details. Three equilibrium mixture models were used in this study. The single constituent with conservation equations (SCCE) model was based on a mass-fraction weighted specific volume and the conservation of mass, momentum, and energy. The single constituent equation-of-state (SCEOS) model was based on a mass-fraction weightedmore » specific volume and the equation-of-state of the constituents. The kinetic energy averaging (KEA) model was based on a mass-fraction weighted particle velocity mixture rule and the conservation equations. The SCEOS model yielded the stiffest TATB EOS (0.121{micro} + 0.4958{micro}{sup 2} + 2.0473{micro}{sup 3}) and, when incorporated in mesoscale simulations of the ICE, demonstrated the best agreement with VISAR velocity data for both specimen thicknesses. The SCCE model yielded a relatively more compliant EOS (0.1999{micro}-0.6967{micro}{sup 2} + 4.9546{micro}{sup 3}) and the KEA model yielded the most compliant EOS (0.1999{micro}-0.6967{micro}{sup 2}+4.9546{micro}{sup 3}) of all the equilibrium mixture models. Mesoscale simulations with the lower density TATB adiabatic EOS data demonstrated the least agreement with VISAR velocity data.« less

Crystal-liquid-vapor equilibrium experiments at high temperature (less than or equal to 1800 C) and low, controlled oxygen and hydrogen pressure (10(-1) to 10(-9) PA)

NASA Technical Reports Server (NTRS)

Mysen, B. O.

1987-01-01

Evidence from carbonaceous chrondrites points to refractory oxides in the system CaO-MgO-Al2O3-TiO2-SiO2-Fe-O as being among the earliest phases to condense from the solar nebula. It is necessary to establish the equilibrium relationships between the relevant crystalline and amorphous phases before the chemical constraints can be meaningfully applied to models of solar system history. Preliminary experiments on earth show that such experiments are feasible. Earth-based experiments suffer from several unavoidable problems. These problems can be overcome by experimentation in the Space Station where the experiments can be conducted under near static pressure conditions and where total pressure equals the sum of controlled hydrogen and oxygen pressures and can be controlled for periods exceeding several hours.

LES Modeling of Supersonic Combustion at SCRAMJET Conditions

NASA Astrophysics Data System (ADS)

Vane, Zachary; Lacaze, Guilhem; Oefelein, Joseph

2016-11-01

Results from a series of large-eddy simulations (LES) of the Hypersonic International Flight Research Experiment (HIFiRE) are examined with emphasis placed on the coupled performance of the wall and combustion models. The test case of interest corresponds to the geometry and conditions found in the ground based experiments performed in the HIFiRE Direct Connect Rig (HDCR) in dual-mode operation. In these calculations, the turbulence and mixing characteristics of the high Reynolds number turbulent boundary layer with multi-species fuel injection are analyzed using a simplified chemical model and combustion closure to predict the heat release measured experimentally. These simulations are then used to identify different flame regimes in the combustor section. Concurrently, the performance of an equilibrium wall-model is evaluated in the vicinity of the fuel injectors and in the flame-holding cavity where regions of boundary layer and thermochemical non-equilibrium are present. Support for this research was provided by the Defense Advanced Research Projects Agency (DARPA).

Latitudinal oscillations of plasma within the Io torus

NASA Technical Reports Server (NTRS)

Cummings, W. D.; Dessler, A. J.; Hill, T. W.

1980-01-01

The equilibrium latitude and the period of oscillations about this equilibrium latitude are calculated for a plasma in a centrifugally dominated tilted dipole magnetic field representing Jupiter's inner magnetosphere. It is found that for a hot plasma the equilibrium latitude in the magnetic equator, for a cold plasma it is the centrifugal equator, and for a warm plasma it is somewhere in between. An illustrative model is adopted in which atoms are sputtered from the Jupiter-facing hemisphere of Io and escape Io's gravity to be subsequently ionized some distance from Io. Finally, it is shown that ionization generally does not occur at the equilibrium altitude, and that the resulting latitudinal oscillations provide an explanation for the irregularities in electron concentration within the torus, as reported by the radioastronomy experiment aboard Voyager I.

Study of nonequilibrium work distributions from a fluctuating lattice Boltzmann model.

PubMed

Nasarayya Chari, S Siva; Murthy, K P N; Inguva, Ramarao

2012-04-01

A system of ideal gas is switched from an initial equilibrium state to a final state not necessarily in equilibrium, by varying a macroscopic control variable according to a well-defined protocol. The distribution of work performed during the switching process is obtained. The equilibrium free energy difference, ΔF, is determined from the work fluctuation relation. Some of the work values in the ensemble shall be less than ΔF. We term these as ones that "violate" the second law of thermodynamics. A fluctuating lattice Boltzmann model has been employed to carry out the simulation of the switching experiment. Our results show that the probability of violation of the second law increases with the increase of switching time (τ) and tends to one-half in the reversible limit of τ→∞.

The Equilibrium Constant for Bromothymol Blue: A General Chemistry Laboratory Experiment Using Spectroscopy

ERIC Educational Resources Information Center

Klotz, Elsbeth; Doyle, Robert; Gross, Erin; Mattson, Bruce

2011-01-01

A simple, inexpensive, and environmentally friendly undergraduate laboratory experiment is described in which students use visible spectroscopy to determine a numerical value for an equilibrium constant, K[subscript c]. The experiment correlates well with the lecture topic of equilibrium even though the subject of the study is an acid-base…

NHPP-Based Software Reliability Models Using Equilibrium Distribution

NASA Astrophysics Data System (ADS)

Xiao, Xiao; Okamura, Hiroyuki; Dohi, Tadashi

Non-homogeneous Poisson processes (NHPPs) have gained much popularity in actual software testing phases to estimate the software reliability, the number of remaining faults in software and the software release timing. In this paper, we propose a new modeling approach for the NHPP-based software reliability models (SRMs) to describe the stochastic behavior of software fault-detection processes. The fundamental idea is to apply the equilibrium distribution to the fault-detection time distribution in NHPP-based modeling. We also develop efficient parameter estimation procedures for the proposed NHPP-based SRMs. Through numerical experiments, it can be concluded that the proposed NHPP-based SRMs outperform the existing ones in many data sets from the perspective of goodness-of-fit and prediction performance.

Lead sorption by waste biomass of hazelnut and almond shell.

PubMed

Pehlivan, Erol; Altun, Türkan; Cetin, Serpil; Iqbal Bhanger, M

2009-08-15

The potential to remove Pb(2+) ion from aqueous solutions using the shells of hazelnut (HNS) (Corylus avellana) and almond (AS) (Prunus dulcis) through biosorption was investigated in batch experiments. The main parameters influencing Pb(2+) ion sorption on HNS and AS were: initial metal ion concentration, amount of adsorbent, contact time and pH value of solution. The influences of initial Pb(2+) ion concentration (0.1-1.0mM), pH (2-9), contact time (10-240 min) and adsorbent amount (0.1-1.0 g) have been investigated. Equilibrium isotherms have been measured and modelled. Adsorption of Pb(2+) ions was in all cases pH-dependent showing a maximum at equilibrium pH values between 6.0 and 7.0, depending on the biomaterial, that corresponded to equilibrium pH values of 6.0 for HNS and 7.0 for AS. The equilibrium sorption capacities of HNS and AS were 28.18 and 8.08 mg/g for lead, respectively after equilibrium time of 2h. The adsorption data fit well with the Langmuir isotherm model and the experimental result inferred that adsorption, chelation and ion exchange are major adsorption mechanisms for binding Pb(2+) ion to the sorbents.

Laboratory-scale experiments and numerical modeling of cosolvent flushing of multi-component NAPLs in saturated porous media

NASA Astrophysics Data System (ADS)

Agaoglu, Berken; Scheytt, Traugott; Copty, Nadim K.

2012-10-01

This study examines the mechanistic processes governing multiphase flow of a water-cosolvent-NAPL system in saturated porous media. Laboratory batch and column flushing experiments were conducted to determine the equilibrium properties of pure NAPL and synthetically prepared NAPL mixtures as well as NAPL recovery mechanisms for different water-ethanol contents. The effect of contact time was investigated by considering different steady and intermittent flow velocities. A modified version of multiphase flow simulator (UTCHEM) was used to compare the multiphase model simulations with the column experiment results. The effect of employing different grid geometries (1D, 2D, 3D), heterogeneity and different initial NAPL saturation configurations was also examined in the model. It is shown that the change in velocity affects the mass transfer rate between phases as well as the ultimate NAPL recovery percentage. The experiments with low flow rate flushing of pure NAPL and the 3D UTCHEM simulations gave similar effluent concentrations and NAPL cumulative recoveries. Model simulations over-estimated NAPL recovery for high specific discharges and rate-limited mass transfer, suggesting a constant mass transfer coefficient for the entire flushing experiment may not be valid. When multi-component NAPLs are present, the dissolution rate of individual organic compounds (namely, toluene and benzene) into the ethanol-water flushing solution is found not to correlate with their equilibrium solubility values.

Design and application of a technologically explicit hybrid energy-economy policy model with micro and macro economic dynamics

NASA Astrophysics Data System (ADS)

Bataille, Christopher G. F.

2005-11-01

Are further energy efficiency gains, or more recently greenhouse gas reductions, expensive or cheap? Analysts provide conflicting advice to policy makers based on divergent modelling perspectives, a 'top-down/bottom-up debate' in which economists use equation based models that equilibrate markets by maximizing consumer welfare, and technologists use technology simulation models that minimize the financial cost of providing energy services. This thesis summarizes a long term research project to find a middle ground between these two positions that is more useful to policy makers. Starting with the individual components of a behaviourally realistic and technologically explicit simulation model (ISTUM---Inter Sectoral Technology Use Model), or "hybrid", the individual sectors of the economy are linked using a framework of micro and macro economic feedbacks. These feedbacks are taken from the economic theory that informs the computable general equilibrium (CGE) family of models. Speaking in the languages of both economists and engineers, the resulting "physical" equilibrium model of Canada (CIMS---Canadian Integrated Modeling System), equilibrates energy and end-product markets, including imports and exports, for seven regions and 15 economic sectors, including primary industry, manufacturing, transportation, commerce, residences, governmental infrastructure and the energy supply sectors. Several different policy experiments demonstrate the value-added of the model and how its results compare to top-down and bottom-up practice. In general, the results show that technical adjustments make up about half the response to simulated energy policy, and macroeconomic demand adjustments the other half. Induced technical adjustments predominate with minor policies, while the importance of macroeconomic demand adjustment increases with the strength of the policy. Results are also shown for an experiment to derive estimates of future elasticity of substitution (ESUB) and autonomous energy efficiency indices (AEEI) from the model, parameters that could be used in long-run computable general equilibrium (CGE) analysis. The thesis concludes with a summary of the strengths and weakness of the new model as a policy tool, a work plan for its further improvement, and a discussion of the general potential for technologically explicit general equilibrium modelling.

Modeling MHD Equilibrium and Dynamics with Non-Axisymmetric Resistive Walls in LTX and HBT-EP

NASA Astrophysics Data System (ADS)

Hansen, C.; Levesque, J.; Boyle, D. P.; Hughes, P.

2017-10-01

In experimental magnetized plasmas, currents in the first wall, vacuum vessel, and other conducting structures can have a strong influence on plasma shape and dynamics. These effects are complicated by the 3D nature of these structures, which dictate available current paths. Results from simulations to study the effect of external currents on plasmas in two different experiments will be presented: 1) The arbitrary geometry, 3D extended MHD code PSI-Tet is applied to study linear and non-linear plasma dynamics in the High Beta Tokamak (HBT-EP) focusing on toroidal asymmetries in the adjustable conducting wall. 2) Equilibrium reconstructions of the Lithium Tokamak eXperiment (LTX) in the presence of non-axisymmetric eddy currents. An axisymmetric model is used to reconstruct the plasma equilibrium, using the PSI-Tri code, along with a set of fixed 3D eddy current distributions in the first wall and vacuum vessel [C. Hansen et al., PoP Apr. 2017]. Simulations of detailed experimental geometries are enabled by use of the PSI-Tet code, which employs a high order finite element method on unstructured tetrahedral grids that are generated directly from CAD models. Further development of PSI-Tet and PSI-Tri will also be presented. This work supported by US DOE contract DE-SC0016256.

Retrading, production, and asset market performance.

PubMed

Gjerstad, Steven D; Porter, David; Smith, Vernon L; Winn, Abel

2015-11-24

Prior studies have shown that traders quickly converge to the price-quantity equilibrium in markets for goods that are immediately consumed, but they produce speculative price bubbles in resalable asset markets. We present a stock-flow model of durable assets in which the existing stock of assets is subject to depreciation and producers may produce additional units of the asset. In our laboratory experiments inexperienced consumers who can resell their units disregard the consumption value of the assets and compete vigorously with producers, depressing prices and production. Consumers who have first participated in experiments without resale learn to heed their consumption values and, when they are given the option to resell, trade at equilibrium prices. Reproducibility is therefore the most natural and most effective treatment for suppression of bubbles in asset market experiments.

Retrading, production, and asset market performance

PubMed Central

Gjerstad, Steven D.; Porter, David; Smith, Vernon L.; Winn, Abel

2015-01-01

Prior studies have shown that traders quickly converge to the price–quantity equilibrium in markets for goods that are immediately consumed, but they produce speculative price bubbles in resalable asset markets. We present a stock-flow model of durable assets in which the existing stock of assets is subject to depreciation and producers may produce additional units of the asset. In our laboratory experiments inexperienced consumers who can resell their units disregard the consumption value of the assets and compete vigorously with producers, depressing prices and production. Consumers who have first participated in experiments without resale learn to heed their consumption values and, when they are given the option to resell, trade at equilibrium prices. Reproducibility is therefore the most natural and most effective treatment for suppression of bubbles in asset market experiments. PMID:26553991

Influence of atomic kinetics in the simulation of plasma microscopic properties and thermal instabilities for radiative bow shock experiments.

PubMed

Espinosa, G; Rodríguez, R; Gil, J M; Suzuki-Vidal, F; Lebedev, S V; Ciardi, A; Rubiano, J G; Martel, P

2017-03-01

Numerical simulations of laboratory astrophysics experiments on plasma flows require plasma microscopic properties that are obtained by means of an atomic kinetic model. This fact implies a careful choice of the most suitable model for the experiment under analysis. Otherwise, the calculations could lead to inaccurate results and inappropriate conclusions. First, a study of the validity of the local thermodynamic equilibrium in the calculation of the average ionization, mean radiative properties, and cooling times of argon plasmas in a range of plasma conditions of interest in laboratory astrophysics experiments on radiative shocks is performed in this work. In the second part, we have made an analysis of the influence of the atomic kinetic model used to calculate plasma microscopic properties of experiments carried out on magpie on radiative bow shocks propagating in argon. The models considered were developed assuming both local and nonlocal thermodynamic equilibrium and, for the latter situation, we have considered in the kinetic model different effects such as external radiation field and plasma mixture. The microscopic properties studied were the average ionization, the charge state distributions, the monochromatic opacities and emissivities, the Planck mean opacity, and the radiative power loss. The microscopic study was made as a postprocess of a radiative-hydrodynamic simulation of the experiment. We have also performed a theoretical analysis of the influence of these atomic kinetic models in the criteria for the onset possibility of thermal instabilities due to radiative cooling in those experiments in which small structures were experimentally observed in the bow shock that could be due to this kind of instability.

Influence of atomic kinetics in the simulation of plasma microscopic properties and thermal instabilities for radiative bow shock experiments

NASA Astrophysics Data System (ADS)

Espinosa, G.; Rodríguez, R.; Gil, J. M.; Suzuki-Vidal, F.; Lebedev, S. V.; Ciardi, A.; Rubiano, J. G.; Martel, P.

2017-03-01

Numerical simulations of laboratory astrophysics experiments on plasma flows require plasma microscopic properties that are obtained by means of an atomic kinetic model. This fact implies a careful choice of the most suitable model for the experiment under analysis. Otherwise, the calculations could lead to inaccurate results and inappropriate conclusions. First, a study of the validity of the local thermodynamic equilibrium in the calculation of the average ionization, mean radiative properties, and cooling times of argon plasmas in a range of plasma conditions of interest in laboratory astrophysics experiments on radiative shocks is performed in this work. In the second part, we have made an analysis of the influence of the atomic kinetic model used to calculate plasma microscopic properties of experiments carried out on magpie on radiative bow shocks propagating in argon. The models considered were developed assuming both local and nonlocal thermodynamic equilibrium and, for the latter situation, we have considered in the kinetic model different effects such as external radiation field and plasma mixture. The microscopic properties studied were the average ionization, the charge state distributions, the monochromatic opacities and emissivities, the Planck mean opacity, and the radiative power loss. The microscopic study was made as a postprocess of a radiative-hydrodynamic simulation of the experiment. We have also performed a theoretical analysis of the influence of these atomic kinetic models in the criteria for the onset possibility of thermal instabilities due to radiative cooling in those experiments in which small structures were experimentally observed in the bow shock that could be due to this kind of instability.

Predicting Transport of 3,5,6-Trichloro-2-Pyridinol Into Saliva Using a Combination Experimental and Computational Approach

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

Smith, Jordan Ned; Carver, Zana A.; Weber, Thomas J.

A combination experimental and computational approach was developed to predict chemical transport into saliva. A serous-acinar chemical transport assay was established to measure chemical transport with non-physiological (standard cell culture medium) and physiological (using surrogate plasma and saliva medium) conditions using 3,5,6-trichloro-2-pyridinol (TCPy) a metabolite of the pesticide chlorpyrifos. High levels of TCPy protein binding was observed in cell culture medium and rat plasma resulting in different TCPy transport behaviors in the two experimental conditions. In the non-physiological transport experiment, TCPy reached equilibrium at equivalent concentrations in apical and basolateral chambers. At higher TCPy doses, increased unbound TCPy was observed,more » and TCPy concentrations in apical and basolateral chambers reached equilibrium faster than lower doses, suggesting only unbound TCPy is able to cross the cellular monolayer. In the physiological experiment, TCPy transport was slower than non-physiological conditions, and equilibrium was achieved at different concentrations in apical and basolateral chambers at a comparable ratio (0.034) to what was previously measured in rats dosed with TCPy (saliva:blood ratio: 0.049). A cellular transport computational model was developed based on TCPy protein binding kinetics and accurately simulated all transport experiments using different permeability coefficients for the two experimental conditions (1.4 vs 0.4 cm/hr for non-physiological and physiological experiments, respectively). The computational model was integrated into a physiologically based pharmacokinetic (PBPK) model and accurately predicted TCPy concentrations in saliva of rats dosed with TCPy. Overall, this study demonstrates an approach to predict chemical transport in saliva potentially increasing the utility of salivary biomonitoring in the future.« less

Traffic experiment reveals the nature of car-following.

PubMed

Jiang, Rui; Hu, Mao-Bin; Zhang, H M; Gao, Zi-You; Jia, Bin; Wu, Qing-Song; Wang, Bing; Yang, Ming

2014-01-01

As a typical self-driven many-particle system far from equilibrium, traffic flow exhibits diverse fascinating non-equilibrium phenomena, most of which are closely related to traffic flow stability and specifically the growth/dissipation pattern of disturbances. However, the traffic theories have been controversial due to a lack of precise traffic data. We have studied traffic flow from a new perspective by carrying out large-scale car-following experiment on an open road section, which overcomes the intrinsic deficiency of empirical observations. The experiment has shown clearly the nature of car-following, which runs against the traditional traffic flow theory. Simulations show that by removing the fundamental notion in the traditional car-following models and allowing the traffic state to span a two-dimensional region in velocity-spacing plane, the growth pattern of disturbances has changed qualitatively and becomes qualitatively or even quantitatively in consistent with that observed in the experiment.

Traffic Experiment Reveals the Nature of Car-Following

PubMed Central

Jiang, Rui; Hu, Mao-Bin; Zhang, H. M.; Gao, Zi-You; Jia, Bin; Wu, Qing-Song; Wang, Bing; Yang, Ming

2014-01-01

As a typical self-driven many-particle system far from equilibrium, traffic flow exhibits diverse fascinating non-equilibrium phenomena, most of which are closely related to traffic flow stability and specifically the growth/dissipation pattern of disturbances. However, the traffic theories have been controversial due to a lack of precise traffic data. We have studied traffic flow from a new perspective by carrying out large-scale car-following experiment on an open road section, which overcomes the intrinsic deficiency of empirical observations. The experiment has shown clearly the nature of car-following, which runs against the traditional traffic flow theory. Simulations show that by removing the fundamental notion in the traditional car-following models and allowing the traffic state to span a two-dimensional region in velocity-spacing plane, the growth pattern of disturbances has changed qualitatively and becomes qualitatively or even quantitatively in consistent with that observed in the experiment. PMID:24740284

Metal/silicate partitioning of Pt and the origin of the "late veneer"

NASA Astrophysics Data System (ADS)

Ertel, W.; Walter, M. J.; Drake, M. J.; Sylvester, P. J.

2002-12-01

Highly siderophile elements (HSEs) are perfect tools for investigating core forming processes in planetary bodies due to their Fe-loving (siderophile) geochemical behavior. Tremendous scientific effort was invested into this field during the past 10 years - mostly in 1 atm experiments. However, little is known about their high-pressure geochemistry and partitioning behavior between core and mantle forming phases. This knowledge is essential to distinguish between equilibrium (Magma Ocean) and non-equilibrium (heterogeneous accretion, late veneer) models for the accretion history for the early Earth. We therefore chose to investigate the partitioning behavior of Pt up to pressures of 140 kbar (14 GPa) and temperatures of 1950°C. The used melt composition - identical to melt systems used in 1 atm experiments - is the eutectic composition of Anorthite-Diopside (AnDi), a pseudo-basalt. A series of runs were performed which were internaly buffered by the piston cylinder apparatus, and were followed by duplicate experiments buffered in the AnDi-C-CO2 system. These experiments constitute reversals since they approach equilibrium from an initially higher and lower Pt solubility (8 ppm in the non-buffered runs, and essentially Pt free in the buffered runs). Experimental charges were encapsulated in Pt capsules which served as source for Pt. Experiments up to 20 kbar were performed in a Quickpress piston cylinder apparatus, while experiments at higher pressures were performed in a Walker-type (Tucson, AZ) and a Kawai-type (Misasa, Japan) multi anvil apparatus. Time series experiments were performed in piston-cylinder runs to determine minimum run durations for the achievement of equilibrium, and to guarantee high-quality partitioning data. 6 hours was found to be sufficient to obtain equilibrium. In practice, all experiments exceeded 12 hours to assure equilibrium. In a second set of runs the temperature dependence of the partitioning behavior of Pt was investigated between the melting point of the 1 atm, AnDi system and the melting point of the Pt capsule material. Over 150 piston cylinder and 12 multi anvil experiments have been performed. Pt solubility is only slightly dependent on temperature, decreasing between 1800 and 1400°C by less than an order of magnitude. In consequence, the partitioning behavior of Pt is mostly determined by its oxygen fugacity dependence, which has only been determined in 1 atm experiments. At 10 kbar, metal/silicate partition coefficients (D's) decrease by about 3 orders of magnitude. The reason for this is not understood, but might be attributed to a first order phase transition as found for, e.g., SiO2 or H2O. Above 10 kbar any increase in pressure does not lead to any further significant decrease in partition coefficients. Solubilities stay roughly constant up to 140 kbar. Abundances of moderately siderophile elements were possibly established by metal/silicate equilibrium in a magma ocean. These results for Pt suggest that the abundances of HSEs were most probably established by the accretion of a chondritic veneer following core formation, as metal/silicate partition coefficients are too high to be consistent with metal/silicate equilibrium in a magma ocean.

An Amorphous Model for Morphological Processing in Visual Comprehension Based on Naive Discriminative Learning

ERIC Educational Resources Information Center

Baayen, R. Harald; Milin, Petar; Durdevic, Dusica Filipovic; Hendrix, Peter; Marelli, Marco

2011-01-01

A 2-layer symbolic network model based on the equilibrium equations of the Rescorla-Wagner model (Danks, 2003) is proposed. The study first presents 2 experiments in Serbian, which reveal for sentential reading the inflectional paradigmatic effects previously observed by Milin, Filipovic Durdevic, and Moscoso del Prado Martin (2009) for unprimed…

A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics.

PubMed

Chapman, Brian

2017-06-01

This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis-Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis- substrate binding, cis → trans bound enzyme shuttling, trans -substrate dissociation and trans → cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive 'tuning' of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force-flux relations, with only a minority of cases having their quasi -linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically 'tuned' to its particular task, dependent on the cis- and trans- substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport.

A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics

PubMed Central

2017-01-01

This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis–Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis-substrate binding, cis→trans bound enzyme shuttling, trans-substrate dissociation and trans→cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive ‘tuning’ of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force–flux relations, with only a minority of cases having their quasi-linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically ‘tuned’ to its particular task, dependent on the cis- and trans-substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport. PMID:28680687

Impact of ionization equilibrium on electrokinetic flow of weak electrolytes in nanochannels

NASA Astrophysics Data System (ADS)

Ji, Ziwei; Huang, Zhuo; Chen, Bowei; He, Yuhui; Tsutsui, Makusu; Miao, Xiangshui

2018-07-01

Weak electrolyte transport in nanochannels or nanopores has been actively explored in recent experiments. In this paper, we establish a new electrokinetic model where the ionization balance effect of weak electrolytes is outlined, and performed numerical calculations for H3PO4 concentration-biased nanochannel systems. By considering the roles of local chemical equilibrium in phosphorous acid ionization, the simulation results show quantitative agreement with experimental observations. Based on the model, we predict that enhanced energy harvesting capacity could be accomplished by utilizing weak electrolytes compared to the conventional strong electrolyte approaches in a concentration gradient-based power-generating system.

Modeling and Uncertainty Quantification of Vapor Sorption and Diffusion in Heterogeneous Polymers

DOE PAGES

Sun, Yunwei; Harley, Stephen J.; Glascoe, Elizabeth A.

2015-08-13

A high-fidelity model of kinetic and equilibrium sorption and diffusion is developed and exercised. The gas-diffusion model is coupled with a triple-sorption mechanism: Henry’s law absorption, Langmuir adsorption, and pooling or clustering of molecules at higher partial pressures. Sorption experiments are conducted and span a range of relative humidities (0-95%) and temperatures (30-60°C). Kinetic and equilibrium sorption properties and effective diffusivity are determined by minimizing the absolute difference between measured and modeled uptakes. Uncertainty quantification and sensitivity analysis methods are described and exercised herein to demonstrate the capability of this modeling approach. Water uptake in silica-filled and unfilled poly(dimethylsiloxane) networksmore » is investigated; however, the model is versatile enough to be used with a wide range of materials and vapors.« less

Implementation of a vibrationally linked chemical reaction model for DSMC

NASA Technical Reports Server (NTRS)

Carlson, A. B.; Bird, Graeme A.

1994-01-01

A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.

Electrical characteristics of TIG arcs in argon from non-equilibrium modelling and experiment

NASA Astrophysics Data System (ADS)

Baeva, Margarita; Uhrlandt, Dirk; Siewert, Erwan

2016-09-01

Electric arcs are widely used in industrial processes so that a thorough understanding of the arc characteristics is highly important to industrial research and development. TIG welding arcs operated with pointed electrodes made of tungsten, doped with cerium oxide, have been studied in order to analyze in detail the electric field and the arc voltage. Newly developed non-equilibrium model of the arc is based on a complete diffusion treatment of particle fluxes, a generalized form of Ohm's law, and boundary conditions accounting for the space-charge sheaths within the magneto-hydrodynamic approach. Experiments have been carried out for electric currents in the range 5-200 A. The electric arc has been initiated between a WC20 cathode and a water-cooled copper plate placed 0.8 mm from each other. The arc length has been continuously increased by 0.1 mm up to 15 mm and the arc voltage has been simultaneously recorded. Modelling and experimental results will be presented and discussed.

Prediction of Temperatures of Austenite Equilibrium Transformations in Steels During Thermomechanical Processing

NASA Astrophysics Data System (ADS)

Samadian, Pedram; Parsa, Mohammad Habibi; Ahmadabadi, M. Nili; Mirzadeh, Hamed

2014-10-01

Knowledge about the transformation temperatures is crucial in processing of steels especially in thermomechanical processes because microstructures and mechanical properties after processing are closely related to the extent and type of transformations. The experimental determination of critical temperatures is costly, and therefore, it is preferred to predict them by mathematical methods. In the current work, new thermodynamically based models were developed for computing the Ae3 and Acm temperatures in the equilibrium cooling conditions when austenite is deformed at elevated temperatures. The main advantage of the proposed models is their capability to predict the temperatures of austenite equilibrium transformations in steels with total alloying elements (Mn + Si + Ni + Cr + Mo + Cu) less than 5 wt.% and Si less than 1 wt.% under the deformation conditions just by using the chemical potential of constituents, without the need for determining the total Gibbs free energy of steel which requires many experiments and computations.

Implications for Core Formation of the Earth from High Pressure-Temperature Au Partitioning Experiments

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Sharp, T. G.; Hervig, R. L.

2005-01-01

Siderophile elements in the Earth.s mantle are depleted relative to chondrites. This is most pronounced for the highly siderophile elements (HSEs), which are approximately 400x lower than chondrites. Also remarkable is the relative chondritic abundances of the HSEs. This signature has been interpreted as representing their sequestration into an iron-rich core during the separation of metal from silicate liquids early in the Earth's history, followed by a late addition of chondritic material. Alternative efforts to explain this trace element signature have centered on element partitioning experiments at varying pressures, temperatures, and compositions (P-T-X). However, first results from experiments conducted at 1 bar did not match the observed mantle abundances, which motivated the model described above, a "late veneer" of chondritic material deposited on the earth and mixed into the upper mantle. Alternatively, the mantle trace element signature could be the result of equilibrium partitioning between metal and silicate in the deep mantle, under P-T-X conditions which are not yet completely identified. An earlier model determined that equilibrium between metal and silicate liquids could occur at a depth of approximately 700 km, 27(plus or minus 6) GPa and approximately 2000 (plus or minus 200) C, based on an extrapolation of partitioning data for a variety of moderately siderophile elements obtained at lower pressures and temperatures. Based on Ni-Co partitioning, the magma ocean may have been as deep as 1450 km. At present, only a small range of possible P-T-X trace element partitioning conditions has been explored, necessitating large extrapolations from experimental to mantle conditions for tests of equilibrium models. Our primary objective was to reduce or remove the additional uncertainty introduced by extrapolation by testing the equilibrium core formation hypothesis at P-T-X conditions appropriate to the mantle.

Equilibrium and stability of flow-dominated Plasmas in the Big Red Ball

NASA Astrophysics Data System (ADS)

Siller, Robert; Flanagan, Kenneth; Peterson, Ethan; Milhone, Jason; Mirnov, Vladimir; Forest, Cary

2017-10-01

The equilibrium and linear stability of flow-dominated plasmas are studied numerically using a spectral techniques to model MRI and dynamo experiments in the Big Red Ball device. The equilibrium code solves for steady-state magnetic fields and plasma flows subject to boundary conditions in a spherical domain. It has been benchmarked with NIMROD (non-ideal MHD with rotation - open discussion), Two different flow scenarios are studied. The first scenario creates a differentially rotating toroidal flow that is peaked at the center. This is done to explore the onset of the magnetorotational instability (MRI) in a spherical geometry. The second scenario creates a counter-rotating von Karman-like flow in the presence of a weak magnetic field. This is done to explore the plasma dynamo instability in the limit of a weak applied field. Both scenarios are numerically modeled as axisymmetric flow to create a steady-state equilibrium solution, the stability and normal modes are studied in the lowest toroidal mode number. The details of the observed flow, and the structure of the fastest growing modes will be shown. DoE, NSF.

Solvable Hydrodynamics of Quantum Integrable Systems

NASA Astrophysics Data System (ADS)

Bulchandani, Vir B.; Vasseur, Romain; Karrasch, Christoph; Moore, Joel E.

2017-12-01

The conventional theory of hydrodynamics describes the evolution in time of chaotic many-particle systems from local to global equilibrium. In a quantum integrable system, local equilibrium is characterized by a local generalized Gibbs ensemble or equivalently a local distribution of pseudomomenta. We study time evolution from local equilibria in such models by solving a certain kinetic equation, the "Bethe-Boltzmann" equation satisfied by the local pseudomomentum density. Explicit comparison with density matrix renormalization group time evolution of a thermal expansion in the XXZ model shows that hydrodynamical predictions from smooth initial conditions can be remarkably accurate, even for small system sizes. Solutions are also obtained in the Lieb-Liniger model for free expansion into vacuum and collisions between clouds of particles, which model experiments on ultracold one-dimensional Bose gases.

The long-term dissolution characteristics of a residually trapped BTX mixture in soil

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

Rixey, W.G.

1996-12-31

A mass transfer limited model is presented to describe the long-term dissolution of organic compounds from a benzene, toluene, and xylenes (BTX) mixture residually trapped in a sandy soil. The model is an extension of a previously presented equilibrium dissolution model which takes into consideration mass transfer limitations that develop later in the leaching process and is similar to that presented by Borden and Kao for modeling BTX dissolution from residually trapped gasoline. The residual nonaqueous phase liquid (NAPL) is divided into multiple regions: one region which undergoes equilibrium dissolution and additional regions in which mass transfer is progressively limited.more » Application of the model to BTX column effluent data indicates that the initial dissolution (exponential decay region) of BTX can be effectively described by equilibrium dissolution. When applied to later dissolution times (Asymptotic region) a multiple-region model is required to rationalize the data for all three components. This explanation of the observed tailing in leaching experiments form residually trapped hydrocarbons if offered as an alternative to the explanation of tailing due to rate-limited desorption from soils. 16 refs., 5 figs., 2 tabs.« less

Equilibrium reconstruction with 3D eddy currents in the Lithium Tokamak eXperiment

DOE PAGES

Hansen, C.; Boyle, D. P.; Schmitt, J. C.; ...

2017-04-18

Axisymmetric free-boundary equilibrium reconstructions of tokamak plasmas in the Lithium Tokamak eXperiment (LTX) are performed using the PSI-Tri equilibrium code. Reconstructions in LTX are complicated by the presence of long-lived non-axisymmetric eddy currents generated by a vacuum vessel and first wall structures. To account for this effect, reconstructions are performed with additional toroidal current sources in these conducting regions. The eddy current sources are fixed in their poloidal distributions, but their magnitude is adjusted as part of the full reconstruction. Eddy distributions are computed by toroidally averaging currents, generated by coupling to vacuum field coils, from a simplified 3D filamentmore » model of important conducting structures. The full 3D eddy current fields are also used to enable the inclusion of local magnetic field measurements, which have strong 3D eddy current pick-up, as reconstruction constraints. Using this method, equilibrium reconstruction yields good agreement with all available diagnostic signals. Here, an accompanying field perturbation produced by 3D eddy currents on the plasma surface with a primarily n = 2, m = 1 character is also predicted for these equilibria.« less

CFD Modeling of LNG Spill: Humidity Effect on Vapor Dispersion

NASA Astrophysics Data System (ADS)

Giannissi, S. G.; Venetsanos, A. G.; Markatos, N.

2015-09-01

The risks entailed by an accidental spill of Liquefied Natural Gas (LNG) should be indentified and evaluated, in order to design measures for prevention and mitigation in LNG terminals. For this purpose, simulations are considered a useful tool to study LNG spills and to understand the mechanisms that influence the vapor dispersion. In the present study, the ADREA-HF CFD code is employed to simulate the TEEX1 experiment. The experiment was carried out at the Brayton Fire Training Field, which is affiliated with the Texas A&M University system and involves LNG release and dispersion over water surface in open- obstructed environment. In the simulation the source was modeled as a two-phase jet enabling the prediction of both the vapor dispersion and the liquid pool spreading. The conservation equations for the mixture are solved along with the mass fraction for natural gas. Due to the low prevailing temperatures during the spill ambient humidity condenses and this might affect the vapor dispersion. This effect was examined in this work by solving an additional conservation equation for the water mass fraction. Two different models were tested: the hydrodynamic equilibrium model which assumes kinetic equilibrium between the phases and the non hydrodynamic equilibrium model, in order to assess the effect of slip velocity on the prediction. The slip velocity is defined as the difference between the liquid phase and the vapor phase and is calculated using the algebraic slip model. Constant droplet diameter of three different sizes and a lognormal distribution of the droplet diameter were applied and the results are discussed and compared with the measurements.

Deposition and transport of Pseudomonas aeruginosa in porous media: lab-scale experiments and model analysis.

PubMed

Kwon, Kyu-Sang; Kim, Song-Bae; Choi, Nag-Choul; Kim, Dong-Ju; Lee, Soonjae; Lee, Sang-Hyup; Choi, Jae-Woo

2013-01-01

In this study, the deposition and transport of Pseudomonas aeruginosa on sandy porous materials have been investigated under static and dynamic flow conditions. For the static experiments, both equilibrium and kinetic batch tests were performed at a 1:3 and 3:1 soil:solution ratio. The batch data were analysed to quantify the deposition parameters under static conditions. Column tests were performed for dynamic flow experiments with KCl solution and bacteria suspended in (1) deionized water, (2) mineral salt medium (MSM) and (3) surfactant + MSM. The equilibrium distribution coefficient (K(d)) was larger at a 1:3 (2.43 mL g(-1)) than that at a 3:1 (0.28 mL g(-1)) soil:solution ratio. Kinetic batch experiments showed that the reversible deposition rate coefficient (k(att)) and the release rate coefficient (k(det)) at a soil:solution ratio of 3:1 were larger than those at a 1:3 ratio. Column experiments showed that an increase in ionic strength resulted in a decrease in peak concentration of bacteria, mass recovery and tailing of the bacterial breakthrough curve (BTC) and that the presence of surfactant enhanced the movement of bacteria through quartz sand, giving increased mass recovery and tailing. Deposition parameters under dynamic condition were determined by fitting BTCs to four different transport models, (1) kinetic reversible, (2) two-site, (3) kinetic irreversible and (4) kinetic reversible and irreversible models. Among these models, Model 4 was more suitable than the others since it includes the irreversible sorption term directly related to the mass loss of bacteria observed in the column experiment. Applicability of the parameters obtained from the batch experiments to simulate the column breakthrough data is evaluated.

[Hypothesis on the equilibrium point and variability of amplitude, speed and time of single-joint movement].

PubMed

Latash, M; Gottleib, G

1990-01-01

Problems of single-joint movement variability are analysed in the framework of the equilibrium-point hypothesis (the lambda-model). Control of the movements is described with three parameters related to movement amplitude speed, and time. Three strategies emerge from this description. Only one of them is likely to lead to a Fitts' type speed-accuracy trade-off. Experiments were performed to test one of the predictions of the model. Subjects performed identical sets of single-joint fast movements with open or closed eyes and some-what different instructions. Movements performed with closed eyes were characterized with higher peak speeds and unchanged variability in seeming violation of the Fitt's law and in a good correspondence to the model.

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

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

Microgravity

NASA Image and Video Library

1996-01-25

Dan Carter and Charles Sisk center a Lysozyme Protein crystal grown aboard the USML-2 shuttle mission. Protein isolated from hen egg-white and functions as a bacteriostatic enzyme by degrading bacterial cell walls. First enzyme ever characterized by protein crystallography. It is used as an excellent model system for better understanding parameters involved in microgravity crystal growth experiments. The goal is to compare kinetic data from microgravity experiments with data from laboratory experiments to study the equilibrium.

Combining stable isotope isotope geochemistry and carbonic anhydrase activity to trace vital effect in carbonate precipitation experiments

NASA Astrophysics Data System (ADS)

Thaler, C.; Ader, M.; Menez, B.; Guyot, F. J.

2013-12-01

Carbonates precipitated by skeleton-forming eukaryotic organisms are often characterized by non-equilibrium isotopic signatures. This specificity is referred to as the "vital effect" and can be used as an isotopic evidence to trace life. Combining stable isotope geochemistry and enzymology (using the enzyme carbonic anhydrase) we aim to demonstrate that prokaryotes are also able to precipitate carbonate with a non-equilibrium d18OCaCO3. Indeed, if in an biomineralization experiment carbonates are precipitated with a vital effect, the addition of carbonic anhydrase should drive the system to isotope equilibrium, And provide a comparison point to estimate the vital effect range. This protocol allowed us to identify a -20‰ vital effect for the d18O of carbonates precipitated by Sporosarcina pasteurii, a bacterial model of carbonatogen metabolisms. This approach is thus a powerfull tool for the understanding of microbe carbonatogen activity and will probably bring new insights into the understanding of bacterial activity in subsurface and during diagenesis.

Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

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

Minelli, Matteo; Doghieri, Ferruccio

2014-05-15

Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps.

A Theory of Age-Dependent Mutation and Senescence

PubMed Central

Moorad, Jacob A.; Promislow, Daniel E. L.

2008-01-01

Laboratory experiments show us that the deleterious character of accumulated novel age-specific mutations is reduced and made less variable with increased age. While theories of aging predict that the frequency of deleterious mutations at mutation–selection equilibrium will increase with the mutation's age of effect, they do not account for these age-related changes in the distribution of de novo mutational effects. Furthermore, no model predicts why this dependence of mutational effects upon age exists. Because the nature of mutational distributions plays a critical role in shaping patterns of senescence, we need to develop aging theory that explains and incorporates these effects. Here we propose a model that explains the age dependency of mutational effects by extending Fisher's geometrical model of adaptation to include a temporal dimension. Using a combination of simple analytical arguments and simulations, we show that our model predicts age-specific mutational distributions that are consistent with observations from mutation-accumulation experiments. Simulations show us that these age-specific mutational effects may generate patterns of senescence at mutation–selection equilibrium that are consistent with observed demographic patterns that are otherwise difficult to explain. PMID:18660535

Laboratory-scale experiments and numerical modeling of cosolvent flushing of multi-component NAPLs in saturated porous media.

PubMed

Agaoglu, Berken; Scheytt, Traugott; Copty, Nadim K

2012-10-01

This study examines the mechanistic processes governing multiphase flow of a water-cosolvent-NAPL system in saturated porous media. Laboratory batch and column flushing experiments were conducted to determine the equilibrium properties of pure NAPL and synthetically prepared NAPL mixtures as well as NAPL recovery mechanisms for different water-ethanol contents. The effect of contact time was investigated by considering different steady and intermittent flow velocities. A modified version of multiphase flow simulator (UTCHEM) was used to compare the multiphase model simulations with the column experiment results. The effect of employing different grid geometries (1D, 2D, 3D), heterogeneity and different initial NAPL saturation configurations was also examined in the model. It is shown that the change in velocity affects the mass transfer rate between phases as well as the ultimate NAPL recovery percentage. The experiments with low flow rate flushing of pure NAPL and the 3D UTCHEM simulations gave similar effluent concentrations and NAPL cumulative recoveries. Model simulations over-estimated NAPL recovery for high specific discharges and rate-limited mass transfer, suggesting a constant mass transfer coefficient for the entire flushing experiment may not be valid. When multi-component NAPLs are present, the dissolution rate of individual organic compounds (namely, toluene and benzene) into the ethanol-water flushing solution is found not to correlate with their equilibrium solubility values. Copyright © 2012 Elsevier B.V. All rights reserved.

Learning dynamics in social dilemmas

PubMed Central

Macy, Michael W.; Flache, Andreas

2002-01-01

The Nash equilibrium, the main solution concept in analytical game theory, cannot make precise predictions about the outcome of repeated mixed-motive games. Nor can it tell us much about the dynamics by which a population of players moves from one equilibrium to another. These limitations, along with concerns about the cognitive demands of forward-looking rationality, have motivated efforts to explore backward-looking alternatives to analytical game theory. Most of the effort has been invested in evolutionary models of population dynamics. We shift attention to a learning-theoretic alternative. Computational experiments with adaptive agents identify a fundamental solution concept for social dilemmas–−stochastic collusion–−based on a random walk from a self-limiting noncooperative equilibrium into a self-reinforcing cooperative equilibrium. However, we show that this solution is viable only within a narrow range of aspiration levels. Below the lower threshold, agents are pulled into a deficient equilibrium that is a stronger attractor than mutual cooperation. Above the upper threshold, agents are dissatisfied with mutual cooperation. Aspirations that adapt with experience (producing habituation to stimuli) do not gravitate into the window of viability; rather, they are the worst of both worlds. Habituation destabilizes cooperation and stabilizes defection. Results from the two-person problem suggest that applications to multiplex and embedded relationships will yield unexpected insights into the global dynamics of cooperation in social dilemmas. PMID:12011402

Non-equilibrium magnetic colloidal dispersions at liquid-air interfaces: dynamic patterns, magnetic order and self-assembled swimmers.

PubMed

Snezhko, Alexey

2011-04-20

Colloidal dispersions of interacting particles subjected to an external periodic forcing often develop nontrivial self-assembled patterns and complex collective behavior. A fundamental issue is how collective ordering in such non-equilibrium systems arises from the dynamics of discrete interacting components. In addition, from a practical viewpoint, by working in regimes far from equilibrium new self-organized structures which are generally not available through equilibrium thermodynamics can be created. In this review spontaneous self-assembly phenomena in magnetic colloidal dispersions suspended at liquid-air interfaces and driven out of equilibrium by an alternating magnetic field are presented. Experiments reveal a new type of nontrivially ordered self-assembled structures emerging in such systems in a certain range of excitation parameters. These dynamic structures emerge as a result of the competition between magnetic and hydrodynamic forces and have complex unconventional magnetic ordering. Nontrivial self-induced hydrodynamic fields accompany each out-of-equilibrium pattern. Spontaneous symmetry breaking of the self-induced surface flows leading to a formation of self-propelled microstructures has been discovered. Some features of the self-localized structures can be understood in the framework of the amplitude equation (Ginzburg-Landau type equation) for parametric waves coupled to the conservation law equation describing the evolution of the magnetic particle density and the Navier-Stokes equation for hydrodynamic flows. To understand the fundamental microscopic mechanisms governing self-assembly processes in magnetic colloidal dispersions at liquid-air interfaces a first-principle model for a non-equilibrium self-assembly is presented. The latter model allows us to capture in detail the entire process of out-of-equilibrium self-assembly in the system and reproduces most of the observed phenomenology.

From rationality to cooperativeness: The totally mixed Nash equilibrium in Markov strategies in the iterated Prisoner's Dilemma.

PubMed

Menshikov, Ivan S; Shklover, Alexsandr V; Babkina, Tatiana S; Myagkov, Mikhail G

2017-01-01

In this research, the social behavior of the participants in a Prisoner's Dilemma laboratory game is explained on the basis of the quantal response equilibrium concept and the representation of the game in Markov strategies. In previous research, we demonstrated that social interaction during the experiment has a positive influence on cooperation, trust, and gratefulness. This research shows that the quantal response equilibrium concept agrees only with the results of experiments on cooperation in Prisoner's Dilemma prior to social interaction. However, quantal response equilibrium does not explain of participants' behavior after social interaction. As an alternative theoretical approach, an examination was conducted of iterated Prisoner's Dilemma game in Markov strategies. We built a totally mixed Nash equilibrium in this game; the equilibrium agrees with the results of the experiments both before and after social interaction.

Fluorescence lifetime components reveal kinetic intermediate states upon equilibrium denaturation of carbonic anhydrase II

NASA Astrophysics Data System (ADS)

Nemtseva, Elena V.; Lashchuk, Olesya O.; Gerasimova, Marina A.; Melnik, Tatiana N.; Nagibina, Galina S.; Melnik, Bogdan S.

2018-01-01

In most cases, intermediate states of multistage folding proteins are not ‘visible’ under equilibrium conditions but are revealed in kinetic experiments. Time-resolved fluorescence spectroscopy was used in equilibrium denaturation studies. The technique allows for detecting changes in the conformation and environment of tryptophan residues in different structural elements of carbonic anhydrase II which in its turn has made it possible to study the intermediate states of carbonic anhydrase II under equilibrium conditions. The results of equilibrium and kinetic experiments using wild-type bovine carbonic anhydrase II and its mutant form with the substitution of leucine for alanine at position 139 (L139A) were compared. The obtained lifetime components of intrinsic tryptophan fluorescence allowed for revealing that, the same as in kinetic experiments, under equilibrium conditions the unfolding of carbonic anhydrase II ensues through formation of intermediate states.

Fluorescence lifetime components reveal kinetic intermediate states upon equilibrium denaturation of carbonic anhydrase II.

PubMed

Nemtseva, Elena V; Lashchuk, Olesya O; Gerasimova, Marina A; Melnik, Tatiana N; Nagibina, Galina S; Melnik, Bogdan S

2017-12-21

In most cases, intermediate states of multistage folding proteins are not 'visible' under equilibrium conditions but are revealed in kinetic experiments. Time-resolved fluorescence spectroscopy was used in equilibrium denaturation studies. The technique allows for detecting changes in the conformation and environment of tryptophan residues in different structural elements of carbonic anhydrase II which in its turn has made it possible to study the intermediate states of carbonic anhydrase II under equilibrium conditions. The results of equilibrium and kinetic experiments using wild-type bovine carbonic anhydrase II and its mutant form with the substitution of leucine for alanine at position 139 (L139A) were compared. The obtained lifetime components of intrinsic tryptophan fluorescence allowed for revealing that, the same as in kinetic experiments, under equilibrium conditions the unfolding of carbonic anhydrase II ensues through formation of intermediate states.

From rationality to cooperativeness: The totally mixed Nash equilibrium in Markov strategies in the iterated Prisoner’s Dilemma

PubMed Central

Myagkov, Mikhail G.

2017-01-01

In this research, the social behavior of the participants in a Prisoner's Dilemma laboratory game is explained on the basis of the quantal response equilibrium concept and the representation of the game in Markov strategies. In previous research, we demonstrated that social interaction during the experiment has a positive influence on cooperation, trust, and gratefulness. This research shows that the quantal response equilibrium concept agrees only with the results of experiments on cooperation in Prisoner’s Dilemma prior to social interaction. However, quantal response equilibrium does not explain of participants’ behavior after social interaction. As an alternative theoretical approach, an examination was conducted of iterated Prisoner's Dilemma game in Markov strategies. We built a totally mixed Nash equilibrium in this game; the equilibrium agrees with the results of the experiments both before and after social interaction. PMID:29190280

Removal Rate of Organic Matter Using Natural Cellulose via Adsorption Isotherm and Kinetic Studies.

PubMed

Din, Mohd Fadhil Md; Ponraj, Mohanadoss; Low, Wen-Pei; Fulazzaky, Mohamad Ali; Iwao, Kenzo; Songip, Ahmad Rahman; Chelliapan, Shreeshivadasan; Ismail, Zulhilmi; Jamal, Mohamad Hidayat

2016-02-01

In this study, the removal of natural organic matter (NOM) using coconut fiber (CF) and palm oil fiber (POF) was investigated. Preliminary analysis was performed using a jar test for the selection of optimal medium before the fabricated column model experiment. The equilibrium studies on isotherms and kinetic models for NOM adsorption were analyzed using linearized correlation coefficient. Results showed that the equilibrium data were fitted to Langmuir isotherm model for both CF and POF. The most suitable adsorption model was the pseudo-first-order kinetic model for POF and pseudo-second-order kinetic model for CF. The adsorption capacities achieved by the CF and POF were 15.67 and 30.8 mg/g respectively. Based on this investigation, it can be concluded that the POF is the most suitable material for the removal of NOM in semi polluted river water.

Probability distributions of molecular observables computed from Markov models. II. Uncertainties in observables and their time-evolution

NASA Astrophysics Data System (ADS)

Chodera, John D.; Noé, Frank

2010-09-01

Discrete-state Markov (or master equation) models provide a useful simplified representation for characterizing the long-time statistical evolution of biomolecules in a manner that allows direct comparison with experiments as well as the elucidation of mechanistic pathways for an inherently stochastic process. A vital part of meaningful comparison with experiment is the characterization of the statistical uncertainty in the predicted experimental measurement, which may take the form of an equilibrium measurement of some spectroscopic signal, the time-evolution of this signal following a perturbation, or the observation of some statistic (such as the correlation function) of the equilibrium dynamics of a single molecule. Without meaningful error bars (which arise from both approximation and statistical error), there is no way to determine whether the deviations between model and experiment are statistically meaningful. Previous work has demonstrated that a Bayesian method that enforces microscopic reversibility can be used to characterize the statistical component of correlated uncertainties in state-to-state transition probabilities (and functions thereof) for a model inferred from molecular simulation data. Here, we extend this approach to include the uncertainty in observables that are functions of molecular conformation (such as surrogate spectroscopic signals) characterizing each state, permitting the full statistical uncertainty in computed spectroscopic experiments to be assessed. We test the approach in a simple model system to demonstrate that the computed uncertainties provide a useful indicator of statistical variation, and then apply it to the computation of the fluorescence autocorrelation function measured for a dye-labeled peptide previously studied by both experiment and simulation.

Listening to the Shepard-Risset Glissando: the Relationship between Emotional Response, Disruption of Equilibrium, and Personality

PubMed Central

Vernooij, Eveline; Orcalli, Angelo; Fabbro, Franco; Crescentini, Cristiano

2016-01-01

The endless scale illusion, obtained by cyclically repeating a chromatic scale made up of Shepard tones, has been used in a variety of musical works. Music psychology and neuroscience has been interested in this particular psychoacoustic phenomenon mainly for studying the cognitive processes of pitch perception involved. In the present study, we investigated the emotional states induced by the Shepard-Risset glissando, a variant of the Shepard scale. For this purpose we chose three musical stimuli: a Matlab-generated Shepard Risset glissando, Jean-Claude Risset's Computer Suite from Little Boy, which presents a Shepard-Risset glissando integrated in the aesthetic context of a composition, and an ordinary orchestral glissando taken from the opening of Iannis Xenakis's Metastasis. Seventy-three volunteers completed a listening experiment during which they rated their emotional response to these stimuli on a seven-point Likert scale and indicated whether they had experienced a disruption of equilibrium. Personality was also measured with the Five-Factor Model of personality traits. The results show that negative emotions were most strongly evoked during listening to each of the stimuli. We also found that the Shepard-Risset glissando illusion, both within the aesthetic context of a musical composition and on its own, was capable of evoking disruption of equilibrium, frequently leading to the associated feeling of falling. Moreover, generally for the Shepard-Risset glissando illusion, higher negative emotional ratings were given by individuals who had experienced a feeling of disturbance of equilibrium relative to those who had not had this experience. Finally, we found a complex pattern of relationships between personality and the subjective experience of the glissando. Openness to experience correlated positively with positive emotion ratings for the Computer Suite, while agreeableness correlated negatively with positive emotion ratings for the Matlab stimulus. Moreover, results indicated higher (Bonferroni-uncorrected) neuroticism for those who experienced an equilibrium disturbance relative to subjects who did not have this experience during listening to the Computer Suite. These findings suggest that musical paradoxes may be of interest not only for the insights they provide on our perceptual system, but also for the richness of the emotional experience elicited during listening. PMID:26973584

Listening to the Shepard-Risset Glissando: the Relationship between Emotional Response, Disruption of Equilibrium, and Personality.

PubMed

Vernooij, Eveline; Orcalli, Angelo; Fabbro, Franco; Crescentini, Cristiano

2016-01-01

The endless scale illusion, obtained by cyclically repeating a chromatic scale made up of Shepard tones, has been used in a variety of musical works. Music psychology and neuroscience has been interested in this particular psychoacoustic phenomenon mainly for studying the cognitive processes of pitch perception involved. In the present study, we investigated the emotional states induced by the Shepard-Risset glissando, a variant of the Shepard scale. For this purpose we chose three musical stimuli: a Matlab-generated Shepard Risset glissando, Jean-Claude Risset's Computer Suite from Little Boy, which presents a Shepard-Risset glissando integrated in the aesthetic context of a composition, and an ordinary orchestral glissando taken from the opening of Iannis Xenakis's Metastasis. Seventy-three volunteers completed a listening experiment during which they rated their emotional response to these stimuli on a seven-point Likert scale and indicated whether they had experienced a disruption of equilibrium. Personality was also measured with the Five-Factor Model of personality traits. The results show that negative emotions were most strongly evoked during listening to each of the stimuli. We also found that the Shepard-Risset glissando illusion, both within the aesthetic context of a musical composition and on its own, was capable of evoking disruption of equilibrium, frequently leading to the associated feeling of falling. Moreover, generally for the Shepard-Risset glissando illusion, higher negative emotional ratings were given by individuals who had experienced a feeling of disturbance of equilibrium relative to those who had not had this experience. Finally, we found a complex pattern of relationships between personality and the subjective experience of the glissando. Openness to experience correlated positively with positive emotion ratings for the Computer Suite, while agreeableness correlated negatively with positive emotion ratings for the Matlab stimulus. Moreover, results indicated higher (Bonferroni-uncorrected) neuroticism for those who experienced an equilibrium disturbance relative to subjects who did not have this experience during listening to the Computer Suite. These findings suggest that musical paradoxes may be of interest not only for the insights they provide on our perceptual system, but also for the richness of the emotional experience elicited during listening.

Equilibrium, kinetic and thermodynamic studies of uranium biosorption by calcium alginate beads.

PubMed

Bai, Jing; Fan, Fangli; Wu, Xiaolei; Tian, Wei; Zhao, Liang; Yin, Xiaojie; Fan, Fuyou; Li, Zhan; Tian, Longlong; Wang, Yang; Qin, Zhi; Guo, Junsheng

2013-12-01

Calcium alginate beads are potential biosorbent for radionuclides removal as they contain carboxyl groups. However, until now limited information is available concerning the uptake behavior of uranium by this polymer gel, especially when sorption equilibrium, kinetics and thermodynamics are concerned. In present work, batch experiments were carried out to study the equilibrium, kinetics and thermodynamics of uranium sorption by calcium alginate beads. The effects of initial solution pH, sorbent amount, initial uranium concentration and temperature on uranium sorption were also investigated. The determined optimal conditions were: initial solution pH of 3.0, added sorbent amount of 40 mg, and uranium sorption capacity increased with increasing initial uranium concentration and temperature. Equilibrium data obtained under different temperatures were fitted better with Langmuir model than Freundlich model, uranium sorption was dominated by a monolayer way. The kinetic data can be well depicted by the pseudo-second-order kinetic model. The activation energy derived from Arrhenius equation was 30.0 kJ/mol and the sorption process had a chemical nature. Thermodynamic constants such as ΔH(0), ΔS(0) and ΔG(0) were also evaluated, results of thermodynamic study showed that the sorption process was endothermic and spontaneous. Copyright © 2013 Elsevier Ltd. All rights reserved.

Stochastic evolutionary voluntary public goods game with punishment in a Quasi-birth-and-death process.

PubMed

Quan, Ji; Liu, Wei; Chu, Yuqing; Wang, Xianjia

2017-11-23

Traditional replication dynamic model and the corresponding concept of evolutionary stable strategy (ESS) only takes into account whether the system can return to the equilibrium after being subjected to a small disturbance. In the real world, due to continuous noise, the ESS of the system may not be stochastically stable. In this paper, a model of voluntary public goods game with punishment is studied in a stochastic situation. Unlike the existing model, we describe the evolutionary process of strategies in the population as a generalized quasi-birth-and-death process. And we investigate the stochastic stable equilibrium (SSE) instead. By numerical experiments, we get all possible SSEs of the system for any combination of parameters, and investigate the influence of parameters on the probabilities of the system to select different equilibriums. It is found that in the stochastic situation, the introduction of the punishment and non-participation strategies can change the evolutionary dynamics of the system and equilibrium of the game. There is a large range of parameters that the system selects the cooperative states as its SSE with a high probability. This result provides us an insight and control method for the evolution of cooperation in the public goods game in stochastic situations.

Uptake of uranium from seawater by amidoxime-based polymeric adsorbent marine testing

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

Tsouris, C.; Kim, J.; Oyola, Y.

2013-07-01

Amidoxime-based polymer adsorbents in the form of functionalized fibers were prepared at the Oak Ridge National Laboratory (ORNL) and screened in laboratory experiments, in terms of uranium uptake capacity, using spiked uranium solution and seawater samples. Batch laboratory experiments conducted with 5-gallon seawater tanks provided equilibrium information. Based on results from 5-gallon experiments, the best adsorbent was selected for field-testing of uranium adsorption from seawater. Flow-through column tests have been performed at different marine sites to investigate the uranium uptake rate and equilibrium capacity under diverse biogeochemistry. The maximum amount of uranium uptake from seawater tests at Sequim, WA, wasmore » 3.3 mg U/g adsorbent after eight weeks of contact of the adsorbent with seawater. This amount was three times higher than the maximum adsorption capacity achieved in this study by a leading adsorbent developed by the Japan Atomic Energy Agency (JAEA), which was 1.1 mg U/g adsorbent at equilibrium. The initial uranium uptake rate of the ORNL adsorbent was 2.6 times higher than that of the JAEA adsorbent under similar conditions. A mathematical model derived from the mass balance of uranium was employed to describe the data. (authors)« less

Kinetic sorption of contaminants of emerging concern by a palygorskite-montmorillonite filter medium.

PubMed

Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D

2017-06-01

Kinetic sorption of bisphenol A (BPA), carbamazepine (CMZ) and ciprofloxacin (CIP) by three palygorskite-montmorillonite (Pal-Mt) granule sizes was studied. For BPA, CMZ and CIP, apparent sorption equilibrium was reached within about 3, 5 and 16 h, respectively. The highest and the lowest sorption capacities were by the small and the large granule sizes, respectively. Experimental results were compared to various sorption kinetics models to gain insights regarding the sorption processes and achieve a predictive capacity. The pseudo-second order (PSO) and the Elovich models performed the best while the pseudo-first order (PFO) model was only adequate for CMZ. The intraparticle-diffusion (IPD) model showed a two-step linear plot of BPA, CMZ and CIP sorption versus square root of time that was indicative of surface-sorption followed by IPD as a rate-limiting process before equilibrium was reached. Using the pseudo-first order (PFO) and the pseudo-second order (PSO) rate constants combined with previously-established Langmuir equilibrium sorption models, the kinetic sorption (k a ) and desorption (k d ) Langmuir kinetic rate constants were theoretically calculated for BPA and CIP. Kinetic sorption was then simulated using these theoretically calculated k a and k d values, and the simulations were compared to the observed behavior. The simulations fit the observed sorbed concentrations better during the early part of the experiments; the observed sorption during later times occurred more slowly than expected, supporting the hypothesis that IPD becomes a rate-limiting process during the course of the experiment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetics of polyelectrolyte adsorption

NASA Astrophysics Data System (ADS)

Cohen Stuart, M. A.; Hoogendam, C. W.; de Keizer, A.

1997-09-01

The kinetics of polyelectrolyte adsorption has been investigated theoretically. In analogy with Kramers' rate theory for chemical reactions we present a model which is based on the assumption that a polyelectrolyte encounters a barrier in its motion towards an adsorbing surface. The height of the barrier, which is of electrostatic origin, is calculated with a self-consistent-field (SCF) model. The salt concentration strongly affects the height of the barrier. At moderate salt concentrations (0953-8984/9/37/009/img1) equilibrium in the adsorption is attained; at low salt concentration (0953-8984/9/37/009/img2) equilibrium is not reached on the time scale of experiments. The attachment process shows resemblances to the classical DLVO theory.

Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

PubMed

Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

2015-04-09

In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions. Copyright © 2014 Elsevier B.V. All rights reserved.

Scientist prepare Lysozyme Protein Crystal

NASA Technical Reports Server (NTRS)

1996-01-01

Dan Carter and Charles Sisk center a Lysozyme Protein crystal grown aboard the USML-2 shuttle mission. Protein isolated from hen egg-white and functions as a bacteriostatic enzyme by degrading bacterial cell walls. First enzyme ever characterized by protein crystallography. It is used as an excellent model system for better understanding parameters involved in microgravity crystal growth experiments. The goal is to compare kinetic data from microgravity experiments with data from laboratory experiments to study the equilibrium.

Modeling and simulation of protein elution in linear pH and salt gradients on weak, strong and mixed cation exchange resins applying an extended Donnan ion exchange model.

PubMed

Wittkopp, Felix; Peeck, Lars; Hafner, Mathias; Frech, Christian

2018-04-13

Process development and characterization based on mathematic modeling provides several advantages and has been applied more frequently over the last few years. In this work, a Donnan equilibrium ion exchange (DIX) model is applied for modelling and simulation of ion exchange chromatography of a monoclonal antibody in linear chromatography. Four different cation exchange resin prototypes consisting of weak, strong and mixed ligands are characterized using pH and salt gradient elution experiments applying the extended DIX model. The modelling results are compared with the results using a classic stoichiometric displacement model. The Donnan equilibrium model is able to describe all four prototype resins while the stoichiometric displacement model fails for the weak and mixed weak/strong ligands. Finally, in silico chromatogram simulations of pH and pH/salt dual gradients are performed to verify the results and to show the consistency of the developed model. Copyright © 2018 Elsevier B.V. All rights reserved.

Non-equilibrium diffusion combustion of a fuel droplet

NASA Astrophysics Data System (ADS)

Tyurenkova, Veronika V.

2012-06-01

A mathematical model for the non-equilibrium combustion of droplets in rocket engines is developed. This model allows to determine the divergence of combustion rate for the equilibrium and non-equilibrium model. Criterion for droplet combustion deviation from equilibrium is introduced. It grows decreasing droplet radius, accommodation coefficient, temperature and decreases on decreasing diffusion coefficient. Also divergence from equilibrium increases on reduction of droplet radius. Droplet burning time essentially increases under non-equilibrium conditions. Comparison of theoretical and experimental data shows that to have adequate solution for small droplets it is necessary to use the non-equilibrium model.

Investigation of Non-Equilibrium Radiation for Earth Entry

NASA Technical Reports Server (NTRS)

Brandis, Aaron; Johnston, Chris; Cruden, Brett

2016-01-01

This paper presents measurements and simulations of non-equilibrium shock layer radiation relevant to high-speed Earth entry data obtained in the NASA Ames Research Center's Electric Arc Shock Tube (EAST) facility. The experiments were aimed at measuring the spatially and spectrally resolved radiance at relevant entry conditions for both an approximate Earth atmosphere (79 N2 : 21 O2) as well as a more accurate composition featuring the trace species Ar and CO2 (78.08 N2 : 20.95 O2 : 0.04 CO2 : 0.93 Ar). The experiments were configured to target a wide range of conditions, of which shots from 8 to 11.5 km/s at 0.2 Torr (26.7 Pa) are examined in this paper. The non-equilibrium component was chosen to be the focus of this study as it can account for a significant percentage of the emitted radiation for Earth entry, and more importantly, non-equilibrium has traditionally been assigned a large uncertainty for vehicle design. The main goals of this study are to present the shock tube data in the form of a non-equilibrium metric, evaluate the level of agreement between the experiment and simulations, identify key discrepancies and to promote discussion about various aspects of modeling non-equilibrium radiating flows. Radiance profiles integrated over discreet wavelength regions, ranging from the VUV through to the NIR, were compared in order to maximize both the spectral coverage and the number of experiments that could be used in the analysis. A previously defined non-equilibrium metric has been used to allow comparisons with several shots and reveal trends in the data. Overall, LAURAHARA is shown to under-predict EAST by as much as 50 and over-predict by as much as 20 depending on the shock speed. DPLRNEQAIR is shown to under-predict EAST by as much as 40 and over-predict by as much as 12 depending on the shock speed. In terms of an upper bound estimate for the absolute error in wall-directed heat flux, at the lower speeds investigated in this paper, 8 to 9 km/s, even though there are some large relative differences, the absolute error in radiance will be less then 1 Wcm2. At the highest shock speed of 11 km/s, the error will be less than 20 W/ sq cm.

Kinetics of Cd(ii) adsorption and desorption on ferrihydrite: experiments and modeling.

PubMed

Liang, Yuzhen; Tian, Lei; Lu, Yang; Peng, Lanfang; Wang, Pei; Lin, Jingyi; Cheng, Tao; Dang, Zhi; Shi, Zhenqing

2018-05-15

The kinetics of Cd(ii) adsorption/desorption on ferrihydrite is an important process affecting the fate, transport, and bioavailability of Cd(ii) in the environment, which was rarely systematically studied and understood at quantitative levels. In this work, a combination of stirred-flow kinetic experiments, batch adsorption equilibrium experiments, high-resolution transmission electron microscopy (HR-TEM), and mechanistic kinetic modeling were used to study the kinetic behaviors of Cd(ii) adsorption/desorption on ferrihydrite. HR-TEM images showed the open, loose, and sponge-like structure of ferrihydrite. The batch adsorption equilibrium experiments revealed that higher pH and initial metal concentration increased Cd(ii) adsorption on ferrihydrite. The stirred-flow kinetic results demonstrated the increased adsorption rate and capacity as a result of the increased pH, influent concentration, and ferrihydrite concentration. The mechanistic kinetic model successfully described the kinetic behaviors of Cd(ii) during the adsorption and desorption stages under various chemistry conditions. The model calculations showed that the adsorption rate coefficients varied as a function of solution chemistry, and the relative contributions of the weak and strong ferrihydrite sites for Cd(ii) binding varied with time at different pH and initial metal concentrations. Our model is able to quantitatively assess the contributions of each individual ferrihydrite binding site to the overall Cd(ii) adsorption/desorption kinetics. This study provided insights into the dynamic behavior of Cd(ii) and a predictive modeling tool for Cd(ii) adsorption/desorption kinetics when ferrihydrite is present, which may be helpful for the risk assessment and management of Cd contaminated sites.

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic, equilibrium, and thermodynamic studies.

PubMed

Calvete, Tatiana; Lima, Eder C; Cardoso, Natali F; Vaghetti, Júlio C P; Dias, Silvio L P; Pavan, Flavio A

2010-08-01

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K. Copyright 2010 Elsevier Ltd. All rights reserved.

NIGHTHAWK - A Program for Modeling Saturated Batch and Column Experiments Incorporating Equilibrium and Kinetic Biogeochemistry

EPA Science Inventory

NIGHTHAWK simulates the fate and transport of biogeochemically reactive contaminants in the saturated subsurface. Version 1.2 supports batch and one- dimensional advective-dispersive-reactive transport involving a number of biogeochemical processes, including: microbially-mediate...

Validating the Equilibrium Stage Model for an Azeotropic System in a Laboratorial Distillation Column

ERIC Educational Resources Information Center

Duarte, B. P. M.; Coelho Pinheiro, M. N.; Silva, D. C. M.; Moura, M. J.

2006-01-01

The experiment described is an excellent opportunity to apply theoretical concepts of distillation, thermodynamics of mixtures and process simulation at laboratory scale, and simultaneously enhance the ability of students to operate, control and monitor complex units.

Quasi-equilibria in reduced Liouville spaces.

PubMed

Halse, Meghan E; Dumez, Jean-Nicolas; Emsley, Lyndon

2012-06-14

The quasi-equilibrium behaviour of isolated nuclear spin systems in full and reduced Liouville spaces is discussed. We focus in particular on the reduced Liouville spaces used in the low-order correlations in Liouville space (LCL) simulation method, a restricted-spin-space approach to efficiently modelling the dynamics of large networks of strongly coupled spins. General numerical methods for the calculation of quasi-equilibrium expectation values of observables in Liouville space are presented. In particular, we treat the cases of a time-independent Hamiltonian, a time-periodic Hamiltonian (with and without stroboscopic sampling) and powder averaging. These quasi-equilibrium calculation methods are applied to the example case of spin diffusion in solid-state nuclear magnetic resonance. We show that there are marked differences between the quasi-equilibrium behaviour of spin systems in the full and reduced spaces. These differences are particularly interesting in the time-periodic-Hamiltonian case, where simulations carried out in the reduced space demonstrate ergodic behaviour even for small spins systems (as few as five homonuclei). The implications of this ergodic property on the success of the LCL method in modelling the dynamics of spin diffusion in magic-angle spinning experiments of powders is discussed.

Dynamic consideration of smog chamber experiments

NASA Astrophysics Data System (ADS)

Chuang, Wayne K.; Donahue, Neil M.

2017-08-01

Recent studies of the α-pinene + ozone reaction that address particle nucleation show relatively high molar yields of highly oxidized multifunctional organic molecules with very low saturation concentrations that can form and grow new particles on their own. However, numerous smog-chamber experiments addressing secondary organic aerosol (SOA) mass yields, interpreted via equilibrium partitioning theory, suggest that the vast majority of SOA from α-pinene is semivolatile. We explore this paradox by employing a dynamic volatility basis set (VBS) model that reproduces the new-particle growth rates observed in the CLOUD experiment at CERN and then modeling SOA mass yield experiments conducted at Carnegie Mellon University (CMU). We find that the base-case simulations do overpredict observed SOA mass but by much less than an equilibrium analysis would suggest; this is because delayed condensation of vapors suppresses the apparent mass yields early in the chamber experiments. We further find that a second VBS model featuring substantial oligomerization of semivolatile monomers can match the CLOUD growth rates with substantially lower SOA mass yields; this is because the lighter monomers have a higher velocity and thus a higher condensation rate for a given mass concentration. The oligomerization simulations are a closer match to the CMU experiments than the base-case simulations, though they overpredict the observations somewhat. However, we also find that if the chemical conditions in CLOUD and the CMU chamber were identical, substantial nucleation would have occurred in the CMU experiments when in fact none occurred. This suggests that the chemical mechanisms differed in the two experiments, perhaps because the high oxidation rates in the SOA formation experiments led to rapid termination of peroxy radical chemistry.

Toward a Multi-scale Phase Transition Kinetics Methodology: From Non-Equilibrium Statistical Mechanics to Hydrodynamics

NASA Astrophysics Data System (ADS)

Belof, Jonathan; Orlikowski, Daniel; Wu, Christine; McLaughlin, Keith

2013-06-01

Shock and ramp compression experiments are allowing us to probe condensed matter under extreme conditions where phase transitions and other non-equilibrium aspects can now be directly observed, but first principles simulation of kinetics remains a challenge. A multi-scale approach is presented here, with non-equilibrium statistical mechanical quantities calculated by molecular dynamics (MD) and then leveraged to inform a classical nucleation and growth kinetics model at the hydrodynamic scale. Of central interest is the free energy barrier for the formation of a critical nucleus, with direct NEMD presenting the challenge of relatively long timescales necessary to resolve nucleation. Rather than attempt to resolve the time-dependent nucleation sequence directly, the methodology derived here is built upon the non-equilibrium work theorem in order to bias the formation of a critical nucleus and thus construct the nucleation and growth rates. Having determined these kinetic terms from MD, a hydrodynamics implementation of Kolmogorov-Johnson-Mehl-Avrami (KJMA) kinetics and metastabilty is applied to the dynamic compressive freezing of water and compared with recent ramp compression experiments [Dolan et al., Nature (2007)] Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.

Development of interactive graphic user interfaces for modeling reaction-based biogeochemical processes in batch systems with BIOGEOCHEM

NASA Astrophysics Data System (ADS)

Chang, C.; Li, M.; Yeh, G.

2010-12-01

The BIOGEOCHEM numerical model (Yeh and Fang, 2002; Fang et al., 2003) was developed with FORTRAN for simulating reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions in batch systems. A complete suite of reactions including aqueous complexation, adsorption/desorption, ion-exchange, redox, precipitation/dissolution, acid-base reactions, and microbial mediated reactions were embodied in this unique modeling tool. Any reaction can be treated as fast/equilibrium or slow/kinetic reaction. An equilibrium reaction is modeled with an implicit finite rate governed by a mass action equilibrium equation or by a user-specified algebraic equation. A kinetic reaction is modeled with an explicit finite rate with an elementary rate, microbial mediated enzymatic kinetics, or a user-specified rate equation. None of the existing models has encompassed this wide array of scopes. To ease the input/output learning curve using the unique feature of BIOGEOCHEM, an interactive graphic user interface was developed with the Microsoft Visual Studio and .Net tools. Several user-friendly features, such as pop-up help windows, typo warning messages, and on-screen input hints, were implemented, which are robust. All input data can be real-time viewed and automated to conform with the input file format of BIOGEOCHEM. A post-processor for graphic visualizations of simulated results was also embedded for immediate demonstrations. By following data input windows step by step, errorless BIOGEOCHEM input files can be created even if users have little prior experiences in FORTRAN. With this user-friendly interface, the time effort to conduct simulations with BIOGEOCHEM can be greatly reduced.

Effect of the cation model on the equilibrium structure of poly-L-glutamate in aqueous sodium chloride solution

NASA Astrophysics Data System (ADS)

Marchand, Gabriel; Soetens, Jean-Christophe; Jacquemin, Denis; Bopp, Philippe A.

2015-12-01

We demonstrate that different sets of Lennard-Jones parameters proposed for the Na+ ion, in conjunction with the empirical combining rules routinely used in simulation packages, can lead to essentially different equilibrium structures for a deprotonated poly-L-glutamic acid molecule (poly-L-glutamate) dissolved in a 0.3M aqueous NaCl solution. It is, however, difficult to discriminate a priori between these model potentials; when investigating the structure of the Na+-solvation shell in bulk NaCl solution, all parameter sets lead to radial distribution functions and solvation numbers in broad agreement with the available experimental data. We do not find any such dependency of the equilibrium structure on the parameters associated with the Cl- ion. This work does not aim at recommending a particular set of parameters for any particular purpose. Instead, it stresses the model dependence of simulation results for complex systems such as biomolecules in solution and thus the difficulties if simulations are to be used for unbiased predictions, or to discriminate between contradictory experiments. However, this opens the possibility of validating a model specifically in view of analyzing experimental data believed to be reliable.

Estimating Irrigation Water Requirements using MODIS Vegetation Indices and Inverse Biophysical Modeling

NASA Technical Reports Server (NTRS)

Imhoff, Marc L.; Bounoua, Lahouari; Harriss, Robert; Harriss, Robert; Wells, Gordon; Glantz, Michael; Dukhovny, Victor A.; Orlovsky, Leah

2007-01-01

An inverse process approach using satellite-driven (MODIS) biophysical modeling was used to quantitatively assess water resource demand in semi-arid and arid agricultural lands by comparing the carbon and water flux modeled under both equilibrium (in balance with prevailing climate) and non-equilibrium (irrigated) conditions. Since satellite observations of irrigated areas show higher leaf area indices (LAI) than is supportable by local precipitation, we postulate that the degree to which irrigated lands vary from equilibrium conditions is related to the amount of irrigation water used. For an observation year we used MODIS vegetation indices, local climate data, and the SiB2 photosynthesis-conductance model to examine the relationship between climate and the water stress function for a given grid-cell and observed leaf area. To estimate the minimum amount of supplemental water required for an observed cell, we added enough precipitation to the prevailing climatology at each time step to minimize the water stress function and bring the soil to field capacity. The experiment was conducted on irrigated lands on the U.S. Mexico border and Central Asia and compared to estimates of irrigation water used.

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

NASA Astrophysics Data System (ADS)

Yang, Chao

My dissertation research investigates interactions of agents' behaviors through social networks when some information is not shared publicly, focusing on solutions to a series of challenging problems in empirical research, including heterogeneous expectations and multiple equilibria. The first chapter, "Social Interactions under Incomplete Information with Heterogeneous Expectations", extends the current literature in social interactions by devising econometric models and estimation tools with private information in not only the idiosyncratic shocks but also some exogenous covariates. For example, when analyzing peer effects in class performances, it was previously assumed that all control variables, including individual IQ and SAT scores, are known to the whole class, which is unrealistic. This chapter allows such exogenous variables to be private information and models agents' behaviors as outcomes of a Bayesian Nash Equilibrium in an incomplete information game. The distribution of equilibrium outcomes can be described by the equilibrium conditional expectations, which is unique when the parameters are within a reasonable range according to the contraction mapping theorem in function spaces. The equilibrium conditional expectations are heterogeneous in both exogenous characteristics and the private information, which makes estimation in this model more demanding than in previous ones. This problem is solved in a computationally efficient way by combining the quadrature method and the nested fixed point maximum likelihood estimation. In Monte Carlo experiments, if some exogenous characteristics are private information and the model is estimated under the mis-specified hypothesis that they are known to the public, estimates will be biased. Applying this model to municipal public spending in North Carolina, significant negative correlations between contiguous municipalities are found, showing free-riding effects. The Second chapter "A Tobit Model with Social Interactions under Incomplete Information", is an application of the first chapter to censored outcomes, corresponding to the situation when agents" behaviors are subjected to some binding restrictions. In an interesting empirical analysis for property tax rates set by North Carolina municipal governments, it is found that there is a significant positive correlation among near-by municipalities. Additionally, some private information about its own residents is used by a municipal government to predict others' tax rates, which enriches current empirical work about tax competition. The third chapter, "Social Interactions under Incomplete Information with Multiple Equilibria", extends the first chapter by investigating effective estimation methods when the condition for a unique equilibrium may not be satisfied. With multiple equilibria, the previous model is incomplete due to the unobservable equilibrium selection. Neither conventional likelihoods nor moment conditions can be used to estimate parameters without further specifications. Although there are some solutions to this issue in the current literature, they are based on strong assumptions such as agents with the same observable characteristics play the same strategy. This paper relaxes those assumptions and extends the all-solution method used to estimate discrete choice games to a setting with both discrete and continuous choices, bounded and unbounded outcomes, and a general form of incomplete information, where the existence of a pure strategy equilibrium has been an open question for a long time. By the use of differential topology and functional analysis, it is found that when all exogenous characteristics are public information, there are a finite number of equilibria. With privately known exogenous characteristics, the equilbria can be represented by a compact set in a Banach space and be approximated by a finite set. As a result, a finite-state probability mass function can be used to specify a probability measure for equilibrium selection, which completes the model. From Monte Carlo experiments about two types of binary choice models, it is found that assuming equilibrium uniqueness can bring in estimation biases when the true value of interaction intensity is large and there are multiple equilibria in the data generating process.

Sedimentation dynamics and equilibrium profiles in multicomponent mixtures of colloidal particles.

PubMed

Spruijt, E; Biesheuvel, P M

2014-02-19

In this paper we give a general theoretical framework that describes the sedimentation of multicomponent mixtures of particles with sizes ranging from molecules to macroscopic bodies. Both equilibrium sedimentation profiles and the dynamic process of settling, or its converse, creaming, are modeled. Equilibrium profiles are found to be in perfect agreement with experiments. Our model reconciles two apparently contradicting points of view about buoyancy, thereby resolving a long-lived paradox about the correct choice of the buoyant density. On the one hand, the buoyancy force follows necessarily from the suspension density, as it relates to the hydrostatic pressure gradient. On the other hand, sedimentation profiles of colloidal suspensions can be calculated directly using the fluid density as apparent buoyant density in colloidal systems in sedimentation-diffusion equilibrium (SDE) as a result of balancing gravitational and thermodynamic forces. Surprisingly, this balance also holds in multicomponent mixtures. This analysis resolves the ongoing debate of the correct choice of buoyant density (fluid or suspension): both approaches can be used in their own domain. We present calculations of equilibrium sedimentation profiles and dynamic sedimentation that show the consequences of these insights. In bidisperse mixtures of colloids, particles with a lower mass density than the homogeneous suspension will first cream and then settle, whereas particles with a suspension-matched mass density form transient, bimodal particle distributions during sedimentation, which disappear when equilibrium is reached. In all these cases, the centers of the distributions of the particles with the lowest mass density of the two, regardless of their actual mass, will be located in equilibrium above the so-called isopycnic point, a natural consequence of their hard-sphere interactions. We include these interactions using the Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) equation of state. Finally, we demonstrate that our model is not limited to hard spheres, by extending it to charged spherical particles, and to dumbbells, trimers and short chains of connected beads.

Covalently bonded ionic liquid onto cellulose for fast adsorption and efficient separation of Cr(VI): Batch, column and mechanism investigation.

PubMed

Dong, Zhen; Zhao, Long

2018-06-01

Combining the advantages of both cellulose and ionic liquid, ionic liquid functionalized cellulose (ILFC) as adsorbent was prepared through radiation grafting glycidyl methacrylate onto cellulose microsphere following by reaction with ionic liquid 1-aminopropyl-3-methyl imidazolium nitrate. Its adsorption properties towards Cr(VI) were investigated in batch and column experiments. In batch experiments, the adsorption kinetics was well fitted with pseudo-second-order mode with equilibrium time of 2 h and the adsorption capacity reached 181.8 mg/g at pH 2 calculated from Langmuir model. In fixed column, both Yoon-Nelson and Thomas models gave satisfactory fit to experimental data and breakthrough curves, and equilibrium adsorption capacity calculated by Thomas model was 161.0 mg/g. Moreover, ILFC exhibited high selectivity towards Cr(VI) even in synthetic chrome-plating wastewater. Besides, adsorption/desorption test revealed ILFC can be regenerated and reused several times without obvious decrease in adsorbed amount. The adsorption process was demonstrated to anion exchange-reduction mechanism via XPS analysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

DSMC simulations of shock tube experiments for the dissociation rate of nitrogen

NASA Astrophysics Data System (ADS)

Bird, G. A.

2012-11-01

The DSMC method has been used to simulate the flow associated with several experiments that led to predictions of the dissociation rate in nitrogen. One involved optical interferometry to determine the density behind strong shock wave and the other involved the measurement of the shock tube end-wall pressure after the reflection of a similar shock wave. DSMC calculations for the un-reflected shock wave were made with the older TCE model that converts rate coefficients to reaction cross-sections, with the newer Q-K model that predicts the rates and with a set of reaction cross-sections for nitrogen dissociation from QCT calculations. A comparison of the resulting density profiles with the measured profile provides a test of the validity of the DSMC chemistry models. The DSMC reaction rates were sampled directly in the DSMC calculation, both far downstream where the flow is in equilibrium and in the non-equilibrium region immediately behind the shock. This permits a critical evaluation of data reduction procedures that were employed to deduce the dissociation rate from the measured quantities.

Dependency of Tearing Mode Stability on Current and Pressure Profiles in DIII-D Hybrid Discharges

NASA Astrophysics Data System (ADS)

Kim, K.; Park, J. M.; Murakami, M.; La Haye, R. J.; Na, Y.-S.; SNU/ORAU; ORNL; Atomics, General; SNU; DIII-D Team

2016-10-01

Understanding the physics of the onset and evolution of tearing modes (TMs) in tokamak plasmas is important for high- β steady-state operation. Based on DIII-D steady-state hybrid experiments with accurate equilibrium reconstruction and well-measured plasma profiles, the 2/1 tearing mode can be more stable with increasing local current and pressure gradient at rational surface and with lower pressure peaking and plasma inductance. The tearing stability index Δ', estimated by the Rutherford equation with experimental mode growth rate was validated against Δ' calculated by linear eigenvalue solver (PEST3); preliminary comprehensive MHD modeling by NIMROD reproduced the TM onset reasonably well. We present a novel integrated modeling for the purpose of predicting TM onset in experiment by combining a model equilibrium reconstruction using IPS/FASTRAN, linear stability Δ' calculation using PEST3, and fitting formula for critical Δ' from NIMROD. Work supported in part by the US DoE under DE-AC05-06OR23100, DE-AC05-00OR22725, and DEFC02-04ER54698.

Toxic metals biosorption by Jatropha curcas deoiled cake: equilibrium and kinetic studies.

PubMed

Rawat, Anand P; Rawat, Monica; Rai, J P N

2013-08-01

The equilibrium sorption of Cr(VI) and Cu(II) from aqueous solution using Jatropha curcas deoiled cake, has been studied with respect to adsorbent dosage, contact time, pH, and initial metal concentration in batch mode experiments. Removal of Cu(II) by deoiled cake was greater than that of Cr(VI). The adsorbent chemical characteristics, studied by Fourier transform-infrared analysis, suggested that the presence of Cr(VI) and Cu(II) in the biomass influenced the bands corresponding to hydroxyl and carboxyl groups. Desorption studies revealed that maximum metals recovery was achieved by HNO3 followed by CH3COOH and HCl. The Freundlich isotherm model showed good fit to the equilibrium adsorption data. The adsorption kinetics followed the pseudo-second-order model, which provided the best correlation for the biosorption process, and suggested that J. curcas deoiled cake can be used as an efficient biosorbent over other commonly used sorbents for decontamination of Cr(VI)- and Cu(II)-containing wastewater.

Demonstrating Phase Changes.

ERIC Educational Resources Information Center

Rohr, Walter

1995-01-01

Presents two experiments that demonstrate phase changes. The first experiment explores phase changes of carbon dioxide using powdered dry ice sealed in a piece of clear plastic tubing. The second experiment demonstrates an equilibrium process in which a crystal grows in equilibrium with its saturated solution. (PVD)

Laboratory simulations of acid-sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars.

PubMed

Marcucci, Emma C; Hynek, Brian M

2014-03-01

We have completed laboratory experiments and thermochemical equilibrium models to investigate secondary mineral formation under conditions akin to volcanic, hydrothermal acid-sulfate weathering systems. Our research used the basaltic mineralogy at Cerro Negro Volcano, Nicaragua, characterized by plagioclase, pyroxene, olivine, and volcanic glass. These individual minerals and whole-rock field samples were reacted in the laboratory with 1 molal sulfuric acid at varying temperatures (65, 150, and 200°C), fluid:rock weight ratios (1:1, 4:1, and 10:1), and durations (1-60 days). Thermochemical equilibrium models were developed using Geochemist's Workbench. To understand the reaction products and fluids, we employed scanning electron microscopy/energy dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma-atomic emission spectroscopy. The results of our experiments and models yielded major alteration minerals that include anhydrite, natroalunite, minor iron oxide, and amorphous Al-Si gel. We found that variations in experimental parameters did not drastically change the suite of minerals produced; instead, abundance, size, and crystallographic shape changed. Our results also suggest that it is essential to separate phases formed during experiments from those formed during fluid evaporation to fully understand the reaction processes. Our laboratory reacted and model predicted products are consistent with the mineralogy observed at places on Mars. However, our results indicate that determination of the formation conditions requires microscopic imagery and regional context, as well as a thorough understanding of contributions from both experiment precipitation and fluid evaporation minerals.

Laboratory simulations of acid-sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars

PubMed Central

Marcucci, Emma C; Hynek, Brian M

2014-01-01

We have completed laboratory experiments and thermochemical equilibrium models to investigate secondary mineral formation under conditions akin to volcanic, hydrothermal acid-sulfate weathering systems. Our research used the basaltic mineralogy at Cerro Negro Volcano, Nicaragua, characterized by plagioclase, pyroxene, olivine, and volcanic glass. These individual minerals and whole-rock field samples were reacted in the laboratory with 1 molal sulfuric acid at varying temperatures (65, 150, and 200°C), fluid:rock weight ratios (1:1, 4:1, and 10:1), and durations (1–60 days). Thermochemical equilibrium models were developed using Geochemist's Workbench. To understand the reaction products and fluids, we employed scanning electron microscopy/energy dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma-atomic emission spectroscopy. The results of our experiments and models yielded major alteration minerals that include anhydrite, natroalunite, minor iron oxide, and amorphous Al-Si gel. We found that variations in experimental parameters did not drastically change the suite of minerals produced; instead, abundance, size, and crystallographic shape changed. Our results also suggest that it is essential to separate phases formed during experiments from those formed during fluid evaporation to fully understand the reaction processes. Our laboratory reacted and model predicted products are consistent with the mineralogy observed at places on Mars. However, our results indicate that determination of the formation conditions requires microscopic imagery and regional context, as well as a thorough understanding of contributions from both experiment precipitation and fluid evaporation minerals. PMID:26213665

Dynamic non-equilibrium wall-modeling for large eddy simulation at high Reynolds numbers

NASA Astrophysics Data System (ADS)

Kawai, Soshi; Larsson, Johan

2013-01-01

A dynamic non-equilibrium wall-model for large-eddy simulation at arbitrarily high Reynolds numbers is proposed and validated on equilibrium boundary layers and a non-equilibrium shock/boundary-layer interaction problem. The proposed method builds on the prior non-equilibrium wall-models of Balaras et al. [AIAA J. 34, 1111-1119 (1996)], 10.2514/3.13200 and Wang and Moin [Phys. Fluids 14, 2043-2051 (2002)], 10.1063/1.1476668: the failure of these wall-models to accurately predict the skin friction in equilibrium boundary layers is shown and analyzed, and an improved wall-model that solves this issue is proposed. The improvement stems directly from reasoning about how the turbulence length scale changes with wall distance in the inertial sublayer, the grid resolution, and the resolution-characteristics of numerical methods. The proposed model yields accurate resolved turbulence, both in terms of structure and statistics for both the equilibrium and non-equilibrium flows without the use of ad hoc corrections. Crucially, the model accurately predicts the skin friction, something that existing non-equilibrium wall-models fail to do robustly.

Application of classical thermodynamics to the conductivity in non-polar media

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

Gourdin-Bertin, S.; Chassagne, C.

Electrical conductivity in non-polar media is a subject which recently regained interest. If most of experiments and theoretical developments were done more than 50 years ago, new experiments and theories have been recently published. As the electrical conductivity describes, at low field, the equilibrium state of a system, it is natural to apply theories based on equilibrium thermodynamics. In this article, well-established classical thermodynamics and solvations models are applied to recently published data. This enables to get a new insight in intriguing phenomena, such as the linear dependence of the conductivity on the concentration of ionic surfactant and the evaluationmore » of conductivity for the mixture of two miscible fluids, such as alcohol and alcane, which have very different conductivities.« less

A predictive model for the tokamak density limit

DOE PAGES

Teng, Q.; Brennan, D. P.; Delgado-Aparicio, L.; ...

2016-07-28

We reproduce the Greenwald density limit, in all tokamak experiments by using a phenomenologically correct model with parameters in the range of experiments. A simple model of equilibrium evolution and local power balance inside the island has been implemented to calculate the radiation-driven thermo-resistive tearing mode growth and explain the density limit. Strong destabilization of the tearing mode due to an imbalance of local Ohmic heating and radiative cooling in the island predicts the density limit within a few percent. Furthermore, we found the density limit and it is a local edge limit and weakly dependent on impurity densities. Ourmore » results are robust to a substantial variation in model parameters within the range of experiments.« less

Centrosomes are autocatalytic droplets of pericentriolar material organized by centrioles

NASA Astrophysics Data System (ADS)

Zwicker, David; Decker, Markus; Jaensch, Steffen; Hyman, Anthony A.; Jülicher, Frank

2014-03-01

We propose a physical description of the centrosome, a membrane-less organelle involved in cell division. In our model, centrosome material occurs in a soluble form in the cytosol and a form that tends to undergo phase separation from the cytosol. We find that an autocatalytic chemical transition between these forms accounts for the temporal evolution observed in experiments. Interestingly, the nucleation of centrosomes can be controlled by an enzymatic activity of the centrioles, which are present at the core of all centrosomes. This non-equilibrium feature also allows for multiple stable centrosomes, a situation which is unstable in equilibrium phase separation. Our theory explains the growth dynamics of centrosomes for all cell sizes down to the eight-cell stage of the C. elegans embryo. It also accounts for data acquired in experiments with aberrant numbers of centrosomes and altered cell volumes. Furthermore, our model can describe unequal centrosome sizes observed in cells with disturbed centrioles. Our example suggests a general picture of the organization of membrane-less organelles.

Performance and modeling of cesium ion exchange by ENGI neered form crystalline silicotitanates

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

Anthony, R.G.; Gu, D.; Huckman, M.

1996-10-01

TAM-5, a hydrous crystalline silicotitanate (CST) powder developed by Sandia National Laboratories and Texas A&M University, and commercialized by UOP as IONSIV{reg_sign} Ion Exchanger Type IE-910, is a highly selective material for removing cesium and strontium from aqueous radioactive wastes such as those found at the Hanford site in Washington. An engineered form of the material suitable for column ion exchange type operations has been developed and tested. Data relevant to processing radioactive tank wastes including equilibrium distribution coefficients and column testing will be presented. The impact of exposure of the engineered form to chemically aggressive environments such as itmore » might experience during waste processing, and to the less aggressive environments it might experience during post processing storage has been assessed. The thermal stability of the material has also been evaluated. The experimental results have been integrated with an effort to model the material`s equilibrium and kinetic behavior.« less

Reactive transport of metal contaminants in alluvium - Model comparison and column simulation

USGS Publications Warehouse

Brown, J.G.; Bassett, R.L.; Glynn, P.D.

2000-01-01

A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

Kinetic and equilibrium lithium acidities of arenes: theory and experiment.

PubMed

Streitwieser, Andrew; Shah, Kamesh; Reyes, Julius R; Zhang, Xingyue; Davis, Nicole R; Wu, Eric C

2010-08-26

Kinetic acidities of arenes, ArH, measured some time ago by hydrogen isotope exchange kinetics with lithium cyclohexylamide (LiCHA) in cyclohexylamine (CHA) show a wide range of reactivities that involve several electronic mechanisms. These experimental reactivities give an excellent Brønsted correlation with equilibrium lithium ion pair acidities (pK(Li)) derived as shown recently from computations of ArLi.2E (E = dimethyl ether). The various electronic mechanisms are well modeled by ab initio HF calculations with modest basis sets. Additional calculations using NH(3) as a model for CHA further characterize the TS of the exchange reactions. The slopes of Brønsted correlations of ion pair systems can vary depending on the nature of the ion pairs.

Stability of Contact Lines in Fluids: 2D Stokes Flow

NASA Astrophysics Data System (ADS)

Guo, Yan; Tice, Ian

2018-02-01

In an effort to study the stability of contact lines in fluids, we consider the dynamics of an incompressible viscous Stokes fluid evolving in a two-dimensional open-top vessel under the influence of gravity. This is a free boundary problem: the interface between the fluid in the vessel and the air above (modeled by a trivial fluid) is free to move and experiences capillary forces. The three-phase interface where the fluid, air, and solid vessel wall meet is known as a contact point, and the angle formed between the free interface and the vessel is called the contact angle. We consider a model of this problem that allows for fully dynamic contact points and angles. We develop a scheme of a priori estimates for the model, which then allow us to show that for initial data sufficiently close to equilibrium, the model admits global solutions that decay to equilibrium exponentially quickly.

Determination of equilibrium and rate constants for complex formation by fluorescence correlation spectroscopy supplemented by dynamic light scattering and Taylor dispersion analysis.

PubMed

Zhang, Xuzhu; Poniewierski, Andrzej; Jelińska, Aldona; Zagożdżon, Anna; Wisniewska, Agnieszka; Hou, Sen; Hołyst, Robert

2016-10-04

The equilibrium and rate constants of molecular complex formation are of great interest both in the field of chemistry and biology. Here, we use fluorescence correlation spectroscopy (FCS), supplemented by dynamic light scattering (DLS) and Taylor dispersion analysis (TDA), to study the complex formation in model systems of dye-micelle interactions. In our case, dyes rhodamine 110 and ATTO-488 interact with three differently charged surfactant micelles: octaethylene glycol monododecyl ether C 12 E 8 (neutral), cetyltrimethylammonium chloride CTAC (positive) and sodium dodecyl sulfate SDS (negative). To determine the rate constants for the dye-micelle complex formation we fit the experimental data obtained by FCS with a new form of the autocorrelation function, derived in the accompanying paper. Our results show that the association rate constants for the model systems are roughly two orders of magnitude smaller than those in the case of the diffusion-controlled limit. Because the complex stability is determined by the dissociation rate constant, a two-step reaction mechanism, including the diffusion-controlled and reaction-controlled rates, is used to explain the dye-micelle interaction. In the limit of fast reaction, we apply FCS to determine the equilibrium constant from the effective diffusion coefficient of the fluorescent components. Depending on the value of the equilibrium constant, we distinguish three types of interaction in the studied systems: weak, intermediate and strong. The values of the equilibrium constant obtained from the FCS and TDA experiments are very close to each other, which supports the theoretical model used to interpret the FCS data.

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

1990-01-01

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

Effect of stress on the diffusion kinetics of methane during gas desorption in coal matrix under different equilibrium pressures

NASA Astrophysics Data System (ADS)

Li, Chengwu; Xue, Honglai; Hu, Po; Guan, Cheng; Liu, Wenbiao

2018-06-01

Stress has a significant influence on gas diffusion, which is a key factor for methane recovery in coal mines. In this study, a series of experiments were performed to investigate effect of stress on the gas diffusivity during desorption in tectonic coal. Additionally, the desorbed data were modeled using the unipore and bidisperse models. The results show that the bidisperse model better describes the diffusion kinetics than the unipore model in this study. Additionally, the modeling results using the bidisperse approach suggest that the stress impact on the macropore diffusivity is greater than the stress on the micropore diffusivity. Under the same equilibrium pressure, the diffusivity varies with stress according to a four-stage function, which shows an ‘M-shape’. As the equilibrium gas pressure increased from 0.6 to 1.7 MPa, the critical point between stage 2 and stage 3 and between stage 3 and stage 4 transferred to a low stress. This difference is attributed to the gas pressure effects on the physical and mechanical properties of coal. These observations indicate that both the stress and gas pressure can significantly impact gas diffusion and may have significant implications on methane recovery in coal mines.

Pore Size Distributions Inferred from Modified Inversion Percolation Modeling of Drainage Curves

NASA Astrophysics Data System (ADS)

Dralus, D. E.; Wang, H. F.; Strand, T. E.; Glass, R. J.; Detwiler, R. L.

2005-12-01

Experiments have been conducted of drainage in sand packs. At equilibrium, the interface between the fluids forms a saturation transition fringe where the saturation decreases monotonically with height. This behavior was observed in a 1-inch thick pack of 20-30 sand contained front and back within two thin, 12-inch-by-24-inch glass plates. The translucent chamber was illuminated from behind by a bank of fluorescent bulbs. Acquired data were in the form of images captured by a CCD camera with resolution on the grain scale. The measured intensity of the transmitted light was used to calculate the average saturation at each point in the chamber. This study used a modified invasion percolation (MIP) model to simulate the drainage experiments to evaluate the relationship between the saturation-versus-height curve at equilibrium and the pore size distribution associated with the granular medium. The simplest interpretation of a drainage curve is in terms of a distribution of capillary tubes whose radii reproduce the the observed distribution of rise heights. However, this apparent radius distribution obtained from direct inversion of the saturation profile did not yield the assumed radius distribution. Further investigation demonstrated that the equilibrium height distribution is controlled primarily by the Bond number (ratio of gravity to capillary forces) with some influence from the width of the pore radius distribution. The width of the equilibrium fringe is quantified in terms of the ratio of Bond number to the standard deviation of the pore throat distribution. The normalized saturation-vs-height curves exhibit a power-law scaling behavior consistent with both Brooks-Corey and Van Genuchten type curves. Fundamental tenets of percolation theory were used to quantify the relationship between the apparent and actual radius distributions as a function of the mean coordination number and of the ratio of Bond number to standard deviation, which was supported by both MIP simulations and corresponding drainage experiments.

A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin

ERIC Educational Resources Information Center

Sattar, Simeen

2011-01-01

Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

Does shaking increase the pressure inside a bottle of champagne?

PubMed

Vreme, A; Pouligny, B; Nadal, F; Liger-Belair, G

2015-02-01

Colas, beers and sparkling wines are all concentrated solutions of carbon dioxide in aqueous solvents. Any such carbonated liquid is ordinarily conditioned inside a closed bottle or a metal can as a liquid-gas 2-phase system. At thermodynamic equilibrium, the partial pressure of carbon-dioxide in the gas phase and its concentration in the liquid are proportional (Henry's law). In practical conditions and use (transport, opening of the container, exterior temperature change, etc.), Henry's equilibrium can be perturbed. The goal of this paper is to describe and understand how the system responds to such perturbations and evolves towards a new equilibrium state. Formally, we investigate the dynamics around Henry's equilibrium of a closed system, through dedicated experiments and modeling. We focus on the response to a sudden pressure change and to mechanical shaking (the latter point inspired the article's title). Observations are rationalized through basic considerations including molecular diffusion, bubble dynamics (based on Epstein-Plesset theory) and chemi-convective hydrodynamic instabilities. Copyright © 2014 Elsevier Inc. All rights reserved.

Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone

NASA Astrophysics Data System (ADS)

Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.

2016-12-01

The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to lower δ44Ca values and a faster approach to isotopic equilibrium. The dependence of δ44Ca resetting on calcite surface areas has broad ramifications for tracing carbonate weathering in the Critical Zone.

Increased Carbon Throughput But No Net Soil Carbon Loss in Field Warming Experiments: Combining Data Assimilation and Meta-Analyses

NASA Astrophysics Data System (ADS)

van Gestel, N.; Shi, Z.; van Groenigen, K. J.; Osenberg, C. W.; Andresen, L. C.; Dukes, J. S.; Hovenden, M. J.; Michelsen, A.; Pendall, E.; Reich, P.; Schuur, E.; Hungate, B. A.

2017-12-01

Minor changes in soil C dynamics in response to warming can strongly modulate climate change. Approaches to estimate long-term changes in soil carbon stocks from shorter-term warming experiments should consider temporal trends in soil carbon dynamics. Here we used data assimilation to take into account the soil carbon time series data collected from the upper soil layer (<15 cm) in 70 field warming experiments located worldwide. We used a soil carbon model with two pools, representing fast- and slow-decaying materials. We show that on average experimental warming enhanced fluxes of incoming and outgoing carbon with no change in predicted equilibrium stocks of carbon. Experimental warming increased the decomposition rates of the fast soil carbon pools by 10.7% on average, but also increased soil carbon input by 8.1%. When projecting the carbon pools to equilibrium stocks we found that warming decreased the size of the fast pool (-3.7%), but did not affect the slow or total carbon pools. We demonstrate that warming increases carbon throughput without an overall effect on total equilibrium carbon stocks. Hence, our findings do not support a generalizable soil carbon-climate feedback for soil carbon in the upper soil layer.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium.Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3−) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Solubility limits in quaternary SnTe-based alloys [Metastability and solubility limits in quaternary SnTe-based alloys guided by combinatorial sputtering

DOE PAGES

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.; ...

2017-05-09

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

Inertial migration of deformable droplets in a microchannel

NASA Astrophysics Data System (ADS)

Chen, Xiaodong; Xue, Chundong; Zhang, Li; Hu, Guoqing; Jiang, Xingyu; Sun, Jiashu

2014-11-01

The microfluidic inertial effect is an effective way of focusing and sorting droplets suspended in a carrier fluid in microchannels. To understand the flow dynamics of microscale droplet migration, we conduct numerical simulations on the droplet motion and deformation in a straight microchannel. The results are compared with preliminary experiments and theoretical analysis. In contrast to most existing literature, the present simulations are three-dimensional and full length in the streamwise direction and consider the confinement effects for a rectangular cross section. To thoroughly examine the effect of the velocity distribution, the release positions of single droplets are varied in a quarter of the channel cross section based on the geometrical symmetries. The migration dynamics and equilibrium positions of the droplets are obtained for different fluid velocities and droplet sizes. Droplets with diameters larger than half of the channel height migrate to the centerline in the height direction and two equilibrium positions are observed between the centerline and the wall in the width direction. In addition to the well-known Segré-Silberberg equilibrium positions, new equilibrium positions closer to the centerline are observed. This finding is validated by preliminary experiments that are designed to introduce droplets at different initial lateral positions. Small droplets also migrate to two equilibrium positions in the quarter of the channel cross section, but the coordinates in the width direction are between the centerline and the wall. The equilibrium positions move toward the centerlines with increasing Reynolds number due to increasing deformations of the droplets. The distributions of the lift forces, angular velocities, and the deformation parameters of droplets along the two confinement direction are investigated in detail. Comparisons are made with theoretical predictions to determine the fundamentals of droplet migration in microchannels. In addition, existence of the inner equilibrium position is linked to the quartic velocity distribution in the width direction through a simple model for the slip angular velocities of droplets.

Long-term aging behaviors in a model soft colloidal system.

PubMed

Li, Qi; Peng, Xiaoguang; McKenna, Gregory B

2017-02-15

Colloidal and molecular systems share similar behaviors near to the glass transition volume fraction or temperature. Here, aging behaviors after volume fraction up-jump (induced by performing temperature down-jumps) conditions for a PS-PNIPAM/AA soft colloidal system were investigated using light scattering (diffusing wave spectroscopy, DWS). Both aging responses and equilibrium dynamics were investigated. For the aging responses, long-term experiments (100 000 s) were performed, and both equilibrium and non-equilibrium behaviors of the system were obtained. In the equilibrium state, as effective volume fraction increases (or temperature decreases), the colloidal dispersion displays a transition from the liquid to a glassy state. The equilibrium α-relaxation dynamics strongly depend on both the effective volume fraction and the initial mass concentration for the studied colloidal systems. Compared with prior results from our lab [X. Di, X. Peng and G. B. McKenna, J. Chem. Phys., 2014, 140, 054903], the effective volume fractions investigated spanned a wider range, to deeper into the glassy domain. The results show that the α-relaxation time τ α of the samples aged into equilibrium deviate from the classical Vogel-Fulcher-Tammann (VFT)-type expectations and the super-Arrhenius signature disappears above the glass transition volume fraction. The non-equilibrium aging response shows that the time for the structural evolution into equilibrium and the α-relaxation time are decoupled. The DWS investigation of the aging behavior after different volume fraction jumps reveals a different non-equilibrium or aging behavior for the considered colloidal systems compared with either molecular glasses or the macroscopic rheology of a similar colloidal dispersions.

Improved understanding of the acoustophoretic focusing of dense suspensions in a microchannel

NASA Astrophysics Data System (ADS)

Karthick, S.; Sen, A. K.

2017-11-01

We provide improved understanding of acoustophoretic focusing of a dense suspension (volume fraction φ >10 % ) in a microchannel subjected to an acoustic standing wave using a proposed theoretical model and experiments. The model is based on the theory of interacting continua and utilizes a momentum transport equation for the mixture, continuity equation, and transport equation for the solid phase. The model demonstrates the interplay between acoustic radiation and shear-induced diffusion (SID) forces that is critical in the focusing of dense suspensions. The shear-induced particle migration model of Leighton and Acrivos, coupled with the acoustic radiation force, is employed to simulate the continuum behavior of particles. In the literature, various closures for the diffusion coefficient Dφ* are available for rigid spheres at high concentrations and nonspherical deformable particles [e.g., red blood cells (RBCs)] at low concentrations. Here we propose a closure for Dφ* for dense suspension of RBCs and validate the proposed model with experimental data. While the available closures for Dφ* fail to predict the acoustic focusing of a dense suspension of nonspherical deformable particles like RBCs, the predictions of the proposed model match experimental data within 15%. Both the model and experiments reveal a competition between acoustic radiation and SID forces that gives rise to an equilibrium width w* of a focused stream of particles at some distance Leq* along the flow direction. Using different shear rates, acoustic energy densities, and particle concentrations, we show that the equilibrium width is governed by Péclet number Pe and Strouhal number Stas w*=1.4(PeSt) -0.5 while the length required to obtain the equilibrium-focused width depends on St as Leq*=3.8 /(St)0.6 . The proposed model and correlations would find significance in the design of microchannels for acoustic focusing of dense suspensions such as undiluted blood.

Kinetic analysis of central ( sup 11 C)raclopride binding to D2-dopamine receptors studied by PET--a comparison to the equilibrium analysis

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

Farde, L.; Eriksson, L.; Blomquist, G.

1989-10-01

(11C)Raclopride binding to central D2-dopamine receptors in humans has previously been examined by positron emission tomography (PET). Based on the rapid occurrence of binding equilibrium, a saturation analysis has been developed for the determination of receptor density (Bmax) and affinity (Kd). For analysis of PET measurements obtained with other ligands, a kinetic three-compartment model has been used. In the present study, the brain uptake of (11C)raclopride was analyzed further by applying both a kinetic and an equilibrium analysis to data obtained from four PET experiments in each of three healthy subjects. First regional CBV was determined. In the second andmore » third experiment, (11C)-raclopride with high and low specific activity was used. In a fourth experiment, the (11C)raclopride enantiomer (11C)FLB472 was used to examine the concentration of free radioligand and nonspecific binding in brain. Radio-activity in arterial blood was measured using an automated blood sampling system. Bmax and Kd values for (11C)raclopride binding could be determined also with the kinetic analysis. As expected theoretically, those values were similar to those obtained with the equilibrium analysis. In addition, the kinetic analysis allowed separate determination of the association and dissociation rate constants, kon and koff, respectively. Examination of (11C)raclopride and (11C)FLB472 uptake in brain regions devoid of specific D2-dopamine receptor binding indicated a fourth compartment in which uptake was reversible, nonstereoselective, and nonsaturable in the dose range studied.« less

Linear-Nonlinear-Poisson Models of Primate Choice Dynamics

ERIC Educational Resources Information Center

Corrado, Greg S.; Sugrue, Leo P.; Seung, H. Sebastian; Newsome, William T.

2005-01-01

The equilibrium phenomenon of matching behavior traditionally has been studied in stationary environments. Here we attempt to uncover the local mechanism of choice that gives rise to matching by studying behavior in a highly dynamic foraging environment. In our experiments, 2 rhesus monkeys ("Macacca mulatta") foraged for juice rewards by making…

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength.

PubMed

Flury, Markus; Czigány, Szabolcs; Chen, Gang; Harsh, James B

2004-07-01

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments. Copyright 2003 Elsevier B.V.

Dynamic circadian modulation in a biomathematical model for the effects of sleep and sleep loss on waking neurobehavioral performance.

PubMed

McCauley, Peter; Kalachev, Leonid V; Mollicone, Daniel J; Banks, Siobhan; Dinges, David F; Van Dongen, Hans P A

2013-12-01

Recent experimental observations and theoretical advances have indicated that the homeostatic equilibrium for sleep/wake regulation--and thereby sensitivity to neurobehavioral impairment from sleep loss--is modulated by prior sleep/wake history. This phenomenon was predicted by a biomathematical model developed to explain changes in neurobehavioral performance across days in laboratory studies of total sleep deprivation and sustained sleep restriction. The present paper focuses on the dynamics of neurobehavioral performance within days in this biomathematical model of fatigue. Without increasing the number of model parameters, the model was updated by incorporating time-dependence in the amplitude of the circadian modulation of performance. The updated model was calibrated using a large dataset from three laboratory experiments on psychomotor vigilance test (PVT) performance, under conditions of sleep loss and circadian misalignment; and validated using another large dataset from three different laboratory experiments. The time-dependence of circadian amplitude resulted in improved goodness-of-fit in night shift schedules, nap sleep scenarios, and recovery from prior sleep loss. The updated model predicts that the homeostatic equilibrium for sleep/wake regulation--and thus sensitivity to sleep loss--depends not only on the duration but also on the circadian timing of prior sleep. This novel theoretical insight has important implications for predicting operator alertness during work schedules involving circadian misalignment such as night shift work.

Connecting Solubility, Equilibrium, and Periodicity in a Green, Inquiry Experiment for the General Chemistry Laboratory

ERIC Educational Resources Information Center

Cacciatore, Kristen L.; Amado, Jose; Evans, Jason J.; Sevian, Hannah

2008-01-01

We present a novel first-year chemistry laboratory experiment that connects solubility, equilibrium, and chemical periodicity concepts. It employs a unique format that asks students to replicate experiments described in different sample lab reports, each lacking some essential information, rather than follow a scripted procedure. This structure is…

Floatabilities of treated coal in water at room temperature

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

Kwon, K.C.; Rohrer, R.L.; Lai, R.W.

1995-04-01

Experiments on equilibrium adsorption loadings of various probe compounds on 60-200 mesh Illinois No. 6 coal (PSOC-1539), Adaville No. 1 coal (PSOC-1544), Wyodak coal (PSOC-1545), and Pittsburgh No. 8 coal (PSOC-1549) were performed. The probe compounds include 2-methyl-1-pentanol (2M1P), 1-heptanol, benzene, and toluene. Equilibrium adsorption loadings of aromatic compounds such as toluene and benzene on the four chosen coals obey the Langmuir isotherm model up to 100 ppm in concentrations of probe compounds. Equilibrium adsorption loadings of higher aliphatic alcohols such as 2M1P and 1-heptanol on the four chosen coals do not follow both the Langmuir isotherm model and themore » Freundlich empirical adsorption model. Flotation of the coals, equilibrated with aqueous solutions of 2M1P and 1-heptanol, increases linearly with equilibrium adsorption loadings of these probe compounds on the coals. The chosen coals were treated with nitrogen and air at 1 atm and 125-225{degrees}C for 24 h. Flotation experiments of the treated coals were conducted at room temperature, using distilled water only as a flotation medium. Flotation of Adaville No. 1 coal and Wyodak coal treated with nitrogen gas is higher than that of the untreated coals and increases with treatment temperatures. Flotation of Adaville No. 1 coal treated with air at 125-225{degrees}C is not significantly different from that of untreated coal. Flotation of Pittsburgh No. 8 coal treated with air is lower than that of untreated coal and decreases with treatment temperatures. Flotation of Illinois No. 6 coal treated with nitrogen with nitrogen only is higher than that of untreated coal. Flotation of Illinois No. 6 coal treated with nitrogen at 125-175{degrees}C increases with treatment temperatures, whereas flotation of Illinois No. 6 coal treated with nitrogen at 174-225{degrees}C decreases with treatment temperatures.« less

Non-Equilibrium Properties from Equilibrium Free Energy Calculations

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Wilson, Michael A.

2012-01-01

Calculating free energy in computer simulations is of central importance in statistical mechanics of condensed media and its applications to chemistry and biology not only because it is the most comprehensive and informative quantity that characterizes the eqUilibrium state, but also because it often provides an efficient route to access dynamic and kinetic properties of a system. Most of applications of equilibrium free energy calculations to non-equilibrium processes rely on a description in which a molecule or an ion diffuses in the potential of mean force. In general case this description is a simplification, but it might be satisfactorily accurate in many instances of practical interest. This hypothesis has been tested in the example of the electrodiffusion equation . Conductance of model ion channels has been calculated directly through counting the number of ion crossing events observed during long molecular dynamics simulations and has been compared with the conductance obtained from solving the generalized Nernst-Plank equation. It has been shown that under relatively modest conditions the agreement between these two approaches is excellent, thus demonstrating the assumptions underlying the diffusion equation are fulfilled. Under these conditions the electrodiffusion equation provides an efficient approach to calculating the full voltage-current dependence routinely measured in electrophysiological experiments.

Non-equilibrium condensation of supercritical carbon dioxide in a converging-diverging nozzle

NASA Astrophysics Data System (ADS)

Ameli, Alireza; Afzalifar, Ali; Turunen-Saaresti, Teemu

2017-03-01

Carbon dioxide (CO2) is a promising alternative as a working fluid for future energy conversion and refrigeration cycles. CO2 has low global warming potential compared to refrigerants and supercritical CO2 Brayton cycle ought to have better efficiency than today’s counter parts. However, there are several issues concerning behaviour of supercritical CO2 in aforementioned applications. One of these issues arises due to non-equilibrium condensation of CO2 for some operating conditions in supercritical compressors. This paper investigates the non-equilibrium condensation of carbon dioxide in the course of an expansion from supercritical stagnation conditions in a converging-diverging nozzle. An external look-up table was implemented, using an in-house FORTRAN code, to calculate the fluid properties in supercritical, metastable and saturated regions. This look-up table is coupled with the flow solver and the non-equilibrium condensation model is introduced to the solver using user defined expressions. Numerical results are compared with the experimental measurements. In agreement with the experiment, the distribution of Mach number in the nozzle shows that the flow becomes supersonic in upstream region near the throat where speed of sound is minimum also the equilibrium reestablishment occurs at the outlet boundary condition.

Temperature in and out of equilibrium: A review of concepts, tools and attempts

NASA Astrophysics Data System (ADS)

Puglisi, A.; Sarracino, A.; Vulpiani, A.

2017-11-01

We review the general aspects of the concept of temperature in equilibrium and non-equilibrium statistical mechanics. Although temperature is an old and well-established notion, it still presents controversial facets. After a short historical survey of the key role of temperature in thermodynamics and statistical mechanics, we tackle a series of issues which have been recently reconsidered. In particular, we discuss different definitions and their relevance for energy fluctuations. The interest in such a topic has been triggered by the recent observation of negative temperatures in condensed matter experiments. Moreover, the ability to manipulate systems at the micro and nano-scale urges to understand and clarify some aspects related to the statistical properties of small systems (as the issue of temperature's ;fluctuations;). We also discuss the notion of temperature in a dynamical context, within the theory of linear response for Hamiltonian systems at equilibrium and stochastic models with detailed balance, and the generalized fluctuation-response relations, which provide a hint for an extension of the definition of temperature in far-from-equilibrium systems. To conclude we consider non-Hamiltonian systems, such as granular materials, turbulence and active matter, where a general theoretical framework is still lacking.

Single and multi-component adsorption of psychiatric pharmaceuticals onto alternative and commercial carbons.

PubMed

Calisto, Vânia; Jaria, Guilaine; Silva, Carla Patrícia; Ferreira, Catarina I A; Otero, Marta; Esteves, Valdemar I

2017-05-01

This work describes the adsorptive removal of three widely consumed psychiatric pharmaceuticals (carbamazepine, paroxetine and oxazepam) from ultrapure water. Two different adsorbents were used: a commercial activated carbon and a non-activated waste-based carbon (PS800-150-HCl), produced by pyrolysis of primary paper mill sludge. These adsorbents were used in single, binary and ternary batch experiments in order to determine the adsorption kinetics and equilibrium isotherms of the considered pharmaceuticals. For the three drugs and both carbons, the equilibrium was quickly attained (with maximum equilibrium times of 15 and 120 min for the waste-based and the commercial carbons, respectively) even in binary and ternary systems. Single component equilibrium data were adequately described by the Langmuir model, with the commercial carbon registering higher maximum adsorption capacities (between 272 ± 10 and 493 ± 12 μmol g -1 ) than PS800-150-HCl (between 64 ± 2 and 74 ± 1 μmol g -1 ). Multi-component equilibrium data were also best fitted by the single component Langmuir isotherm, followed by the Langmuir competitive model. Overall, competitive effects did not largely affect the performance of both adsorbents. Binary and ternary systems maintained fast kinetics, the individual maximum adsorption capacities were not lower than half of the single component systems and both carbons presented improved total adsorption capacities for multi-component solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

CALIBRATION OF EQUILIBRIUM TIDE THEORY FOR EXTRASOLAR PLANET SYSTEMS

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

Hansen, Brad M. S., E-mail: hansen@astro.ucla.ed

2010-11-01

We provide an 'effective theory' of tidal dissipation in extrasolar planet systems by empirically calibrating a model for the equilibrium tide. The model is valid to high order in eccentricity and parameterized by two constants of bulk dissipation-one for dissipation in the planet and one for dissipation in the host star. We are able to consistently describe the distribution of extrasolar planetary systems in terms of period, eccentricity, and mass (with a lower limit of a Saturn mass) with this simple model. Our model is consistent with the survival of short-period exoplanet systems, but not with the circularization period ofmore » equal mass stellar binaries, suggesting that the latter systems experience a higher level of dissipation than exoplanet host stars. Our model is also not consistent with the explanation of inflated planetary radii as resulting from tidal dissipation. The paucity of short-period planets around evolved A stars is explained as the result of enhanced tidal inspiral resulting from the increase in stellar radius with evolution.« less

Predicting mixed-gas adsorption equilibria on activated carbon for precombustion CO2 capture.

PubMed

García, S; Pis, J J; Rubiera, F; Pevida, C

2013-05-21

We present experimentally measured adsorption isotherms of CO2, H2, and N2 on a phenol-formaldehyde resin-based activated carbon, which had been previously synthesized for the separation of CO2 in a precombustion capture process. The single component adsorption isotherms were measured in a magnetic suspension balance at three different temperatures (298, 318, and 338 K) and over a large range of pressures (from 0 to 3000-4000 kPa). These values cover the temperature and pressure conditions likely to be found in a precombustion capture scenario, where CO2 needs to be separated from a CO2/H2/N2 gas stream at high pressure (~1000-1500 kPa) and with a high CO2 concentration (~20-40 vol %). Data on the pure component isotherms were correlated using the Langmuir, Sips, and dual-site Langmuir (DSL) models, i.e., a two-, three-, and four-parameter model, respectively. By using the pure component isotherm fitting parameters, adsorption equilibrium was then predicted for multicomponent gas mixtures by the extended models. The DSL model was formulated considering the energetic site-matching concept, recently addressed in the literature. Experimental gas-mixture adsorption equilibrium data were calculated from breakthrough experiments conducted in a lab-scale fixed-bed reactor and compared with the predictions from the models. Breakthrough experiments were carried out at a temperature of 318 K and five different pressures (300, 500, 1000, 1500, and 2000 kPa) where two different CO2/H2/N2 gas mixtures were used as the feed gas in the adsorption step. The DSL model was found to be the one that most accurately predicted the CO2 adsorption equilibrium in the multicomponent mixture. The results presented in this work highlight the importance of performing experimental measurements of mixture adsorption equilibria, as they are of utmost importance to discriminate between models and to correctly select the one that most closely reflects the actual process.

A Brief Survey of the Equilibrium and Transport Properties of Critical Fluids and the Degree to Which Microgravity is Required for Their Experimental Investigation

NASA Technical Reports Server (NTRS)

Ferrell, Richard A.

1996-01-01

The modern theory of second order phase transitions is very successful in calculating the critical exponents as an asymptotic expansion in powers of epsilon = 4 - D, the deviation of D = 3, the spatial dimension of the actual physical system from that of the abstract four-dimensional reference model. This remarkable mathematical 'tour de force' leaves unanswered, however, many fundamental questions concerning the exact nature of how the fluctuations interact. I discuss here some experiments which would help to further our understanding of the equilibrium critical properties. Especially promising would be a measurement of the temperature dependence of the turbidity very close to the critical point. This has the promise of determining the small and elusive but fundamentally important anomalous dimension exponent eta. I also review various ways of measuring the critical transport coefficients and point out some cases where ground based experiments may usefully supplement flight experiments.

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.

Optimal control of predator-prey mathematical model with infection and harvesting on prey

NASA Astrophysics Data System (ADS)

Diva Amalia, R. U.; Fatmawati; Windarto; Khusnul Arif, Didik

2018-03-01

This paper presents a predator-prey mathematical model with infection and harvesting on prey. The infection and harvesting only occur on the prey population and it assumed that the prey infection would not infect predator population. We analysed the mathematical model of predator-prey with infection and harvesting in prey. Optimal control, which is a prevention of the prey infection, also applied in the model and denoted as U. The purpose of the control is to increase the susceptible prey. The analytical result showed that the model has five equilibriums, namely the extinction equilibrium (E 0), the infection free and predator extinction equilibrium (E 1), the infection free equilibrium (E 2), the predator extinction equilibrium (E 3), and the coexistence equilibrium (E 4). The extinction equilibrium (E 0) is not stable. The infection free and predator extinction equilibrium (E 1), the infection free equilibrium (E 2), also the predator extinction equilibrium (E 3), are locally asymptotically stable with some certain conditions. The coexistence equilibrium (E 4) tends to be locally asymptotically stable. Afterwards, by using the Maximum Pontryagin Principle, we obtained the existence of optimal control U. From numerical simulation, we can conclude that the control could increase the population of susceptible prey and decrease the infected prey.

Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

Stability of choice in the honey bee nest-site selection process.

PubMed

Nevai, Andrew L; Passino, Kevin M; Srinivasan, Parthasarathy

2010-03-07

We introduce a pair of compartment models for the honey bee nest-site selection process that lend themselves to analytic methods. The first model represents a swarm of bees deciding whether a site is viable, and the second characterizes its ability to select between two viable sites. We find that the one-site assessment process has two equilibrium states: a disinterested equilibrium (DE) in which the bees show no interest in the site and an interested equilibrium (IE) in which bees show interest. In analogy with epidemic models, we define basic and absolute recruitment numbers (R(0) and B(0)) as measures of the swarm's sensitivity to dancing by a single bee. If R(0) is less than one then the DE is locally stable, and if B(0) is less than one then it is globally stable. If R(0) is greater than one then the DE is unstable and the IE is stable under realistic conditions. In addition, there exists a critical site quality threshold Q(*) above which the site can attract some interest (at equilibrium) and below which it cannot. We also find the existence of a second critical site quality threshold Q(**) above which the site can attract a quorum (at equilibrium) and below which it cannot. The two-site discrimination process, in which we examine a swarm's ability to simultaneously consider two sites differing in both site quality and discovery time, has a stable DE if and only if both sites' individual basic recruitment numbers are less than one. Numerical experiments are performed to study the influences of site quality on quorum time and the outcome of competition between a lower quality site discovered first and a higher quality site discovered second. 2009 Elsevier Ltd. All rights reserved.

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system from external chemical input and/or the existence of a yet to be defined dissolution/precipitation inhibition mechanism.

A Nonequilibrium Finite-Rate Carbon Ablation Model for Radiating Earth Re-entry Flows

DTIC Science & Technology

2015-09-17

model was a short half-cylinder made of isomolded graphite and was tested in 8.6 km/ s Earth entry ow. The model surface was heated within a temperature...capsule [98, 49, 112]. For the Star- dust return capsule that had an Earth entry velocity of 12 km/ s , equilibrium surface recession was over predicted...was tested at 8.6 km/ s Earth entry ow monitored by ultraviolet (UV) spec- trometry. The experiments pre-heated the model to high temperatures to

Preliminary Experimental Examination Of Controls On Methane Expulsion During Melting Of Natural Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Flemings, P. B.; Bryant, S. L.; You, K.; Polito, P. J.

2013-12-01

Global climate change will cause warming of the oceans and land. This will affect the occurrence, behavior, and location of subseafloor and subterranean methane hydrate deposits. We suggest that in many natural systems local salinity, elevated by hydrate formation or freshened by hydrate dissociation, may control gas transport through the hydrate stability zone. We are performing experiments and modeling the experiments to explore this behavior for different warming scenarios. Initially, we are exploring hydrate association/dissociation in saline systems with constant water mass. We compare experiments run with saline (3.5 wt. %) water vs. distilled water in a sand mixture at an initial water saturation of ~0.5. We increase the pore fluid (methane) pressure to 1050 psig. We then stepwise cool the sample into the hydrate stability field (~3 degrees C), allowing methane gas to enter as hydrate forms. We measure resistivity and the mass of methane consumed. We are currently running these experiments and we predict our results from equilibrium thermodynamics. In the fresh water case, the modeled final hydrate saturation is 63% and all water is consumed. In the saline case, the modeled final hydrate saturation is 47%, the salinity is 12.4 wt. %, and final water saturation is 13%. The fresh water system is water-limited: all the water is converted to hydrate. In the saline system, pore water salinity is elevated and salt is excluded from the hydrate structure during hydrate formation until the salinity drives the system to three phase equilibrium (liquid, gas, hydrate) and no further hydrate forms. In our laboratory we can impose temperature gradients within the column, and we will use this to investigate equilibrium conditions in large samples subjected to temperature gradients and changing temperature. In these tests, we will quantify the hydrate saturation and salinity over our meter-long sample using spatially distributed temperature sensors, spatially distributed resistivity probes, compressional wave velocities, and X-ray computed tomography scanning. Modeling of hydrate formation and dissociation for these conditions indicates that the transport of bulk fluid phases (gas and water) plays a crucial role in the overall behavior, and we will explore open-system boundary conditions in the experiments to test this prediction.

Equilibrium and kinetic modelling of chromium(III) sorption by animal bones.

PubMed

Chojnacka, Katarzyna

2005-04-01

The paper discusses sorption of Cr(III) ions from aqueous solutions by animal bones. Animal bones were found to be an efficient sorbent with the maximum experimentally determined sorption capacity in the range 29-194 mg g(-1) that depended on pH and temperature. The maximum experimentally determined sorption capacity was obtained at 50 degrees C, pH 5. Batch kinetics and equilibrium experiments were performed in order to investigate the influence of contact time, initial concentration of sorbate and sorbent, temperature and pH. It was found that sorption capacity increased with increase of Cr(III) concentration, temperature and initial pH of metal solution. Mathematical models describing kinetics and statics of sorption were proposed. It was found that process kinetics followed the pseudo-second-order pattern. The influence of sorbent concentration was described with Langmuir-type equation and the influence of sorbate concentration was described with empirical dependence. The models were positively verified.

Consequences of hot gas in the broad line region of active galactic nuclei

NASA Technical Reports Server (NTRS)

Kallman, T.; Mushotzky, R.

1985-01-01

Models for hot gas in the broad line region of active galactic nuclei are discussed. The results of the two phase equilibrium models for confinement of broad line clouds by Compton heated gas are used to show that high luminosity quasars are expected to show Fe XXVI L alpha line absorption which will be observed with spectrometers such as those planned for the future X-ray spectroscopy experiments. Two phase equilibrium models also predict that the gas in the broad line clouds and the confining medium may be Compton thick. It is shown that the combined effects of Comptonization and photoabsorption can suppress both the broad emission lines and X-rays in the Einstein and HEAO-1 energy bands. The observed properties of such Compton thick active galaxies are expected to be similar to those of Seyfert 2 nuclei. The implications for polarization and variability are also discussed.

Large-eddy simulation of a boundary layer with concave streamwise curvature

NASA Technical Reports Server (NTRS)

Lund, Thomas S.

1994-01-01

Turbulence modeling continues to be one of the most difficult problems in fluid mechanics. Existing prediction methods are well developed for certain classes of simple equilibrium flows, but are still not entirely satisfactory for a large category of complex non-equilibrium flows found in engineering practice. Direct and large-eddy simulation (LES) approaches have long been believed to have great potential for the accurate prediction of difficult turbulent flows, but the associated computational cost has been prohibitive for practical problems. This remains true for direct simulation but is no longer clear for large-eddy simulation. Advances in computer hardware, numerical methods, and subgrid-scale modeling have made it possible to conduct LES for flows or practical interest at Reynolds numbers in the range of laboratory experiments. The objective of this work is to apply ES and the dynamic subgrid-scale model to the flow of a boundary layer over a concave surface.

KTX circuit model and discharge waveform prediction

NASA Astrophysics Data System (ADS)

Bai, Wei; Lan, T.; Mao, W. Z.; You, W.; Li, H.; Liu, A. D.; Xie, J. L.; Wan, S. D.; Liu, W. D.; Yang, L.; Fu, P.; Xiao, C. J.; Ding, W. X.

2013-10-01

The Keda Torus eXperiment (KTX) is a constructing reversed field pinch (RFP) device in University of Science and Technology of China. The KTX power supply system includes the Ohmic heating, field shaping and toroidal power supply systems, which produce the Ohmic field, equilibrium field and toroidal field, respectively. The detailed circuit model will be introduced in this poster. Another purpose is to predict its discharge waveforms using the modified Bessel function mode (MBFM), which describes the evolution of plasma current and magnetic flux in RFP base on Taylor theory. Furthermore, the power supply requirements of external field shaping winding are also predicted in the model, which will be very helpful for the design of plasma equilibrium controlling system. Supported by ITER-China program (No. 2011GB106000), NNSFC (Nos. 10990210, 10990211, 10335060 and 10905057), CPSF (No. 20080440104), YIF (No. WK2030040019) and KIPCAS (No. kjcx-yw-n28).

A Mathematical Model for Simulating Remediation of Groundwater Contaminated by Heavy Metals using Bio-Carriers with Dead Baccilus sp. B1 and Polysulfone

NASA Astrophysics Data System (ADS)

Seo, H.; Wang, S.; Lee, M.

2010-12-01

The remediation of groundwater contaminated by heavy metals, organic contaminants, etc. using various types of bio-carriers has been widely studied as a novel technology in the literature. In this study, a series of batch experiments were conducted to investigated the fundamental characteristics in the removal process using bio-carriers (beads) with dead Bacillus sp. B1 and polysulfone. Through equilibrium and kinetic sorption experiments, sorption efficiencies for lead and copper under various conditions such as pH, temperature, contaminant concentration, etc. were examined and sorption parameters including maximum sorption capacities were obtained for model applications. Experimental data showed that equilibrium sorption patterns for Pb2+and Cu2+on bio-carrier beads follows Langmuir sorption isotherm and that the sorption dynamics can be described with a pseudo-second-order kinetics. One dimensional advective-dispersive-reactive transport model was also developed for simulating and analyzing the remediation processes. The HSDM (homogeneous surface diffusion model) were incorporated in the model to take into account the mass transfer and sorption mechanisms around/inside the bio-carrier beads. Applying the proposed model, numerical column experiments were carried out and the simulation results reasonably described temporal and spatial distribution of Pb2+and Cu2+in a fixed-bed flow-through sorption column. Experimental and numerical results showed that the main mechanism of the bio-carrier to remove heavy metals is the sorption on/inside of the bio-carriers and the bio-carriers can function as excellent biosorbents for the removal of heavy metal ions from groundwater.

Equilibrium and kinetic modelling of Cd(II) biosorption by algae Gelidium and agar extraction algal waste.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2006-01-01

In this study an industrial algal waste from agar extraction has been used as an inexpensive and effective biosorbent for cadmium (II) removal from aqueous solutions. This biosorbent was compared with the algae Gelidium itself, which is the raw material for agar extraction. Equilibrium data follow both Langmuir and Redlich-Peterson models. The parameters of Langmuir equilibrium model are q(max)=18.0 mgg(-1), b=0.19 mgl(-1) and q(max)=9.7 mgg(-1), b=0.16 mgl(-1), respectively for Gelidium and the algal waste. Kinetic experiments were conducted at initial Cd(II) concentrations in the range 6-91 mgl(-1). Data were fitted to pseudo-first- and second-order Lagergren models. For an initial Cd(II) concentration of 91 mgl(-1) the parameters of the pseudo-first-order Lagergren model are k(1,ads)=0.17 and 0.87 min(-1); q(eq)=16.3 and 8.7 mgg(-1), respectively, for Gelidium and algal waste. Kinetic constants vary with the initial metal concentration. The adsorptive behaviour of biosorbent particles was modelled using a batch reactor mass transfer kinetic model. The model successfully predicts Cd(II) concentration profiles and provides significant insights on the biosorbents performance. The homogeneous diffusivity, D(h), is in the range 0.5-2.2 x10(-8) and 2.1-10.4 x10(-8)cm(2)s(-1), respectively, for Gelidium and algal waste.

Application of linear pH gradients for the modeling of ion exchange chromatography: Separation of monoclonal antibody monomer from aggregates.

PubMed

Kluters, Simon; Wittkopp, Felix; Jöhnck, Matthias; Frech, Christian

2016-02-01

The mobile phase pH is a key parameter of every ion exchange chromatography process. However, mechanistic insights into the pH influence on the ion exchange chromatography equilibrium are rare. This work describes a mechanistic model capturing salt and pH influence in ion exchange chromatography. The pH dependence of the characteristic protein charge and the equilibrium constant is introduced to the steric mass action model based on a protein net charge model considering the number of amino acids interacting with the stationary phase. This allows the description of the adsorption equilibrium of the chromatographed proteins as a function of pH. The model parameters were determined for a monoclonal antibody monomer, dimer, and a higher aggregated species based on a manageable set of pH gradient experiments. Without further modification of the model parameters the transfer to salt gradient elution at fixed pH is demonstrated. A lumped rate model was used to predict the separation of the monoclonal antibody monomer/aggregate mixture in pH gradient elution and for a pH step elution procedure-also at increased protein loadings up to 48 g/L packed resin. The presented model combines both salt and pH influence and may be useful for the development and deeper understanding of an ion exchange chromatography separation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Payload specialists Patrick Baudry conducts equilibrium experiments

NASA Technical Reports Server (NTRS)

1985-01-01

Payload specialists Patrick Baudry participates in an experiment involving equilibrium and vertigo. He is anchored to the orbiter floor by foot restraints and is wearing a device over his eyes to measure angular head movement and up and down eye movement.

Turbulence Modeling Effects on the Prediction of Equilibrium States of Buoyant Shear Flows

NASA Technical Reports Server (NTRS)

Zhao, C. Y.; So, R. M. C.; Gatski, T. B.

2001-01-01

The effects of turbulence modeling on the prediction of equilibrium states of turbulent buoyant shear flows were investigated. The velocity field models used include a two-equation closure, a Reynolds-stress closure assuming two different pressure-strain models and three different dissipation rate tensor models. As for the thermal field closure models, two different pressure-scrambling models and nine different temperature variance dissipation rate, Epsilon(0) equations were considered. The emphasis of this paper is focused on the effects of the Epsilon(0)-equation, of the dissipation rate models, of the pressure-strain models and of the pressure-scrambling models on the prediction of the approach to equilibrium turbulence. Equilibrium turbulence is defined by the time rate (if change of the scaled Reynolds stress anisotropic tensor and heat flux vector becoming zero. These conditions lead to the equilibrium state parameters. Calculations show that the Epsilon(0)-equation has a significant effect on the prediction of the approach to equilibrium turbulence. For a particular Epsilon(0)-equation, all velocity closure models considered give an equilibrium state if anisotropic dissipation is accounted for in one form or another in the dissipation rate tensor or in the Epsilon(0)-equation. It is further found that the models considered for the pressure-strain tensor and the pressure-scrambling vector have little or no effect on the prediction of the approach to equilibrium turbulence.

Unsteady Computational Tests of a Non-Equilibrium

NASA Astrophysics Data System (ADS)

Jirasek, Adam; Hamlington, Peter; Lofthouse, Andrew; Usafa Collaboration; Cu Boulder Collaboration

2017-11-01

A non-equilibrium turbulence model is assessed on simulations of three practically-relevant unsteady test cases; oscillating channel flow, transonic flow around an oscillating airfoil, and transonic flow around the Benchmark Super-Critical Wing. The first case is related to piston-driven flows while the remaining cases are relevant to unsteady aerodynamics at high angles of attack and transonic speeds. Non-equilibrium turbulence effects arise in each of these cases in the form of a lag between the mean strain rate and Reynolds stresses, resulting in reduced kinetic energy production compared to classical equilibrium turbulence models that are based on the gradient transport (or Boussinesq) hypothesis. As a result of the improved representation of unsteady flow effects, the non-equilibrium model provides substantially better agreement with available experimental data than do classical equilibrium turbulence models. This suggests that the non-equilibrium model may be ideally suited for simulations of modern high-speed, high angle of attack aerodynamics problems.

Numerical modeling of a long-term in situ chemical osmosis experiment in the Pierre Shale, South Dakota

USGS Publications Warehouse

Garavito, A.M.; Kooi, H.; Neuzil, C.E.

2006-01-01

We have numerically modeled evolving fluid pressures and concentrations from a nine-year in situ osmosis experiment in the Pierre Shale, South Dakota. These data were obtained and recently interpreted by one of us (C.E.N.) as indicating a potentially significant role for chemical osmosis in media like the Pierre Shale. That analysis considered only the final pressure differentials among boreholes that were assumed to represent osmotic equilibrium. For this study, the system evolution was modeled using a recently developed transient model for membrane transport. The model simulates hydraulically and chemically driven fluid and solute transport. The results yield an estimate of the thickness of the water film between the clay platelets b of 40 A??, which corresponds to an osmotic efficiency ?? of 0.21 for the ambient pore water salinity of 3.5 g/l TDS. These values largely confirm the results of the earlier equilibrium analysis. However, the new model analysis provides additional constraints suggesting that intrinsic permeability k = 1.4 ?? 10-19 m2, specific storage Ss = 1.7 ?? 10-5 m-1, and diffusion coefficient D* = 6 ?? 10-11 m2/s. The k value is larger than certain independent estimates which range from 10-21 to 10-20; it may indicate opening of microcracks during the experiments. The fact that the complex transient pressure and concentration behavior for the individual wells could be reproduced quite accurately, and the inferred parameter values appear to be realistic for the Pierre Shale, suggests that the new model is a useful tool for modeling transient coupled flows in groundwater systems. ?? 2005 Elsevier Ltd. All rights reserved.

A Mathematical Model of Demand-Supply Dynamics with Collectability and Saturation Factors

NASA Astrophysics Data System (ADS)

Li, Y. Charles; Yang, Hong

We introduce a mathematical model on the dynamics of demand and supply incorporating collectability and saturation factors. Our analysis shows that when the fluctuation of the determinants of demand and supply is strong enough, there is chaos in the demand-supply dynamics. Our numerical simulation shows that such a chaos is not an attractor (i.e. dynamics is not approaching the chaos), instead a periodic attractor (of period-3 under the Poincaré period map) exists near the chaos, and coexists with another periodic attractor (of period-1 under the Poincaré period map) near the market equilibrium. Outside the basins of attraction of the two periodic attractors, the dynamics approaches infinity indicating market irrational exuberance or flash crash. The period-3 attractor represents the product’s market cycle of growth and recession, while period-1 attractor near the market equilibrium represents the regular fluctuation of the product’s market. Thus our model captures more market phenomena besides Marshall’s market equilibrium. When the fluctuation of the determinants of demand and supply is strong enough, a three leaf danger zone exists where the basins of attraction of all attractors intertwine and fractal basin boundaries are formed. Small perturbations in the danger zone can lead to very different attractors. That is, small perturbations in the danger zone can cause the market to experience oscillation near market equilibrium, large growth and recession cycle, and irrational exuberance or flash crash.

Adsorption of cesium on cement mortar from aqueous solutions.

PubMed

Volchek, Konstantin; Miah, Muhammed Yusuf; Kuang, Wenxing; DeMaleki, Zack; Tezel, F Handan

2011-10-30

The adsorption of cesium on cement mortar from aqueous solutions was studied in series of bench-scale tests. The effects of cesium concentration, temperature and contact time on process kinetics and equilibrium were evaluated. Experiments were carried out in a range of initial cesium concentrations from 0.0103 to 10.88 mg L(-1) and temperatures from 278 to 313 K using coupons of cement mortar immersed in the solutions. Non-radioactive cesium chloride was used as a surrogate of the radioactive (137)Cs. Solution samples were taken after set periods of time and analyzed by inductively coupled plasma mass spectroscopy. Depending on the initial cesium concentration, its equilibrium concentration in solution ranged from 0.0069 to 8.837 mg L(-1) while the respective surface concentration on coupons varied from 0.0395 to 22.34 μg cm(-2). Equilibrium test results correlated well with the Freundlich isotherm model for the entire test duration. Test results revealed that an increase in temperature resulted in an increase in adsorption rate and a decrease in equilibrium cesium surface concentration. Among several kinetic models considered, the pseudo-second order reaction model was found to be the best to describe the kinetic test results in the studied range of concentrations. The adsorption activation energy determined from Arrhenius equation was found to be approximately 55.9 kJ mol(-1) suggesting that chemisorption was the prevalent mechanism of interaction between cesium ions and cement mortar. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

[Equilibrium sorption isotherm for Cu2+ onto Hydrilla verticillata Royle and Myriophyllum spicatum].

PubMed

Yan, Chang-zhou; Zeng, A-yan; Jin, Xiang-can; Wang, Sheng-rui; Xu, Qiu-jin; Zhao, Jing-zhu

2006-06-01

Equilibrium sorption isotherms for Cu2+ onto Hydrilla verticillata Royle and Myriophyllum spicatum were studied. Both methods of linear and non-linear fitting were applied to describe the sorption isotherms, and their applicability were analyzed and compared. The results were: (1) The applicability of simulated equation can't be compared only by R2 and chi2 when equilibrium sorption model was used to quantify and contrast the performance of different biosorbents. Both methods of linear and non-linear fitting can be applied in different fitting equations to describe the equilibrium sorption isotherms respectively in order to obtain the actual and credible fitting results, and the fitting equation best accorded with experimental data can be selected; (2) In this experiment, the Langmuir model is more suitable to describe the sorption isotherm of Cu2+ biosorption by H. verticillata and M. spicatum, and there is greater difference between the experimental data and the calculated value of Freundlich model, especially for the linear form of Freundlich model; (3) The content of crude cellulose in dry matter is one of the main factor affecting the biosorption capacity of a submerged aquatic plant, and -OH and -CONH2 groups of polysaccharides on cell wall maybe are active center of biosorption; (4) According to the coefficients qm of the linear form of Langmuir model, the maximum sorption capacity of Cu2+ was found to be 21.55 mg/g and 10.80mg/g for H. verticillata and M. spicatum, respectively. The maximum specific surface area for H. verticillata for binding Cu2+ was 3.23m2/g, and it was 1.62m2/g for M. spicatum.

The phenotypic equilibrium of cancer cells: From average-level stability to path-wise convergence.

PubMed

Niu, Yuanling; Wang, Yue; Zhou, Da

2015-12-07

The phenotypic equilibrium, i.e. heterogeneous population of cancer cells tending to a fixed equilibrium of phenotypic proportions, has received much attention in cancer biology very recently. In the previous literature, some theoretical models were used to predict the experimental phenomena of the phenotypic equilibrium, which were often explained by different concepts of stabilities of the models. Here we present a stochastic multi-phenotype branching model by integrating conventional cellular hierarchy with phenotypic plasticity mechanisms of cancer cells. Based on our model, it is shown that: (i) our model can serve as a framework to unify the previous models for the phenotypic equilibrium, and then harmonizes the different kinds of average-level stabilities proposed in these models; and (ii) path-wise convergence of our model provides a deeper understanding to the phenotypic equilibrium from stochastic point of view. That is, the emergence of the phenotypic equilibrium is rooted in the stochastic nature of (almost) every sample path, the average-level stability just follows from it by averaging stochastic samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Adsorptive Removal of Cadmium (II) from Aqueous Solution by Multi-Carboxylic-Functionalized Silica Gel: Equilibrium, Kinetics and Thermodynamics

NASA Astrophysics Data System (ADS)

Li, Min; Meng, Xiaojing; Yuan, Jinhai; Deng, Wenwen; Liang, Xiuke

2018-01-01

In the present study, the adsorption behavior of cadmium (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of various experimental parameters such as pH value, contact time and initial concentration on adsorption capacity of cadmium (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. Equilibrium isotherms for the adsorption of cadmium (II) ion were analyzed by Freundlich and Langmuir isotherm models, the results indicate that Langmuir isotherm model was found to be credible to express the data for cadmium (II) ion from aqueous solution onto the SG-MCF. Various thermodynamics parameters of the adsorption process, including free energy of adsorption (ΔG0 ), the enthalpy of adsorption (ΔH0 ) and standard entropy changes (ΔS0 ), were calculated to predict the nature of adsorption. The positive value of the enthalpy change and the negative value of free energy change indicate that the process is endothermic and spontaneous process.

Criticality in a non-equilibrium, driven system: charged colloidal rods (fd-viruses) in electric fields.

PubMed

Kang, K; Dhont, J K G

2009-11-01

Experiments on suspensions of charged colloidal rods (fd-virus particles) in external electric fields are performed, which show that a non-equilibrium critical point can be identified. Several transition lines of field-induced phases and states meet at this point and it is shown that there is a length- and time-scale which diverge at the non-equilibrium critical point. The off-critical and critical behavior is characterized, with both power law and logarithmic divergencies. These experiments show that analogous features of the classical, critical divergence of correlation lengths and relaxation times in equilibrium systems are also exhibited by driven systems that are far out of equilibrium, related to phases/states that do not exist in the absence of the external field.

Non-equilibrium synergistic effects in atmospheric pressure plasmas.

PubMed

Guo, Heng; Zhang, Xiao-Ning; Chen, Jian; Li, He-Ping; Ostrikov, Kostya Ken

2018-03-19

Non-equilibrium is one of the important features of an atmospheric gas discharge plasma. It involves complicated physical-chemical processes and plays a key role in various actual plasma processing. In this report, a novel complete non-equilibrium model is developed to reveal the non-equilibrium synergistic effects for the atmospheric-pressure low-temperature plasmas (AP-LTPs). It combines a thermal-chemical non-equilibrium fluid model for the quasi-neutral plasma region and a simplified sheath model for the electrode sheath region. The free-burning argon arc is selected as a model system because both the electrical-thermal-chemical equilibrium and non-equilibrium regions are involved simultaneously in this arc plasma system. The modeling results indicate for the first time that it is the strong and synergistic interactions among the mass, momentum and energy transfer processes that determine the self-consistent non-equilibrium characteristics of the AP-LTPs. An energy transfer process related to the non-uniform spatial distributions of the electron-to-heavy-particle temperature ratio has also been discovered for the first time. It has a significant influence for self-consistently predicting the transition region between the "hot" and "cold" equilibrium regions of an AP-LTP system. The modeling results would provide an instructive guidance for predicting and possibly controlling the non-equilibrium particle-energy transportation process in various AP-LTPs in future.

Mathematical modeling of HIV-like particle assembly in vitro.

PubMed

Liu, Yuewu; Zou, Xiufen

2017-06-01

In vitro, the recombinant HIV-1 Gag protein can generate spherical particles with a diameter of 25-30 nm in a fully defined system. It has approximately 80 building blocks, and its intermediates for assembly are abundant in geometry. Accordingly, there are a large number of nonlinear equations in the classical model. Therefore, it is difficult to compute values of geometry parameters for intermediates and make the mathematical analysis using the model. In this work, we develop a new model of HIV-like particle assembly in vitro by using six-fold symmetry of HIV-like particle assembly to decrease the number of geometry parameters. This method will greatly reduce computational costs and facilitate the application of the model. Then, we prove the existence and uniqueness of the positive equilibrium solution for this model with 79 nonlinear equations. Based on this model, we derive the interesting result that concentrations of all intermediates at equilibrium are independent of three important parameters, including two microscopic on-rate constants and the size of nucleating structure. Before equilibrium, these three parameters influence the concentration variation rates of all intermediates. We also analyze the relationship between the initial concentration of building blocks and concentrations of all intermediates. Furthermore, the bounds of concentrations of free building blocks and HIV-like particles are estimated. These results will be helpful to guide HIV-like particle assembly experiments and improve our understanding of the assembly dynamics of HIV-like particles in vitro. Copyright © 2017 Elsevier Inc. All rights reserved.

Vibrational non-equilibrium in the hydrogen-oxygen reaction. Comparison with experiment

NASA Astrophysics Data System (ADS)

Skrebkov, Oleg V.

2015-03-01

A theoretical model is proposed for the chemical and vibrational kinetics of hydrogen oxidation based on consistent accounting of the vibrational non-equilibrium of the HO2 radical that forms as a result of the bimolecular recombination H+O2 → HO2. In the proposed model, the chain branching H+O2 = O+OH and inhibiting H+O2+M = HO2+M formal reactions are treated (in the terms of elementary processes) as a single multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and unimolecular decay of the comparatively long-lived vibrationally excited HO2 radical, which is able to react and exchange energy with the other components of the mixture. The model takes into account the vibrational non-equilibrium of the starting (primary) H2 and O2 molecules, as well as the most important molecular intermediates HO2, OH, O2(1Δ), and the main reaction product H2O. It is shown that the hydrogen-oxygen reaction proceeds in the absence of vibrational equilibrium, and the vibrationally excited HO2(v) radical acts as a key intermediate in a fundamentally important chain branching process and in the generation of electronically excited species O2(1Δ), O(1D), and OH(2Σ+). The calculated results are compared with the shock tube experimental data for strongly diluted H2-O2 mixtures at 1000 < T < 2500 K, 0.5 < p < 4 atm. It is demonstrated that this approach is promising from the standpoint of reconciling the predictions of the theoretical model with experimental data obtained by different authors for various compositions and conditions using different methods. For T < 1500 K, the nature of the hydrogen-oxygen reaction is especially non-equilibrium, and the vibrational non-equilibrium of the HO2 radical is the essence of this process. The quantitative estimation of the vibrational relaxation characteristic time of the HO2 radical in its collisions with H2 molecules has been obtained as a result of the comparison of different experimental data on induction time measurements with the relevant calculations.

Modelling of electronic excitation and radiation in the Direct Simulation Monte Carlo Macroscopic Chemistry Method

NASA Astrophysics Data System (ADS)

Goldsworthy, M. J.

2012-10-01

One of the most useful tools for modelling rarefied hypersonic flows is the Direct Simulation Monte Carlo (DSMC) method. Simulator particle movement and collision calculations are combined with statistical procedures to model thermal non-equilibrium flow-fields described by the Boltzmann equation. The Macroscopic Chemistry Method for DSMC simulations was developed to simplify the inclusion of complex thermal non-equilibrium chemistry. The macroscopic approach uses statistical information which is calculated during the DSMC solution process in the modelling procedures. Here it is shown how inclusion of macroscopic information in models of chemical kinetics, electronic excitation, ionization, and radiation can enhance the capabilities of DSMC to model flow-fields where a range of physical processes occur. The approach is applied to the modelling of a 6.4 km/s nitrogen shock wave and results are compared with those from existing shock-tube experiments and continuum calculations. Reasonable agreement between the methods is obtained. The quality of the comparison is highly dependent on the set of vibrational relaxation and chemical kinetic parameters employed.

Effect of the size of charged spherical macroparticles on their electrostatic interaction in an equilibrium plasma

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

Filippov, A. V., E-mail: fav@triniti.ru; Derbenev, I. N.

The effect of the size of two charged spherical macroparticles on their electrostatic interaction in an equilibrium plasma is analyzed within the linearized Poisson–Botzmann model. It is established that, under the interaction of two charged dielectric macroparticles in an equilibrium plasma, the forces acting on each particle turn out to be generally unequal. The forces become equal only in the case of conducting macroparticles or in the case of dielectric macroparticles of the same size and charge. They also turn out to be equal when the surface potentials of the macroparticles remain constant under the variation of interparticle distances. Formulasmore » are proposed that allow one to calculate the interaction force with a high degree of accuracy under the condition that the radii of macroparticles are much less than the screening length, which is usually satisfied in experiments with dusty plasmas.« less

On the Morphology of a Growing City: A Heuristic Experiment Merging Static Economics with Dynamic Geography.

PubMed

Delloye, Justin; Peeters, Dominique; Thomas, Isabelle

2015-01-01

In this paper, we aim at exploring how individual location decisions affect the shape of a growing city and, more precisely, how they may add up to a configuration that diverges from equilibrium configurations formulated ex-ante. To do so, we provide a two-sector city model merging a static equilibrium analysis with agent-based simulations. Results show that under strong agglomeration effects, urban development is monotonic and ends up with circular, monocentric long-term configurations. For low agglomeration effects however, elongated and multicentric urban configurations may emerge. The occurrence and underlying dynamics of these configurations are also discussed regarding commuting costs and the distance-decay of agglomeration economies between firms. To sum up, our paper warns urban planning policy makers against the difference that may stand between appropriate long-term perspectives, represented here by analytic equilibrium configurations, and short-term urban configurations, simulated here by a multi-agent system.

Cesium sorption reversibility and kinetics on illite, montmorillonite, and kaolinite

DOE PAGES

Durrant, Chad B.; Begg, James D.; Kersting, Annie B.; ...

2017-08-17

Understanding sorption and desorption processes is essential to predicting the mobility of radionuclides in the environment. In this study, we investigate adsorption/desorption of cesium in both binary (Cs + one mineral) and ternary (Cs + two minerals) experiments to study component additivity and sorption reversibility over long time periods (500 days). Binary Cs sorption experiments were performed with illite, montmorillonite, and kaolinite in a 5 mM NaCl/0.7 mM NaHCO3 solution (pH 8) and Cs concentration range of 10 –3 to 10 –11 M. The binary sorption experiments were followed by batch desorption experiments. The sorption behavior was modeled with themore » FIT4FD code and the results used to predict desorption behavior. Sorption to montmorillonite and kaolinite was linear over the entire concentration range but sorption to illite was non-linear, indicating the presence of multiple sorption sites. Based on the 14 day batch desorption data, cesium sorption appeared irreversible at high surface loadings in the case of illite but reversible at all concentrations for montmorillonite and kaolinite. Additionally, a novel experimental approach, using a dialysis membrane, was adopted in the ternary experiments, allowing investigation of the effect of a second mineral on Cs desorption from the original mineral. Cs was first sorbed to illite, montmorillonite or kaolinite, then a 3.5–5 kDalton Float-A-Lyzer® dialysis bag with 0.3 g of illite was introduced to each experiment inducing desorption. Nearly complete Cs desorption from kaolinite and montmorillonite was observed over the experiment, consistent with our equilibrium model, indicating complete Cs desorption from these minerals. Results from the long-term ternary experiments show significantly greater Cs desorption compared to the binary desorption experiments. Approximately ~ 45% of Cs desorbed from illite. However, our equilibrium model predicted ~ 65% desorption. Importantly, the data imply that in some cases, slow desorption kinetics rather than permanent fixation may play an important role in apparent irreversible Cs sorption.« less

Numerical simulation of heat transfer in metal foams

NASA Astrophysics Data System (ADS)

Gangapatnam, Priyatham; Kurian, Renju; Venkateshan, S. P.

2018-02-01

This paper reports a numerical study of forced convection heat transfer in high porosity aluminum foams. Numerical modeling is done considering both local thermal equilibrium and non local thermal equilibrium conditions in ANSYS-Fluent. The results of the numerical model were validated with experimental results, where air was forced through aluminum foams in a vertical duct at different heat fluxes and velocities. It is observed that while the LTE model highly under predicts the heat transfer in these foams, LTNE model predicts the Nusselt number accurately. The novelty of this study is that once hydrodynamic experiments are conducted the permeability and porosity values obtained experimentally can be used to numerically simulate heat transfer in metal foams. The simulation of heat transfer in foams is further extended to find the effect of foam thickness on heat transfer in metal foams. The numerical results indicate that though larger foam thicknesses resulted in higher heat transfer coefficient, this effect weakens with thickness and is negligible in thick foams.

Random walk to a nonergodic equilibrium concept

NASA Astrophysics Data System (ADS)

Bel, G.; Barkai, E.

2006-01-01

Random walk models, such as the trap model, continuous time random walks, and comb models, exhibit weak ergodicity breaking, when the average waiting time is infinite. The open question is, what statistical mechanical theory replaces the canonical Boltzmann-Gibbs theory for such systems? In this paper a nonergodic equilibrium concept is investigated, for a continuous time random walk model in a potential field. In particular we show that in the nonergodic phase the distribution of the occupation time of the particle in a finite region of space approaches U- or W-shaped distributions related to the arcsine law. We show that when conditions of detailed balance are applied, these distributions depend on the partition function of the problem, thus establishing a relation between the nonergodic dynamics and canonical statistical mechanics. In the ergodic phase the distribution function of the occupation times approaches a δ function centered on the value predicted based on standard Boltzmann-Gibbs statistics. The relation of our work to single-molecule experiments is briefly discussed.

Stochastic dynamics and stable equilibrium of evolutionary optional public goods game in finite populations

NASA Astrophysics Data System (ADS)

Quan, Ji; Liu, Wei; Chu, Yuqing; Wang, Xianjia

2018-07-01

Continuous noise caused by mutation is widely present in evolutionary systems. Considering the noise effects and under the optional participation mechanism, a stochastic model for evolutionary public goods game in a finite size population is established. The evolutionary process of strategies in the population is described as a multidimensional ergodic and continuous time Markov process. The stochastic stable state of the system is analyzed by the limit distribution of the stochastic process. By numerical experiments, the influences of the fixed income coefficient for non-participants and the investment income coefficient of the public goods on the stochastic stable equilibrium of the system are analyzed. Through the numerical calculation results, we found that the optional participation mechanism can change the evolutionary dynamics and the equilibrium of the public goods game, and there is a range of parameters which can effectively promote the evolution of cooperation. Further, we obtain the accurate quantitative relationship between the parameters and the probabilities for the system to choose different stable equilibriums, which can be used to realize the control of cooperation.

Some comments on thermodynamic consistency for equilibrium mixture equations of state

DOE PAGES

Grove, John W.

2018-03-28

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

A hierarchical analysis of terrestrial ecosystem model Biome-BGC: Equilibrium analysis and model calibration

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

Thornton, Peter E; Wang, Weile; Law, Beverly E.

2009-01-01

The increasing complexity of ecosystem models represents a major difficulty in tuning model parameters and analyzing simulated results. To address this problem, this study develops a hierarchical scheme that simplifies the Biome-BGC model into three functionally cascaded tiers and analyzes them sequentially. The first-tier model focuses on leaf-level ecophysiological processes; it simulates evapotranspiration and photosynthesis with prescribed leaf area index (LAI). The restriction on LAI is then lifted in the following two model tiers, which analyze how carbon and nitrogen is cycled at the whole-plant level (the second tier) and in all litter/soil pools (the third tier) to dynamically supportmore » the prescribed canopy. In particular, this study analyzes the steady state of these two model tiers by a set of equilibrium equations that are derived from Biome-BGC algorithms and are based on the principle of mass balance. Instead of spinning-up the model for thousands of climate years, these equations are able to estimate carbon/nitrogen stocks and fluxes of the target (steady-state) ecosystem directly from the results obtained by the first-tier model. The model hierarchy is examined with model experiments at four AmeriFlux sites. The results indicate that the proposed scheme can effectively calibrate Biome-BGC to simulate observed fluxes of evapotranspiration and photosynthesis; and the carbon/nitrogen stocks estimated by the equilibrium analysis approach are highly consistent with the results of model simulations. Therefore, the scheme developed in this study may serve as a practical guide to calibrate/analyze Biome-BGC; it also provides an efficient way to solve the problem of model spin-up, especially for applications over large regions. The same methodology may help analyze other similar ecosystem models as well.« less

Progress towards a more predictive model for hohlraum radiation drive and symmetry

NASA Astrophysics Data System (ADS)

Jones, O. S.; Suter, L. J.; Scott, H. A.; Barrios, M. A.; Farmer, W. A.; Hansen, S. B.; Liedahl, D. A.; Mauche, C. W.; Moore, A. S.; Rosen, M. D.; Salmonson, J. D.; Strozzi, D. J.; Thomas, C. A.; Turnbull, D. P.

2017-05-01

For several years, we have been calculating the radiation drive in laser-heated gold hohlraums using flux-limited heat transport with a limiter of 0.15, tabulated values of local thermodynamic equilibrium gold opacity, and an approximate model for not in a local thermodynamic equilibrium (NLTE) gold emissivity (DCA_2010). This model has been successful in predicting the radiation drive in vacuum hohlraums, but for gas-filled hohlraums used to drive capsule implosions, the model consistently predicts too much drive and capsule bang times earlier than measured. In this work, we introduce a new model that brings the calculated bang time into better agreement with the measured bang time. The new model employs (1) a numerical grid that is fully converged in space, energy, and time, (2) a modified approximate NLTE model that includes more physics and is in better agreement with more detailed offline emissivity models, and (3) a reduced flux limiter value of 0.03. We applied this model to gas-filled hohlraum experiments using high density carbon and plastic ablator capsules that had hohlraum He fill gas densities ranging from 0.06 to 1.6 mg/cc and hohlraum diameters of 5.75 or 6.72 mm. The new model predicts bang times to within ±100 ps for most experiments with low to intermediate fill densities (up to 0.85 mg/cc). This model predicts higher temperatures in the plasma than the old model and also predicts that at higher gas fill densities, a significant amount of inner beam laser energy escapes the hohlraum through the opposite laser entrance hole.

Stochastic entangled chain dynamics of dense polymer solutions.

PubMed

Kivotides, Demosthenes; Wilkin, S Louise; Theofanous, Theo G

2010-10-14

We propose an adjustable-parameter-free, entangled chain dynamics model of dense polymer solutions. The model includes the self-consistent dynamics of molecular chains and solvent by describing the former via coarse-grained polymer dynamics that incorporate hydrodynamic interaction effects, and the latter via the forced Stokes equation. Real chain elasticity is modeled via the inclusion of a Pincus regime in the polymer's force-extension curve. Excluded volume effects are taken into account via the combined action of coarse-grained intermolecular potentials and explicit geometric tracking of chain entanglements. We demonstrate that entanglements are responsible for a new (compared to phantom chain dynamics), slow relaxation mode whose characteristic time scale agrees very well with experiment. Similarly good agreement between theory and experiment is also obtained for the equilibrium chain size. We develop methods for the solution of the model in periodic flow domains and apply them to the computation of entangled polymer solutions in equilibrium. We show that the number of entanglements Π agrees well with the number of entanglements expected on the basis of tube theory, satisfactorily reproducing the latter's scaling of Π with the polymer volume fraction φ. Our model predicts diminishing chain size with concentration, thus vindicating Flory's suggestion of excluded volume effects screening in dense solutions. The predicted scaling of chain size with φ is consistent with the heuristic, Flory theory based value.

Non-equilibrium dog-flea model

NASA Astrophysics Data System (ADS)

Ackerson, Bruce J.

2017-11-01

We develop the open dog-flea model to serve as a check of proposed non-equilibrium theories of statistical mechanics. The model is developed in detail. Then it is applied to four recent models for non-equilibrium statistical mechanics. Comparison of the dog-flea solution with these different models allows checking claims and giving a concrete example of the theoretical models.

Insights into the equilibrium, kinetic and thermodynamics of nickel removal by environmental friendly Lansium domesticum peel biosorbent.

PubMed

Lam, Yun Fung; Lee, Lai Yee; Chua, Song Jun; Lim, Siew Shee; Gan, Suyin

2016-05-01

Lansium domesticum peel (LDP), a waste material generated from the fruit consumption, was evaluated as a biosorbent for nickel removal from aqueous media. The effects of dosage, contact time, initial pH, initial concentration and temperature on the biosorption process were investigated in batch experiments. Equilibrium data were fitted by the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models using nonlinear regression method with the best-fit model evaluated based on coefficient of determination (R(2)) and Chi-square (χ(2)). The best-fit isotherm was found to be the Langmuir model exhibiting R(2) very close to unity (0.997-0.999), smallest χ(2) (0.0138-0.0562) and largest biosorption capacity (10.1mg/g) at 30°C. Kinetic studies showed that the initial nickel removal was rapid with the equilibrium state established within 30min. Pseudo-second-order model was the best-fit kinetic model indicating the chemisorption nature of the biosorption process. Further data analysis by the intraparticle diffusion model revealed the involvement of several rate-controlling steps such as boundary layer and intraparticle diffusion. Thermodynamically, the process was exothermic, spontaneous and feasible. Regeneration studies indicated that LDP biosorbent could be regenerated using hydrochloric acid solution with up to 85% efficiency. The present investigation proved that LDP having no economic value can be used as an alternative eco-friendly biosorbent for remediation of nickel contaminated water. Copyright © 2016 Elsevier Inc. All rights reserved.

Design and analysis of SEIQR worm propagation model in mobile internet

NASA Astrophysics Data System (ADS)

Xiao, Xi; Fu, Peng; Dou, Changsheng; Li, Qing; Hu, Guangwu; Xia, Shutao

2017-02-01

The mobile Internet has considerably facilitated daily life in recent years. However, it has become the breeding ground for lots of new worms, including the Bluetooth-based worm, the SMS/MMS-based worm and the Wi-Fi-based worm. At present, Wi-Fi is widely used for mobile devices to connect to the Internet. But it exposes these devices to the dangerous environment. Most current worm propagation models aim to solve the problems of computer worms. They cannot be used directly in the mobile environment, particularly in the Wi-Fi scenario, because of the differences between computers and mobile devices. In this paper, we propose a worm propagation model in the Wi-Fi environment, called SEIQR (Susceptible-Exposed-Infectious- Quarantined-Recovered). In the model, infected nodes can be quarantined by the Wi-Fi base station, and a new state named the Quarantined state (Q) is established to represent these infected nodes. Based on this model, we present an effective method to inhibit the spread of the Wi-Fi-based worms. Furthermore, related stabilities of the worm-free and endemic equilibriums are studied based on the basic reproduction number R0. The worm-free equilibrium is locally and globally asymptotically stable if R0 < 1, whereas the endemic equilibrium is locally asymptotically stable if R0 < 1. Finally, we evaluate the performance of our model by comprehensive experiments with different infection rates and quarantine rates. The results indicate that our mechanism can combat the worms propagated via Wi-Fi.

Experience with turbulence interaction and turbulence-chemistry models at Fluent Inc.

NASA Technical Reports Server (NTRS)

Choudhury, D.; Kim, S. E.; Tselepidakis, D. P.; Missaghi, M.

1995-01-01

This viewgraph presentation discusses (1) turbulence modeling: challenges in turbulence modeling, desirable attributes of turbulence models, turbulence models in FLUENT, and examples using FLUENT; and (2) combustion modeling: turbulence-chemistry interaction and FLUENT equilibrium model. As of now, three turbulence models are provided: the conventional k-epsilon model, the renormalization group model, and the Reynolds-stress model. The renormalization group k-epsilon model has broadened the range of applicability of two-equation turbulence models. The Reynolds-stress model has proved useful for strongly anisotropic flows such as those encountered in cyclones, swirlers, and combustors. Issues remain, such as near-wall closure, with all classes of models.

Comments on PDF methods

NASA Technical Reports Server (NTRS)

Chen, J.-Y.

1992-01-01

Viewgraphs are presented on the following topics: the grand challenge of combustion engineering; research of probability density function (PDF) methods at Sandia; experiments of turbulent jet flames (Masri and Dibble, 1988); departures from chemical equilibrium; modeling turbulent reacting flows; superequilibrium OH radical; pdf modeling of turbulent jet flames; scatter plot for CH4 (methane) and O2 (oxygen); methanol turbulent jet flames; comparisons between predictions and experimental data; and turbulent C2H4 jet flames.

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

Grove, John W.

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

The Separatory Cylinder: A Novel Solvent Extraction System for the Study of Chemical Equilibrium in Solution.

ERIC Educational Resources Information Center

Cwikel, Dori; And Others

1986-01-01

Dicusses the use of the separatory cylinder in student laboratory experiments for investigating equilibrium distribution of a solute between immiscible phases. Describes the procedures for four sets of experiments of this nature. Lists of materials needed and quantities of reagents are provided. (TW)

Analyzing Ligand Depletion in a Saturation Equilibrium Binding Experiment

ERIC Educational Resources Information Center

Claro, Enrique

2006-01-01

I present a proposal for a laboratory practice to generate and analyze data from a saturation equilibrium binding experiment addressed to advanced undergraduate students. [[superscript 3]H]Quinuclidinyl benzilate is a nonselective muscarinic ligand with very high affinity and very low nonspecific binding to brain membranes, which contain a high…

A New Application for Radioimmunoassay: Measurement of Thermodynamic Constants.

ERIC Educational Resources Information Center

Angstadt, Carol N.; And Others

1983-01-01

Describes a laboratory experiment in which an equilibrium radioimmunoassay (RIA) is used to estimate thermodynamic parameters such as equilibrium constants. The experiment is simple and inexpensive, and it introduces a technique that is important in the clinical chemistry and research laboratory. Background information, procedures, and results are…

Mathematical analysis of tuberculosis transmission model with delay

NASA Astrophysics Data System (ADS)

Lapaan, R. D.; Collera, J. A.; Addawe, J. M.

2016-11-01

In this paper, a delayed Tuberculosis infection model is formulated and investigated. We showed the existence of disease free equilibrium and endemic equilibrium points. We used La Salle-Lyapunov Invariance Principle to show that if the reproductive number R0 < 1, the disease-free equilibrium of the model is globally asymptotically stable. Numerical simulations are then performed to illustrate the existence of the disease free equilibrium and the endemic equilibrium point for a given value of R0. Thus, when R0 < 1, the disease dies out in the population.

Equilibrium partitioning of organic compounds to OASIS HLB® as a function of compound concentration, pH, temperature and salinity.

PubMed

Jeong, Yoonah; Schäffer, Andreas; Smith, Kilian

2017-05-01

Oasis hydrophilic lipophilic balance ® (Oasis HLB) is commonly employed in solid phase extraction (SPE) of environmental contaminants and within polar organic chemical integrative passive samplers (POCIS). In this study batch experiments were carried out to evaluate the relative affinity of a range of relevant organic pollutants to Oasis HLB in aqueous systems. The influence of sorbate concentration, temperature, pH, and salinity on the equilibrium sorption was investigated. Equilibrium partition ratios (K D ) of 28 compounds were determined, ranging over three orders of magnitude from 1.16 × 10 3  L/kg (atenolol) to 1.07 × 10 6  L/kg (isoproturon). The Freundlich model was able to describe the equilibrium partitioning to Oasis HLB, and an analysis of the thermodynamic parameters revealed the spontaneous and exothermic nature of the partitioning process. Ionic strength had only a minor effect on the partitioning, whereas pH had a considerable effect but only for ionizable compounds. The results show that apolar interactions between the Oasis HLB and analyte mainly determine the equilibrium partitioning. These research findings can be used to optimize the application of SPE and POCIS for analyses of environmental contaminants even in complex mixtures. Copyright © 2017 Elsevier Ltd. All rights reserved.

Stability analysis of the Euler discretization for SIR epidemic model

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

Suryanto, Agus

2014-06-19

In this paper we consider a discrete SIR epidemic model obtained by the Euler method. For that discrete model, existence of disease free equilibrium and endemic equilibrium is established. Sufficient conditions on the local asymptotical stability of both disease free equilibrium and endemic equilibrium are also derived. It is found that the local asymptotical stability of the existing equilibrium is achieved only for a small time step size h. If h is further increased and passes the critical value, then both equilibriums will lose their stability. Our numerical simulations show that a complex dynamical behavior such as bifurcation or chaosmore » phenomenon will appear for relatively large h. Both analytical and numerical results show that the discrete SIR model has a richer dynamical behavior than its continuous counterpart.« less

Individual and competitive adsorption of phenol and nickel onto multiwalled carbon nanotubes

PubMed Central

Abdel-Ghani, Nour T.; El-Chaghaby, Ghadir A.; Helal, Farag S.

2014-01-01

Individual and competitive adsorption studies were carried out to investigate the removal of phenol and nickel ions by adsorption onto multiwalled carbon nanotubes (MWCNTs). The carbon nanotubes were characterized by different techniques such as X-ray diffraction, scanning electron microscopy, thermal analysis and Fourier transformation infrared spectroscopy. The different experimental conditions affecting the adsorption process were investigated. Kinetics and equilibrium models were tested for fitting the adsorption experimental data. The characterization experimental results proved that the studied adsorbent possess different surface functional groups as well as typical morphological features. The batch experiments revealed that 300 min of contact time was enough to achieve equilibrium for the adsorption of both phenol and nickel at an initial adsorbate concentration of 25 mg/l, an adsorbent dosage of 5 g/l, and a solution pH of 7. The adsorption of phenol and nickel by MWCNTs followed the pseudo-second order kinetic model and the intraparticle diffusion model was quite good in describing the adsorption mechanism. The Langmuir equilibrium model fitted well the experimental data indicating the homogeneity of the adsorbent surface sites. The maximum Langmuir adsorption capacities were found to be 32.23 and 6.09 mg/g, for phenol and Ni ions, respectively. The removal efficiency of MWCNTs for nickel ions or phenol in real wastewater samples at the optimum conditions reached up to 60% and 70%, respectively. PMID:26257938

Late-time behaviour of the tilted Bianchi type VIh models

NASA Astrophysics Data System (ADS)

Hervik, S.; van den Hoogen, R. J.; Lim, W. C.; Coley, A. A.

2007-08-01

We study tilted perfect fluid cosmological models with a constant equation of state parameter in spatially homogeneous models of Bianchi type VIh using dynamical systems methods and numerical experimentation, with an emphasis on their future asymptotic evolution. We determine all of the equilibrium points of the type VIh state space (which correspond to exact self-similar solutions of the Einstein equations, some of which are new), and their stability is investigated. We find that there are vacuum plane-wave solutions that act as future attractors. In the parameter space, a 'loophole' is shown to exist in which there are no stable equilibrium points. We then show that a Hopf-bifurcation can occur resulting in a stable closed orbit (which we refer to as the Mussel attractor) corresponding to points both inside the loophole and points just outside the loophole; in the former case the closed curves act as late-time attractors while in the latter case these attracting curves will co-exist with attracting equilibrium points. In the special Bianchi type III case, centre manifold theory is required to determine the future attractors. Comprehensive numerical experiments are carried out to complement and confirm the analytical results presented. We note that the Bianchi type VIh case is of particular interest in that it contains many different subcases which exhibit many of the different possible future asymptotic behaviours of Bianchi cosmological models.

Gas evolution in eruptive conduits: Combining insights from high temperature and pressure decompression experiments with steady-state flow modeling

USGS Publications Warehouse

Mangan, M.; Mastin, L.; Sisson, T.

2004-01-01

In this paper we examine the consequences of bubble nucleation mechanism on eruptive degassing of rhyolite magma. We use the results of published high temperature and pressure decompression experiments as input to a modified version of CONFLOW, the numerical model of Mastin and Ghiorso [(2000) U.S.G.S. Open-File Rep. 00-209, 53 pp.] and Mastin [(2002) Geochem. Geophys. Geosyst. 3, 10.1029/2001GC000192] for steady, two-phase flow in vertical conduits. Synthesis of the available experimental data shows that heterogeneous nucleation is triggered at ??P 120-150 MPa, and leads to disequilibrium degassing at extreme H2O supersaturation. In this latter case, nucleation is an ongoing process controlled by changing supersaturation conditions. Exponential bubble size distributions are often produced with number densities of 106-109 bubbles/cm3. Our numerical analysis adopts an end-member approach that specifically compares equilibrium degassing with delayed, disequilibrium degassing characteristic of homogeneously-nucleating systems. The disequilibrium simulations show that delaying nucleation until ??P =150 MPa restricts degassing to within ???1500 m of the surface. Fragmentation occurs at similar porosity in both the disequilibrium and equilibrium modes (???80 vol%), but at the distinct depths of ???500 m and ???2300 m, respectively. The vesiculation delay leads to higher pressures at equivalent depths in the conduit, and the mass flux and exit pressure are each higher by a factor of ???2.0. Residual water contents in the melt reaching the vent are between 0.5 and 1.0 wt%, roughly twice that of the equilibrium model. ?? 2003 Elsevier B.V. All rights reserved.

Rapid removal of uranium from aqueous solutions using magnetic Fe3O4@SiO2 composite particles.

PubMed

Fan, Fang-Li; Qin, Zhi; Bai, Jing; Rong, Wei-Dong; Fan, Fu-You; Tian, Wei; Wu, Xiao-Lei; Wang, Yang; Zhao, Liang

2012-04-01

Rapid removal of U(VI) from aqueous solutions was investigated using magnetic Fe(3)O(4)@SiO(2) composite particles as the novel adsorbent. Batch experiments were conducted to study the effects of initial pH, amount of adsorbent, shaking time and initial U(VI) concentrations on uranium sorption efficiency as well as the desorbing of U(VI). The sorption of uranium on Fe(3)O(4)@SiO(2) composite particles was pH-dependent, and the optimal pH was 6.0. In kinetics studies, the sorption equilibrium can be reached within 180 min, and the experimental data were well fitted by the pseudo-second-order model, and the equilibrium sorption capacities calculated by the model were almost the same as those determined by experiments. The Langmuir sorption isotherm model correlates well with the uranium sorption equilibrium data for the concentration range of 20-200 mg/L. The maximum uranium sorption capacity onto magnetic Fe(3)O(4)@SiO(2) composite particles was estimated to be about 52 mg/g at 25 °C. The highest values of uranium desorption (98%) was achieved using 0.01 M HCl as the desorbing agent. Fe(3)O(4)@SiO(2) composite particles showed a good selectivity for uranium from aqueous solution with other interfering cation ions. Present study suggested that magnetic Fe(3)O(4)@SiO(2) composite particles can be used as a potential adsorbent for sorption uranium and also provided a simple, fast separation method for removal of heavy metal ion from aqueous solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

The NEUF-DIX space project - Non-EquilibriUm Fluctuations during DIffusion in compleX liquids.

PubMed

Baaske, Philipp; Bataller, Henri; Braibanti, Marco; Carpineti, Marina; Cerbino, Roberto; Croccolo, Fabrizio; Donev, Aleksandar; Köhler, Werner; Ortiz de Zárate, José M; Vailati, Alberto

2016-12-01

Diffusion and thermal diffusion processes in a liquid mixture are accompanied by long-range non-equilibrium fluctuations, whose amplitude is orders of magnitude larger than that of equilibrium fluctuations. The mean-square amplitude of the non-equilibrium fluctuations presents a scale-free power law behavior q -4 as a function of the wave vector q, but the divergence of the amplitude of the fluctuations at small wave vectors is prevented by the presence of gravity. In microgravity conditions the non-equilibrium fluctuations are fully developed and span all the available length scales up to the macroscopic size of the systems in the direction parallel to the applied gradient. Available theoretical models are based on linearized hydrodynamics and provide an adequate description of the statics and dynamics of the fluctuations in the presence of small temperature/concentration gradients and under stationary or quasi-stationary conditions. We describe a project aimed at the investigation of Non-EquilibriUm Fluctuations during DIffusion in compleX liquids (NEUF-DIX). The focus of the project is on the investigation in micro-gravity conditions of the non-equilibrium fluctuations in complex liquids, trying to tackle several challenging problems that emerged during the latest years, such as the theoretical predictions of Casimir-like forces induced by non-equilibrium fluctuations; the understanding of the non-equilibrium fluctuations in multi-component mixtures including a polymer, both in relation to the transport coefficients and to their behavior close to a glass transition; the understanding of the non-equilibrium fluctuations in concentrated colloidal suspensions, a problem closely related with the detection of Casimir forces; and the investigation of the development of fluctuations during transient diffusion. We envision to parallel these experiments with state-of-the-art multi-scale simulations.

Flat-roof phenomenon of dynamic equilibrium phase in the negative bias temperature instability effect on a power MOSFET

NASA Astrophysics Data System (ADS)

Zhang, Yue; Zhuo, Qing-Qing; Liu, Hong-Xia; Ma, Xiao-Hua; Hao, Yue

2014-05-01

The effect of the static negative bias temperature (NBT) stress on a p-channel power metal—oxide—semiconductor field-effect transistor (MOSFET) is investigated by experiment and simulation. The time evolution of the negative bias temperature instability (NBTI) degradation has the trend predicted by the reaction—diffusion (R—D) model but with an exaggerated time scale. The phenomena of the flat-roof section are observed under various stress conditions, which can be considered as the dynamic equilibrium phase in the R—D process. Based on the simulated results, the variation of the flat-roof section with the stress condition can be explained.

Solubility Model for Ferrous Iron Hydroxide, Hibbingite, Siderite, and Chukanovite in High Saline Solutions of Sodium Chloride, Sodium Sulfate, and Sodium Carbonate

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

Kim, Sungtae; Marrs, Cassandra; Nemer, Martin

Here, a solubility model is presented for ferrous iron hydroxide (Fe(OH) 2(s)), hibbingite (Fe 2Cl(OH) 3(s)), siderite (FeCO 3(s)), and chukanovite (Fe 2CO 3(OH) 2(s)). The Pitzer activity coefficient equation was utilized in developing the model to account for the excess free energies of aqueous species in the background solutions of high ionic strength. Solubility limiting minerals were analyzed before and after experiments using X-ray diffraction. Formation of Fe(OH) 2(s) was observed in the experiments that were initiated with Fe 2Cl(OH) 3(s) in Na 2SO 4 solution. Coexistence of siderite and chukanovite was observed in the experiments in Na 2COmore » 3 + NaCl solutions. Two equilibrium constants that had been reported by us for the dissolution of Fe(OH) 2(s) and Fe 2Cl(OH) 3(s) (Nemer et al.) were rederived in this paper, using newer thermodynamic data selected from the literature to maintain internal consistency of the series of our data analyses in preparation, including this paper. Three additional equilibrium constants for the following reactions were determined in this paper: dissolution of siderite and chukanovite and dissociation of the aqueous species Fe(CO 3) 2 –2. Five Pitzer interaction parameters were derived in this paper: β (0), β (1), and C φ parameters for the species pair Fe +2/SO 4 –2; β (0) and β (1) parameters for the species pair Na+/Fe(CO3)2–2. Our model predicts that, among the four inorganic ferrous iron minerals, siderite is the stable mineral in two WIPP-related brines (WIPP: Waste Isolation Pilot Plant), i.e., GWB and ERDA6 (Brush and Domski), and the electrochemical equilibrium between elemental iron and siderite provides a low oxygen fugacity (10 –91.2 atm) that can keep the actinides at their lowest oxidation states. (Nemer et al., Brush and Domski; references numbered 1 and 2 in the main text).« less

Solubility Model for Ferrous Iron Hydroxide, Hibbingite, Siderite, and Chukanovite in High Saline Solutions of Sodium Chloride, Sodium Sulfate, and Sodium Carbonate

DOE PAGES

Kim, Sungtae; Marrs, Cassandra; Nemer, Martin; ...

2017-11-20

Here, a solubility model is presented for ferrous iron hydroxide (Fe(OH) 2(s)), hibbingite (Fe 2Cl(OH) 3(s)), siderite (FeCO 3(s)), and chukanovite (Fe 2CO 3(OH) 2(s)). The Pitzer activity coefficient equation was utilized in developing the model to account for the excess free energies of aqueous species in the background solutions of high ionic strength. Solubility limiting minerals were analyzed before and after experiments using X-ray diffraction. Formation of Fe(OH) 2(s) was observed in the experiments that were initiated with Fe 2Cl(OH) 3(s) in Na 2SO 4 solution. Coexistence of siderite and chukanovite was observed in the experiments in Na 2COmore » 3 + NaCl solutions. Two equilibrium constants that had been reported by us for the dissolution of Fe(OH) 2(s) and Fe 2Cl(OH) 3(s) (Nemer et al.) were rederived in this paper, using newer thermodynamic data selected from the literature to maintain internal consistency of the series of our data analyses in preparation, including this paper. Three additional equilibrium constants for the following reactions were determined in this paper: dissolution of siderite and chukanovite and dissociation of the aqueous species Fe(CO 3) 2 –2. Five Pitzer interaction parameters were derived in this paper: β (0), β (1), and C φ parameters for the species pair Fe +2/SO 4 –2; β (0) and β (1) parameters for the species pair Na+/Fe(CO3)2–2. Our model predicts that, among the four inorganic ferrous iron minerals, siderite is the stable mineral in two WIPP-related brines (WIPP: Waste Isolation Pilot Plant), i.e., GWB and ERDA6 (Brush and Domski), and the electrochemical equilibrium between elemental iron and siderite provides a low oxygen fugacity (10 –91.2 atm) that can keep the actinides at their lowest oxidation states. (Nemer et al., Brush and Domski; references numbered 1 and 2 in the main text).« less

Treatment of wastewater containing toxic chromium using new activated carbon developed from date palm seed.

PubMed

El Nemr, Ahmed; Khaled, Azza; Abdelwahab, Ola; El-Sikaily, Amany

2008-03-21

The use of a new activated carbon developed from date palm seed wastes, generated in the jam industry, for removing toxic chromium from aqueous solution has been investigated. The activated carbon has been achieved from date palm seed by dehydrating methods using concentrated sulfuric acid. The batch experiments were conducted to determine the adsorption capacity of the biomass. The effect of initial metal concentration (25-125mgl(-1)), pH, contact time, and concentration of date palm seed carbon have been studied at room temperature. A strong dependence of the adsorption capacity on pH was observed, the capacity increase as pH value decrease and the optimum pH value is pH 1.0. Kinetics and adsorption equilibrium were studied at different sorbent doses. The adsorption process was fast and the equilibrium was reached within 180min. The maximum removal was 100% for 75mgl(-1) of Cr(+ concentration on 4gl(-1) carbon concentration and the maximum adsorption capacity was 120.48mgg(-1). The kinetic data were analyzed using various kinetic models - pseudo-first order equation, pseudo-second order equation, Elovich equation and intraparticle diffusion equation - and the equilibrium data were tested using several isotherm models, Langmuir, Freundlich, Koble-Corrigan, Redlich-Peterson, Tempkin, Dubinin-Radushkevich and Generalized isotherm equations. The Elovich equation and pseudo-second order equation provide the greatest accuracy for the kinetic data and Koble-Corrigan and Langmuir models the closest fit for the equilibrium data. Activation energy of sorption has also been evaluated as 0.115 and 0.229kJmol(-1).

Rates and equilibrium constants of the ligand-induced conformational transition of an HCN ion channel protein domain determined by DEER spectroscopy.

PubMed

Collauto, Alberto; DeBerg, Hannah A; Kaufmann, Royi; Zagotta, William N; Stoll, Stefan; Goldfarb, Daniella

2017-06-14

Ligand binding can induce significant conformational changes in proteins. The mechanism of this process couples equilibria associated with the ligand binding event and the conformational change. Here we show that by combining the application of W-band double electron-electron resonance (DEER) spectroscopy with microfluidic rapid freeze quench (μRFQ) it is possible to resolve these processes and obtain both equilibrium constants and reaction rates. We studied the conformational transition of the nitroxide labeled, isolated carboxy-terminal cyclic-nucleotide binding domain (CNBD) of the HCN2 ion channel upon binding of the ligand 3',5'-cyclic adenosine monophosphate (cAMP). Using model-based global analysis, the time-resolved data of the μRFQ DEER experiments directly provide fractional populations of the open and closed conformations as a function of time. We modeled the ligand-induced conformational change in the protein using a four-state model: apo/open (AO), apo/closed (AC), bound/open (BO), bound/closed (BC). These species interconvert according to AC + L ⇌ AO + L ⇌ BO ⇌ BC. By analyzing the concentration dependence of the relative contributions of the closed and open conformations at equilibrium, we estimated the equilibrium constants for the two conformational equilibria and the open-state ligand dissociation constant. Analysis of the time-resolved μRFQ DEER data gave estimates for the intrinsic rates of ligand binding and unbinding as well as the rates of the conformational change. This demonstrates that DEER can quantitatively resolve both the thermodynamics and the kinetics of ligand binding and the associated conformational change.

Description of the General Equilibrium Model of Ecosystem Services (GEMES)

Treesearch

Travis Warziniack; David Finnoff; Jenny Apriesnig

2017-01-01

This paper serves as documentation for the General Equilibrium Model of Ecosystem Services (GEMES). GEMES is a regional computable general equilibrium model that is composed of values derived from natural capital and ecosystem services. It models households, producing sectors, and governments, linked to one another through commodity and factor markets. GEMES was...

Ammonium stability and nitrogen isotope fractionations for NH4+-NH3(aq)-NH3(gas) systems at 20-70 °C and pH of 2-13: Applications to habitability and nitrogen cycling in low-temperature hydrothermal systems

NASA Astrophysics Data System (ADS)

Li, Long; Lollar, Barbara Sherwood; Li, Hong; Wortmann, Ulrich G.; Lacrampe-Couloume, Georges

2012-05-01

Ammonium/ammonia is an essential nutrient and energy source to support life in oceanic and terrestrial hydrothermal systems. Thus the stability of ammonium is crucial to determine the habitability or ecological structure in hydrothermal environments, but still not well understood. To date, the lack of constraints on nitrogen isotope fractionations between ammonium and ammonia has limited the application of nitrogen isotopes to trace (bio)geochemical processes in such environments. In this study, we carried out laboratory experiments to (1) examine the stability of ammonium in an ammonium sulfate solution under temperature conditions from 20 to 70 °C and pH from 2.1 to 12.6 and (2) determine nitrogen isotope fractionation between ammonium and ammonia. Our experimental results show that ammonium is stable under the experimental temperatures when pH is less than 6. In experiments with starting pH greater than 8, significant ammonium was lost as a result of dissociation of ammonium and degassing of ammonia product. Nitrogen concentrations in the fluids decreased by more than 50% in the first two hours, indicating extremely fast effusion rates of ammonia. This implies that ammonium at high pH fluids (e.g., Lost City Hydrothermal Vents, Oman ophiolite hyperalkaline springs) may not be stable. Habitable environments may be more favorable at the leading edge of a pH gradient toward more acidic conditions, where the fluid can efficiently trap any ammonia transferred from a high pH vent. Although modeling shows that high temperature, low pH hydrothermal vents (e.g., Rainbow hydrothermal vent) may have the capability to retain ammonium, their high temperatures may limit habitability. The habitable zone associated with such a hydrothermal vent is likely at the lower front of a temperature gradient. In contrast, modeling of ammonium in deep terrestrial systems, suggests that saline fracture waters in crystalline rocks such as described in the Canadian Shield and in the Witwatersrand Basin, South Africa may also provide habitable environments for life. The nitrogen isotope results of remaining ammonium from the partial dissociation experiments fit well with a batch equilibrium model, indicating equilibrium nitrogen isotope fractionations have been reached between ammonium and its dissociation product aqueous ammonia. Modeling yielded nitrogen isotope fractionations between ammonium and aqueous ammonia were 45.4‰ at 23 °C, 37.7‰ at 50 °C, and 33.5‰ at 70 °C, respectively. A relationship between nitrogen equilibrium isotope fractionation and temperature is determined for the experimental temperature range as: 103·lnα(aq)=25.94×{103}/{T}-42.25 Integrated with three previous theoretical estimates on nitrogen isotope equilibrium fractionations between ammonium and gaseous ammonia, we achieved three possible temperature-dependent nitrogen isotope equilibrium fractionation between aqueous ammonia and gaseous ammonia:

Towards Non-Equilibrium Dynamics with Trapped Ions

NASA Astrophysics Data System (ADS)

Silbert, Ariel; Jubin, Sierra; Doret, Charlie

2016-05-01

Atomic systems are superbly suited to the study of non-equilibrium dynamics. These systems' exquisite isolation from environmental perturbations leads to long relaxation times that enable exploration of far-from-equilibrium phenomena. One example of particular relevance to experiments in trapped ion quantum information processing, metrology, and precision spectroscopy is the approach to thermal equilibrium of sympathetically cooled linear ion chains. Suitable manipulation of experimental parameters permits exploration of the quantum-to-classical crossover between ballistic transport and diffusive, Fourier's Law conduction, a topic of interest not only to the trapped ion community but also for the development of microelectronic devices and other nanoscale structures. We present progress towards trapping chains of multiple co-trapped calcium isotopes geared towards measuring thermal equilibration and discuss plans for future experiments in non-equilibrium statistical mechanics. This work is supported by Cottrell College Science Award from the Research Corporation for Science Advancement and by Williams College.

Validation of the thermal transport model used for ITER startup scenario predictions with DIII-D experimental data

DOE PAGES

Casper, T. A.; Meyer, W. H.; Jackson, G. L.; ...

2010-12-08

We are exploring characteristics of ITER startup scenarios in similarity experiments conducted on the DIII-D Tokamak. In these experiments, we have validated scenarios for the ITER current ramp up to full current and developed methods to control the plasma parameters to achieve stability. Predictive simulations of ITER startup using 2D free-boundary equilibrium and 1D transport codes rely on accurate estimates of the electron and ion temperature profiles that determine the electrical conductivity and pressure profiles during the current rise. Here we present results of validation studies that apply the transport model used by the ITER team to DIII-D discharge evolutionmore » and comparisons with data from our similarity experiments.« less

Modeling cesium ion exchange on fixed-bed columns of crystalline silicotitanate granules

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

Latheef, I.M.; Huckman, M.E.; Anthony, R.G.

2000-05-01

A mathematical model is presented to simulate Cs exchange in fixed-bed columns of a novel crystalline silicotitanate (CST) material, UOP IONSIV IE-911. A local equilibrium is assumed between the macropores and the solid crystals for the particle material balance. Axial dispersed flow and film mass-transfer resistance are incorporated into the column model. Cs equilibrium isotherms and diffusion coefficients were measured experimentally, and dispersion and film mass-transfer coefficients were estimated from correlations. Cs exchange column experiments were conducted in 5--5.7 M Na solutions and simulated using the proposed model. Best-fit diffusion coefficients from column simulations were compared with previously reported batchmore » values of Gu et al. and Huckman. Cs diffusion coefficients for the column were between 2.5 and 5.0 x 10{sup {minus}11} m{sup 2}/s for 5--5.7 M Na solutions. The effect of the isotherm shape on the Cs diffusion coefficient was investigated. The proposed model provides good fits to experimental data and may be utilized in designing commercial-scale units.« less

Probing leptogenesis

NASA Astrophysics Data System (ADS)

Chun, E. J.; Cvetič, G.; Dev, P. S. B.; Drewes, M.; Fong, C. S.; Garbrecht, B.; Hambye, T.; Harz, J.; Hernández, P.; Kim, C. S.; Molinaro, E.; Nardi, E.; Racker, J.; Rius, N.; Zamora-Saa, J.

2018-02-01

The focus of this paper lies on the possible experimental tests of leptogenesis scenarios. We consider both leptogenesis generated from oscillations, as well as leptogenesis from out-of-equilibrium decays. As the Akhmedov-Rubakov-Smirnov (ARS) mechanism allows for heavy neutrinos in the GeV range, this opens up a plethora of possible experimental tests, e.g. at neutrino oscillation experiments, neutrinoless double beta decay, and direct searches for neutral heavy leptons at future facilities. In contrast, testing leptogenesis from out-of-equilibrium decays is a quite difficult task. We comment on the necessary conditions for having successful leptogenesis at the TeV-scale. We further discuss possible realizations and their model specific testability in extended seesaw models, models with extended gauge sectors, and supersymmetric leptogenesis. Not being able to test high-scale leptogenesis directly, we present a way to falsify such scenarios by focusing on their washout processes. This is discussed specifically for the left-right symmetric model and the observation of a heavy WR, as well as model independently when measuring ΔL = 2 washout processes at the LHC or neutrinoless double beta decay.

Thermal Equilibrium in Plastic and Glass Microscale Containers

ERIC Educational Resources Information Center

Curbelo, Estela; Cerda, Maria F.; Mendez, Eduardo

2007-01-01

The study describes the various thermal equilibrium conditions, which should be taken care for while designing or selecting the plastic and glass microscale containers for physical chemistry experiments. The results show that the thermal equilibrium completely depends on the material of the container for the same volume and thickness.

Dependence of pesticide degradation on sorption: nonequilibrium model and application to soil reactors

NASA Astrophysics Data System (ADS)

Guo, Lei; Jury, William A.; Wagenet, Robert J.; Flury, Markus

2000-04-01

The effect of sorption on degradation of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in a soil amended with various amounts of activated carbon (AC). The relationship between sorption and decay of 2,4-D was analyzed using analytical solutions for equilibrium sorption and to a two-site nonequilibrium adsorption model coupled with two first-order degradation terms for the dissolved and sorbed pesticide, respectively. The sorption parameters in the latter model were determined based on data obtained from batch sorption experiments, while those for degradation were obtained from incubation experiments. The adsorption coefficients, ranging from 0.811 to >315 ml g -1, increased at higher AC, and were negatively related to degradation as measured by the first-order rate constant, implying that degradation is faster from the liquid phase than from the sorbed phase. A nonlinear fit of the decay curves to the nonequilibrium model revealed that degradation rate constants were 0.157 and 0.00243 day -1 for the liquid and sorbed phases, respectively, differing by a factor of 65. Similar results were also obtained using the equilibrium model. A parameter sensitivity analysis of the nonequilibrium model indicates that nonequilibrium sorption will initially favor degradation; however, over the long term, will decrease degradation when desorption kinetics becomes the limiting factor in the degradation process. In the presence of a lag phase that allows appreciable amounts of chemical to diffuse into kinetic sorption sites, nonequilibrium sorption will only impede degradation.

The synthesis and characterization of environmentally-responsive water-swellable and water-soluble polymers for wastewater remediation

NASA Astrophysics Data System (ADS)

Armentrout, Rodney Scott

The primary research goal is the development of new polymeric materials that demonstrate the environmentally-responsive sequestration of common water foulants, including surfactants and oils. Water-swellable and water-soluble polymers have been synthesized, structurally characterized, and their physical properties have been determined. In addition, the ability of the materials to sequester model water foulants has been evaluated. Anionic crosslinked polymer networks of 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylamide, and methylene bisacrylamide have been synthesized and characterized by determining the equilibrium water contents as a function of ionic content of the polymer network. The molar ratio of bound surfactant to ionic group was determined to be less than one for all hydrogels studied, indicating an ion-exchange binding mechanism with minimal hydrophobic interactions between bound and unbound surfactant molecules is responsible for surfactant binding. Cationic crosslinked cyclopolymer networks of N,N-diallyl- N-methyl amine (DAMA) and N,N,N,N-tetraallyl ammonium chloride (TAAC) have been synthesized and characterized by determining the equilibrium water content as a function of pH. A maximum in the equilibrium water content is observed for pH-6 when the polymer is fully ionized. The solubilization of a model water foulant, p-cresol, by the polymeric surfactant, Pluronic F127, has been studied via equilibrium dialysis, dynamic light scattering and ultrafiltration experiments. It has been shown that at 25°C p-cresol is readily solubilized by F127 since the polymeric surfactant exists in a multimer conformation. Ultrafiltration experiments have demonstrated that the polymer-foulant binding interactions are largely unaffected by shear in a hollow fiber membrane. Copolymers of the zwitterionic monomer, 3-(N,N-diallyl- N-methyl ammonio) propane sulfonate (DAMAPS) and N,N-diallyl- N,N-dimethylammonium chloride (DADMAC) (the DADS series) or the pH-responsive hydrophobic monomer, N,N-diallyl-N-methyl amine (DAMA) (the DAMS series) have been prepared in a 0.5 M NaCl aqueous solution using 2-hydroxy-1-[4-(hydroxy-ethoxy)phenyl]-2-methyl-1-propanone (Irgacure 2959) as the free-radical photoinitiator. 13C NMR data indicate that the resulting polymers maintain the five-membered ring structure in the cis conformation common to diallylammonium salts. Equilibrium dialysis experiments demonstrate that pH-responsive hydrophobic microdomain formation may be utilized to control the solubilization of the organic solute, p-cresol. Ultrafiltration experiments have demonstrated that the polymer-foulant binding interactions are largely unaffected by shear in a hollow fiber membrane. Macromolecular aggregates of the poly( N,N-diallyl-N-methyl amine)/p-cresol complexes lead to fouling of the ultrafiltration membrane. However, incorporation of the sulfobetaine moiety hinders the formation of the macroscopic structures and higher permeate flux rates are achieved. (Abstract shortened by UMI.)

Density effects on electronic configurations in dense plasmas

NASA Astrophysics Data System (ADS)

Faussurier, Gérald; Blancard, Christophe

2018-02-01

We present a quantum mechanical model to describe the density effects on electronic configurations inside a plasma environment. Two different approaches are given by starting from a quantum average-atom model. Illustrations are shown for an aluminum plasma in local thermodynamic equilibrium at solid density and at a temperature of 100 eV and in the thermodynamic conditions of a recent experiment designed to characterize the effects of the ionization potential depression treatment. Our approach compares well with experiment and is consistent in that case with the approach of Stewart and Pyatt to describe the ionization potential depression rather than with the method of Ecker and Kröll.

Modeling and Laboratory Investigations of Radiative Shocks

NASA Astrophysics Data System (ADS)

Grun, Jacob; Laming, J. Martin; Manka, Charles; Moore, Christopher; Jones, Ted; Tam, Daniel

2001-10-01

Supernova remnants are often inhomogeneous, with knots or clumps of material expanding in ambient plasma. This structure may be initiated by hydrodynamic instabilities occurring during the explosion, but it may plausibly be amplified by instabilities of the expanding shocks such as, for example, corrugation instabilities described by D’yakov in 1954, Vishniac in 1983, and observed in the laboratory by Grun et al. in 1991. Shock instability can occur when radiation lowers the effective adiabatic index of the gas. In view of the difficulty of modeling radiation in non-equilibrium plasmas, and the dependence of shock instabilities on such radiation, we are performing a laboratory experiment to study radiative shocks. The shocks are generated in a miniature, laser-driven shock tube. The gas density inside the tube at any instant in time is measured using time and space-resolved interferometry, and the emission spectrum of the gas is measured with time-resolved spectroscopy. We simulate the experiment with a 1D code that models time dependent post-shock ionization and non-equilibrium radiative cooling. S. P. D’yakov, Zhurnal Eksperimentalnoi Teoreticheskoi Fiziki 27, 288 (1954); see also section 90 in L.D. Landau and E.M. Lifshitz, Fluid Mechanics (Butterworth-Heinemann 1987); E.T. Vishniac, Astrophys. J. 236, 880 (1983); J. Grun, et al., Phys. Rev. Lett., 66, 2738 (1991)

Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

USGS Publications Warehouse

Rosenbauer, Robert J.; Thomas, Burt; Bischoff, James L.; Palandri, James

2012-01-01

Basaltic rocks are potential repositories for sequestering carbon dioxide (CO2) because of their capacity for trapping CO2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO2-charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO2, an average basaltic MgO content of 8% is equivalent to 2.6 × 108 metric ton CO2/km3 basalt.

Application of zeolite-activated carbon macrocomposite for the adsorption of Acid Orange 7: isotherm, kinetic and thermodynamic studies.

PubMed

Lim, Chi Kim; Bay, Hui Han; Neoh, Chin Hong; Aris, Azmi; Abdul Majid, Zaiton; Ibrahim, Zaharah

2013-10-01

In this study, the adsorption behavior of azo dye Acid Orange 7 (AO7) from aqueous solution onto macrocomposite (MC) was investigated under various experimental conditions. The adsorbent, MC, which consists of a mixture of zeolite and activated carbon, was found to be effective in removing AO7. The MC were characterized by scanning electron microscopy (SEM), energy dispersive X-ray, point of zero charge, and Brunauer-Emmett-Teller surface area analysis. A series of experiments were performed via batch adsorption technique to examine the effect of the process variables, namely, contact time, initial dye concentration, and solution pH. The dye equilibrium adsorption was investigated, and the equilibrium data were fitted to Langmuir, Freundlich, and Tempkin isotherm models. The Langmuir isotherm model fits the equilibrium data better than the Freundlich isotherm model. For the kinetic study, pseudo-first-order, pseudo-second-order, and intraparticle diffusion model were used to fit the experimental data. The adsorption kinetic was found to be well described by the pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process is a spontaneous and endothermic process. The SEM, Fourier transform infrared spectroscopy, ultraviolet-visible spectral and high performance liquid chromatography analysis were carried out before and after the adsorption process. For the phytotoxicity test, treated AO7 was found to be less toxic. Thus, the study indicated that MC has good potential use as an adsorbent for the removal of azo dye from aqueous solution.

Mechanical behavior of cells in microinjection: a minimum potential energy study.

PubMed

Liu, Fei; Wu, Dan; Chen, Ken

2013-08-01

Microinjection is a widely used technique to deliver foreign materials into biological cells. We propose a mathematical model to study the mechanical behavior of a cell in microinjection. Firstly, a cell is modeled by a hyperelastic membrane and interior cytoplasm. Then, based on the fact that the equilibrium configuration of a cell would minimize the potential energy, the energy function during microinjection is analyzed. With Lagrange multiplier and Rayleigh-Ritz technique, we successfully minimize the potential energy and obtain the equilibrium configuration. Upon this model, the injection force, the injection distance, the radius of the microinjector and the membrane stress are studied. The analysis demonstrates that the microinjector radius has a significant influence on the cell mechanical behavior: (1) the larger radius generates larger injection force and larger interior pressure at the same injection distance; (2) the radius determines the place where the membrane is most likely to rupture by governing the membrane stress distribution. For a fine microinjector with radius less than 20% of the cell radius, the most likely rupture point located at the edge of the contact area between the microinjector and the membrane; however, it may move to the middle of the equilibrium configuration as the radius increases. To verify our model, some experiments were conducted on zebrafish egg cells. The results show that the computational analysis agrees with the experimental data, which supports the findings from the theoretical model. Copyright © 2013 Elsevier Ltd. All rights reserved.

Drop-tower experiments for capillary surfaces in an exotic container

NASA Technical Reports Server (NTRS)

Concus, Paul; Finn, Robert; Weislogel, Mark

1991-01-01

Low-gravity drop-tower experiments are carried out for an 'exotic' rotationally-symmetric container, which admits an entire continuum of distinct equilibrium symmetric capillary free surfaces. It is found that an initial equilibrium planer interface, a member of the continuum, will reorient toward a non-symmetric interface, as predicted by recent mathematical theory.

Fluctuation-dissipation relation and stationary distribution of an exactly solvable many-particle model for active biomatter far from equilibrium.

PubMed

Netz, Roland R

2018-05-14

An exactly solvable, Hamiltonian-based model of many massive particles that are coupled by harmonic potentials and driven by stochastic non-equilibrium forces is introduced. The stationary distribution and the fluctuation-dissipation relation are derived in closed form for the general non-equilibrium case. Deviations from equilibrium are on one hand characterized by the difference of the obtained stationary distribution from the Boltzmann distribution; this is possible because the model derives from a particle Hamiltonian. On the other hand, the difference between the obtained non-equilibrium fluctuation-dissipation relation and the standard equilibrium fluctuation-dissipation theorem allows us to quantify non-equilibrium in an alternative fashion. Both indicators of non-equilibrium behavior, i.e., deviations from the Boltzmann distribution and deviations from the equilibrium fluctuation-dissipation theorem, can be expressed in terms of a single non-equilibrium parameter α that involves the ratio of friction coefficients and random force strengths. The concept of a non-equilibrium effective temperature, which can be defined by the relation between fluctuations and the dissipation, is by comparison with the exactly derived stationary distribution shown not to hold, even if the effective temperature is made frequency dependent. The analysis is not confined to close-to-equilibrium situations but rather is exact and thus holds for arbitrarily large deviations from equilibrium. Also, the suggested harmonic model can be obtained from non-linear mechanical network systems by an expansion in terms of suitably chosen deviatory coordinates; the obtained results should thus be quite general. This is demonstrated by comparison of the derived non-equilibrium fluctuation dissipation relation with experimental data on actin networks that are driven out of equilibrium by energy-consuming protein motors. The comparison is excellent and allows us to extract the non-equilibrium parameter α from experimental spectral response and fluctuation data.

Fluctuation-dissipation relation and stationary distribution of an exactly solvable many-particle model for active biomatter far from equilibrium

NASA Astrophysics Data System (ADS)

Netz, Roland R.

2018-05-01

An exactly solvable, Hamiltonian-based model of many massive particles that are coupled by harmonic potentials and driven by stochastic non-equilibrium forces is introduced. The stationary distribution and the fluctuation-dissipation relation are derived in closed form for the general non-equilibrium case. Deviations from equilibrium are on one hand characterized by the difference of the obtained stationary distribution from the Boltzmann distribution; this is possible because the model derives from a particle Hamiltonian. On the other hand, the difference between the obtained non-equilibrium fluctuation-dissipation relation and the standard equilibrium fluctuation-dissipation theorem allows us to quantify non-equilibrium in an alternative fashion. Both indicators of non-equilibrium behavior, i.e., deviations from the Boltzmann distribution and deviations from the equilibrium fluctuation-dissipation theorem, can be expressed in terms of a single non-equilibrium parameter α that involves the ratio of friction coefficients and random force strengths. The concept of a non-equilibrium effective temperature, which can be defined by the relation between fluctuations and the dissipation, is by comparison with the exactly derived stationary distribution shown not to hold, even if the effective temperature is made frequency dependent. The analysis is not confined to close-to-equilibrium situations but rather is exact and thus holds for arbitrarily large deviations from equilibrium. Also, the suggested harmonic model can be obtained from non-linear mechanical network systems by an expansion in terms of suitably chosen deviatory coordinates; the obtained results should thus be quite general. This is demonstrated by comparison of the derived non-equilibrium fluctuation dissipation relation with experimental data on actin networks that are driven out of equilibrium by energy-consuming protein motors. The comparison is excellent and allows us to extract the non-equilibrium parameter α from experimental spectral response and fluctuation data.

Equilibrium and kinetic models for colloid release under transient solution chemistry conditions

USDA-ARS?s Scientific Manuscript database

We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and...

Systematic investigation of NLTE phenomena in the limit of small departures from LTE

NASA Astrophysics Data System (ADS)

Libby, S. B.; Graziani, F. R.; More, R. M.; Kato, T.

1997-04-01

In this paper, we begin a systematic study of Non-Local Thermal Equilibrium (NLTE) phenomena in near equilibrium (LTE) high energy density, highly radiative plasmas. It is shown that the principle of minimum entropy production rate characterizes NLTE steady states for average atom rate equations in the case of small departures form LTE. With the aid of a novel hohlraum-reaction box thought experiment, we use the principles of minimum entropy production and detailed balance to derive Onsager reciprocity relations for the NLTE responses of a near equilibrium sample to non-Planckian perturbations in different frequency groups. This result is a significant symmetry constraint on the linear corrections to Kirchoff's law. We envisage applying our strategy to a number of test problems which include: the NLTE corrections to the ionization state of an ion located near the edge of an otherwise LTE medium; the effect of a monochromatic radiation field perturbation on an LTE medium; the deviation of Rydberg state populations from LTE in recombining or ionizing plasmas; multi-electron temperature models such as that of Busquet; and finally, the effect of NLTE population shifts on opacity models.

Impedance measures in analysis and characterization of multistable structures subjected to harmonic excitation

NASA Astrophysics Data System (ADS)

Harne, Ryan L.; Goodpaster, Benjamin A.

2018-01-01

Structural components susceptible to adverse, post-buckled dynamic behaviors have long challenged the success of applications requiring lightweight, slender curved structures, while researchers have begun to leverage such bistable systems in emerging applications for novel energy attenuation and shape-changing properties. To expedite development and deployment of these built-up platforms containing post-buckled constituents, efficient approaches are required to complement time-consuming full-field models in the prediction of the near- and far-from-equilibrium dynamics. This research meets the need by introducing a semi-analytical model framework to enable the characterization of steady-state responses in multi degree-of-freedom (DOF) and multistable structural systems subjected to harmonic excitation. In so doing, the pathway for assessing impedance measures is created here so as to identify how energy travels and returns within built-up multistable structures. Verified by simulations and qualitatively validated by experiments, the analysis is shown to accurately reproduce both near- and far-from-equilibrium responses including different classes of energetic snap-through dynamics that only exist in such multistable structures. A first look at the impedance measures of different dynamic regimes reveals a connection between damping in multistable structures and the sustainability of far-from-equilibrium oscillations.

Separation of aflatoxin B1 from synthetic physiological fluids using talc and diatomite: Kinetic and isotherm aspects.

PubMed

Sprynskyy, Myroslav; Krzemień-Konieczka, Iwona; Gadzała-Kopciuch, Renata; Buszewski, Bogusław

2018-01-01

The objective of the study was to examine adsorption of the aflatoxin B1 from synthetic gastric fluid and synthetic intestinal fluid by talc, raw and calcined diatomite. The kinetic and equilibrium adsorption processes were studied in the batch adsorption experiments applying high performance liquid chromatography for the aflatoxin B1 determination. The kinetic study showed a very fast adsorption of the aflatoxin B1 onto the selected adsorbents from the both physiological fluids with reaching equilibrium within 1-15min. The aflatoxin B1 was almost completely adsorbed in initial linear step of the kinetic process that can be described well by the zero-order kinetics model. The experimental data of the equilibrium adsorption were characterized using the Langmuir and Freundlich isotherm models. The high adsorption effectiveness was found in a range of 90%-100% and 60%-100% for the diatomite samples and the talc respectively at the initial concentrations of the aflatoxin B1 as 31-300ng/mL. The possible mechanisms of the aflatoxin adsorption onto the used mineral adsorbents are also discussed in the work. Copyright © 2017 Elsevier B.V. All rights reserved.

NON-EQUILIBRIUM HELIUM IONIZATION IN AN MHD SIMULATION OF THE SOLAR ATMOSPHERE

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

Golding, Thomas Peter; Carlsson, Mats; Leenaarts, Jorrit, E-mail: thomas.golding@astro.uio.no, E-mail: mats.carlsson@astro.uio.no, E-mail: jorrit.leenaarts@astro.su.se

The ionization state of the gas in the dynamic solar chromosphere can depart strongly from the instantaneous statistical equilibrium commonly assumed in numerical modeling. We improve on earlier simulations of the solar atmosphere that only included non-equilibrium hydrogen ionization by performing a 2D radiation-magnetohydrodynamics simulation featuring non-equilibrium ionization of both hydrogen and helium. The simulation includes the effect of hydrogen Lyα and the EUV radiation from the corona on the ionization and heating of the atmosphere. Details on code implementation are given. We obtain helium ion fractions that are far from their equilibrium values. Comparison with models with local thermodynamicmore » equilibrium (LTE) ionization shows that non-equilibrium helium ionization leads to higher temperatures in wavefronts and lower temperatures in the gas between shocks. Assuming LTE ionization results in a thermostat-like behavior with matter accumulating around the temperatures where the LTE ionization fractions change rapidly. Comparison of DEM curves computed from our models shows that non-equilibrium ionization leads to more radiating material in the temperature range 11–18 kK, compared to models with LTE helium ionization. We conclude that non-equilibrium helium ionization is important for the dynamics and thermal structure of the upper chromosphere and transition region. It might also help resolve the problem that intensities of chromospheric lines computed from current models are smaller than those observed.« less

Equilibrium statistical-thermal models in high-energy physics

NASA Astrophysics Data System (ADS)

Tawfik, Abdel Nasser

2014-05-01

We review some recent highlights from the applications of statistical-thermal models to different experimental measurements and lattice QCD thermodynamics that have been made during the last decade. We start with a short review of the historical milestones on the path of constructing statistical-thermal models for heavy-ion physics. We discovered that Heinz Koppe formulated in 1948, an almost complete recipe for the statistical-thermal models. In 1950, Enrico Fermi generalized this statistical approach, in which he started with a general cross-section formula and inserted into it, the simplifying assumptions about the matrix element of the interaction process that likely reflects many features of the high-energy reactions dominated by density in the phase space of final states. In 1964, Hagedorn systematically analyzed the high-energy phenomena using all tools of statistical physics and introduced the concept of limiting temperature based on the statistical bootstrap model. It turns to be quite often that many-particle systems can be studied with the help of statistical-thermal methods. The analysis of yield multiplicities in high-energy collisions gives an overwhelming evidence for the chemical equilibrium in the final state. The strange particles might be an exception, as they are suppressed at lower beam energies. However, their relative yields fulfill statistical equilibrium, as well. We review the equilibrium statistical-thermal models for particle production, fluctuations and collective flow in heavy-ion experiments. We also review their reproduction of the lattice QCD thermodynamics at vanishing and finite chemical potential. During the last decade, five conditions have been suggested to describe the universal behavior of the chemical freeze-out parameters. The higher order moments of multiplicity have been discussed. They offer deep insights about particle production and to critical fluctuations. Therefore, we use them to describe the freeze-out parameters and suggest the location of the QCD critical endpoint. Various extensions have been proposed in order to take into consideration the possible deviations of the ideal hadron gas. We highlight various types of interactions, dissipative properties and location-dependences (spatial rapidity). Furthermore, we review three models combining hadronic with partonic phases; quasi-particle model, linear sigma model with Polyakov potentials and compressible bag model.

Economic communication model set

NASA Astrophysics Data System (ADS)

Zvereva, Olga M.; Berg, Dmitry B.

2017-06-01

This paper details findings from the research work targeted at economic communications investigation with agent-based models usage. The agent-based model set was engineered to simulate economic communications. Money in the form of internal and external currencies was introduced into the models to support exchanges in communications. Every model, being based on the general concept, has its own peculiarities in algorithm and input data set since it was engineered to solve the specific problem. Several and different origin data sets were used in experiments: theoretic sets were estimated on the basis of static Leontief's equilibrium equation and the real set was constructed on the basis of statistical data. While simulation experiments, communication process was observed in dynamics, and system macroparameters were estimated. This research approved that combination of an agent-based and mathematical model can cause a synergetic effect.

A single particle model to simulate the dynamics of entangled polymer melts.

PubMed

Kindt, P; Briels, W J

2007-10-07

We present a computer simulation model of polymer melts representing each chain as one single particle. Besides the position coordinate of each particle, we introduce a parameter n(ij) for each pair of particles i and j within a specified distance from each other. These numbers, called entanglement numbers, describe the deviation of the system of ignored coordinates from its equilibrium state for the given configuration of the centers of mass of the polymers. The deviations of the entanglement numbers from their equilibrium values give rise to transient forces, which, together with the conservative forces derived from the potential of mean force, govern the displacements of the particles. We have applied our model to a melt of C(800)H(1602) chains at 450 K and have found good agreement with experiments and more detailed simulations. Properties addressed in this paper are radial distribution functions, dynamic structure factors, and linear as well as nonlinear rheological properties.

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

Choi, Jeong

The research program reported here is focused on critical issues that represent conspicuous gaps in current understanding of rapid solidification, limiting our ability to predict and control microstructural evolution (i.e. morphological dynamics and microsegregation) at high undercooling, where conditions depart significantly from local equilibrium. More specifically, through careful application of phase-field modeling, using appropriate thin-interface and anti-trapping corrections and addressing important details such as transient effects and a velocity-dependent (i.e. adaptive) numerics, the current analysis provides a reasonable simulation-based picture of non-equilibrium solute partitioning and the corresponding oscillatory dynamics associated with single-phase rapid solidification and show that this method ismore » a suitable means for a self-consistent simulation of transient behavior and operating point selection under rapid growth conditions. Moving beyond the limitations of conventional theoretical/analytical treatments of non-equilibrium solute partitioning, these results serve to substantiate recent experimental findings and analytical treatments for single-phase rapid solidification. The departure from the equilibrium solid concentration at the solid-liquid interface was often observed during rapid solidification, and the energetic associated non-equilibrium solute partitioning has been treated in detail, providing possible ranges of interface concentrations for a given growth condition. Use of these treatments for analytical description of specific single-phase dendritic and cellular operating point selection, however, requires a model for solute partitioning under a given set of growth conditions. Therefore, analytical solute trapping models which describe the chemical partitioning as a function of steady state interface velocities have been developed and widely utilized in most of the theoretical investigations of rapid solidification. However, these solute trapping models are not rigorously verified due to the difficulty in experimentally measuring under rapid growth conditions. Moreover, since these solute trapping models include kinetic parameters which are difficult to directly measure from experiments, application of the solute trapping models or the associated analytic rapid solidification model is limited. These theoretical models for steady state rapid solidification which incorporate the solute trapping models do not describe the interdependency of solute diffusion, interface kinetics, and alloy thermodynamics. The phase-field approach allows calculating, spontaneously, the non-equilibrium growth effects of alloys and the associated time-dependent growth dynamics, without making the assumptions that solute partitioning is an explicit function of velocity, as is the current convention. In the research described here, by utilizing the phase-field model in the thin-interface limit, incorporating the anti-trapping current term, more quantitatively valid interface kinetics and solute diffusion across the interface are calculated. In order to sufficiently resolve the physical length scales (i.e. interface thickness and diffusion boundary length), grid spacings are continually adjusted in calculations. The full trajectories of transient planar growth dynamics under rapid directional solidification conditions with different pulling velocities are described. As a validation of a model, the predicted steady state conditions are consistent with the analytic approach for rapid growth. It was confirmed that rapid interface dynamics exhibits the abrupt acceleration of the planar front when the effect of the non-equilibrium solute partitioning at the interface becomes signi ficant. This is consistent with the previous linear stability analysis for the non-equilibrium interface dynamics. With an appropriate growth condition, the continuous oscillation dynamics was able to be simulated using continually adjusting grid spacings. This oscillatory dynamics including instantaneous jump of interface velocities are consistent with a previous phenomenological model by and a numerical investigation, which may cause the formation of banded structures. Additionally, the selection of the steady state growth dynamics in the highly undercooled melt is demonstrated. The transition of the growth morphology, interface velocity selection, and solute trapping phenomenon with increasing melt supersaturations was described by the phase-field simulation. The tip selection for the dendritic growth was consistent with Ivantsov's function, and the non-equilibrium chemical partitioning behavior shows good qualitative agreement with the Aziz's solute trapping model even though the model parameter(V D) remains as an arbitrary constant. This work is able to show the possibility of comprehensive description of rapid alloy growth over the entire time-dependent non-equilibrium phenomenon.« less

Experimental partitioning of rare earth elements and scandium among armalcolite, ilmenite, olivine and mare basalt liquid

NASA Technical Reports Server (NTRS)

Irving, A. J.; Merrill, R. B.; Singleton, D. E.

1978-01-01

An experimental study was carried out to measure partition coefficients for two rare-earth elements (Sm and Tm) and Sc among armalcolite, ilmenite, olivine and liquid coexisting in a system modeled on high-Ti mare basalt 74275. This 'primitive' sample was chosen for study because its major and trace element chemistry as well as its equilibrium phase relations at atmospheric pressure are known from previous studies. Beta-track analytical techniques were used so that partition coefficients could be measured in an environment whose bulk trace element composition is similar to that of the natural basalt. Partition coefficients for Cr and Mn were determined in the same experiments by microprobe analysis. The only equilibrium partial melting model appears to be one in which ilmenite is initially present in the source region but is consumed by melting before segregation of the high-Ti mare basalt liquid from the residue.

Laboratory longitudinal diffusion tests: 1. Dimensionless formulations and validity of simplified solutions

NASA Astrophysics Data System (ADS)

Takeda, M.; Nakajima, H.; Zhang, M.; Hiratsuka, T.

2008-04-01

To obtain reliable diffusion parameters for diffusion testing, multiple experiments should not only be cross-checked but the internal consistency of each experiment should also be verified. In the through- and in-diffusion tests with solution reservoirs, test interpretation of different phases often makes use of simplified analytical solutions. This study explores the feasibility of steady, quasi-steady, equilibrium and transient-state analyses using simplified analytical solutions with respect to (i) valid conditions for each analytical solution, (ii) potential error, and (iii) experimental time. For increased generality, a series of numerical analyses are performed using unified dimensionless parameters and the results are all related to dimensionless reservoir volume (DRV) which includes only the sorptive parameter as an unknown. This means the above factors can be investigated on the basis of the sorption properties of the testing material and/or tracer. The main findings are that steady, quasi-steady and equilibrium-state analyses are applicable when the tracer is not highly sorptive. However, quasi-steady and equilibrium-state analyses become inefficient or impractical compared to steady state analysis when the tracer is non-sorbing and material porosity is significantly low. Systematic and comprehensive reformulation of analytical models enables the comparison of experimental times between different test methods. The applicability and potential error of each test interpretation can also be studied. These can be applied in designing, performing, and interpreting diffusion experiments by deducing DRV from the available information for the target material and tracer, combined with the results of this study.

Dimerization and conformation-related free energy landscapes of dye-tagged amyloid-β12-28 linked to FRET experiments.

PubMed

Kulesza, Alexander; Daly, Steven; Dugourd, Philippe

2017-04-05

We have investigated the free energy landscape of Aβ-peptide dimer models in connection to gas-phase FRET experiments. We use a FRET-related distance coordinate and one conformation-related coordinate per monomer for accelerated structural exploration with well-tempered metadynamics in solvent and in vacuo. The free energy profiles indicate that FRET under equilibrium conditions should be significantly affected by the de-solvation upon the transfer of ions to the gas-phase. In contrast, a change in the protonation state is found to be less impacting once de-solvated. Comparing F19P and WT alloforms, for which we measure different FRET efficiencies in the gas-phase, we predict only the relevant structural differences in the solution populations, not under gas-phase equilibrium conditions. This finding supports the hypothesis that the gas-phase action-FRET measurement after ESI operates under non-equilibrium conditions, with a memory of the solution conditions - even for the dimer of this relatively short peptide. The structural differences in solution are rationalized in terms of conformational propensities around residue 19, which show a transition to a poly-proline type of pattern upon mutation to F19P - a difference that gets lost in the gas-phase.

Capacity withholding in wholesale electricity markets: The experience in England and Wales

NASA Astrophysics Data System (ADS)

Quinn, James Arnold

This thesis examines the incentives wholesale electricity generators face to withhold generating capacity from centralized electricity spot markets. The first chapter includes a brief history of electricity industry regulation in England and Wales and in the United States, including a description of key institutional features of England and Wales' restructured electricity market. The first chapter also includes a review of the literature on both bid price manipulation and capacity bid manipulation in centralized electricity markets. The second chapter details a theoretical model of wholesale generator behavior in a single price electricity market. A duopoly model is specified under the assumption that demand is non-stochastic. This model assumes that duopoly generators offer to sell electricity at their marginal cost, but can withhold a continuous segment of their capacity from the market. The Nash equilibrium withholding strategy of this model involves each duopoly generator withholding so that it produces the Cournot equilibrium output. A monopoly model along the lines of the duopoly model is specified and simulated under the assumption that demand is stochastic. The optimal strategy depends on the degree of demand uncertainty. When there is a moderate degree of demand uncertainty, the optimal withholding strategy involves production inefficiencies. When there is a high degree of demand uncertainty, the optimal monopoly quantity is greater than the optimal output level when demand is non-stochastic. The third chapter contains an empirical examination of the behavior of generators in the wholesale electricity market in England and Wales in the early 1990's. The wholesale market in England and Wales is analyzed because the industry structure in the early 1990's created a natural experiment, which is described in this chapter, whereby one of the two dominant generators had no incentive to behave non-competitively. This chapter develops a classification methodology consistent with the equilibrium identified in the second chapter. The availability of generating units owned by the two dominant generators is analyzed based on this classification system. This analysis includes the use of sample statistics as well as estimates from a dynamic random effects probit model. The analysis suggests a minimal degree of capacity withholding.

Measurement of the equilibrium relative humidity for common precipitant concentrations: facilitating controlled dehydration experiments.

PubMed

Wheeler, Matthew J; Russi, Silvia; Bowler, Michael G; Bowler, Matthew W

2012-01-01

The dehydration of crystals of macromolecules has long been known to have the potential to increase their diffraction quality. A number of methods exist to change the relative humidity that surrounds crystals, but for reproducible results, with complete characterization of the changes induced, a precise humidity-control device coupled with an X-ray source is required. The first step in these experiments is to define the relative humidity in equilibrium with the mother liquor of the system under study; this can often be quite time-consuming. In order to reduce the time spent on this stage of the experiment, the equilibrium relative humidity for a range of concentrations of the most commonly used precipitants has been measured. The relationship between the precipitant solution and equilibrium relative humidity is explained by Raoult's law for the equilibrium vapour pressure of water above a solution. The results also have implications for the choice of cryoprotectant and solutions used to dehydrate crystals. For the most commonly used precipitants (10-30% PEG 2000-8000), the starting point will be a relative humidity of 99.5%. © 2012 International Union of Crystallography. All rights reserved.

Ab Initio Studies of Shock-Induced Chemical Reactions of Inter-Metallics

NASA Astrophysics Data System (ADS)

Zaharieva, Roussislava; Hanagud, Sathya

2009-06-01

Shock-induced and shock assisted chemical reactions of intermetallic mixtures are studied by many researchers, using both experimental and theoretical techniques. The theoretical studies are primarily at continuum scales. The model frameworks include mixture theories and meso-scale models of grains of porous mixtures. The reaction models vary from equilibrium thermodynamic model to several non-equilibrium thermodynamic models. The shock-effects are primarily studied using appropriate conservation equations and numerical techniques to integrate the equations. All these models require material constants from experiments and estimates of transition states. Thus, the objective of this paper is to present studies based on ab initio techniques. The ab inito studies, to date, use ab inito molecular dynamics. This paper presents a study that uses shock pressures, and associated temperatures as starting variables. Then intermetallic mixtures are modeled as slabs. The required shock stresses are created by straining the lattice. Then, ab initio binding energy calculations are used to examine the stability of the reactions. Binding energies are obtained for different strain components super imposed on uniform compression and finite temperatures. Then, vibrational frequencies and nudge elastic band techniques are used to study reactivity and transition states. Examples include Ni and Al.

Laboratory study of low-β forces in arched, line-tied magnetic flux ropes

NASA Astrophysics Data System (ADS)

Myers, C. E.; Yamada, M.; Ji, H.; Yoo, J.; Jara-Almonte, J.; Fox, W.

2016-11-01

The loss-of-equilibrium is a solar eruption mechanism whereby a sudden breakdown of the magnetohydrodynamic force balance in the Sun's corona ejects a massive burst of particles and energy into the heliosphere. Predicting a loss-of-equilibrium, which has more recently been formulated as the torus instability, relies on a detailed understanding of the various forces that hold the pre-eruption magnetic flux rope in equilibrium. Traditionally, idealized analytical force expressions are used to derive simplified eruption criteria that can be compared to solar observations and modeling. What is missing, however, is a validation that these idealized analytical force expressions can be applied to the line-tied, low-aspect-ratio conditions of the corona. In this paper, we address this shortcoming by using a laboratory experiment to study the forces that act on long-lived, arched, line-tied magnetic flux ropes. Three key force terms are evaluated over a wide range of experimental conditions: (1) the upward hoop force; (2) the downward strapping force; and (3) the downward toroidal field tension force. First, the laboratory force measurements show that, on average, the three aforementioned force terms cancel to produce a balanced line-tied equilibrium. This finding validates the laboratory force measurement techniques developed here, which were recently used to identify a dynamic toroidal field tension force that can prevent flux rope eruptions [Myers et al., Nature 528, 526 (2015)]. The verification of magnetic force balance also confirms the low-β assumption that the plasma thermal pressure is negligible in these experiments. Next, the measured force terms are directly compared to corresponding analytical expressions. While the measured and analytical forces are found to be well correlated, the low-aspect-ratio, line-tied conditions in the experiment are found to both reduce the measured hoop force and increase the measured tension force with respect to analytical expectations. These two co-directed effects combine to generate laboratory flux rope equilibria at lower altitudes than are predicted analytically. Such considerations are expected to modify the loss-of-equilibrium eruption criteria for analogous flux ropes in the solar corona.

Laboratory study of low- β forces in arched, line-tied magnetic flux ropes

DOE PAGES

Myers, C. E.; Yamada, M.; Ji, H.; ...

2016-11-04

Here, the loss-of-equilibrium is a solar eruption mechanism whereby a sudden breakdown of the magnetohydrodynamic force balance in the Sun's corona ejects a massive burst of particles and energy into the heliosphere. Predicting a loss-of-equilibrium, which has more recently been formulated as the torus instability, relies on a detailed understanding of the various forces that hold the pre-eruption magnetic flux rope in equilibrium. Traditionally, idealized analytical force expressions are used to derive simplified eruption criteria that can be compared to solar observations and modeling. What is missing, however, is a validation that these idealized analytical force expressions can be appliedmore » to the line-tied, low-aspect-ratio conditions of the corona. In this paper, we address this shortcoming by using a laboratory experiment to study the forces that act on long-lived, arched, line-tied magnetic flux ropes. Three key force terms are evaluated over a wide range of experimental conditions: (1) the upward hoop force; (2) the downward strapping force; and (3) the downward toroidal field tension force. First, the laboratory force measurements show that, on average, the three aforementioned force terms cancel to produce a balanced line-tied equilibrium. This finding validates the laboratory force measurement techniques developed here, which were recently used to identify a dynamic toroidal field tension force that can prevent flux rope eruption. The verification of magnetic force balance also confirms the low-beta assumption that the plasma thermal pressure is negligible in these experiments. Next, the measured force terms are directly compared to corresponding analytical expressions. While the measured and analytical forces are found to be well correlated, the low-aspect-ratio, line-tied conditions in the experiment are found to both reduce the measured hoop force and increase the measured tension force with respect to analytical expectations. These two co-directed effects combine to generate laboratory flux rope equilibria at lower altitudes than are predicted analytically. Such considerations are expected to modify the loss-of-equilibrium eruption criteria for analogous flux ropes in the solar corona.« less

Laboratory study of low- β forces in arched, line-tied magnetic flux ropes

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

Myers, C. E.; Yamada, M.; Ji, H.

Here, the loss-of-equilibrium is a solar eruption mechanism whereby a sudden breakdown of the magnetohydrodynamic force balance in the Sun's corona ejects a massive burst of particles and energy into the heliosphere. Predicting a loss-of-equilibrium, which has more recently been formulated as the torus instability, relies on a detailed understanding of the various forces that hold the pre-eruption magnetic flux rope in equilibrium. Traditionally, idealized analytical force expressions are used to derive simplified eruption criteria that can be compared to solar observations and modeling. What is missing, however, is a validation that these idealized analytical force expressions can be appliedmore » to the line-tied, low-aspect-ratio conditions of the corona. In this paper, we address this shortcoming by using a laboratory experiment to study the forces that act on long-lived, arched, line-tied magnetic flux ropes. Three key force terms are evaluated over a wide range of experimental conditions: (1) the upward hoop force; (2) the downward strapping force; and (3) the downward toroidal field tension force. First, the laboratory force measurements show that, on average, the three aforementioned force terms cancel to produce a balanced line-tied equilibrium. This finding validates the laboratory force measurement techniques developed here, which were recently used to identify a dynamic toroidal field tension force that can prevent flux rope eruption. The verification of magnetic force balance also confirms the low-beta assumption that the plasma thermal pressure is negligible in these experiments. Next, the measured force terms are directly compared to corresponding analytical expressions. While the measured and analytical forces are found to be well correlated, the low-aspect-ratio, line-tied conditions in the experiment are found to both reduce the measured hoop force and increase the measured tension force with respect to analytical expectations. These two co-directed effects combine to generate laboratory flux rope equilibria at lower altitudes than are predicted analytically. Such considerations are expected to modify the loss-of-equilibrium eruption criteria for analogous flux ropes in the solar corona.« less

MINTEQA2

EPA Science Inventory

MINTEQA2 is a equilibrium speciation model that can be used to calculate the equilibrium composition of dilute aqueous solutions in the laboratory or in natural aqueous systems. The model is useful for calculating the equilibrium mass distribution among dissolved species, adsorb...

A Colorful Demonstration to Visualize and Inquire into Essential Elements of Chemical Equilibrium

ERIC Educational Resources Information Center

Eilks, Ingo; Gulacar, Ozcan

2016-01-01

One of the topics that chemistry teachers have a great challenge introducing is chemical equilibrium. When being introduced to chemical equilibrium, many students have difficulties in understanding that some reactions do not go to completion, as this contrasts most of their supposed prior experiences in chemistry lessons. Students may also…

An Initial Non-Equilibrium Porous-Media Model for CFD Simulation of Stirling Regenerators

NASA Technical Reports Server (NTRS)

Tew, Roy C.; Simon, Terry; Gedeon, David; Ibrahim, Mounir; Rong, Wei

2006-01-01

The objective of this paper is to define empirical parameters for an initial thermal non-equilibrium porous-media model for use in Computational Fluid Dynamics (CFD) codes for simulation of Stirling regenerators. The two codes currently used at Glenn Research Center for Stirling modeling are Fluent and CFD-ACE. The codes porous-media models are equilibrium models, which assume solid matrix and fluid are in thermal equilibrium. This is believed to be a poor assumption for Stirling regenerators; Stirling 1-D regenerator models, used in Stirling design, use non-equilibrium regenerator models and suggest regenerator matrix and gas average temperatures can differ by several degrees at a given axial location and time during the cycle. Experimentally based information was used to define: hydrodynamic dispersion, permeability, inertial coefficient, fluid effective thermal conductivity, and fluid-solid heat transfer coefficient. Solid effective thermal conductivity was also estimated. Determination of model parameters was based on planned use in a CFD model of Infinia's Stirling Technology Demonstration Converter (TDC), which uses a random-fiber regenerator matrix. Emphasis is on use of available data to define empirical parameters needed in a thermal non-equilibrium porous media model for Stirling regenerator simulation. Such a model has not yet been implemented by the authors or their associates.

Fractional reactive extraction for symmetrical separation of 4-nitro-D,L-phenylalanine in centrifugal contactor separators: experiments and modeling.

PubMed

Tang, Kewen; Wen, Ping; Zhang, Panliang; Huang, Yan

2015-01-01

The enantioselective liquid-liquid extraction of 4-nitro-D,L-phenylalanine (D,L-Nphy) using PdCl2 {(s)-BINAP} as extractant in dichloroethane was studied experimentally in a countercurrent cascade of 10 centrifugal contactor separators (CCSs) at 5°C, involving flow ratio, extractant concentration, and Cl(-) concentration. The steady-state enantiomeric excess (ee) in both stream exits was 90.86% at a 93.29% yield. The predicted value was modeled using an equilibrium stage approach. The correlation between model and experiment was satisfactory. The model was applied to optimize the production of both enantiomers in >97% ee and >99% ee. 14 stages and 16 stages are required for 97% ee and 99% ee for both enantiomers, respectively. © 2014 Wiley Periodicals, Inc.

Equilibrium Configurations of a Fiber in a Flow

NASA Astrophysics Data System (ADS)

Guerron, Pamela; Berghout, Christopher; Nita, Bogdan; Vaidya, Ashwin

2013-11-01

The aim of this study is to understand the coupled dynamics of flexible fibers in a fluid flow. In particular, we examine the equilibrium configurations of the fiber with changing Reynolds numbers, orientations and lengths of the fiber. Our study is motivated by biological phenomena such as ciliary bending, flexing of plants and trees in winds etc. Our approach to resolving this problem has been threefold: experimental, numerical and theoretical. In our experiments we create physical models of variable length fibers inserted into a basal body structure, which is then suspended in a flow tank and positioned at different angles. The structure (fibers) are subjected to different velocities of water flow, ranging from 0m/s to 0.53 m/s in increments of 0.038 m/s. The results of the experiment were analyzed using Adobe Photoshop and the effect of the above mentioned parameters upon the shape of the fiber is analyzed. In addition, we also simulate this problem using the software Comsol and also create a simple, toy mathematical model incorporating the competing effects of tension and fluid drag on the fiber to obtain a closed form expression. Our various approaches point to consistent results.

DSMC Shock Simulation of Saturn Entry Probe Conditions

NASA Technical Reports Server (NTRS)

Higdon, Kyle J.; Cruden, Brett A.; Brandis, Aaron; Liechty, Derek S.; Goldstein, David B.; Varghese, Philip L.

2016-01-01

This work describes the direct simulation Monte Carlo (DSMC) investigation of Saturn entry probe scenarios and the influence of non-equilibrium phenomena on Saturn entry conditions. The DSMC simulations coincide with rarefied hypersonic shock tube experiments of a hydrogen-helium mixture performed in the Electric Arc Shock Tube (EAST) at NASA Ames Research Center. The DSMC simulations are post-processed through the NEQAIR line-by-line radiation code to compare directly to the experimental results. Improved collision cross-sections, inelastic collision parameters, and reaction rates are determined for a high temperature DSMC simulation of a 7-species H2-He mixture and an electronic excitation model is implemented in the DSMC code. Simulation results for 27.8 and 27.4 kms shock waves are obtained at 0.2 and 0.1 Torr respectively and compared to measured spectra in the VUV, UV, visible, and IR ranges. These results confirm the persistence of non-equilibrium for several centimeters behind the shock and the diffusion of atomic hydrogen upstream of the shock wave. Although the magnitude of the radiance did not match experiments and an ionization inductance period was not observed in the simulations, the discrepancies indicated where improvements are needed in the DSMC and NEQAIR models.

DSMC Shock Simulation of Saturn Entry Probe Conditions

NASA Technical Reports Server (NTRS)

Higdon, Kyle J.; Cruden, Brett A.; Brandis, Aaron M.; Liechty, Derek S.; Goldstein, David B.; Varghese, Philip L.

2016-01-01

This work describes the direct simulation Monte Carlo (DSMC) investigation of Saturn entry probe scenarios and the influence of non-equilibrium phenomena on Saturn entry conditions. The DSMC simulations coincide with rarefied hypersonic shock tube experiments of a hydrogen-helium mixture performed in the Electric Arc Shock Tube (EAST) at the NASA Ames Research Center. The DSMC simulations are post-processed through the NEQAIR line-by-line radiation code to compare directly to the experimental results. Improved collision cross-sections, inelastic collision parameters, and reaction rates are determined for a high temperature DSMC simulation of a 7-species H2-He mixture and an electronic excitation model is implemented in the DSMC code. Simulation results for 27.8 and 27.4 km/s shock waves are obtained at 0.2 and 0.1 Torr, respectively, and compared to measured spectra in the VUV, UV, visible, and IR ranges. These results confirm the persistence of non-equilibrium for several centimeters behind the shock and the diffusion of atomic hydrogen upstream of the shock wave. Although the magnitude of the radiance did not match experiments and an ionization inductance period was not observed in the simulations, the discrepancies indicated where improvements are needed in the DSMC and NEQAIR models.

Equilibrium between Different Coordination Geometries in Oxidovanadium(IV) Complexes

ERIC Educational Resources Information Center

Ugone, Valeria; Garribba, Eugenio; Micera, Giovanni; Sanna, Daniele

2015-01-01

In this laboratory activity, the equilibrium between square pyramidal and octahedral V(IV)O[superscript 2+] complexes is described. We propose a set of experiments to synthesize and characterize two types of V(IV)O[superscript 2+] complexes. The experiment allows great flexibility and may be effectively used at a variety of levels and the activity…

Utilization of a Microcomputer for the Study of an Iodine Oxidation and Equilibrium Reaction: A Physical Chemistry Experiment.

ERIC Educational Resources Information Center

Julien, L. M.

1984-01-01

Describes a physical chemistry experiment which incorporates the use of a microcomputer to enhance understanding of combined kinetic and equilibrium phenomena, to increase experimental capabilities when working with large numbers of students and limited equipment, and for the student to develop a better understanding of experimental design. (JN)

Viscous dewetting of metastable liquid films on substrates with microgrooves.

PubMed

Kim, Taehong; Kim, Wonjung

2018-06-15

We present a combined experimental and theoretical investigation of dewetting on substrates with parallel microgrooves. A thin, static liquid film has an equilibrium thickness so as to minimize the sum of the surface free energy and the gravitational potential energy. When the thickness of a liquid film is less than the equilibrium thickness, the film seeks the equilibrium through contraction of the wetted area, which is referred to as dewetting. We experimentally observed the dewetting of thin, metastable liquid films on substrates with parallel microgrooves. The experiments revealed that the films retract in the direction along the grooves and leaves liquid residues with various morphologies. We classify the residue morphologies into three modes and elucidate the dependence of the mode selection on the groove geometry and the equilibrium contact angle of the liquid. We also experimentally examined the dynamic motion of the receding contact lines of the dewetting films, and developed a mechanical model for the receding speed. Our results provide a basis for controlling liquid films using microstructures, which is useful for lubricant-impregnated surface production, painting, spray cooling, and surface cleaning. Copyright © 2018 Elsevier Inc. All rights reserved.

Competitive Abilities in Experimental Microcosms Are Accurately Predicted by a Demographic Index for R*

PubMed Central

Murrell, Ebony G.; Juliano, Steven A.

2012-01-01

Resource competition theory predicts that R*, the equilibrium resource amount yielding zero growth of a consumer population, should predict species' competitive abilities for that resource. This concept has been supported for unicellular organisms, but has not been well-tested for metazoans, probably due to the difficulty of raising experimental populations to equilibrium and measuring population growth rates for species with long or complex life cycles. We developed an index (Rindex) of R* based on demography of one insect cohort, growing from egg to adult in a non-equilibrium setting, and tested whether Rindex yielded accurate predictions of competitive abilities using mosquitoes as a model system. We estimated finite rate of increase (λ′) from demographic data for cohorts of three mosquito species raised with different detritus amounts, and estimated each species' Rindex using nonlinear regressions of λ′ vs. initial detritus amount. All three species' Rindex differed significantly, and accurately predicted competitive hierarchy of the species determined in simultaneous pairwise competition experiments. Our Rindex could provide estimates and rigorous statistical comparisons of competitive ability for organisms for which typical chemostat methods and equilibrium population conditions are impractical. PMID:22970128

Adsorption equilibrium and kinetics of monomer-dimer monoclonal antibody mixtures on a cation exchange resin.

PubMed

Reck, Jason M; Pabst, Timothy M; Hunter, Alan K; Wang, Xiangyang; Carta, Giorgio

2015-07-10

Adsorption equilibrium and kinetics are determined for a monoclonal antibody (mAb) monomer and dimer species, individually and in mixtures, on a macroporous cation exchange resin both under the dilute limit of salt gradient elution chromatography and at high protein loads and low salt based on batch adsorption equilibrium and confocal laser scanning microscopy (CLSM) experiments. In the dilute limit and weak binding conditions, the dimer/monomer selectivity in 10mM phosphate at pH 7 varies between 8.7 and 2.3 decreasing with salt concentration in the range of 170-230mM NaCl. At high protein loads and strong binding conditions (0-60mM NaCl), the selectivity in the same buffer is near unity with no NaCl added, but increases gradually with salt concentration reaching high values between 2 and 15 with 60mM added NaCl. For these conditions, the two-component adsorption kinetics is controlled by pore diffusion and is predicted approximately by a dual shrinking core model using parameters based on single component equilibrium and kinetics measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

Consequences of Molecular-Scale Non-Equilibrium Activity on the Dynamics and Mechanics of Self-Assembled Actin-Based Structures and Materials

NASA Astrophysics Data System (ADS)

Marshall Mccall, Patrick

Living cells are hierarchically self-organized forms of active soft matter: molecules on the nanometer scale form functional structures and organelles on the micron scale, which then compose cells on the scale of 10s of microns. While the biological functions of intracellular organelles are defined by the composition and properties of the structures themselves, how those bulk properties emerge from the properties and interactions of individual molecules remains poorly understood. Actin, a globular protein which self-assembles into dynamic semi-flexible polymers, is the basic structural material of cells and the major component of many functional organelles. In this thesis, I have used purified actin as a model system to explore the interplay between molecular-scale dynamics and organelle-scale functionality, with particular focus on the role of molecular-scale non-equilibrium activity. One of the most canonical forms of molecular-scale non-equilibrium activity is that of mechanoenzymes, also called motor proteins. These proteins utilized the free energy liberated by hydrolysis of ATP to perform mechanical work, thereby introducing non-equilibrium "active" stresses on the molecular scale. Combining experiments with mathematical modeling, we demonstrate in this thesis that non-equilibrium motor activity is sufficient to drive self-organization and pattern formation of the multimeric actin-binding motor protein Myosin II on 1D reconstituted actomyosin bundles. Like myosin, actin is itself an ATPase. However, nono-equilibrium ATP hydrolysis on actin is known to regulate the stability and assembly kinetics of actin filaments rather than generate active stresses per se. At the level of single actin filaments, the inhomogeneous nucleotide composition generated along the filament length by hydrolysis directs binding of regulatory proteins like cofilin, which mediate filament disassembly and thereby accelerate actin filament turnover. The concequences of this non-equilibrium turnover on the steady-state properties of collections of filaments remained unclear. Here, I reconstituted tunable, non-equilibrium actin turnover dynamics in entangled solutions of actin filaments as a model of the actin cortex of living cells. We found that this non-equilibrium turnover decouples solution mechanics from microstructure, enabling structurally indistinguishable materials to behave effectively as either viscous fluids or elastic gels. Additionally, we employed computer simulations to identify the dynamical regime in which actin turnover controls the effective viscosity of 2D cross-linked actin networks in the presence of motors. Additionally, I examine in this thesis the localization and self-assembly of actin filaments in condensed liquid phases called polyelectrolyte coacervates as a model membrane-less organelle. We find that concentration of actin through spontaneous partitioning preferentially to the coacervate phase accelerates the assembly of filaments. These filaments then localize to the coacervate-bulk interface, generating particles with visco-elastic shells surrounding liquid cores. In this case, the properties of the condensed phase enable regulation of actin assembly dynamics.

An experimental study of the Online Information Paradox: Does en-route information improve road network performance?

PubMed

Wijayaratna, Kasun P; Dixit, Vinayak V; Denant-Boemont, Laurent; Waller, S Travis

2017-01-01

This study investigates the empirical presence of a theoretical transportation paradox, defined as the "Online Information Paradox" (OIP). The paradox suggests that, for certain road networks, the provision of online information deteriorate travel conditions for all users of that network relative to the situation where no online information is provided to users. The analytical presence of the paradox was derived for a specific network structure by using two equilibrium models, the first being the Expected User Equilibrium (EUE) solution (no information scenario) and the other being the User Equilibrium with Recourse (UER) solution (with information scenario). An incentivised computerised route choice game was designed using the concepts of experimental economics and administered in a controlled laboratory environment to investigate the physical presence of the paradox. Aggregate statistics of path flows and Total System Travel Costs (TSTC) were used to compare the experimental results with the theoretical findings. A total of 12 groups of 12 participants completed the experiment and the OIP and the occurrence of the OIP being significant was observed in 11 of the 12 cases. Though information increased travel costs for users on average, it reduced the volatility of travel costs experienced in the no information scenario indicating that information can achieve a more reliable system. Further replications of similar experiments and more importantly field based identification of the phenomena will force transport professionals to be aware of the emergence of the paradox. In addition, studies such as this emphasise the need for the adoption of adaptive traffic assignment techniques to appropriately model the acquisition of information on a road network.

Shape-retainment control using an antagonistic shape memory alloy system

NASA Astrophysics Data System (ADS)

Ikeda, T.; Sawamura, K.; Senba, A.; Tamayama, M.

2015-04-01

Since shape memory alloy (SMA) actuators can generate large force per unit weight, they are expected as one of the next generation actuators for aircraft. To keep a position of conventional control surfaces or morphing wings with SMA actuators, the SMA actuators must keep being heated, and the heating energy is not small. To save the energy, a new control method proposed for piezoelectric actuators utilizing hysteresis in deformation [Ikeda and Takahashi, Proc. SPIE 8689 (2013), 86890C] is applied to an antagonistic SMA system. By using the control method any position can be an equilibrium point within hysteresis of stress-strain diagrams. To confirm a feasibility of the control method, a fundamental experiment is performed. The SMA wires are heated by applying electric current to the wires. When a pulsed current is applied to the two SMA wires alternately, the equilibrium position changes between two positions alternately, and when a series of pulse whose amplitude increases gradually is applied to one SMA wire, the equilibrium position changes like a staircase. However, just after the pulse the position returns slightly, that is, overshoot takes place. To investigate such a behavior of the system, numerical simulation is also performed. The one-dimensional phase transformation model [Ikeda, Proc. SPIE 5757 (2005), 344-352] is used for a constitutive model of the SMA wires. The simulated result agrees with the experiment qualitatively, including the overshoot. By examining volume fraction of each phase, it is found that the overshoot is caused by that austenite phase transforms into stress-induced martensite phase during the cooling process after the pulse.

Numerical treatment of free surface problems in ferrohydrodynamics

NASA Astrophysics Data System (ADS)

Lavrova, O.; Matthies, G.; Mitkova, T.; Polevikov, V.; Tobiska, L.

2006-09-01

The numerical treatment of free surface problems in ferrohydrodynamics is considered. Starting from the general model, special attention is paid to field-surface and flow-surface interactions. Since in some situations these feedback interactions can be partly or even fully neglected, simpler models can be derived. The application of such models to the numerical simulation of dissipative systems, rotary shaft seals, equilibrium shapes of ferrofluid drops, and pattern formation in the normal-field instability of ferrofluid layers is given. Our numerical strategy is able to recover solitary surface patterns which were discovered recently in experiments.

Gypsum-wallboard formaldehyde-sorption model

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

Silberstein, S.

1989-11-01

Gypsum wallboard was shown to absorb formaldehyde in a prototype house and in a measuring chamber, as reported previously by researchers at Oak Ridge National Laboratory (ORNL). Also as reported previously, formaldehyde concentrations attained equilibrium in two phases in response to a change in the air exchange rate or to the removal of the formaldehyde source. A rapid initial phase was followed by a slow phase lasting several days. A formaldehyde sorption model that accounts for the biphasic concentration pattern is presented here. Experiments for testing the predictability of the model are proposed.

Parametric Symmetry Breaking in a Nonlinear Resonator

NASA Astrophysics Data System (ADS)

Leuch, Anina; Papariello, Luca; Zilberberg, Oded; Degen, Christian L.; Chitra, R.; Eichler, Alexander

2016-11-01

Much of the physical world around us can be described in terms of harmonic oscillators in thermodynamic equilibrium. At the same time, the far-from-equilibrium behavior of oscillators is important in many aspects of modern physics. Here, we investigate a resonating system subject to a fundamental interplay between intrinsic nonlinearities and a combination of several driving forces. We have constructed a controllable and robust realization of such a system using a macroscopic doubly clamped string. We experimentally observe a hitherto unseen double hysteresis in both the amplitude and the phase of the resonator's response function and present a theoretical model that is in excellent agreement with the experiment. Our work unveils that the double hysteresis is a manifestation of an out-of-equilibrium symmetry breaking between parametric phase states. Such a fundamental phenomenon, in the most ubiquitous building block of nature, paves the way for the investigation of new dynamical phases of matter in parametrically driven many-body systems and motivates applications ranging from ultrasensitive force detection to low-energy computing memory units.

On the Morphology of a Growing City: A Heuristic Experiment Merging Static Economics with Dynamic Geography

PubMed Central

Delloye, Justin; Peeters, Dominique; Thomas, Isabelle

2015-01-01

In this paper, we aim at exploring how individual location decisions affect the shape of a growing city and, more precisely, how they may add up to a configuration that diverges from equilibrium configurations formulated ex-ante. To do so, we provide a two-sector city model merging a static equilibrium analysis with agent-based simulations. Results show that under strong agglomeration effects, urban development is monotonic and ends up with circular, monocentric long-term configurations. For low agglomeration effects however, elongated and multicentric urban configurations may emerge. The occurrence and underlying dynamics of these configurations are also discussed regarding commuting costs and the distance-decay of agglomeration economies between firms. To sum up, our paper warns urban planning policy makers against the difference that may stand between appropriate long-term perspectives, represented here by analytic equilibrium configurations, and short-term urban configurations, simulated here by a multi-agent system. PMID:26308858

Analyzing slowly exchanging protein conformations by ion mobility mass spectrometry: study of the dynamic equilibrium of prolyl oligopeptidase.

PubMed

López, Abraham; Vilaseca, Marta; Madurga, Sergio; Varese, Monica; Tarragó, Teresa; Giralt, Ernest

2016-07-01

Ion mobility mass spectrometry (IMMS) is a biophysical technique that allows the separation of isobaric species on the basis of their size and shape. The high separation capacity, sensitivity and relatively fast time scale measurements confer IMMS great potential for the study of proteins in slow (µs-ms) conformational equilibrium in solution. However, the use of this technique for examining dynamic proteins is still not generalized. One of the major limitations is the instability of protein ions in the gas phase, which raises the question as to what extent the structures detected reflect those in solution. Here, we addressed this issue by analyzing the conformational landscape of prolyl oligopeptidase (POP) - a model of a large dynamic enzyme in the µs-ms range - by native IMMS and compared the results obtained in the gas phase with those obtained in solution. In order to interpret the experimental results, we used theoretical simulations. In addition, the stability of POP gaseous ions was explored by charge reduction and collision-induced unfolding experiments. Our experiments disclosed two species of POP in the gas phase, which correlated well with the open and closed conformations in equilibrium in solution; moreover, a gas-phase collapsed form of POP was also detected. Therefore, our findings not only support the potential of IMMS for the study of multiple co-existing conformations of large proteins in slow dynamic equilibrium in solution but also stress the need for careful data analysis to avoid artifacts. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Experiments with a Regional Vector-Vorticity Model, and Comparison with Other Models

NASA Astrophysics Data System (ADS)

Konor, C. S.; Dazlich, D. A.; Jung, J.; Randall, D. A.

2017-12-01

The Vector-Vorticity Model (VVM) is an anelastic model with a unique dynamical core that predicts the three-dimensional vorticity instead of the three-dimensional momentum. The VVM is used in the CRMs of the Global Quasi-3D Multiscale Modeling Framework, which is discussed by Joon-Hee Jung and collaborators elsewhere in this session. We are updating the physics package of the VVM, replacing it with the physics package of the System for Atmosphere Modeling (SAM). The new physics package includes a double-moment microphysics, Mellor-Yamada turbulence, Monin-Obukov surface fluxes, and the RRTMG radiation parameterization. We briefly describe the VVM and show results from standard test cases, including TWP-ICE. We compare the results with those obtained using the earlier physics. We also show results from experiments on convection aggregation in radiative-convective equilibrium, and compare with those obtained using both SAM and the Regional Atmospheric Modeling System (RAMS).

Treatment of radioactive liquid waste (Co-60) by sorption on Zeolite Na-A prepared from Iraqi kaolin.

PubMed

Mustafa, Yasmen A; Zaiter, Maysoon J

2011-11-30

Iraqi synthetic zeolite type Na-A has been suggested as ion exchange material to treat cobalt-60 in radioactive liquid waste which came from neutron activation for corrosion products. Batch experiments were conducted to find out the equilibrium isotherm for source sample. The equilibrium isotherm for radioactive cobalt in the source sample showed unfavorable type, while the equilibrium isotherm for the total cobalt (the radioactive and nonradioactive cobalt) in the source sample showed a favorable type. The ability of Na-A zeolite to remove cobalt from wastewater was checked for high cobalt concentration (822 mg/L) in addition to low cobalt concentration in the source sample (0.093 mg/L). A good fitting for the experimental data with Langmuir equilibrium model was observed. Langmuir constant qm which is related to monolayer adsorption capacity for low and high cobalt concentration was determined to be 0.021 and 140 mg/g(zeolite). The effects of important design variables on the zeolite column performance were studied these include initial concentration, flow rate, and bed depth. The experimental results have shown that high sorption capacity can be obtained at high influent concentration, low flow rate, and high bed depth. Higher column performance was obtained at higher bed depth. Thomas model was employed to predict the breakthrough carves for the above variables. A good fitting was observed with correlation coefficients between 0.915 and 0.985. Copyright © 2011 Elsevier B.V. All rights reserved.

An Initial Non-Equilibrium Porous-Media Model for CFD Simulation of Stirling Regenerators

NASA Technical Reports Server (NTRS)

Tew, Roy; Simon, Terry; Gedeon, David; Ibrahim, Mounir; Rong, Wei

2006-01-01

The objective of this paper is to define empirical parameters (or closwre models) for an initial thermai non-equilibrium porous-media model for use in Computational Fluid Dynamics (CFD) codes for simulation of Stirling regenerators. The two CFD codes currently being used at Glenn Research Center (GRC) for Stirling engine modeling are Fluent and CFD-ACE. The porous-media models available in each of these codes are equilibrium models, which assmne that the solid matrix and the fluid are in thermal equilibrium at each spatial location within the porous medium. This is believed to be a poor assumption for the oscillating-flow environment within Stirling regenerators; Stirling 1-D regenerator models, used in Stirling design, we non-equilibrium regenerator models and suggest regenerator matrix and gas average temperatures can differ by several degrees at a given axial location end time during the cycle. A NASA regenerator research grant has been providing experimental and computational results to support definition of various empirical coefficients needed in defining a noa-equilibrium, macroscopic, porous-media model (i.e., to define "closure" relations). The grant effort is being led by Cleveland State University, with subcontractor assistance from the University of Minnesota, Gedeon Associates, and Sunpower, Inc. Friction-factor and heat-transfer correlations based on data taken with the NASAlSunpower oscillating-flow test rig also provide experimentally based correlations that are useful in defining parameters for the porous-media model; these correlations are documented in Gedeon Associates' Sage Stirling-Code Manuals. These sources of experimentally based information were used to define the following terms and parameters needed in the non-equilibrium porous-media model: hydrodynamic dispersion, permeability, inertial coefficient, fluid effective thermal conductivity (including themal dispersion and estimate of tortuosity effects}, and fluid-solid heat transfer coefficient. Solid effective thermal conductivity (including the effect of tortuosity) was also estimated. Determination of the porous-media model parameters was based on planned use in a CFD model of Infinia's Stirling Technology Demonstration Convertor (TDC), which uses a random-fiber regenerator matrix. The non-equilibrium porous-media model presented is considered to be an initial, or "draft," model for possible incorporation in commercial CFD codes, with the expectation that the empirical parameters will likely need to be updated once resulting Stirling CFD model regenerator and engine results have been analyzed. The emphasis of the paper is on use of available data to define empirical parameters (and closure models) needed in a thermal non-equilibrium porous-media model for Stirling regenerator simulation. Such a model has not yet been implemented by the authors or their associates. However, it is anticipated that a thermal non-equilibrium model such as that presented here, when iacorporated in the CFD codes, will improve our ability to accurately model Stirling regenerators with CFD relative to current thermal-equilibrium porous-media models.

A Viscoelastic Constitutive Model Can Accurately Represent Entire Creep Indentation Tests of Human Patella Cartilage

PubMed Central

Pal, Saikat; Lindsey, Derek P.; Besier, Thor F.; Beaupre, Gary S.

2013-01-01

Cartilage material properties provide important insights into joint health, and cartilage material models are used in whole-joint finite element models. Although the biphasic model representing experimental creep indentation tests is commonly used to characterize cartilage, cartilage short-term response to loading is generally not characterized using the biphasic model. The purpose of this study was to determine the short-term and equilibrium material properties of human patella cartilage using a viscoelastic model representation of creep indentation tests. We performed 24 experimental creep indentation tests from 14 human patellar specimens ranging in age from 20 to 90 years (median age 61 years). We used a finite element model to reproduce the experimental tests and determined cartilage material properties from viscoelastic and biphasic representations of cartilage. The viscoelastic model consistently provided excellent representation of the short-term and equilibrium creep displacements. We determined initial elastic modulus, equilibrium elastic modulus, and equilibrium Poisson’s ratio using the viscoelastic model. The viscoelastic model can represent the short-term and equilibrium response of cartilage and may easily be implemented in whole-joint finite element models. PMID:23027200

Retention and Migration of Chlorpyrifos in Aquatic Sediments and Soils

NASA Astrophysics Data System (ADS)

Gebremariam, S. Y.; Beutel, M.; Yonge, D.; Flury, M.; Harsh, J. B.

2010-12-01

The accurate description of the fate and transport of potentially toxic agricultural pesticides in sediments and soils is of great interest to environmental scientists and regulators. Of particular concern is the widely documented detection of agricultural pesticides and their byproducts in drinking water wells. This presentation discusses results of a study of the fate and transport of chlorpyrifos, a strongly hydrophobic organophosphate-pesticide, in sediments and soils collected from a range of aquatic environments. Using radio-labeled chlorpyrifos, this study is unique in its comprehensive nature and focus on aquatic sediments, for which studies involving pesticide fate and transport are limited. Study components include: (1) batch equilibrium experiments to evaluate sorption/desorption parameters; (2) kinetic and non-equilibrium sorption experiments using miniaturized flow-cells; (3) column experiments to understand patterns of pesticide break through; and (4) numerical modeling of chlorpyrifos transport through aquatic sediments and soils. Initial results show that chlorpyrifos sorption, when corrected for reversible sorption to container walls, exhibited two component sorption, a large irreversible fraction and a smaller reversible fraction that can act as a secondary source. In addition, of a wide range of soil parameters measured, organic carbon content exhibited the highest correlation with chlorpyrifos retention in cranberry field soils. Simulation models developed in this study, which account for hysteretic and nonlinear sorption, will help to better predict the fate of chlorpyrifos and other hydrophobic chemicals in sediments and soils.

A study of pH-dependent photodegradation of amiloride by a multivariate curve resolution approach to combined kinetic and acid-base titration UV data.

PubMed

De Luca, Michele; Ioele, Giuseppina; Mas, Sílvia; Tauler, Romà; Ragno, Gaetano

2012-11-21

Amiloride photostability at different pH values was studied in depth by applying Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) to the UV spectrophotometric data from drug solutions exposed to stressing irradiation. Resolution of all degradation photoproducts was possible by simultaneous spectrophotometric analysis of kinetic photodegradation and acid-base titration experiments. Amiloride photodegradation showed to be strongly dependent on pH. Two hard modelling constraints were sequentially used in MCR-ALS for the unambiguous resolution of all the species involved in the photodegradation process. An amiloride acid-base system was defined by using the equilibrium constraint, and the photodegradation pathway was modelled taking into account the kinetic constraint. The simultaneous analysis of photodegradation and titration experiments revealed the presence of eight different species, which were differently distributed according to pH and time. Concentration profiles of all the species as well as their pure spectra were resolved and kinetic rate constants were estimated. The values of rate constants changed with pH and under alkaline conditions the degradation pathway and photoproducts also changed. These results were compared to those obtained by LC-MS analysis from drug photodegradation experiments. MS analysis allowed the identification of up to five species and showed the simultaneous presence of more than one acid-base equilibrium.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Biosorption of metal ions from aqueous solutions

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

Chen, Jiaping; Yiacoumi, Sotira

1997-01-01

Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role inmore » the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.« less

In sæcula sæculorum: A lab activity to create with students a radioactive secular equilibrium model⋆

NASA Astrophysics Data System (ADS)

Santostasi, D.

2017-03-01

The teaching of radioactivity in the high school is often difficult to implement, especially from an experimental point of view. In this paper an activity based on a laboratory experiment on radioactivity is presented. The activity was proposed to high school students in their fourth year of studies attending the summer internship organized by the University of Pavia at the Department of Physics. The experiement concerns the radon decay chain, and in particular the measurement of the activity of 214Bi , both in absence and in presence of its progenitor 222Rn . This way it is possible to observe two different decay curves: the first provides a 214Bi decay constant in agreement with the theoretical one, whereas the trend of the second one can be understood only through the hypothesis of secular equilibrium with 222Rn . Using an engaging and interesting game with dice, a model of radioactive decay was developed and performed with students divided in small groups.

Kinetic modeling of particle dynamics in H- negative ion sources (invited)

NASA Astrophysics Data System (ADS)

Hatayama, A.; Shibata, T.; Nishioka, S.; Ohta, M.; Yasumoto, M.; Nishida, K.; Yamamoto, T.; Miyamoto, K.; Fukano, A.; Mizuno, T.

2014-02-01

Progress in the kinetic modeling of particle dynamics in H- negative ion source plasmas and their comparisons with experiments are reviewed, and discussed with some new results. Main focus is placed on the following two topics, which are important for the research and development of large negative ion sources and high power H- ion beams: (i) Effects of non-equilibrium features of EEDF (electron energy distribution function) on H- production, and (ii) extraction physics of H- ions and beam optics.

Test of bootstrap current models using high- β p EAST-demonstration plasmas on DIII-D

DOE PAGES

Ren, Qilong; Lao, Lang L.; Garofalo, Andrea M.; ...

2015-01-12

Magnetic measurements together with kinetic profile and motional Stark effect measurements are used in full kinetic equilibrium reconstructions to test the Sauter and NEO bootstrap current models in a DIII-D high-more » $${{\\beta}_{\\text{p}}}$$ EAST-demonstration experiment. This aims at developing on DIII-D a high bootstrap current scenario to be extended on EAST for a demonstration of true steady-state at high performance and uses EAST-similar operational conditions: plasma shape, plasma current, toroidal magnetic field, total heating power and current ramp-up rate. It is found that the large edge bootstrap current in these high-$${{\\beta}_{\\text{p}}}$$ plasmas allows the use of magnetic measurements to clearly distinguish the two bootstrap current models. In these high collisionality and high-$${{\\beta}_{\\text{p}}}$$ plasmas, the Sauter model overpredicts the peak of the edge current density by about 30%, while the first-principle kinetic NEO model is in close agreement with the edge current density of the reconstructed equilibrium. Furthermore, these results are consistent with recent work showing that the Sauter model largely overestimates the edge bootstrap current at high collisionality.« less

Tropical Convection and Climate Processes in a Cumulus Ensemble Model

NASA Technical Reports Server (NTRS)

Sui, Chung-Hsiung

1999-01-01

Local convective-radiative equilibrium states of the tropical atmosphere are determined by the following external forcing: 1) Insolation, 2) Surface heat and moisture exchanges (primarily radiation and evaporation), 3) Heating and moistening induced by large-scale circulation. Understanding the equilibrium states of the tropical atmosphere in different external forcing conditions is of vital importance for studying cumulus parameterization, climate feedbacks, and climate changes. We extend our previous study using the Goddard Cumulus Ensemble (GCE) Model which resolves convective-radiative processes more explicitly than global climate models do. Several experiments are carried out under fixed insolation and sea surface temperature. The prescribed SST consists of a uniform warm pool (29C) surrounded by uniform cold SST (26C). The model produces "Walker"-type circulation with the ascending branch of the model atmosphere more humid than the descending part, but the vertically integrated temperature does not show a horizontal gradient. The results are compared with satellite measured moisture by SSM/I (Special Sensor Microwave/Imager) and temperature by MSU in the ascending and descending tropical atmosphere. The vertically integrated temperature and humidity in the two model regimes are comparable to the observed values in the tropics.

Numerical approach on dynamic self-assembly of colloidal particles

NASA Astrophysics Data System (ADS)

Ibrahimi, Muhamet; Ilday, Serim; Makey, Ghaith; Pavlov, Ihor; Yavuz, Özgàn; Gulseren, Oguz; Ilday, Fatih Omer

Far from equilibrium systems of artificial ensembles are crucial for understanding many intelligent features in self-organized natural systems. However, the lack of established theory underlies a need for numerical implementations. Inspired by a novel work, we simulate a solution-suspended colloidal system that dynamically self assembles due to convective forces generated in the solvent when heated by a laser. In order to incorporate with random fluctuations of particles and continuously changing flow, we exploit a random-walk based Brownian motion model and a fluid dynamics solver prepared for games, respectively. Simulation results manage to fit to experiments and show many quantitative features of a non equilibrium dynamic self assembly, including phase space compression and an ensemble-energy input feedback loop.

Non-equilibrium processes in ash-laden volcanic plumes: new insights from 3D multiphase flow simulations

NASA Astrophysics Data System (ADS)

Esposti Ongaro, Tomaso; Cerminara, Matteo

2016-10-01

In the framework of the IAVCEI (International Association of Volcanology and Chemistry of the Earth Interior) initiative on volcanic plume models intercomparison, we discuss three-dimensional numerical simulations performed with the multiphase flow model PDAC (Pyroclastic Dispersal Analysis Code). The model describes the dynamics of volcanic and atmospheric gases (in absence of wind) and two pyroclastic phases by adopting a non-equilibrium Eulerian-Eulerian formulation. Accordingly, gas and particulate phases are treated as interpenetrating fluids, interacting with each other through momentum (drag) and heat exchange. Numerical results describe the time-wise and spatial evolution of weak (mass eruption rate: 1.5 × 106 kg/s) and strong (mass eruption rate: 1.5 × 109 kg/s) plumes. The two tested cases display a remarkably different phenomenology, associated with the different roles of atmospheric stratification, compressibility and mechanism of buoyancy reversal, reflecting in a different structure of the plume, of the turbulent eddies and of the atmospheric circulation. This also brings about different rates of turbulent mixing and atmospheric air entrainment. The adopted multiphase flow model allows to quantify temperature and velocity differences between the gas and particles, including settling, preferential concentration by turbulence and thermal non-equilibrium, as a function of their Stokes number, i.e., the ratio between their kinetic equilibrium time and the characteristic large-eddy turnover time of the turbulent plume. As a result, the spatial and temporal distribution of coarse ash in the atmosphere significantly differs from that of the fine ash, leading to a modification of the plume shape. Finally, three-dimensional numerical results have been averaged in time and across horizontal slices in order to obtain a one-dimensional picture of the plume in a stationary regime. For the weak plume, the results are consistent with one-dimensional models, at least in the buoyant plume region, and allow to reckon a variable, effective entrainment coefficient with a mean value around 0.1 (consistently with laboratory experiments). For the strong plume, analysis of the results reveals that the two most critical assumptions of one-dimensional integral models are the self-similarity and the pressure equilibrium. In such a case, the plume appears to be controlled by the dynamics in the jet stage (below the buoyancy reversal) and by mesoscale vorticity associated with the development of the umbrella.

Swelling equilibrium of dentin adhesive polymers formed on the water-adhesive phase boundary: Experiments and micromechanical model

PubMed Central

Misra, Anil; Parthasarathy, Ranganathan; Ye, Qiang; Singh, Viraj; Spencer, Paulette

2013-01-01

During their application to the wet, oral environment, dentin adhesives can experience phase separation and composition change which can compromise the quality of the hybrid layer formed at the dentin-adhesive interface. The chemical composition of polymer phases formed in the hybrid layer can be represented using a ternary water-adhesive phase diagram. In this paper, these polymer phases have been characterized using a suite of mechanical tests and swelling experiments. The experimental results were evaluated using granular micromechanics based model that incorporates poro-mechanical effects and polymer-solvent thermodynamics. The variation of the model parameters and model-predicted polymer properties has been studied as a function of composition along the phase boundary. The resulting structure-property correlations provide insight into interactions occurring at the molecular level in the saturated polymer system. These correlations can be used for modeling the mechanical behavior of hybrid layer, and are expected to aid in the design and improvement of water-compatible dentin adhesive polymers. PMID:24076070

Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments.

PubMed

Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

2015-01-01

In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0-2.2 M) than the formation of the native state (0-1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7-2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin.

Equilibrium of Global Amphibian Species Distributions with Climate

PubMed Central

Munguía, Mariana; Rahbek, Carsten; Rangel, Thiago F.; Diniz-Filho, Jose Alexandre F.; Araújo, Miguel B.

2012-01-01

A common assumption in bioclimatic envelope modeling is that species distributions are in equilibrium with contemporary climate. A number of studies have measured departures from equilibrium in species distributions in particular regions, but such investigations were never carried out for a complete lineage across its entire distribution. We measure departures of equilibrium with contemporary climate for the distributions of the world amphibian species. Specifically, we fitted bioclimatic envelopes for 5544 species using three presence-only models. We then measured the proportion of the modeled envelope that is currently occupied by the species, as a metric of equilibrium of species distributions with climate. The assumption was that the greater the difference between modeled bioclimatic envelope and the occupied distribution, the greater the likelihood that species distribution would not be at equilibrium with contemporary climate. On average, amphibians occupied 30% to 57% of their potential distributions. Although patterns differed across regions, there were no significant differences among lineages. Species in the Neotropic, Afrotropics, Indo-Malay, and Palaearctic occupied a smaller proportion of their potential distributions than species in the Nearctic, Madagascar, and Australasia. We acknowledge that our models underestimate non equilibrium, and discuss potential reasons for the observed patterns. From a modeling perspective our results support the view that at global scale bioclimatic envelope models might perform similarly across lineages but differently across regions. PMID:22511938

Predicting RNA folding thermodynamics with a reduced chain representation model

PubMed Central

CAO, SONG; CHEN, SHI-JIE

2005-01-01

Based on the virtual bond representation for the nucleotide backbone, we develop a reduced conformational model for RNA. We use the experimentally measured atomic coordinates to model the helices and use the self-avoiding walks in a diamond lattice to model the loop conformations. The atomic coordinates of the helices and the lattice representation for the loops are matched at the loop–helix junction, where steric viability is accounted for. Unlike the previous simplified lattice-based models, the present virtual bond model can account for the atomic details of realistic three-dimensional RNA structures. Based on the model, we develop a statistical mechanical theory for RNA folding energy landscapes and folding thermodynamics. Tests against experiments show that the theory can give much more improved predictions for the native structures, the thermal denaturation curves, and the equilibrium folding/unfolding pathways than the previous models. The application of the model to the P5abc region of Tetrahymena group I ribozyme reveals the misfolded intermediates as well as the native-like intermediates in the equilibrium folding process. Moreover, based on the free energy landscape analysis for each and every loop mutation, the model predicts five lethal mutations that can completely alter the free energy landscape and the folding stability of the molecule. PMID:16251382

Spread of Ebola disease with susceptible exposed infected isolated recovered (SEIIhR) model

NASA Astrophysics Data System (ADS)

Azizah, Afina; Widyaningsih, Purnami; Retno Sari Saputro, Dewi

2017-06-01

Ebola is a deadly infectious disease and has caused an epidemic on several countries in West Africa. Mathematical modeling to study the spread of Ebola disease has been developed, including through models susceptible infected removed (SIR) and susceptible exposed infected removed (SEIR). Furthermore, susceptible exposed infected isolated recovered (SEIIhR) model has been derived. The aims of this research are to derive SEIIhR model for Ebola disease, to determine the patterns of its spread, to determine the equilibrium point and stability of the equilibrium point using phase plane analysis, and also to apply the SEIIhR model on Ebola epidemic in Sierra Leone in 2014. The SEIIhR model is a differential equation system. Pattern of ebola disease spread with SEIIhR model is solution of the differential equation system. The equilibrium point of SEIIhR model is unique and it is a disease-free equilibrium point that stable. Application of the model is based on the data Ebola epidemic in Sierra Leone. The free-disease equilibrium point (Se; Ee; Ie; Ihe; Re )=(5743865, 0, 0, 0, 0) is stable.

Wall ablation of heated compound-materials into non-equilibrium discharge plasmas

NASA Astrophysics Data System (ADS)

Wang, Weizong; Kong, Linghan; Geng, Jinyue; Wei, Fuzhi; Xia, Guangqing

2017-02-01

The discharge properties of the plasma bulk flow near the surface of heated compound-materials strongly affects the kinetic layer parameters modeled and manifested in the Knudsen layer. This paper extends the widely used two-layer kinetic ablation model to the ablation controlled non-equilibrium discharge due to the fact that the local thermodynamic equilibrium (LTE) approximation is often violated as a result of the interaction between the plasma and solid walls. Modifications to the governing set of equations, to account for this effect, are derived and presented by assuming that the temperature of the electrons deviates from that of the heavy particles. The ablation characteristics of one typical material, polytetrafluoroethylene (PTFE) are calculated with this improved model. The internal degrees of freedom as well as the average particle mass and specific heat ratio of the polyatomic vapor, which strongly depends on the temperature, pressure and plasma non-equilibrium degree and plays a crucial role in the accurate determination of the ablation behavior by this model, are also taken into account. Our assessment showed the significance of including such modifications related to the non-equilibrium effect in the study of vaporization of heated compound materials in ablation controlled arcs. Additionally, a two-temperature magneto-hydrodynamic (MHD) model accounting for the thermal non-equilibrium occurring near the wall surface is developed and applied into an ablation-dominated discharge for an electro-thermal chemical launch device. Special attention is paid to the interaction between the non-equilibrium plasma and the solid propellant surface. Both the mass exchange process caused by the wall ablation and plasma species deposition as well as the associated momentum and energy exchange processes are taken into account. A detailed comparison of the results of the non-equilibrium model with those of an equilibrium model is presented. The non-equilibrium results show a non-equilibrium region near the plasma-wall interaction region and this indicates the need for the consideration of the influence of the possible departure from LTE in the plasma bulk on the determination of ablation rate.

Evaporation in equilibrium, in vacuum, and in hydrogen gas

NASA Technical Reports Server (NTRS)

Nagahara, Hiroko

1993-01-01

Evaporation experiments were conducted for SiO2 in three different conditions: in equilibrium, in vacuum, and in hydrogen gas. Evaporation rate in vacuum is about two orders of magnitude smaller than that in equilibrium, which is consistent with previous works. The rate in hydrogen gas changes depending on hydrogen pressure. The rate at 10 exp -7 bar of hydrogen pressure is as small as that of free evaporation, but at 10 exp -5 bar of hydrogen pressure it is larger than that in equilibrium. In equilibrium and in vacuum, the evaporation rate is limited by decomposition of SiO2 on the crystal surface, but it is limited by a diffusion process for evaporation in hydrogen gas. Therefore, evaporation rate of minerals in the solar nebula can be shown neither by that in equilibrium nor by that in vacuum. The maximum temperature of the solar nebula at the midplane at 2-3 AU where chondrites are believed to have originated is calculated to be as low as 150 K, 1500 K, or in between them. The temperature is, in any case, not high enough for total evaporation of the interstellar materials. Therefore, evaporation of interstellar materials is one of the most important processes for the origin and fractionation of solid materials. The fundamental process of evaporation of minerals has been intensively studied for these several years. Those experiments were carried out either in equilibrium or in vacuum; however, evaporation in the solar nebula is in hydrogen (and much smaller amount of helium) gas. In order to investigate evaporation rate and compositional (including isotopic) fractionation during evaporation, vaporization experiments for various minerals in various conditions are conducted. At first, SiO2 was adopted for a starting material, because thermochemical data and its nature of congruent vaporization are well known. Experiments were carried out in a vacuum furnace system.

Rapid determination of molar mass in modified Archibald experiments using direct fitting of the Lamm equation.

PubMed

Schuck, P; Millar, D B

1998-05-15

A new method is described that allows measurement of the molar mass of the solute within 15 to 30 min after start of a conventional long-column sedimentation equilibrium experiment. A series of scans of the concentration distribution in close vicinity of the meniscus, taken in rapid succession after the start of the centrifuge run, is analyzed by direct fitting using the Lamm equation and the Svedberg equation. In case of a single solute, this analysis of the initial depletion at the meniscus reveals its buoyant molar mass and sedimentation coefficient with an accuracy of approximately 10% and provides gross information about sample heterogeneity. This method can be used to study macromolecules that do not possess the prolonged stability needed in conventional sedimentation equilibrium experiments and it can increase the efficiency of sedimentation equilibrium experiments of previously uncharacterized samples.

Transitions between multiple equilibria of paleo climate: a glimpse in to the dynamics of abrupt climate change

NASA Astrophysics Data System (ADS)

Ferreira, David; Marshall, John; Ito, Takamitsu; McGee, David; Moreno-Chamarro, Eduardo

2017-04-01

The dynamics regulating large climatic transitions such as glacial-interglacial cycles or DO events remains a puzzle. Forcings behind these transitions are not robustly identified and potential candidates (e.g. Milankovitch cycles, freshwater perturbations) often appear too weak to explain such dramatic transitions. A potential solution to this long-standing puzzle is that Earth's climate is endowed with multiple equilibrium states of global extent. Such states are commonly found in low-order or conceptual climate models, but it is unclear whether a system as complex as Earth's climate can sustain multiple equilibrium states. Here we report that multiple equilibrium states of the climate system are also possible in a complex, fully dynamical coupled ocean-atmosphere-sea ice GCM with idealized Earth-like geometry, resolved weather systems and a hydrological cycle. In our model, two equilibrium states coexist for the same parameters and external forcings: a Warm climate with a small Northern hemisphere sea ice cap and a large southern one and a Cold climate with large ice caps at both poles. The dynamical states of the Warm and Cold solutions exhibit striking similarities with our present-day climate and the climate of the Last Glacial Maximum, respectively. A carbon cycle model driven by the two dynamical states produces an atmospheric pCO2 draw-down of about 110 pm between the Warm and Cold states, close to Glacial-Interglacial differences found in ice cores. Mechanism controlling the existence of the multiple states and changes in the atmospheric CO2 will be briefly presented. Finally we willdescribe transition experiments from the Cold to the Warm state, focusing on the lead-lags in the system, notably between the Northern and Southern Hemispheres climates.

Validation of a coupled core-transport, pedestal-structure, current-profile and equilibrium model

NASA Astrophysics Data System (ADS)

Meneghini, O.

2015-11-01

The first workflow capable of predicting the self-consistent solution to the coupled core-transport, pedestal structure, and equilibrium problems from first-principles and its experimental tests are presented. Validation with DIII-D discharges in high confinement regimes shows that the workflow is capable of robustly predicting the kinetic profiles from on axis to the separatrix and matching the experimental measurements to within their uncertainty, with no prior knowledge of the pedestal height nor of any measurement of the temperature or pressure. Self-consistent coupling has proven to be essential to match the experimental results, and capture the non-linear physics that governs the core and pedestal solutions. In particular, clear stabilization of the pedestal peeling ballooning instabilities by the global Shafranov shift and destabilization by additional edge bootstrap current, and subsequent effect on the core plasma profiles, have been clearly observed and documented. In our model, self-consistency is achieved by iterating between the TGYRO core transport solver (with NEO and TGLF for neoclassical and turbulent flux), and the pedestal structure predicted by the EPED model. A self-consistent equilibrium is calculated by EFIT, while the ONETWO transport package evolves the current profile and calculates the particle and energy sources. The capabilities of such workflow are shown to be critical for the design of future experiments such as ITER and FNSF, which operate in a regime where the equilibrium, the pedestal, and the core transport problems are strongly coupled, and for which none of these quantities can be assumed to be known. Self-consistent core-pedestal predictions for ITER, as well as initial optimizations, will be presented. Supported by the US Department of Energy under DE-FC02-04ER54698, DE-SC0012652.

Exploring the anisotropic Kondo model in and out of equilibrium with alkaline-earth atoms

NASA Astrophysics Data System (ADS)

Kanász-Nagy, Márton; Ashida, Yuto; Shi, Tao; Moca, Cǎtǎlin Paşcu; Ikeda, Tatsuhiko N.; Fölling, Simon; Cirac, J. Ignacio; Zaránd, Gergely; Demler, Eugene A.

2018-04-01

We propose a scheme to realize the Kondo model with tunable anisotropy using alkaline-earth atoms in an optical lattice. The new feature of our setup is Floquet engineering of interactions using time-dependent Zeeman shifts, that can be realized either using state-dependent optical Stark shifts or magnetic fields. The properties of the resulting Kondo model strongly depend on the anisotropy of the ferromagnetic interactions. In particular, easy-plane couplings give rise to Kondo singlet formation even though microscopic interactions are all ferromagnetic. We discuss both equilibrium and dynamical properties of the system that can be measured with ultracold atoms, including the impurity spin susceptibility, the impurity spin relaxation rate, as well as the equilibrium and dynamical spin correlations between the impurity and the ferromagnetic bath atoms. We analyze the nonequilibrium time evolution of the system using a variational non-Gaussian approach, which allows us to explore coherent dynamics over both short and long timescales, as set by the bandwidth and the Kondo singlet formation, respectively. In the quench-type experiments, when the Kondo interaction is suddenly switched on, we find that real-time dynamics shows crossovers reminiscent of poor man's renormalization group flow used to describe equilibrium systems. For bare easy-plane ferromagnetic couplings, this allows us to follow the formation of the Kondo screening cloud as the dynamics crosses over from ferromagnetic to antiferromagnetic behavior. On the other side of the phase diagram, our scheme makes it possible to measure quantum corrections to the well-known Korringa law describing the temperature dependence of the impurity spin relaxation rate. Theoretical results discussed in our paper can be measured using currently available experimental techniques.

Effect of Electron Energy Distribution on the Hysteresis of Plasma Discharge: Theory, Experiment, and Modeling.

PubMed

Lee, Hyo-Chang; Chung, Chin-Wook

2015-10-20

Hysteresis, which is the history dependence of physical systems, is one of the most important topics in physics. Interestingly, bi-stability of plasma with a huge hysteresis loop has been observed in inductive plasma discharges. Despite long plasma research, how this plasma hysteresis occurs remains an unresolved question in plasma physics. Here, we report theory, experiment, and modeling of the hysteresis. It was found experimentally and theoretically that evolution of the electron energy distribution (EED) makes a strong plasma hysteresis. In Ramsauer and non-Ramsauer gas experiments, it was revealed that the plasma hysteresis is observed only at high pressure Ramsauer gas where the EED deviates considerably from a Maxwellian shape. This hysteresis was presented in the plasma balance model where the EED is considered. Because electrons in plasmas are usually not in a thermal equilibrium, this EED-effect can be regarded as a universal phenomenon in plasma physics.

Effect of Electron Energy Distribution on the Hysteresis of Plasma Discharge: Theory, Experiment, and Modeling

PubMed Central

Lee, Hyo-Chang; Chung, Chin-Wook

2015-01-01

Hysteresis, which is the history dependence of physical systems, is one of the most important topics in physics. Interestingly, bi-stability of plasma with a huge hysteresis loop has been observed in inductive plasma discharges. Despite long plasma research, how this plasma hysteresis occurs remains an unresolved question in plasma physics. Here, we report theory, experiment, and modeling of the hysteresis. It was found experimentally and theoretically that evolution of the electron energy distribution (EED) makes a strong plasma hysteresis. In Ramsauer and non-Ramsauer gas experiments, it was revealed that the plasma hysteresis is observed only at high pressure Ramsauer gas where the EED deviates considerably from a Maxwellian shape. This hysteresis was presented in the plasma balance model where the EED is considered. Because electrons in plasmas are usually not in a thermal equilibrium, this EED-effect can be regarded as a universal phenomenon in plasma physics. PMID:26482650

Sir Fred Hoyle and the theory of the synthesis of the elements

NASA Astrophysics Data System (ADS)

Arnett, David

Some of Fred Hoyle's pioneering ideas about the site and the nature of the synthesis of the elements are examined in a modern context of theory, experiment and observations. Hoyle's ideas concerning the nucleosynthesis cycle of stellar birth and death, rotational instability of supernovae, the onion-skin model of presupernovae, neutronization, nuclear statistical equilibrium and core collapse, thermonuclear supernovae, nucleosynthesis processes and freeze-out are discussed. The history of the clash of theory and experiment on the second excited state of 8Be and helium ignition in red giants is reviewed.

Ageing dynamics of a superspin glass

NASA Astrophysics Data System (ADS)

Svante Andersson, Mikael; De Toro, Jose Angel; Lee, Su Seong; Mathieu, Roland; Nordblad, Per

2014-10-01

Magnetization dynamics of a model superspin glass system consisting of nearly monodispersed close-packed maghemite particles of diameter 8 nm is investigated. The observed non-equilibrium features of the dynamics are qualitatively similar to those of atomic spin glass systems. The intrinsic relaxation function, as observed in zero-field-cooled magnetization relaxation experiments, depends on the time the sample has been kept at constant temperature (ageing). Accompanying low-field experiments show that the archetypal spin glass characteristics —ageing, memory and rejuvenation— are reproduced in this dense system of dipolar-dipolar interacting superspins.

Adsorption laboratory experiment for undergraduate chemical engineering: Introducing kinetic, equilibrium and thermodynamic concepts

NASA Astrophysics Data System (ADS)

Muryanto, S.; Djatmiko Hadi, S.

2016-11-01

Adsorption laboratory experiment for undergraduate chemical engineering program is discussed. The experiment demonstrated adsorption of copper ions commonly found in wastewater using bio-sorbent, i.e. agricultural wastes. The adsorption was performed in a batch mode under various parameters: adsorption time (up to 120 min), initial pH (2 to 6), adsorbent dose (2.0 to 12.0 g L-1), adsorbent size (50 to 170 mesh), initial Cu2+ concentration (25 to 100 ppm) and temperatures (room temp to 40°C). The equilibrium and kinetic data of the experiments were calculated using the two commonly used isotherms: Langmuir and Lagergren pseudo-first-order kinetics. The maximum adsorption capacity for Cu2+ was found as 94.34 mg g-1. Thermodynamically, the adsorption process was spontaneous and endothermic. The calculated activation energy for the adsorption was observed as high as 127.94 kJ mol-1. Pedagogically, the experiment was assumed to be important in increasing student understanding of kinetic, equilibrium and thermodynamic concepts.

Equilibrium Conformations of Concentric-tube Continuum Robots

PubMed Central

Rucker, D. Caleb; Webster, Robert J.; Chirikjian, Gregory S.; Cowan, Noah J.

2013-01-01

Robots consisting of several concentric, preshaped, elastic tubes can work dexterously in narrow, constrained, and/or winding spaces, as are commonly found in minimally invasive surgery. Previous models of these “active cannulas” assume piecewise constant precurvature of component tubes and neglect torsion in curved sections of the device. In this paper we develop a new coordinate-free energy formulation that accounts for general preshaping of an arbitrary number of component tubes, and which explicitly includes both bending and torsion throughout the device. We show that previously reported models are special cases of our formulation, and then explore in detail the implications of torsional flexibility for the special case of two tubes. Experiments demonstrate that this framework is more descriptive of physical prototype behavior than previous models; it reduces model prediction error by 82% over the calibrated bending-only model, and 17% over the calibrated transmissional torsion model in a set of experiments. PMID:25125773

Models of supply function equilibrium with applications to the electricity industry

NASA Astrophysics Data System (ADS)

Aromi, J. Daniel

Electricity market design requires tools that result in a better understanding of incentives of generators and consumers. Chapter 1 and 2 provide tools and applications of these tools to analyze incentive problems in electricity markets. In chapter 1, models of supply function equilibrium (SFE) with asymmetric bidders are studied. I prove the existence and uniqueness of equilibrium in an asymmetric SFE model. In addition, I propose a simple algorithm to calculate numerically the unique equilibrium. As an application, a model of investment decisions is considered that uses the asymmetric SFE as an input. In this model, firms can invest in different technologies, each characterized by distinct variable and fixed costs. In chapter 2, option contracts are introduced to a supply function equilibrium (SFE) model. The uniqueness of the equilibrium in the spot market is established. Comparative statics results on the effect of option contracts on the equilibrium price are presented. A multi-stage game where option contracts are traded before the spot market stage is considered. When contracts are optimally procured by a central authority, the selected profile of option contracts is such that the spot market price equals marginal cost for any load level resulting in a significant reduction in cost. If load serving entities (LSEs) are price takers, in equilibrium, there is no trade of option contracts. Even when LSEs have market power, the central authority's solution cannot be implemented in equilibrium. In chapter 3, we consider a game in which a buyer must repeatedly procure an input from a set of firms. In our model, the buyer is able to sign long term contracts that establish the likelihood with which the next period contract is awarded to an entrant or the incumbent. We find that the buyer finds it optimal to favor the incumbent, this generates more intense competition between suppliers. In a two period model we are able to completely characterize the optimal mechanism.

Equilibrium points, stability and numerical solutions of fractional-order predator-prey and rabies models

NASA Astrophysics Data System (ADS)

Ahmed, E.; El-Sayed, A. M. A.; El-Saka, H. A. A.

2007-01-01

In this paper we are concerned with the fractional-order predator-prey model and the fractional-order rabies model. Existence and uniqueness of solutions are proved. The stability of equilibrium points are studied. Numerical solutions of these models are given. An example is given where the equilibrium point is a centre for the integer order system but locally asymptotically stable for its fractional-order counterpart.

Magnetospheric equilibrium configurations and slow adiabatic convection

NASA Technical Reports Server (NTRS)

Voigt, Gerd-Hannes

1986-01-01

This review paper demonstrates how the magnetohydrostatic equilibrium (MHE) theory can be used to describe the large-scale magnetic field configuration of the magnetosphere and its time evolution under the influence of magnetospheric convection. The equilibrium problem is reviewed, and levels of B-field modelling are examined for vacuum models, quasi-static equilibrium models, and MHD models. Results from two-dimensional MHE theory as they apply to the Grad-Shafranov equation, linear equilibria, the asymptotic theory, magnetospheric convection and the substorm mechanism, and plasma anisotropies are addressed. Results from three-dimensional MHE theory are considered as they apply to an intermediate analytical magnetospheric model, magnetotail configurations, and magnetopause boundary conditions and the influence of the IMF.

Examples of equilibrium and non-equilibrium behavior in evolutionary systems

NASA Astrophysics Data System (ADS)

Soulier, Arne

With this thesis, we want to shed some light into the darkness of our understanding of simply defined statistical mechanics systems and the surprisingly complex dynamical behavior they exhibit. We will do so by presenting in turn one equilibrium and then one non-equilibrium system with evolutionary dynamics. In part 1, we will present the seceder-model, a newly developed system that cannot equilibrate. We will then study several properties of the system and obtain an idea of the richness of the dynamics of the seceder model, which is particular impressive given the minimal amount of modeling necessary in its setup. In part 2, we will present extensions to the directed polymer in random media problem on a hypercube and its connection to the Eigen model of evolution. Our main interest will be the influence of time-dependent and time-independent changes in the fitness landscape viewed by an evolving population. This part contains the equilibrium dynamics. The stochastic models and the topic of evolution and non-equilibrium in general will allow us to point out similarities to the various lines of thought in game theory.

Evaluating Status Change of Soil Potassium from Path Model

PubMed Central

He, Wenming; Chen, Fang

2013-01-01

The purpose of this study is to determine critical environmental parameters of soil K availability and to quantify those contributors by using a proposed path model. In this study, plot experiments were designed into different treatments, and soil samples were collected and further analyzed in laboratory to investigate soil properties influence on soil potassium forms (water soluble K, exchangeable K, non-exchangeable K). Furthermore, path analysis based on proposed path model was carried out to evaluate the relationship between potassium forms and soil properties. Research findings were achieved as followings. Firstly, key direct factors were soil S, ratio of sodium-potassium (Na/K), the chemical index of alteration (CIA), Soil Organic Matter in soil solution (SOM), Na and total nitrogen in soil solution (TN), and key indirect factors were Carbonate (CO3), Mg, pH, Na, S, and SOM. Secondly, path model can effectively determine direction and quantities of potassium status changes between Exchangeable potassium (eK), Non-exchangeable potassium (neK) and water-soluble potassium (wsK) under influences of specific environmental parameters. In reversible equilibrium state of , K balance state was inclined to be moved into β and χ directions in treatments of potassium shortage. However in reversible equilibrium of , K balance state was inclined to be moved into θ and λ directions in treatments of water shortage. Results showed that the proposed path model was able to quantitatively disclose moving direction of K status and quantify its equilibrium threshold. It provided a theoretical and practical basis for scientific and effective fertilization in agricultural plants growth. PMID:24204659

Dynamical analysis of a fractional SIR model with birth and death on heterogeneous complex networks

NASA Astrophysics Data System (ADS)

Huo, Jingjing; Zhao, Hongyong

2016-04-01

In this paper, a fractional SIR model with birth and death rates on heterogeneous complex networks is proposed. Firstly, we obtain a threshold value R0 based on the existence of endemic equilibrium point E∗, which completely determines the dynamics of the model. Secondly, by using Lyapunov function and Kirchhoff's matrix tree theorem, the globally asymptotical stability of the disease-free equilibrium point E0 and the endemic equilibrium point E∗ of the model are investigated. That is, when R0 < 1, the disease-free equilibrium point E0 is globally asymptotically stable and the disease always dies out; when R0 > 1, the disease-free equilibrium point E0 becomes unstable and in the meantime there exists a unique endemic equilibrium point E∗, which is globally asymptotically stable and the disease is uniformly persistent. Finally, the effects of various immunization schemes are studied and compared. Numerical simulations are given to demonstrate the main results.

Simulation Analysis of Zero Mean Flow Edge Turbulence in LAPD

NASA Astrophysics Data System (ADS)

Friedman, Brett Cory

I model, simulate, and analyze the turbulence in a particular experiment on the Large Plasma Device (LAPD) at UCLA. The experiment, conducted by Schaffner et al. [D. Schaffner et al., Phys. Rev. Lett. 109, 135002 (2012)], nulls out the intrinsic mean flow in LAPD by limiter biasing. The model that I use in the simulation is an electrostatic reduced Braginskii two-fluid model that describes the time evolution of density, electron temperature, electrostatic potential, and parallel electron velocity fluctuations in the edge region of LAPD. The spatial domain is annular, encompassing the radial coordinates over which a significant equilibrium density gradient exists. My model breaks the independent variables in the equations into time-independent equilibrium parts and time-dependent fluctuating parts, and I use experimentally obtained values as input for the equilibrium parts. After an initial exponential growth period due to a linear drift wave instability, the fluctuations saturate and the frequency and azimuthal wavenumber spectra become broadband with no visible coherent peaks, at which point the fluctuations become turbulent. The turbulence develops intermittent pressure and flow filamentary structures that grow and dissipate, but look much different than the unstable linear drift waves, primarily in the extremely long axial wavelengths that the filaments possess. An energy dynamics analysis that I derive reveals the mechanism that drives these structures. The long k|| ˜ 0 intermittent potential filaments convect equilibrium density across the equilibrium density gradient, setting up local density filaments. These density filaments, also with k || ˜ 0, produce azimuthal density gradients, which drive radially propagating secondary drift waves. These finite k|| drift waves nonlinearly couple to one another and reinforce the original convective filament, allowing the process to bootstrap itself. The growth of these structures is by nonlinear instability because they require a finite amplitude to start, and they require nonlinear terms in the equations to sustain their growth. The reason why k|| ˜ 0 structures can grow and support themselves in a dynamical system with no k|| = 0 linear instability is because the linear eigenmodes of the system are nonorthogonal. Nonorthogonal eigenmodes that individually decay under linear dynamics can transiently inject energy into the system, allowing for instability. The instability, however, can only occur when the fluctuations have a finite starting amplitude, and nonlinearities are available to mix energy among eigenmodes. Finally, I attempt to figure out how many effective degrees of freedom control the turbulence to determine whether it is stochastic or deterministic. Using two different methods - permutation entropy analysis by means of time delay trajectory reconstruction and Proper Orthogonal Decomposition - I determine that more than a few degrees of freedom, possibly even dozens or hundreds, are all active. The turbulence, while not stochastic, is not a manifestation of low-dimensional chaos - it is high-dimensional.

Equilibrium high entropy alloy phase stability from experiments and thermodynamic modeling

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

Saal, James E.; Berglund, Ida S.; Sebastian, Jason T.

Long-term stability of high entropy alloys (HEAs) is a critical consideration for the design and practical application of HEAs. It has long been assumed that many HEAs are a kinetically-stabilized metastable structure, and recent experiments have confirmed this hypothesis by observing HEA ecomposition after long-termequilibration. In the presentwork,we demonstrate the use of the CALculation of PHAse Diagrams (CALPHAD) approach to predict HEA stability and processing parameters, comparing experimental long-term annealing observations to CALPHAD phase diagrams from a commercially-available HEA database. As a result, we find good agreement between single- and multi-phase predictions and experiments.

Equilibrium high entropy alloy phase stability from experiments and thermodynamic modeling

DOE PAGES

Saal, James E.; Berglund, Ida S.; Sebastian, Jason T.; ...

2017-10-29

Long-term stability of high entropy alloys (HEAs) is a critical consideration for the design and practical application of HEAs. It has long been assumed that many HEAs are a kinetically-stabilized metastable structure, and recent experiments have confirmed this hypothesis by observing HEA ecomposition after long-termequilibration. In the presentwork,we demonstrate the use of the CALculation of PHAse Diagrams (CALPHAD) approach to predict HEA stability and processing parameters, comparing experimental long-term annealing observations to CALPHAD phase diagrams from a commercially-available HEA database. As a result, we find good agreement between single- and multi-phase predictions and experiments.

Assimilation of Altimeter Data into a Quasigeostrophic Model of the Gulf Stream System. Part 1; Dynamical Considerations

NASA Technical Reports Server (NTRS)

Capotondi, Antonietta; Malanotte-Rizzoli, Paola; Holland, William R.

1995-01-01

The dynamical consequences of constraining a numerical model with sea surface height data have been investigated. The model used for this study is a quasigeostrophic model of the Gulf Stream region. The data that have been assimilated are maps of sea surface height obtained as the superposition of sea surface height variability deduced from the Geosat altimeter measurements and a mean field constructed from historical hydrographic data. The method used for assimilating the data is the nudging technique. Nudging has been implemented in such a way as to achieve a high degree of convergence of the surface model fields toward the observations. The assimilation of the surface data is thus equivalent to the prescription of a surface pressure boundary condition. The authors analyzed the mechanisms of the model adjustment and the characteristics of the resultant equilibrium state when the surface data are assimilated. Since the surface data are the superposition of a mean component and an eddy component, in order to understand the relative role of these two components in determining the characteristics of the final equilibrium state, two different experiments have been considered: in the first experiment only the climatological mean field is assimilated, while in the second experiment the total surface streamfunction field (mean plus eddies) has been used. It is shown that the model behavior in the presence of the surface data constraint can be conveniently described in terms of baroclinic Fofonoff modes. The prescribed mean component of the surface data acts as a 'surface topography' in this problem. Its presence determines a distortion of the geostrophic contours in the subsurface layers, thus constraining the mean circulation in those layers. The intensity of the mean flow is determined by the inflow/outflow conditions at the open boundaries, as well as by eddy forcing and dissipation.

Coupling of Higgs and Leggett modes in non-equilibrium superconductors.

PubMed

Krull, H; Bittner, N; Uhrig, G S; Manske, D; Schnyder, A P

2016-06-21

In equilibrium systems amplitude and phase collective modes are decoupled, as they are mutually orthogonal excitations. The direct detection of these Higgs and Leggett collective modes by linear-response measurements is not possible, because they do not couple directly to the electromagnetic field. In this work, using numerical exact simulations we show for the case of two-gap superconductors, that optical pump-probe experiments excite both Higgs and Leggett modes out of equilibrium. We find that this non-adiabatic excitation process introduces a strong interaction between the collective modes, which is absent in equilibrium. Moreover, we propose a type of pump-probe experiment, which allows to probe and coherently control the Higgs and Leggett modes, and thus the order parameter directly. These findings go beyond two-band superconductors and apply to general collective modes in quantum materials.

Coupled phase and aqueous species equilibrium of the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

NASA Astrophysics Data System (ADS)

Duan, Zhenhao; Li, Dedong

2008-10-01

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H +, Na +, Ca 2+, CaHCO3+, Ca(OH) +, OH -, Cl -, HCO3-, CO32-, CO 2(aq) and CaCO 3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO 2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T- P- m range, hence calcite solubility, CO 2 gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data. One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO 2 can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility. The functionality of pH value, alkalinity, CO 2 gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl (aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.

Particle orbits in two-dimensional equilibrium models for the magnetotail

NASA Technical Reports Server (NTRS)

Karimabadi, H.; Pritchett, P. L.; Coroniti, F. V.

1990-01-01

Assuming that there exist an equilibrium state for the magnetotail, particle orbits are investigated in two-dimensional kinetic equilibrium models for the magnetotail. Particle orbits in the equilibrium field are compared with those calculated earlier with one-dimensional models, where the main component of the magnetic field (Bx) was approximated as either a hyperbolic tangent or a linear function of z with the normal field (Bz) assumed to be a constant. It was found that the particle orbits calculated with the two types of models are significantly different, mainly due to the neglect of the variation of Bx with x in the one-dimensional fields.

Metronidazole removal in powder-activated carbon and concrete-containing graphene adsorption systems: Estimation of kinetic, equilibrium and thermodynamic parameters and optimization of adsorption by a central composite design.

PubMed

Manjunath, S V; Kumar, S Mathava; Ngo, Huu Hao; Guo, Wenshan

2017-12-06

Metronidazole (MNZ) removal by two adsorbents, i.e., concrete-containing graphene (CG) and powder-activated carbon (PAC), was investigated via batch-mode experiments and the outcomes were used to analyze the kinetics, equilibrium and thermodynamics of MNZ adsorption. MNZ sorption on CG and PAC has followed the pseudo-second-order kinetic model, and the thermodynamic parameters revealed that MNZ adsorption was spontaneous on PAC and non-spontaneous on CG. Subsequently, two-parameter isotherm models, i.e., Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Elovich models, were applied to evaluate the MNZ adsorption capacity. The maximum MNZ adsorption capacities ([Formula: see text]) of PAC and CG were found to be between 25.5-32.8 mg/g and 0.41-0.002 mg/g, respectively. Subsequently, the effects of pH, temperature and adsorbent dosage on MNZ adsorption were evaluated by a central composite design (CCD) approach. The CCD experiments have pointed out the complete removal of MNZ at a much lower PAC dosage by increasing the system temperature (i.e., from 20°C to 40°C). On the other hand, a desorption experiment has shown 3.5% and 1.7% MNZ removal from the surface of PAC and CG, respectively, which was insignificant compared to the sorbed MNZ on the surface by adsorption. The overall findings indicate that PAC and CG with higher graphene content could be useful in MNZ removal from aqueous systems.

Relation between magnetization and Faraday angles produced by ultrafast spin-flip processes within the three-level Λ-type system

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

Hinschberger, Y.; Lavoine, J. P.

2015-08-07

Ultrafast magneto-optical (MO) experiments constitute a powerful tool to explore the magnetization dynamics of diverse materials. Over the last decade, there have been many theoretical and experimental developments on this subject. However, the relation between the magnetization dynamics and the transient MO response still remains unclear. In this work, we calculate the magnetization of a material, as well as the magneto-optical rotation and ellipticity angles measured in a single-beam experiment. Then, we compare the magnetization to the MO response. The magnetic material is modeled by a three-level Λ-type system, which represents a simple model to describe MO effects induced bymore » an ultrafast laser pulse. Our calculations use the density matrix formalism, while the dynamics of the system is obtained by solving the Lindblad equation taking into account population relaxation and dephasing processes. Furthermore, we consider the Faraday rotation of the optical waves that simultaneously causes spin-flip. We show that the Faraday angles remain proportional to the magnetization only if the system has reached the equilibrium-state, and that this proportionality is directly related to the population and coherence decay rates. For the non-equilibrium situation, the previous proportionality relation is no longer valid. We show that our model is able to interpret some recent experimental results obtained in a single-pulse experiment. We further show that, after a critical pulse duration, the decrease of the ellipticity as a function of the absorbed energy is a characteristic of the system.« less

Evidence for out-of-equilibrium states in warm dense matter probed by x-ray Thomson scattering.

PubMed

Clérouin, Jean; Robert, Grégory; Arnault, Philippe; Ticknor, Christopher; Kress, Joel D; Collins, Lee A

2015-01-01

A recent and unexpected discrepancy between ab initio simulations and the interpretation of a laser shock experiment on aluminum, probed by x-ray Thomson scattering (XRTS), is addressed. The ion-ion structure factor deduced from the XRTS elastic peak (ion feature) is only compatible with a strongly coupled out-of-equilibrium state. Orbital free molecular dynamics simulations with ions colder than the electrons are employed to interpret the experiment. The relevance of decoupled temperatures for ions and electrons is discussed. The possibility that it mimics a transient, or metastable, out-of-equilibrium state after melting is also suggested.

Modeling the heating and atomic kinetics of a photoionized neon plasma experiment

NASA Astrophysics Data System (ADS)

Lockard, Tom E.

Motivated by gas cell photoionized plasma experiments performed by our group at the Z facility of Sandia National Laboratories, we discuss in this dissertation a modeling study of the heating and ionization of the plasma for conditions characteristic of these experiments. Photoionized plasmas are non-equilibrium systems driven by a broadband x-ray radiation flux. They are commonly found in astrophysics but rarely seen in the laboratory. Several modeling tools have been employed: (1) a view-factor computer code constrained with side x-ray power and gated monochromatic image measurements of the z-pinch radiation, to model the time-history of the photon-energy resolved x-ray flux driving the photoionized plasma, (2) a Boltzmann self-consistent electron and atomic kinetics model to simulate the electron distribution function and configuration-averaged atomic kinetics, (3) a radiation-hydrodynamics code with inline non-equilibrium atomic kinetics to perform a comprehensive numerical simulation of the experiment and plasma heating, and (4) steady-state and time-dependent collisional-radiative atomic kinetics calculations with fine-structure energy level description to assess transient effects in the ionization and charge state distribution of the plasma. The results indicate that the photon-energy resolved x-ray flux impinging on the front window of the gas cell is very well approximated by a linear combination of three geometrically-diluted Planckian distributions. Knowledge of the spectral details of the x-ray drive turned out to be important for the heating and ionization of the plasma. The free electrons in the plasma thermalize quickly relative to the timescales associated with the time-history of the x-ray drive and the plasma atomic kinetics. Hence, electrons are well described by a Maxwellian energy distribution of a single temperature. This finding is important to support the application of a radiation-hydrodynamic model to simulate the experiment. It is found that the computed plasma heating compares well with experimental observation when the effects of the windows, hydrodynamics, and non-equilbirium neon emissivity and opacity are employed. The atomic kinetics shows significant time-dependent effects because the timescale of the x-ray drive is too short compared to that of the photoionization process. These modeling and simulation results are important to test theory and modeling assumptions and approximations, and also to provide guidance on data interpretation and analysis.

Representing ductile damage with the dual domain material point method

DOE PAGES

Long, C. C.; Zhang, D. Z.; Bronkhorst, C. A.; ...

2015-12-14

In this study, we incorporate a ductile damage material model into a computational framework based on the Dual Domain Material Point (DDMP) method. As an example, simulations of a flyer plate experiment involving ductile void growth and material failure are performed. The results are compared with experiments performed on high purity tantalum. We also compare the numerical results obtained from the DDMP method with those obtained from the traditional Material Point Method (MPM). Effects of an overstress model, artificial viscosity, and physical viscosity are investigated. Our results show that a physical bulk viscosity and overstress model are important in thismore » impact and failure problem, while physical shear viscosity and artificial shock viscosity have negligible effects. A simple numerical procedure with guaranteed convergence is introduced to solve for the equilibrium plastic state from the ductile damage model.« less

IS THE SIZE DISTRIBUTION OF URBAN AEROSOLS DETERMINED BY THERMODYNAMIC EQUILIBRIUM? (R826371C005)

EPA Science Inventory

A size-resolved equilibrium model, SELIQUID, is presented and used to simulate the size–composition distribution of semi-volatile inorganic aerosol in an urban environment. The model uses the efflorescence branch of aerosol behavior to predict the equilibrium partitioni...

Simultaneous Laser-induced Fluorescence of Nitric Oxide and Atomic Oxygen in the Hypersonic Materials Environment Test System Arcjet Facility

NASA Technical Reports Server (NTRS)

Johansen, Craig; Lincoln, Daniel; Bathel, Brett; Inman, Jennifer; Danehy, Paul

2014-01-01

Simultaneous nitric oxide (NO) and atomic oxygen (O) laser induced fluorescence (LIF) experiments were performed in the Hypersonic Materials Environmental Test System (HYMETS) facility at the NASA Langley Research Center. The data serves as an experimental database for validation for chemical and thermal nonequilibrium models used in hypersonic flows. Measurements were taken over a wide range of stagnation enthalpies (6.7 - 18.5 MJ/kg) using an Earth atmosphere simulant with a composition of 75% N2, 20% O2, and 5% Ar (by volume). These are the first simultaneous measurements of NO and O LIF to be reported in literature for the HYMETS facility. The maximum O LIF mean signal intensity was observed at a stagnation enthalpy of approximately 12 MJ/kg while the maximum NO LIF mean signal intensity was observed at a stagnation enthalpy of 6.7 MJ/kg. Experimental results were compared to simple fluorescence model that assumes equilibrium conditions in the plenum and frozen chemistry in the isentropic nozzle expansion (Mach 5). The equilibrium calculations were performed using CANTERA v2.1.1 with 16 species. The fluorescence model captured the correlation in mean O and NO LIF signal intensities over the entire range of stagnation enthalpies tested. Very weak correlations between single-shot O and NO LIF intensities were observed in the experiments at all of the stagnation enthalpy conditions.

How do changes in suspended sediment concentration alone influence the size of mud flocs under steady turbulent shearing?

NASA Astrophysics Data System (ADS)

Tran, Duc; Kuprenas, Rachel; Strom, Kyle

2018-04-01

Modeling the size and settling velocity of sediment under the influence of flocculation is crucial for the accurate prediction of mud movement and deposition in sediment transport modeling of environments such as agricultural streams, large coastal rivers, estuaries, river plumes, and turbidity currents. Yet, collecting accurate and high resolution data on mud flocs is difficult. As a result, models that account for the influence of flocculation on mud settling velocity are based on sparse data that often present non-congruent relationship in floc properties with basic influencers of flocculations such as suspended sediment concentration. This study examines the influence of suspended sediment concentration on floc size populations within a turbulent suspension. Specifically, the work investigates: (1) the relationship between the equilibrium floc size and suspended sediment concentration under conditions of steady concentration and turbulent shearing; and (2) the speed at which mature flocs adapt to an unsteady drop in the concentration when turbulent shear is constant. Two sets of experiments were used to investigate the target processes. All work was conducted in laboratory mixing tanks using a floc camera and a newly developed image acquisition method. The new method allows for direct imaging and sizing of flocs within turbulent suspensions of clay in concentrations ranging from 15 to 400 mg/L, so that no transfer of the sample to another settling column or imaging tank is needed. The primary conclusions from the two sets of experiments are: (1) that the equilibrium floc size in an energetic turbulent suspension is linearly and positively related to concentration over the range of C = 50 to 400 mg/L, yet with a smaller-than-expected slope based on previous data and models from low-energy environments; and (2) that floc sizes decrease quickly (with a time lag on the order of 1-15 min) to time-varying decreases in concentration at turbulent shearing of G = 50s-1 . Overall the data illustrate that equilibrium floc size is a positive function of concentration, but that the rate of increase is weaker than expected. The data also suggest that approximating the size or settling velocity of some muds with a simple equilibrium model might be appropriate if the time steps of interest are on the order of 10 min or larger. The data also shows the importance of calibrating historic mud settling velocity equations for accurate predictions.

Dynamic Circadian Modulation in a Biomathematical Model for the Effects of Sleep and Sleep Loss on Waking Neurobehavioral Performance

PubMed Central

McCauley, Peter; Kalachev, Leonid V.; Mollicone, Daniel J.; Banks, Siobhan; Dinges, David F.; Van Dongen, Hans P. A.

2013-01-01

Recent experimental observations and theoretical advances have indicated that the homeostatic equilibrium for sleep/wake regulation—and thereby sensitivity to neurobehavioral impairment from sleep loss—is modulated by prior sleep/wake history. This phenomenon was predicted by a biomathematical model developed to explain changes in neurobehavioral performance across days in laboratory studies of total sleep deprivation and sustained sleep restriction. The present paper focuses on the dynamics of neurobehavioral performance within days in this biomathematical model of fatigue. Without increasing the number of model parameters, the model was updated by incorporating time-dependence in the amplitude of the circadian modulation of performance. The updated model was calibrated using a large dataset from three laboratory experiments on psychomotor vigilance test (PVT) performance, under conditions of sleep loss and circadian misalignment; and validated using another large dataset from three different laboratory experiments. The time-dependence of circadian amplitude resulted in improved goodness-of-fit in night shift schedules, nap sleep scenarios, and recovery from prior sleep loss. The updated model predicts that the homeostatic equilibrium for sleep/wake regulation—and thus sensitivity to sleep loss—depends not only on the duration but also on the circadian timing of prior sleep. This novel theoretical insight has important implications for predicting operator alertness during work schedules involving circadian misalignment such as night shift work. Citation: McCauley P; Kalachev LV; Mollicone DJ; Banks S; Dinges DF; Van Dongen HPA. Dynamic circadian modulation in a biomathematical model for the effects of sleep and sleep loss on waking neurobehavioral performance. SLEEP 2013;36(12):1987-1997. PMID:24293775

Prediction of U-Mo dispersion nuclear fuels with Al-Si alloy using artificial neural network

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

Susmikanti, Mike, E-mail: mike@batan.go.id; Sulistyo, Jos, E-mail: soj@batan.go.id

2014-09-30

Dispersion nuclear fuels, consisting of U-Mo particles dispersed in an Al-Si matrix, are being developed as fuel for research reactors. The equilibrium relationship for a mixture component can be expressed in the phase diagram. It is important to analyze whether a mixture component is in equilibrium phase or another phase. The purpose of this research it is needed to built the model of the phase diagram, so the mixture component is in the stable or melting condition. Artificial neural network (ANN) is a modeling tool for processes involving multivariable non-linear relationships. The objective of the present work is to developmore » code based on artificial neural network models of system equilibrium relationship of U-Mo in Al-Si matrix. This model can be used for prediction of type of resulting mixture, and whether the point is on the equilibrium phase or in another phase region. The equilibrium model data for prediction and modeling generated from experimentally data. The artificial neural network with resilient backpropagation method was chosen to predict the dispersion of nuclear fuels U-Mo in Al-Si matrix. This developed code was built with some function in MATLAB. For simulations using ANN, the Levenberg-Marquardt method was also used for optimization. The artificial neural network is able to predict the equilibrium phase or in the phase region. The develop code based on artificial neural network models was built, for analyze equilibrium relationship of U-Mo in Al-Si matrix.« less

Magma degassing: novel experiments with multiple volatile species on H2O, CO2, S and Cl and development of a new thermodynamic model

NASA Astrophysics Data System (ADS)

Lesne, P.; Witham, F.; Kohn, S.; Blundy, J.; Botcharnikov, R. E.; Behrens, H.

2010-12-01

Geochemical measurements, from chemistry of melt inclusion to gas fluxes and compositions, give important clues to help understand magma and gas transport from a magma chamber towards the surface. These data are of the utmost importance to constrain models of the mass transport processes occurring in volcanic systems. Experimental work is central to testing such models. The behaviour of water and carbon dioxide fluids in basaltic melts have been well studied in previous works (i.e. Dixon et al., 1995; Newman & Lowenstern, 2002; Papale et al., 2006). The various models agree that the gases exsolved at high pressures are rich in CO_{2}, and at lower pressures, when most of the CO_{2} has already moved to the fluid phase, H_{2}O strongly partitions into the fluid and the melt become dehydrated (e.g. Newman & Lowenstern, 2002; Papale et al, 2006). S and Cl are much less abundant in the atmosphere than H_{2}O and CO_{2} and therefore give much higher signal ratio to noise ratios than volcanogenic H_{2}O and CO_{2}. H_{2}O, CO_{2}, S and Cl being the major volatiles measured at vent in melt inclusions in volcanic systems, a detailed model of S and Cl behaviour in basaltic melts is highly valuable in order to better understand volcanic gas emissions, and to test models of degassing processes. We have developed a model for mixed C-O-H-S-Cl fluids in equilibrium with basalt. The model is based on the premise that the volumetrically dominant volatile components, H_{2}O and CO_{2}, will determine the behaviour of S and Cl. Equilibrium experiments between a C-O-H-S-Cl fluid and basaltic melts from Stromboli and Masaya have been performed, at 1150°C, under oxidized conditions and at pressure from 25 to 400MPa. Analyses of volatiles dissolved in the melt and determined fluid composition allow us to determine equilibrium constants and partition coefficients of S and Cl between a CO_{2}-H_{2}O-rich fluid phase and basaltic melt. Equilibrium constants were parameterized using a S-rich basaltic composition (Stromboli), and have been tested against independent S-poor basaltic composition melts for Stromboli, and two volatile compositions from Masaya volcano. Our model reproduces all these experimental data with good agreement. The geochemical model will be published as a user-friendly software package, SolEx, to allow easy prediction of melt and fluid phase chemistries. We hope that this will facilitate comparisons between fluid-mechanical models of volcanic behaviour and measurements of melt inclusion chemistry and emitted gas compositions and fluxes. Dixon et al., 1995, J. Pet., 36, 1607-1631; Newman & Lowenstern, 2002, Computers & Geosciences, 28, 597-604; Papale et al., 2006, Chem. Geol., 229, 78-95.

Profiles of equilibrium constants for self-association of aromatic molecules

NASA Astrophysics Data System (ADS)

Beshnova, Daria A.; Lantushenko, Anastasia O.; Davies, David B.; Evstigneev, Maxim P.

2009-04-01

Analysis of the noncovalent, noncooperative self-association of identical aromatic molecules assumes that the equilibrium self-association constants are either independent of the number of molecules (the EK-model) or change progressively with increasing aggregation (the AK-model). The dependence of the self-association constant on the number of molecules in the aggregate (i.e., the profile of the equilibrium constant) was empirically derived in the AK-model but, in order to provide some physical understanding of the profile, it is proposed that the sources for attenuation of the equilibrium constant are the loss of translational and rotational degrees of freedom, the ordering of molecules in the aggregates and the electrostatic contribution (for charged units). Expressions are derived for the profiles of the equilibrium constants for both neutral and charged molecules. Although the EK-model has been widely used in the analysis of experimental data, it is shown in this work that the derived equilibrium constant, KEK, depends on the concentration range used and hence, on the experimental method employed. The relationship has also been demonstrated between the equilibrium constant KEK and the real dimerization constant, KD, which shows that the value of KEK is always lower than KD.

Near-equilibrium dumb-bell-shaped figures for cohesionless small bodies

NASA Astrophysics Data System (ADS)

Descamps, Pascal

2016-02-01

In a previous paper (Descamps, P. [2015]. Icarus 245, 64-79), we developed a specific method aimed to retrieve the main physical characteristics (shape, density, surface scattering properties) of highly elongated bodies from their rotational lightcurves through the use of dumb-bell-shaped equilibrium figures. The present work is a test of this method. For that purpose we introduce near-equilibrium dumb-bell-shaped figures which are base dumb-bell equilibrium shapes modulated by lognormal statistics. Such synthetic irregular models are used to generate lightcurves from which our method is successfully applied. Shape statistical parameters of such near-equilibrium dumb-bell-shaped objects are in good agreement with those calculated for example for the Asteroid (216) Kleopatra from its dog-bone radar model. It may suggest that such bilobed and elongated asteroids can be approached by equilibrium figures perturbed be the interplay with a substantial internal friction modeled by a Gaussian random sphere.

Dynamical behaviors of inter-out-of-equilibrium state intervals in Korean futures exchange markets

NASA Astrophysics Data System (ADS)

Lim, Gyuchang; Kim, SooYong; Kim, Kyungsik; Lee, Dong-In; Scalas, Enrico

2008-05-01

A recently discovered feature of financial markets, the two-phase phenomenon, is utilized to categorize a financial time series into two phases, namely equilibrium and out-of-equilibrium states. For out-of-equilibrium states, we analyze the time intervals at which the state is revisited. The power-law distribution of inter-out-of-equilibrium state intervals is shown and we present an analogy with discrete-time heat bath dynamics, similar to random Ising systems. In the mean-field approximation, this model reduces to a one-dimensional multiplicative process. By varying global and local model parameters, the relevance between volatilities in financial markets and the interaction strengths between agents in the Ising model are investigated and discussed.

Adsorption of Methyl Tertiary Butyl Ether on Granular Zeolites: Batch and Column Studies

PubMed Central

Abu-Lail, Laila; Bergendahl, John A.; Thompson, Robert W.

2010-01-01

Methyl tertiary butyl ether (MTBE) has been shown to be readily removed from water with powdered zeolites, but the passage of water through fixed beds of very small powdered zeolites produces high friction losses not encountered in flow through larger sized granular materials. In this study, equilibrium and kinetic adsorption of MTBE onto granular zeolites, a coconut shell granular activated carbon (CS-1240), and a commercial carbon adsorbent (CCA) sample was evaluated. In addition, the effect of natural organic matter (NOM) on MTBE adsorption was evaluated. Batch adsorption experiments determined that ZSM-5 was the most effective granular zeolite for MTBE adsorption. Further equilibrium and kinetic experiments verified that granular ZSM-5 is superior to CS-1240 and CCA in removing MTBE from water. No competitive-adsorption effects between NOM and MTBE were observed for adsorption to granular ZSM-5 or CS-1240, however there was competition between NOM and MTBE for adsorption onto the CCA granules. Fixed-bed adsorption experiments for longer run times were performed using granular ZSM-5. The bed depth service time model (BDST) was used to analyze the breakthrough data. PMID:20153106

Nonequilibrium Kondo effect by the equilibrium numerical renormalization group method: The hybrid Anderson model subject to a finite spin bias

NASA Astrophysics Data System (ADS)

Fang, Tie-Feng; Guo, Ai-Min; Sun, Qing-Feng

2018-06-01

We investigate Kondo correlations in a quantum dot with normal and superconducting electrodes, where a spin bias voltage is applied across the device and the local interaction U is either attractive or repulsive. When the spin current is blockaded in the large-gap regime, this nonequilibrium strongly correlated problem maps into an equilibrium model solvable by the numerical renormalization group method. The Kondo spectra with characteristic splitting due to the nonequilibrium spin accumulation are thus obtained at high precision. It is shown that while the bias-induced decoherence of the spin Kondo effect is partially compensated by the superconductivity, the charge Kondo effect is enhanced out of equilibrium and undergoes an additional splitting by the superconducting proximity effect, yielding four Kondo peaks in the local spectral density. In the charge Kondo regime, we find a universal scaling of charge conductance in this hybrid device under different spin biases. The universal conductance as a function of the coupling to the superconducting lead is peaked at and hence directly measures the Kondo temperature. Our results are of direct relevance to recent experiments realizing a negative-U charge Kondo effect in hybrid oxide quantum dots [Nat. Commun. 8, 395 (2017), 10.1038/s41467-017-00495-7].

The effects of finite-rate reactions at the gas/surface interface in support of thermal protection system design

NASA Astrophysics Data System (ADS)

Beerman, Adam Farrell

2011-12-01

Gas-surface modeling is dependent on material type and atmospheric reentry conditions. Lower molecular collisions at the low pressure trajectories make it more likely for occurrences of nonequilibrium, or finite-rate, reactions. Equilibrium is often assumed at the surface of a material as it is a subset of nonequilibrium and is easier to compute, though it can lead to overly conservative predictions. A case where a low density material experiences a low pressure trajectory and designed for equilibrium is the Stardust Return Capsule (SRC) with the Phenolic Impregnated Carbon Ablator (PICA) as its heatshield. Post-flight analysis of the recession on the SRC found that the prediction from the equilibrium model can be more than 50% larger than the measured recession. The Modified Park Model was chosen as the finite-rate model as it contains simple four reactions (oxidation, sublimation, and nitridation) and has been previously used to study individual points of the SRC trajectory. The Modified Park Model cannot model equilibrium so a model BFIAT was developed that allows finite-rate reactions to be applied to the surface for a certain length of time. Finite-rate sublimation was determined to be reaction of importance in the Park Model for SRC-like conditions. The predicted recession on the SRC heatshield experienced a reduction in its overprediction; the finite-rate predictions fall with the measurement error of the recession at three points on the heatshield. The recession reduction was driven by a significant reduction in char formation. There was little change in the pyrolysis gas rate. The finite-rate model was also applied to simulations of various arc-jet tests that covered a range of heating conditions on the surface of the PICA material. Comparison to this experimental data further showed the role of finite-rate reactions and sublimation in the Park Model and conditions that favor the nonequilibrium assumption (heating over 1000 W/cm2). For the emerging PICA material, used for the Mars Science Laboratory and one of two material choices for the Crew Exploration Vehicle, and SRC-like trajectories, a finite-rate model was developed such that the more robust nonequilibrium assumption can be applied to design processes to reduce heatshield mass.

Ultrasonically assisted antioxidant extraction from grape stalks and olive leaves

NASA Astrophysics Data System (ADS)

Cárcel, Juan A.; García-Pérez, José V.; Mulet, Antonio; Rodríguez, Ligia; Riera, Enrique

2010-01-01

Grape stalks and olive leaves present high amount of phenolic compounds with antioxidant properties. The extraction of these compounds may be considered a way to increase in value both agro-food by-products. Ultrasound is widely applied in extraction due to its effects (cavitation, microstirring or sponge effect) over the process. The goal of this work was to address the application of ultrasound on the antioxidant extraction of olive leaves and grape stalk. For that purpose, the extraction of antioxidant compounds from grape stalks and olive leaves, previously dried at 100 °C, were carried out using a ethanolic solution (80 % v/v) at 60 °C. Extractions were carried out with (US; 30 kHz; 600W)) and agitation (AG) without ultrasound application. In the AG experiments, the solution was agitated with a stirrer. Samples were obtained at different extraction time (10, 30, 60, 120, 180, 240, 360, 480 and 1440 min) and their antioxidant capacity was measured using FRAP method. The Naik model was used to model the extraction kinetics, being identified the antioxidant capacity of extracts at the equilibrium (Y eq) and the initial velocity of extraction (Y eq/B). For grape stalks, the antioxidant capacity of extracts at the equilibrium (Y eq) and the initial velocity of extraction (Y eq/B) were higher in AG experiments than in US experiments. In the olive leaves extractions, the Y eq/B was of the same order for both treatments but Y eq was significantly higher for US experiments. The different influence of ultrasound for both by-products can be explained from their different geometry and structure.

Experimental determination of iron isotope fractionations among Fe aq 2 + -FeSaq-Mackinawite at low temperatures: Implications for the rock record

NASA Astrophysics Data System (ADS)

Wu, Lingling; Druschel, Greg; Findlay, Alyssa; Beard, Brian L.; Johnson, Clark M.

2012-07-01

The Fe isotope fractionation factors among aqueous ferrous iron (Fe aq 2 +), aqueous FeS clusters (FeSaq), and nanoparticulate mackinawite under neutral and mildly acidic and alkaline pH conditions have been determined using the three-isotope method. Combined voltammetric analysis and geochemical modeling were used to determine the Fe speciation in the experimental systems. The equilibrium 56Fe/54Fe fractionation factor at 20 °C and pH 7 has been determined to be -0.32 ± 0.29 (2σ)‰ between Fe aq 2 + (minor FeSaq also present in the experiment) and mackinawite. This fractionation factor was essentially constant when pH was changed to 6 or 8. When equal molarity of HS- and Fe aq 2 + were added to the system, however, the isotopic fractionation at pH 7 changed to -0.64 ± 0.36 (2σ)‰, correlating with a significant increase in the proportion of FeHS+ and FeSaq. These results highlight a more important role of aqueous Fe-S speciation in the equilibrium Fe isotope fractionation factor than recognized in previous studies. The isotopic fractionation remained constant when temperature was increased from 20 °C to 35 °C for fractionation factors between Fe aq 2 + , and mackinawite and between dominantly FeHS+ and mackinawite. Synthesis experiments similar to those of Butler et al. (2005) and Guilbaud et al. (2010) at pH 4 show consistent results: over time, the aqueous Fe-mackinawite fractionation decreases but even after 38 days of aging the fractionation factor is far from the equilibrium value inferred using the three-isotope method. In contrast, at near-neutral pH the fractionation factor for the synthesis experiment reached the equilibrium value in 38 days. These differences are best explained by noting that at low pH the FeS mackinawite particles coarsen more rapidly via particle aggregation, which limits isotopic exchange, whereas at higher pH mackinawite aggregation is limited, and Fe isotope exchange occurs more rapidly, converging on the equilibrium value. These results suggest that mackinawite formed in natural environments at near-neutral or alkaline pH are unlikely to retain kinetic isotope fractionations, but are more likely to reflect equilibrium isotope compositions. This in turn has important implications for interpreting iron isotope compositions of Fe sulfides in natural systems.

Biomechanical stability analysis of the lambda-model controlling one joint.

PubMed

Lan, L; Zhu, K Y

2007-06-01

Computer modeling and control of the human motor system might be helpful for understanding the mechanism of human motor system and for the diagnosis and treatment of neuromuscular disorders. In this paper, a brief view of the equilibrium point hypothesis for human motor system modeling is given, and the lambda-model derived from this hypothesis is studied. The stability of the lambda-model based on equilibrium and Jacobian matrix is investigated. The results obtained in this paper suggest that the lambda-model is stable and has a unique equilibrium point under certain conditions.

Modelling the effect of immigration on drinking behaviour.

PubMed

Xiang, Hong; Zhu, Cheng-Cheng; Huo, Hai-Feng

2017-12-01

A drinking model with immigration is constructed. For the model with problem drinking immigration, the model admits only one problem drinking equilibrium. For the model without problem drinking immigration, the model has two equilibria, one is problem drinking-free equilibrium and the other is problem drinking equilibrium. By employing the method of Lyapunov function, stability of all kinds of equilibria is obtained. Numerical simulations are also provided to illustrate our analytical results. Our results show that alcohol immigrants increase the difficulty of the temperance work of the region.

Insights: Simple Models for Teaching Equilibrium and Le Chatelier's Principle.

ERIC Educational Resources Information Center

Russell, Joan M.

1988-01-01

Presents three models that have been effective for teaching chemical equilibrium and Le Chatelier's principle: (1) the liquid transfer model, (2) the fish model, and (3) the teeter-totter model. Explains each model and its relation to Le Chatelier's principle. (MVL)

Thermal characterization assessment of rigid and flexible water models in a nanogap using molecular dynamics

NASA Astrophysics Data System (ADS)

Akıner, Tolga; Mason, Jeremy; Ertürk, Hakan

2017-11-01

The thermal properties of the TIP3P and TIP5P water models are investigated using equilibrium and non-equilibrium molecular dynamics techniques in the presence of solid surfaces. The performance of the non-equilibrium technique for rigid molecules is found to depend significantly on the distribution of atomic degrees of freedom. An improved approach to distribute atomic degrees of freedom is proposed for which the thermal conductivity of the TIP5P model agrees more closely with equilibrium molecular dynamics and experimental results than the existing state of the art.

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.

Relationship between the line of density anomaly and the lines of melting, crystallization, cavitation, and liquid spinodal in coarse-grained water models

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

Lu, Jibao; Molinero, Valeria, E-mail: Valeria.Molinero@utah.edu; Chakravarty, Charusita

2016-06-21

Liquid water has several anomalous properties, including a non-monotonous dependence of density with temperature and an increase of thermodynamic response functions upon supercooling. Four thermodynamic scenarios have been proposed to explain the anomalies of water, but it is not yet possible to decide between them from experiments because of the crystallization and cavitation of metastable liquid water. Molecular simulations provide a versatile tool to study the anomalies and phase behavior of water, assess their agreement with the phenomenology of water under conditions accessible to experiments, and provide insight into the behavior of water in regions that are challenging to probemore » in the laboratory. Here we investigate the behavior of the computationally efficient monatomic water models mW and mTIP4P/2005{sup REM}, with the aim of unraveling the relationships between the lines of density extrema in the p-T plane, and the lines of melting, liquid-vapor spinodal and non-equilibrium crystallization and cavitation. We focus particularly on the conditions for which the line of density maxima (LDM) in the liquid emerges and disappears as the pressure is increased. We find that these models present a retracing LDM, same as previously found for atomistic water models and models of other tetrahedral liquids. The low-pressure end of the LDM occurs near the pressure of maximum of the melting line, a feature that seems to be general to models that produce tetrahedrally coordinated crystals. We find that the mW water model qualitatively reproduces several key properties of real water: (i) the LDM is terminated by cavitation at low pressures and by crystallization of ice I{sub h} at high pressures, (ii) the LDM meets the crystallization line close to the crossover in crystallization from ice I{sub h} to a non-tetrahedral four-coordinated crystal, and (iii) the density of the liquid at the crossover in crystallization from ice I{sub h} to a four-coordinated non-tetrahedral crystal coincides with the locus of maximum in diffusivity as a function of pressure. The similarities in equilibrium and non-equilibrium phase behavior between the mW model and real water provide support to the quest to find a compressibility extremum, and determine whether it presents a maximum, in the doubly metastable region.« less

Relationship between the line of density anomaly and the lines of melting, crystallization, cavitation, and liquid spinodal in coarse-grained water models.

PubMed

Lu, Jibao; Chakravarty, Charusita; Molinero, Valeria

2016-06-21

Liquid water has several anomalous properties, including a non-monotonous dependence of density with temperature and an increase of thermodynamic response functions upon supercooling. Four thermodynamic scenarios have been proposed to explain the anomalies of water, but it is not yet possible to decide between them from experiments because of the crystallization and cavitation of metastable liquid water. Molecular simulations provide a versatile tool to study the anomalies and phase behavior of water, assess their agreement with the phenomenology of water under conditions accessible to experiments, and provide insight into the behavior of water in regions that are challenging to probe in the laboratory. Here we investigate the behavior of the computationally efficient monatomic water models mW and mTIP4P/2005(REM), with the aim of unraveling the relationships between the lines of density extrema in the p-T plane, and the lines of melting, liquid-vapor spinodal and non-equilibrium crystallization and cavitation. We focus particularly on the conditions for which the line of density maxima (LDM) in the liquid emerges and disappears as the pressure is increased. We find that these models present a retracing LDM, same as previously found for atomistic water models and models of other tetrahedral liquids. The low-pressure end of the LDM occurs near the pressure of maximum of the melting line, a feature that seems to be general to models that produce tetrahedrally coordinated crystals. We find that the mW water model qualitatively reproduces several key properties of real water: (i) the LDM is terminated by cavitation at low pressures and by crystallization of ice Ih at high pressures, (ii) the LDM meets the crystallization line close to the crossover in crystallization from ice Ih to a non-tetrahedral four-coordinated crystal, and (iii) the density of the liquid at the crossover in crystallization from ice Ih to a four-coordinated non-tetrahedral crystal coincides with the locus of maximum in diffusivity as a function of pressure. The similarities in equilibrium and non-equilibrium phase behavior between the mW model and real water provide support to the quest to find a compressibility extremum, and determine whether it presents a maximum, in the doubly metastable region.

Out-of-equilibrium relaxation of the thermal Casimir effect in a model polarizable material

NASA Astrophysics Data System (ADS)

Dean, David S.; Démery, Vincent; Parsegian, V. Adrian; Podgornik, Rudolf

2012-03-01

Relaxation of the thermal Casimir or van der Waals force (the high temperature limit of the Casimir force) for a model dielectric medium is investigated. We start with a model of interacting polarization fields with a dynamics that leads to a frequency dependent dielectric constant of the Debye form. In the static limit, the usual zero frequency Matsubara mode component of the Casimir force is recovered. We then consider the out-of-equilibrium relaxation of the van der Waals force to its equilibrium value when two initially uncorrelated dielectric bodies are brought into sudden proximity. For the interaction between dielectric slabs, it is found that the spatial dependence of the out-of-equilibrium force is the same as the equilibrium one, but it has a time dependent amplitude, or Hamaker coefficient, which increases in time to its equilibrium value. The final relaxation of the force to its equilibrium value is exponential in systems with a single or finite number of polarization field relaxation times. However, in systems, such as those described by the Havriliak-Negami dielectric constant with a broad distribution of relaxation times, we observe a much slower power law decay to the equilibrium value.

An experimental study of the Online Information Paradox: Does en-route information improve road network performance?

PubMed Central

2017-01-01

This study investigates the empirical presence of a theoretical transportation paradox, defined as the “Online Information Paradox” (OIP). The paradox suggests that, for certain road networks, the provision of online information deteriorate travel conditions for all users of that network relative to the situation where no online information is provided to users. The analytical presence of the paradox was derived for a specific network structure by using two equilibrium models, the first being the Expected User Equilibrium (EUE) solution (no information scenario) and the other being the User Equilibrium with Recourse (UER) solution (with information scenario). An incentivised computerised route choice game was designed using the concepts of experimental economics and administered in a controlled laboratory environment to investigate the physical presence of the paradox. Aggregate statistics of path flows and Total System Travel Costs (TSTC) were used to compare the experimental results with the theoretical findings. A total of 12 groups of 12 participants completed the experiment and the OIP and the occurrence of the OIP being significant was observed in 11 of the 12 cases. Though information increased travel costs for users on average, it reduced the volatility of travel costs experienced in the no information scenario indicating that information can achieve a more reliable system. Further replications of similar experiments and more importantly field based identification of the phenomena will force transport professionals to be aware of the emergence of the paradox. In addition, studies such as this emphasise the need for the adoption of adaptive traffic assignment techniques to appropriately model the acquisition of information on a road network. PMID:28902854

Kinetic limitations on tracer partitioning in ganglia dominated source zones.

PubMed

Ervin, Rhiannon E; Boroumand, Ali; Abriola, Linda M; Ramsburg, C Andrew

2011-11-01

Quantification of the relationship between dense nonaqueous phase liquid (DNAPL) source strength, source longevity and spatial distribution is increasingly recognized as important for effective remedial design. Partitioning tracers are one tool that may permit interrogation of DNAPL architecture. Tracer data are commonly analyzed under the assumption of linear, equilibrium partitioning, although the appropriateness of these assumptions has not been fully explored. Here we focus on elucidating the nonlinear and nonequilibrium partitioning behavior of three selected alcohol tracers - 1-pentanol, 1-hexanol and 2-octanol in a series of batch and column experiments. Liquid-liquid equilibria for systems comprising water, TCE and the selected alcohol illustrate the nonlinear distribution of alcohol between the aqueous and organic phases. Complete quantification of these equilibria facilitates delineation of the limits of applicability of the linear partitioning assumption, and assessment of potential inaccuracies associated with measurement of partition coefficients at a single concentration. Column experiments were conducted under conditions of non-equilibrium to evaluate the kinetics of the reversible absorption of the selected tracers in a sandy medium containing a uniform entrapped saturation of TCE-DNAPL. Experimental tracer breakthrough data were used, in conjunction with mathematical models and batch measurements, to evaluate alternative hypotheses for observed deviations from linear equilibrium partitioning behavior. Analyses suggest that, although all tracers accumulate at the TCE-DNAPL/aqueous interface, surface accumulation does not influence transport at concentrations typically employed for tracer tests. Moreover, results reveal that the kinetics of the reversible absorption process are well described using existing mass transfer correlations originally developed to model aqueous boundary layer resistance for pure-component NAPL dissolution. Copyright © 2011 Elsevier B.V. All rights reserved.

Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, Charles A.

2015-01-01

Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO2 mass transfer rate constant (kL,CO2a). The value of kL,CO2a estimated for the stream (0.010 min−1) was within the range for the batch aeration experiments (0–0.033 min−1). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO2 outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).

Wall-modeled large eddy simulation of high-lift devices from low to post-stall angle of attacks

NASA Astrophysics Data System (ADS)

Bodart, Julien; Larsson, Johan; Moin, Parviz

2013-11-01

The flow around a McDonnell-Douglas 30P/30N multi-element airfoil at the flight Reynolds number of 9 million (based on chord) is computed using LES with an equilibrium wall-model with special treatment for transitional flows. Several different angles of attack are considered, up to and including stall, challenging the wall-model in several flow regimes. The maximum lift coefficient, which is generally difficult to predict with RANS approaches, is accurately predicted, as compared to experiments performed in the NASA LPT wind-tunnel. NASA grant: NNX11AI60A.

Non-equilibrium mechanisms of light in the microwave region

NASA Astrophysics Data System (ADS)

Mortenson, Juliana H. J.

2011-09-01

Quantum mechanics and quantum chemistry have taught for more than 100 years that "photons" associated with microwaves cannot exert photochemical effects because their "photon energies" are smaller than chemical bond energies. Those quantum theories have been strongly contradicted within the last few decades by physical experiments demonstrating non-equilibrium, photochemical and photomaterial activity by microwaves. Reactions among scientists to these real physical models and proofs have varied from disbelief and denial, to acceptance of the real physical phenomena and demands for revisions to quantum theory. At the previous "Nature of Light" meeting, an advance in the foundations of quantum mechanics was presented. Those discoveries have revealed the source of these conflicts between quantum theory and microwave experiments. Critical variables and constants were missing from quantum theory due to a minor mathematical inadvertence in Planck's original quantum work. As a result, erroneous concepts were formed nearly a century ago regarding the energetics and mechanisms of lower frequency light, such as in the microwave region. The new discoveries have revealed that the traditional concept of "photons" mistakenly attributed elementary particle status to what is actually an arbitrarily time-based collection of sub-photonic, elementary particles. In a mathematical dimensional sense, those time-based energy measurements cannot be mathematically equivalent to bond energies as historically believed. Only an "isolated quantity of energy", as De Broglie referred to it, can be equivalent to bond energy. With the aid of the new variables and constants, the non-equilibrium mechanisms of light in the microwave region can now be described. They include resonant absorption, splitting frequency stimulation leading to electronic excitation, and resonant acoustic transduction. Numerous practical engineering applications can be envisioned for non-equilibrium microwaves.

Soil Moisture Flow and Nitrate Movement Simulation through Deep and Heterogeneous Vadose Zone using Dual-porosity Approach

NASA Astrophysics Data System (ADS)

Yadav, B. K.; Tomar, J.; Harter, T.

2014-12-01

We investigate nitrate movement from non-point sources in deep, heterogeneous vadose zones, using multi-dimensional variably saturated flow and transport simulations. We hypothesize that porous media heterogeneity causes saturation variability that leads to preferential flow systems such that a significant portion of the vadose zone does not significantly contribute to flow. We solve Richards' equation and the advection-dispersion equation to simulate soil moisture and nitrate transport regimes in plot-scale experiments conducted in the San Joaquin Valley, California. We compare equilibrium against non-equilibrium (dual-porosity) approaches. In the equilibrium approach we consider each soil layer to have unique hydraulic properties as a whole, while in the dual-porosity approach we assume that large fractions of the porous flow domain are immobile. However we consider exchange of water and solute between mobile and immobile zone using the appropriate mass transfer terms. The results indicate that flow and transport in a nearly 16 m deep stratified vadose zone comprised of eight layers of unconsolidated alluvium experiences highly non-uniform, localized preferential flow and transport patterns leading to accelerated nitrate transfer. The equilibrium approach largely under-predicted the leaching of nitrate to groundwater while the dual-porosity approach showed higher rates of nitrate leaching, consistent with field observations. The dual-porosity approach slightly over-predicted nitrogen storage in the vadose zone, which may be the result of limited matrix flow or denitrification not accounted for in the model. Results of this study may be helpful to better predict fertilizer and pesticide retention times in deep vadose zone, prior to recharge into the groundwater flow system. Keywords: Nitrate, Preferential flow, Heterogeneous vadose zone, Dual-porosity approach

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Bullen, T.D.

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Development and application of a ray-tracing code integrating with 3D equilibrium mapping in LHD ECH experiments

NASA Astrophysics Data System (ADS)

Tsujimura, T., Ii; Kubo, S.; Takahashi, H.; Makino, R.; Seki, R.; Yoshimura, Y.; Igami, H.; Shimozuma, T.; Ida, K.; Suzuki, C.; Emoto, M.; Yokoyama, M.; Kobayashi, T.; Moon, C.; Nagaoka, K.; Osakabe, M.; Kobayashi, S.; Ito, S.; Mizuno, Y.; Okada, K.; Ejiri, A.; Mutoh, T.

2015-11-01

The central electron temperature has successfully reached up to 7.5 keV in large helical device (LHD) plasmas with a central high-ion temperature of 5 keV and a central electron density of 1.3× {{10}19} m-3. This result was obtained by heating with a newly-installed 154 GHz gyrotron and also the optimisation of injection geometry in electron cyclotron heating (ECH). The optimisation was carried out by using the ray-tracing code ‘LHDGauss’, which was upgraded to include the rapid post-processing three-dimensional (3D) equilibrium mapping obtained from experiments. For ray-tracing calculations, LHDGauss can automatically read the relevant data registered in the LHD database after a discharge, such as ECH injection settings (e.g. Gaussian beam parameters, target positions, polarisation and ECH power) and Thomson scattering diagnostic data along with the 3D equilibrium mapping data. The equilibrium map of the electron density and temperature profiles are then extrapolated into the region outside the last closed flux surface. Mode purity, or the ratio between the ordinary mode and the extraordinary mode, is obtained by calculating the 1D full-wave equation along the direction of the rays from the antenna to the absorption target point. Using the virtual magnetic flux surfaces, the effects of the modelled density profiles and the magnetic shear at the peripheral region with a given polarisation are taken into account. Power deposition profiles calculated for each Thomson scattering measurement timing are registered in the LHD database. The adjustment of the injection settings for the desired deposition profile from the feedback provided on a shot-by-shot basis resulted in an effective experimental procedure.

Impacts of energy consumption and emissions on the trip cost without late arrival at the equilibrium state

NASA Astrophysics Data System (ADS)

Tang, Tie-Qiao; Wang, Tao; Chen, Liang; Shang, Hua-Yan

2017-08-01

In this paper, we apply a car-following model, fuel consumption model, emission model and electricity consumption model to explore the influences of energy consumption and emissions on each commuter's trip costs without late arrival at the equilibrium state. The numerical results show that the energy consumption and emissions have significant impacts on each commuter's trip cost without late arrival at the equilibrium state. The fuel cost and emission cost prominently enhance each commuter's trip cost and the trip cost increases with the number of vehicles, which shows that considering the fuel cost and emission cost in the trip cost will destroy the equilibrium state. However, the electricity cost slightly enhances each commuter's trip cost, but the trip cost is still approximately a constant, which indicates that considering the electricity cost in the trip cost does not destroy the equilibrium state.

Linear theory for filtering nonlinear multiscale systems with model error

PubMed Central

Berry, Tyrus; Harlim, John

2014-01-01

In this paper, we study filtering of multiscale dynamical systems with model error arising from limitations in resolving the smaller scale processes. In particular, the analysis assumes the availability of continuous-time noisy observations of all components of the slow variables. Mathematically, this paper presents new results on higher order asymptotic expansion of the first two moments of a conditional measure. In particular, we are interested in the application of filtering multiscale problems in which the conditional distribution is defined over the slow variables, given noisy observation of the slow variables alone. From the mathematical analysis, we learn that for a continuous time linear model with Gaussian noise, there exists a unique choice of parameters in a linear reduced model for the slow variables which gives the optimal filtering when only the slow variables are observed. Moreover, these parameters simultaneously give the optimal equilibrium statistical estimates of the underlying system, and as a consequence they can be estimated offline from the equilibrium statistics of the true signal. By examining a nonlinear test model, we show that the linear theory extends in this non-Gaussian, nonlinear configuration as long as we know the optimal stochastic parametrization and the correct observation model. However, when the stochastic parametrization model is inappropriate, parameters chosen for good filter performance may give poor equilibrium statistical estimates and vice versa; this finding is based on analytical and numerical results on our nonlinear test model and the two-layer Lorenz-96 model. Finally, even when the correct stochastic ansatz is given, it is imperative to estimate the parameters simultaneously and to account for the nonlinear feedback of the stochastic parameters into the reduced filter estimates. In numerical experiments on the two-layer Lorenz-96 model, we find that the parameters estimated online, as part of a filtering procedure, simultaneously produce accurate filtering and equilibrium statistical prediction. In contrast, an offline estimation technique based on a linear regression, which fits the parameters to a training dataset without using the filter, yields filter estimates which are worse than the observations or even divergent when the slow variables are not fully observed. This finding does not imply that all offline methods are inherently inferior to the online method for nonlinear estimation problems, it only suggests that an ideal estimation technique should estimate all parameters simultaneously whether it is online or offline. PMID:25002829

Bridge pressure flow scour for clear water conditions

DOT National Transportation Integrated Search

2009-10-01

The equilibrium scour at a bridge caused by pressure flow with critical approach velocity in clear-water simulation conditions was studied both analytically and experimentally. The flume experiments revealed that (1) the measured equilibrium scour pr...

Modeling of Resistive Wall Modes in Tokamak and Reversed Field Pinch Configurations of KTX

NASA Astrophysics Data System (ADS)

Han, Rui; Zhu, Ping; Bai, Wei; Lan, Tao; Liu, Wandong

2016-10-01

Resistive wall mode is believed to be one of the leading causes for macroscopic degradation of plasma confinement in tokamaks and reversed field pinches (RFP). In this study, we evaluate the linear RWM instability of Keda Torus eXperiment (KTX) in both tokamak and RFP configurations. For the tokamak configuration, the extended MHD code NIMROD is employed for calculating the dependence of the RWM growth rate on the position and conductivity of the vacuum wall for a model tokamak equilibrium of KTX in the large aspect-ratio approximation. For the RFP configuration, the standard formulation of dispersion relation for RWM based on the MHD energy principle has been evaluated for a cylindrical α- Θ model of KTX plasma equilibrium, in an effort to investigate the effects of thin wall on the RWM in KTX. Full MHD calculations of RWM in the RFP configuration of KTX using the NIMROD code are also being developed. Supported by National Magnetic Confinement Fusion Science Program of China Grant Nos. 2014GB124002, 2015GB101004, 2011GB106000, and 2011GB106003.

Helical core reconstruction of a DIII-D hybrid scenario tokamak discharge

DOE PAGES

Cianciosa, Mark; Wingen, Andreas; Hirshman, Steven P.; ...

2017-05-18

Our paper presents the first fully 3-dimensional (3D) equilibrium reconstruction of a helical core in a tokamak device. Using a new parallel implementation of the Variational Moments Equilibrium Code (PARVMEC) coupled to V3FIT, 3D reconstructions can be performed at resolutions necessary to produce helical states in nominally axisymmetric tokamak equilibria. In a flux pumping experiment performed on DIII-D, an external n=1 field was applied while a 3/2 neoclassical tearing mode was suppressed using ECCD. The externally applied field was rotated past a set of fixed diagnostics at a 20 Hz frequency. Furthermore, the modulation, were found to be strongest in the core SXR and MSE channels, indicates a localized rotating 3D structure locked in phase with the applied field. Signals from multiple time slices are converted to a virtual rotation of modeled diagnostics adding 3D signal information. In starting from an axisymmetric equilibrium reconstruction solution, the reconstructed broader current profile flattens the q-profile, resulting in an m=1, n=1 perturbation of the magnetic axis that ismore » $$\\sim 50\\times $$ larger than the applied n=1 deformation of the edge. Error propagation confirms that the displacement of the axis is much larger than the uncertainty in the axis position validating the helical equilibrium.« less

Probing receptor-ligand interactions by sedimentation equilibrium

NASA Astrophysics Data System (ADS)

Philo, John S.

1997-05-01

While sedimentation equilibrium is most commonly used to characterize the molecular weight and state of association of single proteins, this technique is also a very powerful tool for probing the interactions between two or more different proteins, and can characterize both the binding stoichiometry and the equilibrium constants. To resolve the complex binding interactions that can occur in such systems, it is crucial to globally fit data from many experiments to a common binding model, including samples made with different mixing ratios and a wide range of total concentration. It is often also essential to constrain the parameters during fitting so that the fits correctly reproduce the molar ratio of proteins used in making each sample. We have applied this methodology to probe mechanisms of receptor activation for a number of hematopoietic receptors and their cognate ligands, using receptor extracellular domains expressed as soluble proteins. Such data can potentially help in the design of improved or new protein therapeutics, as well as in efforts to create small- molecular mimetics of protein hormones through structure- based drug design. Sedimentation equilibrium has shown that stem cell factor, erythropoietin, and granulocyte-colony stimulating factor can each dimerize their respective receptors in solution, but the mechanism of ligand-induced receptor dimerization for these three systems are strikingly different.

The removal of fluoride from aqueous solution by a lateritic soil adsorption: Kinetic and equilibrium studies.

PubMed

Iriel, Analia; Bruneel, Stijn P; Schenone, Nahuel; Cirelli, Alicia Fernández

2018-03-01

The use of natural sorbents to remove fluoride from drinking water is a promising alternative because of its low-cost and easy implementation. In this article, fluoride adsorption on a latosol soil from Misiones province (Argentina) was studied regarding kinetic and equilibrium aspects. Experiments were conducted in batch at room temperature under controlled conditions of pH 4-8) and ionic strength (1-10mM KNO 3 ). Experimental data indicated that adsorption processes followed a PSO kinetic where initial rates have showed to be influenced by pH solution. The necessary time to reach an equilibrium state had resulted approximately 30min. Equilibrium adsorption studies were performed at pH 8 which is similar to the natural groundwater. For that, fluoride adsorption data were successfully adjusted to Dubinin-Ataskhov model determining that the fluoride adsorption onto soil particles mainly followed a physical mechanism with a removal capacity of 0.48mgg -1 . Finally, a natural groundwater was tested with laterite obtaining a reduction close to 30% from initial concentration and without changing significantly the physicochemical properties of the natural water. Therefore, it was concluded that the use of lateritic soils for fluoride removal is very promising on a domestic scale. Copyright © 2017 Elsevier Inc. All rights reserved.

Helical core reconstruction of a DIII-D hybrid scenario tokamak discharge

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

Cianciosa, Mark; Wingen, Andreas; Hirshman, Steven P.

Our paper presents the first fully 3-dimensional (3D) equilibrium reconstruction of a helical core in a tokamak device. Using a new parallel implementation of the Variational Moments Equilibrium Code (PARVMEC) coupled to V3FIT, 3D reconstructions can be performed at resolutions necessary to produce helical states in nominally axisymmetric tokamak equilibria. In a flux pumping experiment performed on DIII-D, an external n=1 field was applied while a 3/2 neoclassical tearing mode was suppressed using ECCD. The externally applied field was rotated past a set of fixed diagnostics at a 20 Hz frequency. Furthermore, the modulation, were found to be strongest in the core SXR and MSE channels, indicates a localized rotating 3D structure locked in phase with the applied field. Signals from multiple time slices are converted to a virtual rotation of modeled diagnostics adding 3D signal information. In starting from an axisymmetric equilibrium reconstruction solution, the reconstructed broader current profile flattens the q-profile, resulting in an m=1, n=1 perturbation of the magnetic axis that ismore » $$\\sim 50\\times $$ larger than the applied n=1 deformation of the edge. Error propagation confirms that the displacement of the axis is much larger than the uncertainty in the axis position validating the helical equilibrium.« less

Testing electrostatic equilibrium in the ionosphere by detailed comparison of ground magnetic deflection and incoherent scatter radar.

NASA Astrophysics Data System (ADS)

Cosgrove, R. B.; Schultz, A.; Imamura, N.

2016-12-01

Although electrostatic equilibrium is always assumed in the ionosphere, there is no good theoretical or experimental justification for the assumption. In fact, recent theoretical investigations suggest that the electrostatic assumption may be grossly in error. If true, many commonly used modeling methods are placed in doubt. For example, the accepted method for calculating ionospheric conductance??field line integration??may be invalid. In this talk we briefly outline the theoretical research that places the electrostatic assumption in doubt, and then describe how comparison of ground magnetic field data with incoherent scatter radar (ISR) data can be used to test the electrostatic assumption in the ionosphere. We describe a recent experiment conducted for the purpose, where an array of magnetometers was temporalily installed under the Poker Flat AMISR.

Elastic behavior of a red blood cell with the membrane's nonuniform natural state: equilibrium shape, motion transition under shear flow, and elongation during tank-treading motion.

PubMed

Tsubota, Ken-Ichi; Wada, Shigeo; Liu, Hao

2014-08-01

Direct numerical simulations of the mechanics of a single red blood cell (RBC) were performed by considering the nonuniform natural state of the elastic membrane. A RBC was modeled as an incompressible viscous fluid encapsulated by an elastic membrane. The in-plane shear and area dilatation deformations of the membrane were modeled by Skalak constitutive equation, while out-of-plane bending deformation was formulated by the spring model. The natural state of the membrane with respect to in-plane shear deformation was modeled as a sphere ([Formula: see text]), biconcave disk shape ([Formula: see text]) and their intermediate shapes ([Formula: see text]) with the nonuniformity parameter [Formula: see text], while the natural state with respect to out-of-plane bending deformation was modeled as a flat plane. According to the numerical simulations, at an experimentally measured in-plane shear modulus of [Formula: see text] and an out-of-plane bending rigidity of [Formula: see text] of the cell membrane, the following results were obtained. (i) The RBC shape at equilibrium was biconcave discoid for [Formula: see text] and cupped otherwise; (ii) the experimentally measured fluid shear stress at the transition between tumbling and tank-treading motions under shear flow was reproduced for [Formula: see text]; (iii) the elongation deformation of the RBC during tank-treading motion from the simulation was consistent with that from in vitro experiments, irrespective of the [Formula: see text] value. Based on our RBC modeling, the three phenomena (i), (ii), and (iii) were mechanically consistent for [Formula: see text]. The condition [Formula: see text] precludes a biconcave discoid shape at equilibrium (i); however, it gives appropriate fluid shear stress at the motion transition under shear flow (ii), suggesting that a combined effect of [Formula: see text] and the natural state with respect to out-of-plane bending deformation is necessary for understanding details of the RBC mechanics at equilibrium. Our numerical results demonstrate that moderate nonuniformity in a membrane's natural state with respect to in-plane shear deformation plays a key role in RBC mechanics.

A Simplified Undergraduate Laboratory Experiment to Evaluate the Effect of the Ionic Strength on the Equilibrium Concentration Quotient of the Bromcresol Green Dye

ERIC Educational Resources Information Center

Rodriguez, Hernan B.; Mirenda, Martin

2012-01-01

A modified laboratory experiment for undergraduate students is presented to evaluate the effects of the ionic strength, "I", on the equilibrium concentration quotient, K[subscript c], of the acid-base indicator bromcresol green (BCG). The two-step deprotonation of the acidic form of the dye (sultone form), as it is dissolved in water, yields…

High beta and second stability region transport and stability analysis. Final report

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

Hughes, M.H.; Phillips, M.W.

1996-01-01

This report describes MHD equilibrium and stability studies carried out at Northrop Grumman`s Advanced Technology and Development Center during the period March 1 to December 31, 1995. Significant progress is reported in both ideal and resistive MHD modeling of TFTR plasmas. Specifically, attention is concentrated on analysis of Advanced Tokamak experiments at TFTR involving plasmas in which the q-profiles were non-monotonic.

Pre-equilibrium dynamics and heavy-ion observables

NASA Astrophysics Data System (ADS)

Heinz, Ulrich; Liu, Jia

2016-12-01

To bracket the importance of the pre-equilibrium stage on relativistic heavy-ion collision observables, we compare simulations where it is modeled by either free-streaming partons or fluid dynamics. These cases implement the assumptions of extremely weak vs. extremely strong coupling in the initial collision stage. Accounting for flow generated in the pre-equilibrium stage, we study the sensitivity of radial, elliptic and triangular flow on the switching time when the hydrodynamic description becomes valid. Using the hybrid code iEBE-VISHNU [C. Shen, Z. Qiu, H. Song, J. Bernhard, S. Bass and U. Heinz, Comput. Phys. Commun. 199 (2016) 61] we perform a multi-parameter search, constrained by particle ratios, integrated elliptic and triangular charged hadron flow, the mean transverse momenta of pions, kaons and protons, and the second moment < pT2 > of the proton transverse momentum spectrum, to identify optimized values for the switching time τs from pre-equilibrium to hydrodynamics, the specific shear viscosity η / s, the normalization factor of the temperature-dependent specific bulk viscosity (ζ / s) (T), and the switching temperature Tsw from viscous hydrodynamics to the hadron cascade UrQMD. With the optimized parameters, we predict and compare with experiment the pT-distributions of π, K, p, Λ, Ξ and Ω yields and their elliptic flow coefficients, focusing specifically on the mass-ordering of the elliptic flow for protons and Lambda hyperons which is incorrectly described by VISHNU without pre-equilibrium flow.

Noise analysis and relaxation experiments of transport of hydrophobic anions across lipid membranes at equilibrium and nonequilibrium.

PubMed

Junges, R; Kolb, H A

1983-06-01

Under equilibrium and nonequilibrium steady-state conditions, the spectral intensity of current noise SJ(f) generated by the transport of hydrophobic anions across lipid bilayer membranes was investigated. The experimental results were compared with different reaction models. SJ(f) showed a characteristic increase proportional to f2 between frequency-independent tails at low and high frequencies. This gradient was found to be independent of applied voltage which indicates the contribution of a single voltage-dependent reaction step of ion translocation across the membrane. From the shape of SJ(f) at low frequencies the rate constant of ion desorption from the membrane into the aqueous phase could be estimated. Unambiguous evidence for the application of a general model, which includes the coupling of slow ion diffusion in the aqueous phase to ion adsorption/desorption at the membrane interface, could not be obtained from the low-frequency shape of SJ(f). The shot noise of this ion transport determines the amplitude of SJ(f) at high frequencies which decreases with increasing voltage applied. Analysis of voltage-jump current-relaxation experiments and of current noise carried out on one membrane yielded significant differences of the derived ion partition coefficient. This deviation is qualitatively described on the basis of incomplete reaction steps.

Zero Power Non-Contact Suspension System with Permanent Magnet Motion Feedback

NASA Astrophysics Data System (ADS)

Sun, Feng; Oka, Koichi

This paper proposes a zero power control method for a permanent magnetic suspension system consisting mainly of a permanent magnet, an actuator, sensors, a suspended iron ball and a spring. A system using this zero power control method will consume quasi-zero power when the levitated object is suspended in an equilibrium state. To realize zero power control, a spring is installed in the magnetic suspension device to counterbalance the gravitational force on the actuator in the equilibrium position. In addition, an integral feedback loop in the controller affords zero actuator current when the device is in a balanced state. In this study, a model was set up for feasibility analysis, a prototype was manufactured for experimental confirmation, numerical simulations of zero power control with nonlinear attractive force were carried out based on the model, and experiments were completed to confirm the practicality of the prototype. The simulations and experiments were performed under varied conditions, such as without springs and without zero power control, with springs and without zero power control, with springs and with zero power control, using different springs and integral feedback gains. Some results are shown and analyzed in this paper. All results indicate that this zero power control method is feasible and effective for use in this suspension system with a permanent magnet motion feedback loop.

A Dealer Model of Foreign Exchange Market with Finite Assets

NASA Astrophysics Data System (ADS)

Hamano, Tomoya; Kanazawa, Kiyoshi; Takayasu, Hideki; Takayasu, Misako

An agent-based model is introduced to study the finite-asset effect in foreign exchange markets. We find that the transacted price asymptotically approaches an equilibrium price, which is determined by the monetary balance between the pair of currencies. We phenomenologically derive a formula to estimate the equilibrium price, and we model its relaxation dynamics around the equilibrium price on the basis of a Langevin-like equation.

Analysis of non-equilibrium phenomena in inductively coupled plasma generators

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

Zhang, W.; Panesi, M., E-mail: mpanesi@illinois.edu; Lani, A.

This work addresses the modeling of non-equilibrium phenomena in inductively coupled plasma discharges. In the proposed computational model, the electromagnetic induction equation is solved together with the set of Navier-Stokes equations in order to compute the electromagnetic and flow fields, accounting for their mutual interaction. Semi-classical statistical thermodynamics is used to determine the plasma thermodynamic properties, while transport properties are obtained from kinetic principles, with the method of Chapman and Enskog. Particle ambipolar diffusive fluxes are found by solving the Stefan-Maxwell equations with a simple iterative method. Two physico-mathematical formulations are used to model the chemical reaction processes: (1) Amore » Local Thermodynamics Equilibrium (LTE) formulation and (2) a thermo-chemical non-equilibrium (TCNEQ) formulation. In the TCNEQ model, thermal non-equilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules is accounted for. The electronic states of the chemical species are assumed in equilibrium with the vibrational temperature, whereas the rotational energy mode is assumed to be equilibrated with translation. Three different physical models are used to account for the coupling of chemistry and energy transfer processes. Numerical simulations obtained with the LTE and TCNEQ formulations are used to characterize the extent of non-equilibrium of the flow inside the Plasmatron facility at the von Karman Institute. Each model was tested using different kinetic mechanisms to assess the sensitivity of the results to variations in the reaction parameters. A comparison of temperatures and composition profiles at the outlet of the torch demonstrates that the flow is in non-equilibrium for operating conditions characterized by pressures below 30 000 Pa, frequency 0.37 MHz, input power 80 kW, and mass flow 8 g/s.« less

Analysis of non-equilibrium phenomena in inductively coupled plasma generators

NASA Astrophysics Data System (ADS)

Zhang, W.; Lani, A.; Panesi, M.

2016-07-01

This work addresses the modeling of non-equilibrium phenomena in inductively coupled plasma discharges. In the proposed computational model, the electromagnetic induction equation is solved together with the set of Navier-Stokes equations in order to compute the electromagnetic and flow fields, accounting for their mutual interaction. Semi-classical statistical thermodynamics is used to determine the plasma thermodynamic properties, while transport properties are obtained from kinetic principles, with the method of Chapman and Enskog. Particle ambipolar diffusive fluxes are found by solving the Stefan-Maxwell equations with a simple iterative method. Two physico-mathematical formulations are used to model the chemical reaction processes: (1) A Local Thermodynamics Equilibrium (LTE) formulation and (2) a thermo-chemical non-equilibrium (TCNEQ) formulation. In the TCNEQ model, thermal non-equilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules is accounted for. The electronic states of the chemical species are assumed in equilibrium with the vibrational temperature, whereas the rotational energy mode is assumed to be equilibrated with translation. Three different physical models are used to account for the coupling of chemistry and energy transfer processes. Numerical simulations obtained with the LTE and TCNEQ formulations are used to characterize the extent of non-equilibrium of the flow inside the Plasmatron facility at the von Karman Institute. Each model was tested using different kinetic mechanisms to assess the sensitivity of the results to variations in the reaction parameters. A comparison of temperatures and composition profiles at the outlet of the torch demonstrates that the flow is in non-equilibrium for operating conditions characterized by pressures below 30 000 Pa, frequency 0.37 MHz, input power 80 kW, and mass flow 8 g/s.

A Model for Siderophile Element Distribution in Planetary Differentiation

NASA Technical Reports Server (NTRS)

Humayun, M.; Rushmer, T.; Rankenburg, K.; Brandon, A. D.

2005-01-01

Planetary differentiation begins with partial melting of small planetesimals. At low degrees of partial melting, a sulfur-rich liquid segregates by physical mechanisms including deformation-assisted porous flow. Experimental studies of the physical mechanisms by which Fe-S melts segregate from the silicate matrix of a molten H chondrite are part of a companion paper. Geochemical studies of these experimental products revealed that metallic liquids were in equilibrium with residual metal in the H chondrite matrix. This contribution explores the geochemical signatures produced by early stages of core formation. Particularly, low-degree partial melt segregation of Fe-S liquids leaves residual metal in the silicate matrix. Some achondrites appear to be residues of partial melting, e.g., ureilites, which are known to contain metal. The metal in these achondrites may show a distinct elemental signature. To quantify the effect of sulfur on siderophile element contents of residual metal we have developed a model based on recent parametrizations of equilibrium solid metal-liquid metal partitioning experiments.

Adsorption of Zn(II) and Cd(II) ions in batch system by using the Eichhornia crassipes.

PubMed

Módenes, A N; Espinoza-Quiñones, F R; Borba, C E; Trigueros, D E G; Lavarda, F L; Abugderah, M M; Kroumov, A D

2011-01-01

In this work, the displacement effects on the sorption capacities of zinc and cadmium ions of the Eichornia crassipes-type biosorbent in batch binary system has been studied. Preliminary single metal sorption experiments were carried out. An improvement on the Zn(II) and Cd(II) ions removal was achieved by working at 30 °C temperature and with non-uniform biosorbent grain sizes. A 60 min equilibrium time was achieved for both Zn(II) and Cd(II) ions. Furthermore, it was found that the overall kinetic data were best described by the pseudo second-order kinetic model. Classical multi-component adsorption isotherms have been tested as well as a modified extended Langmuir isotherm model, showing good agreement with the equilibrium binary data. Around 0.65 mequiv./g maximum metal uptake associated with the E. crassipes biosorbent was attained and the E. crassipes biosorbent has shown higher adsorption affinity for the zinc ions than for the cadmium ones in the binary system.

Interactions of lysozyme in concentrated electrolyte solutions from dynamic light-scattering measurements.

PubMed Central

Kuehner, D E; Heyer, C; Rämsch, C; Fornefeld, U M; Blanch, H W; Prausnitz, J M

1997-01-01

The diffusion of hen egg-white lysozyme has been studied by dynamic light scattering in aqueous solutions of ammonium sulfate as a function of protein concentration to 30 g/liter. Experiments were conducted under the following conditions: pH 4-7 and ionic strength 0.05-5.0 M. Diffusivity data for ionic strengths up to 0.5 M were interpreted in the context of a two-body interaction model for monomers. From this analysis, two potential-of-mean-force parameters, the effective monomer charge, and the Hamaker constant were obtained. At higher ionic strength, the data were analyzed using a model that describes the diffusion coefficient of a polydisperse system of interacting protein aggregates in terms of an isodesmic, indefinite aggregation equilibrium constant. Data analysis incorporated multicomponent virial and hydrodynamic effects. The resulting equilibrium constants indicate that lysozyme does not aggregate significantly as ionic strength increases, even at salt concentrations near the point of salting-out precipitation. PMID:9414232

Photophysical behavior of polyatomic molecules

NASA Astrophysics Data System (ADS)

Ware, W. R.

1980-10-01

Part one of this report deals with attempts over the past several years to devise a more sophisticated theory of diffusion controlled reactions than that presented by Collins and Kimball. In particular, the investigators were interested in a more realistic formulation of the problem of high concentration quenching where quenches in the vicinity of the molecular to be quenched must be considered. It was desired however, to obtain a formalism which was tractable mathematically and which contained parameters which would be related to experiment. Part two deals with the photophysics of systems exhibiting molecular association both in the ground and excited states has been studied. The emphasis has been on kinetic models, the measurement of rate constants associated with these models, and the determination of activation parameters and equilibrium thermodynamic parameters associated with the exciplex formation and disappearance. Studies of solvent effects and steric effects on the behavior of exciplex systems have been carried out. The case of rapid equilibrium where the monomer and exciplex decay with the same rate constant has also been examined.

Identifying protein complexes in PPI network using non-cooperative sequential game.

PubMed

Maulik, Ujjwal; Basu, Srinka; Ray, Sumanta

2017-08-21

Identifying protein complexes from protein-protein interaction (PPI) network is an important and challenging task in computational biology as it helps in better understanding of cellular mechanisms in various organisms. In this paper we propose a noncooperative sequential game based model for protein complex detection from PPI network. The key hypothesis is that protein complex formation is driven by mechanism that eventually optimizes the number of interactions within the complex leading to dense subgraph. The hypothesis is drawn from the observed network property named small world. The proposed multi-player game model translates the hypothesis into the game strategies. The Nash equilibrium of the game corresponds to a network partition where each protein either belong to a complex or form a singleton cluster. We further propose an algorithm to find the Nash equilibrium of the sequential game. The exhaustive experiment on synthetic benchmark and real life yeast networks evaluates the structural as well as biological significance of the network partitions.

Multiagent Reinforcement Learning With Sparse Interactions by Negotiation and Knowledge Transfer.

PubMed

Zhou, Luowei; Yang, Pei; Chen, Chunlin; Gao, Yang

2017-05-01

Reinforcement learning has significant applications for multiagent systems, especially in unknown dynamic environments. However, most multiagent reinforcement learning (MARL) algorithms suffer from such problems as exponential computation complexity in the joint state-action space, which makes it difficult to scale up to realistic multiagent problems. In this paper, a novel algorithm named negotiation-based MARL with sparse interactions (NegoSIs) is presented. In contrast to traditional sparse-interaction-based MARL algorithms, NegoSI adopts the equilibrium concept and makes it possible for agents to select the nonstrict equilibrium-dominating strategy profile (nonstrict EDSP) or meta equilibrium for their joint actions. The presented NegoSI algorithm consists of four parts: 1) the equilibrium-based framework for sparse interactions; 2) the negotiation for the equilibrium set; 3) the minimum variance method for selecting one joint action; and 4) the knowledge transfer of local Q -values. In this integrated algorithm, three techniques, i.e., unshared value functions, equilibrium solutions, and sparse interactions are adopted to achieve privacy protection, better coordination and lower computational complexity, respectively. To evaluate the performance of the presented NegoSI algorithm, two groups of experiments are carried out regarding three criteria: 1) steps of each episode; 2) rewards of each episode; and 3) average runtime. The first group of experiments is conducted using six grid world games and shows fast convergence and high scalability of the presented algorithm. Then in the second group of experiments NegoSI is applied to an intelligent warehouse problem and simulated results demonstrate the effectiveness of the presented NegoSI algorithm compared with other state-of-the-art MARL algorithms.

Solar heating of common lunar minerals for the production of oxygen

NASA Technical Reports Server (NTRS)

Senior, C. L.

1991-01-01

The purpose of this work was to demonstrate the feasibility of vapor-phase reduction (pyrolysis) of lunar materials to produce oxygen. Solar furnace experiments were conducted on two common lunar minerals, ilmenite and anorthite. Thermodynamic equilibrium calculations predicted that ilmenite should show a larger pressure increase than anorthite under conditions of the experiments and this was confirmed by the experiments. The measured mass loss of the ilmenite sample was consistent with loss of oxygen by reduction of iron in the liquid phase; this result was also predicted from equilibrium calculations. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2500 K, giving total gas pressures of 0.01 to 1 torr. Bulk regolith can be used as a feedstock without extensive beneficiation. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts from the process.

Watching Faults Grow in Sand

NASA Astrophysics Data System (ADS)

Cooke, M. L.

2015-12-01

Accretionary sandbox experiments provide a rich environment for investigating the processes of fault development. These experiments engage students because 1) they enable direct observation of fault growth, which is impossible in the crust (type 1 physical model), 2) they are not only representational but can also be manipulated (type 2 physical model), 3) they can be used to test hypotheses (type 3 physical model) and 4) they resemble experiments performed by structural geology researchers around the world. The structural geology courses at UMass Amherst utilize a series of accretionary sandboxes experiments where students first watch a video of an experiment and then perform a group experiment. The experiments motivate discussions of what conditions they would change and what outcomes they would expect from these changes; hypothesis development. These discussions inevitably lead to calculations of the scaling relationships between model and crustal fault growth and provide insight into the crustal processes represented within the dry sand. Sketching of the experiments has been shown to be a very effective assessment method as the students reveal which features they are analyzing. Another approach used at UMass is to set up a forensic experiment. The experiment is set up with spatially varying basal friction before the meeting and students must figure out what the basal conditions are through the experiment. This experiment leads to discussions of equilibrium and force balance within the accretionary wedge. Displacement fields can be captured throughout the experiment using inexpensive digital image correlation techniques to foster quantitative analysis of the experiments.

Tidal Heating in Enceladus

NASA Astrophysics Data System (ADS)

Meyer, Jennifer; Wisdom, J.

2007-07-01

The heating in Enceladus in an equilibrium resonant configuration with other saturnian satellites can be estimated independently of the physical properties of Enceladus. Our results update the values obtained for the equilibrium tidal heating found by Lissauer et al. (1984) and Peale (2003). We find that equilibrium tidal heating cannot account for the heat that is observed to be coming from Enceladus, and current heating rates are even less for conventional estimates of the Love number for Enceladus. Even allowing for a much larger dynamic Love number, as can occur in viscoelastic models (Ross and Schubert, 1989), the equilibrium tidal heating is less than the heat observed to be coming from Enceladus. One resolution is that the tidal equilibrium is unstable and that the system oscillates about equilibrium. Yoder (1981) suggested that Enceladus might oscillate about equilibrium if the Q of Enceladus is stress dependent. An alternate suggestion was made by Ojakangas and Stevenson (1986), who emphasized the possible temperature dependence of Q. In these models Enceladus would now be releasing heat stored during a recent high eccentricity phase. However, we have shown that the Ojakangas and Stevenson model does not produce oscillations for parameters appropriate for Enceladus. Other low-order resonance configurations are possible for the saturnian satellites in the past. These include the 3:2 Mimas-Enceladus and the 3:4 Enceladus-Tethys resonances. The latter resonance has no equilibrium because the orbits are diverging, and the former has an equilibrium heating rate of only 0.48 GW. So equilibrium heating at past resonances is no more successful at explaining past resurfacing events than equilibrium heating is at explaining the present activity.

The negotiated equilibrium model of spinal cord function.

PubMed

Wolpaw, Jonathan R

2018-04-16

The belief that the spinal cord is hardwired is no longer tenable. Like the rest of the CNS, the spinal cord changes during growth and aging, when new motor behaviours are acquired, and in response to trauma and disease. This paper describes a new model of spinal cord function that reconciles its recently appreciated plasticity with its long recognized reliability as the final common pathway for behaviour. According to this model, the substrate of each motor behaviour comprises brain and spinal plasticity: the plasticity in the brain induces and maintains the plasticity in the spinal cord. Each time a behaviour occurs, the spinal cord provides the brain with performance information that guides changes in the substrate of the behaviour. All the behaviours in the repertoire undergo this process concurrently; each repeatedly induces plasticity to preserve its key features despite the plasticity induced by other behaviours. The aggregate process is a negotiation among the behaviours: they negotiate the properties of the spinal neurons and synapses that they all use. The ongoing negotiation maintains the spinal cord in an equilibrium - a negotiated equilibrium - that serves all the behaviours. This new model of spinal cord function is supported by laboratory and clinical data, makes predictions borne out by experiment, and underlies a new approach to restoring function to people with neuromuscular disorders. Further studies are needed to test its generality, to determine whether it may apply to other CNS areas such as the cerebral cortex, and to develop its therapeutic implications. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

USGS Publications Warehouse

Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

2003-01-01

In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Application of Empirical Peleg Model to Study the Water Adsorption of Full Cream Milk in Drying Process

NASA Astrophysics Data System (ADS)

Hashib, S. Abd; Rosli, H.; Suzihaque, M. U. H.; Zaki, N. A. Md; Ibrahim, U. K.

2017-06-01

The ability of spray dryer in producing full cream milk at different inlet temperatures and the effectiveness of empirical model used in order to interpret the drying process data is evaluated in this study. In this study, a lab-scale spray dryer was used to dry full cream milk into powder with inlet temperature from 100 to 160°C with a constant pump speed 4rpm. Peleg empirical model was chosen in order to manipulate the drying data into the mathematical equation. This research was carry out specifically to determine the equilibrium moisture content of full cream milk powder at various inlet temperature and to evaluate the effectiveness of Peleg empirical model equation in order to describe the moisture sorption curves for full cream milk. There were two conditions set for this experiments; in the first condition (C1), further drying process of milk powder in the oven at 98°C to 100°C while the second condition (C2) is mixing the milk powder with different salt solutions like Magnesium Chloride (MgCl), Potassium Nitrite (KNO2), Sodium Nitrite (NaNO2) and Ammonium Sulfate ((NH4)2SO4). For C1, the optimum temperature were 160°C with equilibrium moisture content at 3.16 weight dry basis and slowest sorption rates (dM/dt) at 0.0743 weight dry basis/hr. For C2, the best temperature for the mixture of dry samples with MgCl is at 115°C with equilibrium moisture content and sorption rates is -78.079 weight dry basis and 0.01 weight dry basis/hr. The best temperature for the mixture of milk powder with KNO2 is also at 115°C with equilibrium moisture content and sorption rates at -83.9645 weight dry basis and 0.0008 weight dry basis/hr respectively. For mixture of dry samples with NaNO2, the best temperature is 160°C with equilibrium moisture content and sorption rates at 84.1306 weight dry basis and 0.0013 weight dry basis/hr respectively. Lastly, the mixture of dry samples with ((NH4)2SO4 where the best temperature is at 115°C with equilibrium moisture content -83.8778 weight dry basis and sorption rates at 0.0021 weight dry basis/hr. The best temperature selected best on the lowest moisture content formed and also the slowest sorption rates.

Mechanical approach to chemical transport

PubMed Central

Kocherginsky, Nikolai; Gruebele, Martin

2016-01-01

Nonequilibrium thermodynamics describes the rates of transport phenomena with the aid of various thermodynamic forces, but often the phenomenological transport coefficients are not known, and the description is not easily connected with equilibrium relations. We present a simple and intuitive model to address these issues. Our model is based on Lagrangian dynamics for chemical systems with dissipation, so one may think of the model as physicochemical mechanics. Using one main equation, the model allows a systematic derivation of all transport and equilibrium equations, subject to the limitation that heat generated or absorbed in the system must be small for the model to be valid. A table with all major examples of transport and equilibrium processes described using physicochemical mechanics is given. In equilibrium, physicochemical mechanics reduces to standard thermodynamics and the Gibbs–Duhem relation, and we show that the First and Second Laws of thermodynamics are satisfied for our system plus bath model. Out of equilibrium, our model provides relationships between transport coefficients and describes system evolution in the presence of several simultaneous external fields. The model also leads to an extension of the Onsager–Casimir reciprocal relations for properties simultaneously transported by many components. PMID:27647899

Workshop on the Physics and Chemistry of Magma Oceans from 1 Bar to 4 Mbar

NASA Technical Reports Server (NTRS)

Agee, Carl B. (Editor); Longhi, John (Editor)

1992-01-01

Evidence for the existence of magma oceans is discussed in great detail, and among the many new items introduced were high-pressure phase equilibrium experiments, calculations of depth of impact-produced melting, models incorporating crystal growth rates with degree of crystallinity and convection, and models of hard turbulent convection. It was agreed that before we can point to some present-day observable parameters and confidently establish the existence of magma oceans, we must learn much more about their phase equilibria and solidification dynamics.

Equilibrium pricing in an order book environment: Case study for a spin model

NASA Astrophysics Data System (ADS)

Meudt, Frederik; Schmitt, Thilo A.; Schäfer, Rudi; Guhr, Thomas

2016-07-01

When modeling stock market dynamics, the price formation is often based on an equilibrium mechanism. In real stock exchanges, however, the price formation is governed by the order book. It is thus interesting to check if the resulting stylized facts of a model with equilibrium pricing change, remain the same or, more generally, are compatible with the order book environment. We tackle this issue in the framework of a case study by embedding the Bornholdt-Kaizoji-Fujiwara spin model into the order book dynamics. To this end, we use a recently developed agent based model that realistically incorporates the order book. We find realistic stylized facts. We conclude for the studied case that equilibrium pricing is not needed and that the corresponding assumption of a ;fundamental; price may be abandoned.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

Simplified Thermo-Chemical Modelling For Hypersonic Flow

NASA Astrophysics Data System (ADS)

Sancho, Jorge; Alvarez, Paula; Gonzalez, Ezequiel; Rodriguez, Manuel

2011-05-01

Hypersonic flows are connected with high temperatures, generally associated with strong shock waves that appear in such flows. At high temperatures vibrational degrees of freedom of the molecules may become excited, the molecules may dissociate into atoms, the molecules or free atoms may ionize, and molecular or ionic species, unimportant at lower temperatures, may be formed. In order to take into account these effects, a chemical model is needed, but this model should be simplified in order to be handled by a CFD code, but with a sufficient precision to take into account the physics more important. This work is related to a chemical non-equilibrium model validation, implemented into a commercial CFD code, in order to obtain the flow field around bodies in hypersonic flow. The selected non-equilibrium model is composed of seven species and six direct reactions together with their inverse. The commercial CFD code where the non- equilibrium model has been implemented is FLUENT. For the validation, the X38/Sphynx Mach 20 case is rebuilt on a reduced geometry, including the 1/3 Lref forebody. This case has been run in laminar regime, non catalytic wall and with radiative equilibrium wall temperature. The validated non-equilibrium model is applied to the EXPERT (European Experimental Re-entry Test-bed) vehicle at a specified trajectory point (Mach number 14). This case has been run also in laminar regime, non catalytic wall and with radiative equilibrium wall temperature.

Spatio-temporal patterns of bacteria caused by collective motion

NASA Astrophysics Data System (ADS)

Kitsunezaki, So

2006-04-01

In incubation experiments on bacterial colonies of Proteus mirabilis, collective motion of bacteria is found to generate macroscopic turbulent patterns on the surface of agar media. We propose a mathematical model to describe the time evolution of the positional and directional distributions of motile bacteria in such systems, and investigate this model both numerically and analytically. It is shown that as the average density of bacteria increases, nonuniform swarming patterns emerge from a uniform stationary state. For a sufficient large density, we find that spiral patterns are caused by interactions between the local bacteria densities and the rotational mode of the collective motion. Unidirectional spiral patterns similar to those observed in experiments appear in the case in which the equilibrium directional distribution is asymmetric.

Improving fast-ion confinement in high-performance discharges by suppressing Alfvén eigenmodes

DOE PAGES

Kramer, Geritt J.; Podestà, Mario; Holcomb, Christopher; ...

2017-03-28

Here, we show that the degradation of fast-ion confinement in steady-state DIII-D discharges is quantitatively consistent with predictions based on the effects of multiple unstable Alfven eigenmodes on beam-ion transport. Simulation and experiment show that increasing the radius where the magnetic safety factor has its minimum is effective in minimizing beam-ion transport. This is favorable for achieving high performance steady-state operation in DIII-D and future reactors. A comparison between the experiments and a critical gradient model, in which only equilibrium profiles were used to predict the most unstable modes, show that in a number of cases this model reproduces themore » measured neutron rate well.« less

Modélisation morphodynamique cross-shore d'un estran vaseux

NASA Astrophysics Data System (ADS)

Waeles, Benoı̂t; Le Hir, Pierre; Silva Jacinto, Ricardo

2004-08-01

Numerical experiments were performed to simulate the profile evolution of an intertidal mudflat with a 1D cross-shore morphodynamical model. First, the hydrodynamical forcing is a cross-shore tidal current due to semi-diurnal variations of the free surface elevation at the open boundary. Further, considering the conservation of the action density of surface gravity waves, a wave height (and resulting bottom shear stress) calculation is added to the morphodynamical model. Results of the numerical experiments show that the shape of the profile reaches equilibrium. The mudflat progrades continually when the forcing is tide only, whereas it can be steady under the simultaneous action of tide and waves. To cite this article: B. Waeles et al., C. R. Geoscience 336 (2004).

Equilibrium Climate Sensitivity Obtained From Multimillennial Runs of Two GFDL Climate Models

NASA Astrophysics Data System (ADS)

Paynter, D.; Frölicher, T. L.; Horowitz, L. W.; Silvers, L. G.

2018-02-01

Equilibrium climate sensitivity (ECS), defined as the long-term change in global mean surface air temperature in response to doubling atmospheric CO2, is usually computed from short atmospheric simulations over a mixed layer ocean, or inferred using a linear regression over a short-time period of adjustment. We report the actual ECS from multimillenial simulations of two Geophysical Fluid Dynamics Laboratory (GFDL) general circulation models (GCMs), ESM2M, and CM3 of 3.3 K and 4.8 K, respectively. Both values are 1 K higher than estimates for the same models reported in the Fifth Assessment Report of the Intergovernmental Panel on Climate Change obtained by regressing the Earth's energy imbalance against temperature. This underestimate is mainly due to changes in the climate feedback parameter (-α) within the first century after atmospheric CO2 has stabilized. For both GCMs it is possible to estimate ECS with linear regression to within 0.3 K by increasing CO2 at 1% per year to doubling and using years 51-350 after CO2 is constant. We show that changes in -α differ between the two GCMs and are strongly tied to the changes in both vertical velocity at 500 hPa (ω500) and estimated inversion strength that the GCMs experience during the progression toward the equilibrium. This suggests that while cloud physics parametrizations are important for determining the strength of -α, the substantially different atmospheric state resulting from a changed sea surface temperature pattern may be of equal importance.

Computing molecular fluctuations in biochemical reaction systems based on a mechanistic, statistical theory of irreversible processes.

PubMed

Kulasiri, Don

2011-01-01

We discuss the quantification of molecular fluctuations in the biochemical reaction systems within the context of intracellular processes associated with gene expression. We take the molecular reactions pertaining to circadian rhythms to develop models of molecular fluctuations in this chapter. There are a significant number of studies on stochastic fluctuations in intracellular genetic regulatory networks based on single cell-level experiments. In order to understand the fluctuations associated with the gene expression in circadian rhythm networks, it is important to model the interactions of transcriptional factors with the E-boxes in the promoter regions of some of the genes. The pertinent aspects of a near-equilibrium theory that would integrate the thermodynamical and particle dynamic characteristics of intracellular molecular fluctuations would be discussed, and the theory is extended by using the theory of stochastic differential equations. We then model the fluctuations associated with the promoter regions using general mathematical settings. We implemented ubiquitous Gillespie's algorithms, which are used to simulate stochasticity in biochemical networks, for each of the motifs. Both the theory and the Gillespie's algorithms gave the same results in terms of the time evolution of means and variances of molecular numbers. As biochemical reactions occur far away from equilibrium-hence the use of the Gillespie algorithm-these results suggest that the near-equilibrium theory should be a good approximation for some of the biochemical reactions. © 2011 Elsevier Inc. All rights reserved.

Hawking radiation and nonequilibrium quantum critical current noise.

PubMed

Sonner, Julian; Green, A G

2012-08-31

The dynamical scaling of quantum critical systems in thermal equilibrium may be inherited in the driven steady state, leading to universal out-of-equilibrium behavior. This attractive notion has been demonstrated in just a few cases. We demonstrate how holography-a mapping between the quantum critical system and a gravity dual-provides an illuminating perspective and new results. Nontrivial out-of-equilibrium universality is particularly apparent in current noise, which is dual to Hawking radiation in the gravitational system. We calculate this in a two-dimensional system driven by a strong in-plane electric field and deduce a universal scaling function interpolating between previously established equilibrium and far-from-equilibrium current noise. Since this applies at all fields, out-of-equilibrium experiments no longer require very high fields for comparison with theory.

Local thermodynamic equilibrium for globally disequilibrium open systems under stress

NASA Astrophysics Data System (ADS)

Podladchikov, Yury

2016-04-01

Predictive modeling of far and near equilibrium processes is essential for understanding of patterns formation and for quantifying of natural processes that are never in global equilibrium. Methods of both equilibrium and non-equilibrium thermodynamics are needed and have to be combined. For example, predicting temperature evolution due to heat conduction requires simultaneous use of equilibrium relationship between internal energy and temperature via heat capacity (the caloric equation of state) and disequilibrium relationship between heat flux and temperature gradient. Similarly, modeling of rocks deforming under stress, reactions in system open for the porous fluid flow, or kinetic overstepping of the equilibrium reaction boundary necessarily needs both equilibrium and disequilibrium material properties measured under fundamentally different laboratory conditions. Classical irreversible thermodynamics (CIT) is the well-developed discipline providing the working recipes for the combined application of mutually exclusive experimental data such as density and chemical potential at rest under constant pressure and temperature and viscosity of the flow under stress. Several examples will be presented.

Batch and fixed-bed column studies for biosorption of Zn(II) ions onto pongamia oil cake (Pongamia pinnata) from biodiesel oil extraction.

PubMed

Shanmugaprakash, M; Sivakumar, V

2015-12-01

The present work, analyzes the potential of defatted pongamia oil cake (DPOC) for the biosorption of Zn(II) ions from aqueous solutions in the both batch and column mode. Batch experiments were conducted to evaluate the optimal pH, effect of adsorbent dosage, initial Zn(II) ions concentration and contact time. The biosorption equilibrium and kinetics data for Zn(II) ions onto the DPOC were studied in detail, using several models, among all it was found to be that, Freundlich and the second-order model explained the equilibrium data well. The calculated thermodynamic parameters had shown that the biosorption of Zn(II) ions was exothermic and spontaneous in nature. Batch desorption studies showed that the maximum Zn(II) recovery occurred, using 0.1 M EDTA. The Bed Depth Service Time (BDST) and the Thomas model was successfully employed to evaluate the model parameters in the column mode. The results indicated that the DPOC can be applied as an effective and eco-friendly biosorbent for the removal of Zn(II) ions in polluted wastewater. Copyright © 2015 Elsevier Ltd. All rights reserved.

The deconfining phase transition in and out of equilibrium

NASA Astrophysics Data System (ADS)

Bazavov, Oleksiy

Recent experiments carried out at the Relativistic Heavy Ion Collider at the Brookhaven National Laboratory provide strong evidence that a matter can be driven from a confined, low-temperature phase, observed in our every day world into a deconfined high-temperature phase of liberated quarks and gluons. The equilibrium and dynamical properties of the deconfining phase transition are thus of great theoretical interest, since they also provide an information about the first femtoseconds of the evolution of our Universe, when the hot primordial soup while cooling has undergone a chain of phase transitions. The aspects of the deconfining phase transition studied in this work include: the dynamics of the SU(3) gauge theory after the heating quench (which models rapid heating in the heavy-ion collisions), equilibrium properties of the phase transition in the SU(3) gauge theory with boundaries at low temperature (small volumes at RHIC suggest that boundary effects cannot be neglected and periodic boundary conditions normally used in lattice simulations do not correspond to the experimental situation), and a study of the order of the transition in U(1) gauge theory.

Response surface methodology for cadmium biosorption on Pseudomonas aeruginosa.

PubMed

Ahmady-Asbchin, Salman

2016-01-01

In this research the effects of various physicochemical factors on Cd(2+) biosorption such as initial metal concentration, pH and contact exposure time were studied. This study has shown a Cd(2+) biosorption, equilibrium time of about 5 min for Pseudomonas aeruginosa and the adsorption equilibrium data were well described by Langmuir equation. The maximum capacity for biosorption has been extrapolated to 0.56 mmol.g(-1) for P. aeruginosa. The thermodynamic properties ΔG(0), ΔH(0), and ΔS(0) of Cd(2+) for biosorption were analyzed by the equilibrium constant value obtained from experimented data at different temperatures. The results show that biosorption of Cd(2+) by P. aeruginosa are endothermic and spontaneous with ΔH value of 36.35 J.mol(-1). By response surface methodology, the quadratic model has adequately described the experimental data based on the adjusted determination coefficient (R(2) = 0.98). The optimum conditions for maximum uptake onto the biosorbent were established at 0.5 g.l(-1) biosorbent concentration, pH 6 for the aqueous solution, and a temperature of 30 °C.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection

NASA Astrophysics Data System (ADS)

Cox, Courtney E.; Phifer, Jeremy R.; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T.; O'Loughlin, Elizabeth J.; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T.; Paluch, Andrew S.

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection.

PubMed

Cox, Courtney E; Phifer, Jeremy R; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T; O'Loughlin, Elizabeth J; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T; Paluch, Andrew S

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

New Target for Cosmic Axion Searches.

PubMed

Baumann, Daniel; Green, Daniel; Wallisch, Benjamin

2016-10-21

Future cosmic microwave background experiments have the potential to probe the density of relativistic species at the subpercent level. This sensitivity allows light thermal relics to be detected up to arbitrarily high decoupling temperatures. Conversely, the absence of a detection would require extra light species never to have been in equilibrium with the Standard Model. In this Letter, we exploit this feature to demonstrate the sensitivity of future cosmological observations to the couplings of axions to photons, gluons, and charged fermions. In many cases, the constraints achievable from cosmology will surpass existing bounds from laboratory experiments and astrophysical observations by orders of magnitude.

Climate simulations and projections with a super-parameterized climate model

DOE PAGES

Stan, Cristiana; Xu, Li

2014-07-01

The mean climate and its variability are analyzed in a suite of numerical experiments with a fully coupled general circulation model in which subgrid-scale moist convection is explicitly represented through embedded 2D cloud-system resolving models. Control simulations forced by the present day, fixed atmospheric carbon dioxide concentration are conducted using two horizontal resolutions and validated against observations and reanalyses. The mean state simulated by the higher resolution configuration has smaller biases. Climate variability also shows some sensitivity to resolution but not as uniform as in the case of mean state. The interannual and seasonal variability are better represented in themore » simulation at lower resolution whereas the subseasonal variability is more accurate in the higher resolution simulation. The equilibrium climate sensitivity of the model is estimated from a simulation forced by an abrupt quadrupling of the atmospheric carbon dioxide concentration. The equilibrium climate sensitivity temperature of the model is 2.77 °C, and this value is slightly smaller than the mean value (3.37 °C) of contemporary models using conventional representation of cloud processes. As a result, the climate change simulation forced by the representative concentration pathway 8.5 scenario projects an increase in the frequency of severe droughts over most of the North America.« less

The stability of amino acids at submarine hydrothermal vent temperatures

NASA Technical Reports Server (NTRS)

Bada, Jeffrey L.; Miller, Stanley L.; Zhao, Meixun

1995-01-01

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Ionization and excitation in cool giant stars. I - Hydrogen and helium

NASA Technical Reports Server (NTRS)

Luttermoser, Donald G.; Johnson, Hollis R.

1992-01-01

The influence that non-LTE radiative transfer has on the electron density, ionization equilibrium, and excitation equilibrium in model atmospheres representative of both oxygen-rich and carbon-rich red giant stars is demonstrated. The radiative transfer and statistical equilibrium equations are solved self-consistently for H, H(-), H2, He I, C I, C II, Na I, Mg I, Mg II, Ca I, and Ca II in a plane-parallel static medium. Calculations are made for both radiative-equilibrium model photospheres alone and model photospheres with attached chromospheric models as determined semiempirically with IUE spectra of g Her (M6 III) and TX Psc (C6, 2). The excitation and ionization results for hydrogen and helium are reported.

Model non-equilibrium molecular dynamics simulations of heat transfer from a hot gold surface to an alkylthiolate self-assembled monolayer.

PubMed

Zhang, Yue; Barnes, George L; Yan, Tianying; Hase, William L

2010-05-07

Model non-equilibrium molecular dynamics (MD) simulations are presented of heat transfer from a hot Au {111} substrate to an alkylthiolate self-assembled monolayer (H-SAM) to assist in obtaining an atomic-level understanding of experiments by Wang et al. (Z. Wang, J. A. Carter, A. Lagutchev, Y. K. Koh, N.-H. Seong, D. G. Cahill, and D. D. Dlott, Science, 2007, 317, 787). Different models are considered to determine how they affect the heat transfer dynamics. They include temperature equilibrated (TE) and temperature gradient (TG) thermostat models for the Au(s) surface, and soft and stiff S/Au(s) models for bonding of the S-atoms to the Au(s) surface. A detailed analysis of the non-equilibrium heat transfer at the heterogeneous interface is presented. There is a short time temperature gradient within the top layers of the Au(s) surface. The S-atoms heat rapidly, much faster than do the C-atoms in the alkylthiolate chains. A high thermal conductivity in the H-SAM, perpendicular to the interface, results in nearly identical temperatures for the CH(2) and CH(3) groups versus time. Thermal-induced disorder is analyzed for the Au(s) substrate, the S/Au(s) interface and the H-SAM. Before heat transfer occurs from the hot Au(s) substrate to the H-SAM, there is disorder at the S/Au(s) interface and within the alkylthiolate chains arising from heat-induced disorder near the surface of hot Au(s). The short-time rapid heating of the S-atoms enhances this disorder. The increasing disorder of H-SAM chains with time results from both disorder at the Au/S interface and heat transfer to the H-SAM chains.

Ignition conditions relaxation for central hot-spot ignition with an ion-electron non-equilibrium model

NASA Astrophysics Data System (ADS)

Fan, Zhengfeng; Liu, Jie

2016-10-01

We present an ion-electron non-equilibrium model, in which the hot-spot ion temperature is higher than its electron temperature so that the hot-spot nuclear reactions are enhanced while energy leaks are considerably reduced. Theoretical analysis shows that the ignition region would be significantly enlarged in the hot-spot rhoR-T space as compared with the commonly used equilibrium model. Simulations show that shocks could be utilized to create and maintain non-equilibrium conditions within the hot spot, and the hot-spot rhoR requirement is remarkably reduced for achieving self-heating. In NIF high-foot implosions, it is observed that the x-ray enhancement factors are less than unity, which is not self-consistent and is caused by assuming Te =Ti. And from this non-consistency, we could infer that ion-electron non-equilibrium exists in the high-foot implosions and the ion temperature could be 9% larger than the equilibrium temperature.

Non-equilibrium phase transitions in a driven-dissipative system of interacting bosons

NASA Astrophysics Data System (ADS)

Young, Jeremy T.; Foss-Feig, Michael; Gorshkov, Alexey V.; Maghrebi, Mohammad F.

2017-04-01

Atomic, molecular, and optical systems provide unique opportunities to study simple models of driven-dissipative many-body quantum systems. Typically, one is interested in the resultant steady state, but the non-equilibrium nature of the physics involved presents several problems in understanding its behavior theoretically. Recently, it has been shown that in many of these models, it is possible to map the steady-state phase transitions onto classical equilibrium phase transitions. In the language of Keldysh field theory, this relation typically only becomes apparent after integrating out massive fields near the critical point, leaving behind a single massless field undergoing near-equilibrium dynamics. In this talk, we study a driven-dissipative XXZ bosonic model and discover critical points at which two fields become gapless. Each critical point separates three different possible phases: a uniform phase, an anti-ferromagnetic phase, and a limit cycle phase. Furthermore, a description in terms of an equilibrium phase transition does not seem possible, so the associated phase transitions appear to be inherently non-equilibrium.

Radiation-induced equilibrium is a balance between tumor cell proliferation and T cell-mediated killing

PubMed Central

Liang, Hua; Deng, Liufu; Chmura, Steven; Burnette, Byron; Liadis, Nicole; Darga, Thomas; Beckett, Michael A.; Lingen, Mark W.; Witt, MaryEllyn; Weichselbaum, Ralph R.; Fu, Yang-Xin

2013-01-01

Local failures following radiation therapy are multifactorial and the contributions of the tumor and the host are complex. Current models of tumor equilibrium suggest that a balance exists between cell birth and cell death due to insufficient angiogenesis, immune effects, or intrinsic cellular factors. We investigated whether host immune responses contribute to radiation induced tumor equilibrium in animal models. We report an essential role for immune cells and their cytokines in suppressing tumor cell regrowth in two experimental animal model systems. Depletion of T cells or neutralization of interferon-gamma reversed radiation-induced equilibrium leading to tumor regrowth. We also demonstrate that PD-L1 blockade augments T cell responses leading to rejection of tumors in radiation induced equilibrium. We identify an active interplay between tumor cells and immune cells that occurs in radiation-induced tumor equilibrium and suggest a potential role for disruption of the PD-L1/PD-1 axis in increasing local tumor control. PMID:23630355

Magnetic Reconnection Results on the Swarthmore Spheromak Experiment

NASA Astrophysics Data System (ADS)

Kornack, T. W.; Sollins, P. K.; Brown, M. R.

1997-11-01

Linear and 2D arrays of magnetic probes are used to study magnetic reconnection in the Swarthmore Spheromak Experiment (SSX). Opposing coaxial plasma guns form two identical spheromaks into adjacent 0.5 m diameter copper flux conservers. The flux conservers have symmetrical openings that allow the spheromaks to merge in a controlled manner. The stable equilibrium of the spheromaks provides a reservoir of magnetic flux for reconnection experiments. Currently, the magnetic configuration of the spheromaks allows the study of counter-helicity reconnection. Preliminary analysis will be presented and may include 2D B field movies of the reconnection region, measurement of the reconnection rate and comparison to the Sweet-Parker and standard Petschek models.

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

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

Robinson, Troy A

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2] x; (with x > 1). By substituting lanthanum (La 3+) for Nd 3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.« less

Dynamics of internal models in game players

NASA Astrophysics Data System (ADS)

Taiji, Makoto; Ikegami, Takashi

1999-10-01

A new approach for the study of social games and communications is proposed. Games are simulated between cognitive players who build the opponent’s internal model and decide their next strategy from predictions based on the model. In this paper, internal models are constructed by the recurrent neural network (RNN), and the iterated prisoner’s dilemma game is performed. The RNN allows us to express the internal model in a geometrical shape. The complicated transients of actions are observed before the stable mutually defecting equilibrium is reached. During the transients, the model shape also becomes complicated and often experiences chaotic changes. These new chaotic dynamics of internal models reflect the dynamical and high-dimensional rugged landscape of the internal model space.

Diffusion model validation and interpretation of stable isotopes in river and lake ice

USGS Publications Warehouse

Ferrick, M.G.; Calkins, D.J.; Perron, N.M.; Cragin, J.H.; Kendall, C.

2002-01-01

The stable isotope stratigraphy of river- and lake-ice archives winter hydroclimatic conditions, and can potentially be used to identify changing water sources or to provide important insights into ice formation processes and growth rates. However, accurate interpretations rely on known isotopic fractionation during ice growth. A one-dimensional diffusion model of the liquid boundary layer adjacent to an advancing solid interface, originally developed to simulate solute rejection by growing crystals, has been used without verification to describe non-equilibrium fractionation during congelation ice growth. Results are not in agreement, suggesting the presence of important uncertainties. In this paper we seek validation of the diffusion model for this application using large-scale laboratory experiments with controlled freezing rates and frequent sampling. We obtained consistent, almost constant, isotopic boundary layer thicknesses over a representative range of ice growth rates on both quiescent and well-mixed water. With the 18O boundary layer thickness from the laboratory, the model successfully quantified reduced river-ice growth rates relative to those of a nearby lake. These results were more representative and easier to obtain than those of a conventional thermal ice-growth model. This diffusion model validation and boundary layer thickness determination provide a powerful tool for interpreting the stable isotope stratigraphy of floating ice. The laboratory experiment also replicated successive fractionation events in response to a freeze-thaw-refreeze cycle, providing a mechanism for apparent ice fractionation that exceeds equilibrium. Analysis of the composition of snow ice and frazil ice in river and lake cores indicated surprising similarities between these ice forms. Published in 2002 by John Wiley & Sons, Ltd.

Design-for-manufacture of gradient-index optical systems using time-varying boundary condition diffusion

NASA Astrophysics Data System (ADS)

Harkrider, Curtis Jason

2000-08-01

The incorporation of gradient-index (GRIN) material into optical systems offers novel and practical solutions to lens design problems. However, widespread use of gradient-index optics has been limited by poor correlation between gradient-index designs and the refractive index profiles produced by ion exchange between glass and molten salt. Previously, a design-for- manufacture model was introduced that connected the design and fabrication processes through use of diffusion modeling linked with lens design software. This project extends the design-for-manufacture model into a time- varying boundary condition (TVBC) diffusion model. TVBC incorporates the time-dependent phenomenon of melt poisoning and introduces a new index profile control method, multiple-step diffusion. The ions displaced from the glass during the ion exchange fabrication process can reduce the total change in refractive index (Δn). Chemical equilibrium is used to model this melt poisoning process. Equilibrium experiments are performed in a titania silicate glass and chemically analyzed. The equilibrium model is fit to ion concentration data that is used to calculate ion exchange boundary conditions. The boundary conditions are changed purposely to control the refractive index profile in multiple-step TVBC diffusion. The glass sample is alternated between ion exchange with a molten salt bath and annealing. The time of each diffusion step can be used to exert control on the index profile. The TVBC computer model is experimentally verified and incorporated into the design- for-manufacture subroutine that runs in lens design software. The TVBC design-for-manufacture model is useful for fabrication-based tolerance analysis of gradient-index lenses and for the design of manufactureable GRIN lenses. Several optical elements are designed and fabricated using multiple-step diffusion, verifying the accuracy of the model. The strength of multiple-step diffusion process lies in its versatility. An axicon, imaging lens, and curved radial lens, all with different index profile requirements, are designed out of a single glass composition.

Thermodynamics of the Rhodamine B Lactone--Zwitterion Equilibrium.

ERIC Educational Resources Information Center

Hinckley, Daniel A.; Seybold, Paul G.

1987-01-01

Discusses the benefits of thermochromic transformations for studying thermodynamic properties. Describes an experiment that uses a commercially available dye, attains equilibrium rapidly, employs a simple, single-beam spectrophotometer, and is suitable for both physical chemistry and introductory chemistry laboratories. (TW)

LONG-TERM STABLE EQUILIBRIA FOR SYNCHRONOUS BINARY ASTEROIDS

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

Jacobson, Seth A.; Scheeres, Daniel J.

Synchronous binary asteroids may exist in a long-term stable equilibrium, where the opposing torques from mutual body tides and the binary YORP (BYORP) effect cancel. Interior of this equilibrium, mutual body tides are stronger than the BYORP effect and the mutual orbit semimajor axis expands to the equilibrium; outside of the equilibrium, the BYORP effect dominates the evolution and the system semimajor axis will contract to the equilibrium. If the observed population of small (0.1-10 km diameter) synchronous binaries are in static configurations that are no longer evolving, then this would be confirmed by a null result in the observationalmore » tests for the BYORP effect. The confirmed existence of this equilibrium combined with a shape model of the secondary of the system enables the direct study of asteroid geophysics through the tidal theory. The observed synchronous asteroid population cannot exist in this equilibrium if described by the canonical 'monolithic' geophysical model. The 'rubble pile' geophysical model proposed by Goldreich and Sari is sufficient, however it predicts a tidal Love number directly proportional to the radius of the asteroid, while the best fit to the data predicts a tidal Love number inversely proportional to the radius. This deviation from the canonical and Goldreich and Sari models motivates future study of asteroid geophysics. Ongoing BYORP detection campaigns will determine whether these systems are in an equilibrium, and future determination of secondary shapes will allow direct determination of asteroid geophysical parameters.« less

Modeling Viral Capsid Assembly

PubMed Central

2014-01-01

I present a review of the theoretical and computational methodologies that have been used to model the assembly of viral capsids. I discuss the capabilities and limitations of approaches ranging from equilibrium continuum theories to molecular dynamics simulations, and I give an overview of some of the important conclusions about virus assembly that have resulted from these modeling efforts. Topics include the assembly of empty viral shells, assembly around single-stranded nucleic acids to form viral particles, and assembly around synthetic polymers or charged nanoparticles for nanotechnology or biomedical applications. I present some examples in which modeling efforts have promoted experimental breakthroughs, as well as directions in which the connection between modeling and experiment can be strengthened. PMID:25663722

Self-Organisation and Intermittent Coherent Oscillations in the EXTRAP T2 Reversed Field Pinch

NASA Astrophysics Data System (ADS)

Cecconello, M.; Malmberg, J.-A.; Sallander, E.; Drake, J. R.

Many reversed-field pinch (RFP) experiments exhibit a coherent oscillatory behaviour that is characteristic of discrete dynamo events and is associated with intermittent current profile self-organisation phenomena. However, in the vast majority of the discharges in the resistive shell RFP experiment EXTRAP T2, the dynamo activity does not show global, coherent oscillatory behaviour. The internally resonant tearing modes are phase-aligned and wall-locked resulting in a large localised magnetic perturbation. Equilibrium and plasma parameters have a level of high frequency fluctuations but the average values are quasi-steady. For some discharges, however, the equilibrium parameters exhibit the oscillatory behaviour characteristic of the discrete dynamo events. For these discharges, the trend observed in the tearing mode spectra, associated with the onset of the discrete relaxation event behaviour, is a relative higher amplitude of m = 0 mode activity and relative lower amplitude of the m = 1 mode activity compared with their average values. Global plasma parameters and model profile calculations for sample discharges representing the two types of relaxation dynamics are presented.

Passive non-linear microrheology for determining extensional viscosity

NASA Astrophysics Data System (ADS)

Hsiao, Kai-Wen; Dinic, Jelena; Ren, Yi; Sharma, Vivek; Schroeder, Charles M.

2017-12-01

Extensional viscosity is a key property of complex fluids that greatly influences the non-equilibrium behavior and processing of polymer solutions, melts, and colloidal suspensions. In this work, we use microfluidics to determine steady extensional viscosity for polymer solutions by directly observing particle migration in planar extensional flow. Tracer particles are suspended in semi-dilute solutions of DNA and polyethylene oxide, and a Stokes trap is used to confine single particles in extensional flows of polymer solutions in a cross-slot device. Particles are observed to migrate in the direction transverse to flow due to normal stresses, and particle migration is tracked and quantified using a piezo-nanopositioning stage during the microfluidic flow experiment. Particle migration trajectories are then analyzed using a second-order fluid model that accurately predicts that migration arises due to normal stress differences. Using this analytical framework, extensional viscosities can be determined from particle migration experiments, and the results are in reasonable agreement with bulk rheological measurements of extensional viscosity based on a dripping-onto-substrate method. Overall, this work demonstrates that non-equilibrium properties of complex fluids can be determined by passive yet non-linear microrheology.

Editorial: Focus on Dynamics and Thermalization in Isolated Quantum Many-Body Systems

NASA Astrophysics Data System (ADS)

Cazalilla, M. A.; Rigol, M.

2010-05-01

The dynamics and thermalization of classical systems have been extensively studied in the past. However, the corresponding quantum phenomena remain, to a large extent, uncharted territory. Recent experiments with ultracold quantum gases have at last allowed exploration of the coherent dynamics of isolated quantum systems, as well as observation of non-equilibrium phenomena that challenge our current understanding of the dynamics of quantum many-body systems. These experiments have also posed many new questions. How can we control the dynamics to engineer new states of matter? Given that quantum dynamics is unitary, under which conditions can we expect observables of the system to reach equilibrium values that can be predicted by conventional statistical mechanics? And, how do the observables dynamically approach their statistical equilibrium values? Could the approach to equilibrium be hampered if the system is trapped in long-lived metastable states characterized, for example, by a certain distribution of topological defects? How does the dynamics depend on the way the system is perturbed, such as changing, as a function of time and at a given rate, a parameter across a quantum critical point? What if, conversely, after relaxing to a steady state, the observables cannot be described by the standard equilibrium ensembles of statistical mechanics? How would they depend on the initial conditions in addition to the other properties of the system, such as the existence of conserved quantities? The search for answers to questions like these is fundamental to a new research field that is only beginning to be explored, and to which researchers with different backgrounds, such as nuclear, atomic, and condensed-matter physics, as well as quantum optics, can make, and are making, important contributions. This body of knowledge has an immediate application to experiments in the field of ultracold atomic gases, but can also fundamentally change the way we approach and understand many-body quantum systems. This focus issue of New Journal Physics brings together both experimentalists and theoreticians working on these problems to provide a comprehensive picture of the state of the field. Focus on Dynamics and Thermalization in Isolated Quantum Many-Body Systems Contents Spin squeezing of high-spin, spatially extended quantum fields Jay D Sau, Sabrina R Leslie, Marvin L Cohen and Dan M Stamper-Kurn Thermodynamic entropy of a many-body energy eigenstate J M Deutsch Ground states and dynamics of population-imbalanced Fermi condensates in one dimension Masaki Tezuka and Masahito Ueda Relaxation dynamics in the gapped XXZ spin-1/2 chain Jorn Mossel and Jean-Sébastien Caux Canonical thermalization Peter Reimann Minimally entangled typical thermal state algorithms E M Stoudenmire and Steven R White Manipulation of the dynamics of many-body systems via quantum control methods Julie Dinerman and Lea F Santos Multimode analysis of non-classical correlations in double-well Bose-Einstein condensates Andrew J Ferris and Matthew J Davis Thermalization in a quasi-one-dimensional ultracold bosonic gas I E Mazets and J Schmiedmayer Two simple systems with cold atoms: quantum chaos tests and non-equilibrium dynamics Cavan Stone, Yassine Ait El Aoud, Vladimir A Yurovsky and Maxim Olshanii On the speed of fluctuations around thermodynamic equilibrium Noah Linden, Sandu Popescu, Anthony J Short and Andreas Winter A quantum central limit theorem for non-equilibrium systems: exact local relaxation of correlated states M Cramer and J Eisert Quantum quench dynamics of the sine-Gordon model in some solvable limits A Iucci and M A Cazalilla Nonequilibrium quantum dynamics of atomic dark solitons A D Martin and J Ruostekoski Quantum quenches in the anisotropic spin-1⁄2 Heisenberg chain: different approaches to many-body dynamics far from equilibrium Peter Barmettler, Matthias Punk, Vladimir Gritsev, Eugene Demler and Ehud Altman Crossover from adiabatic to sudden interaction quenches in the Hubbard model: prethermalization and non-equilibrium dynamics Michael Moeckel and Stefan Kehrein Quantum quenches in integrable field theories Davide Fioretto and Giuseppe Mussardo Dynamical delocalization of Majorana edge states by sweeping across a quantum critical point A Bermudez, L Amico and M A Martin-Delgado Thermometry with spin-dependent lattices D McKay and B DeMarco Near-adiabatic parameter changes in correlated systems: influence of the ramp protocol on the excitation energy Martin Eckstein and Marcus Kollar Sudden change of the thermal contact between two quantum systems J Restrepo and S Camalet Reflection of a Lieb-Liniger wave packet from the hard-wall potential D Jukić and H Buljan Probing interaction-induced ferromagnetism in optical superlattices J von Stecher, E Demler, M D Lukin and A M Rey Sudden interaction quench in the quantum sine-Gordon model Javier Sabio and Stefan Kehrein Dynamics of an inhomogeneous quantum phase transition Jacek Dziarmaga and Marek M Rams

Phylogenies support out-of-equilibrium models of biodiversity.

PubMed

Manceau, Marc; Lambert, Amaury; Morlon, Hélène

2015-04-01

There is a long tradition in ecology of studying models of biodiversity at equilibrium. These models, including the influential Neutral Theory of Biodiversity, have been successful at predicting major macroecological patterns, such as species abundance distributions. But they have failed to predict macroevolutionary patterns, such as those captured in phylogenetic trees. Here, we develop a model of biodiversity in which all individuals have identical demographic rates, metacommunity size is allowed to vary stochastically according to population dynamics, and speciation arises naturally from the accumulation of point mutations. We show that this model generates phylogenies matching those observed in nature if the metacommunity is out of equilibrium. We develop a likelihood inference framework that allows fitting our model to empirical phylogenies, and apply this framework to various mammalian families. Our results corroborate the hypothesis that biodiversity dynamics are out of equilibrium. © 2015 John Wiley & Sons Ltd/CNRS.

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

USGS Publications Warehouse

Brown, J.G.; Glynn, P.D.

2003-01-01

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Variational multiscale models for charge transport.

PubMed

Wei, Guo-Wei; Zheng, Qiong; Chen, Zhan; Xia, Kelin

2012-01-01

This work presents a few variational multiscale models for charge transport in complex physical, chemical and biological systems and engineering devices, such as fuel cells, solar cells, battery cells, nanofluidics, transistors and ion channels. An essential ingredient of the present models, introduced in an earlier paper (Bulletin of Mathematical Biology, 72, 1562-1622, 2010), is the use of differential geometry theory of surfaces as a natural means to geometrically separate the macroscopic domain from the microscopic domain, meanwhile, dynamically couple discrete and continuum descriptions. Our main strategy is to construct the total energy functional of a charge transport system to encompass the polar and nonpolar free energies of solvation, and chemical potential related energy. By using the Euler-Lagrange variation, coupled Laplace-Beltrami and Poisson-Nernst-Planck (LB-PNP) equations are derived. The solution of the LB-PNP equations leads to the minimization of the total free energy, and explicit profiles of electrostatic potential and densities of charge species. To further reduce the computational complexity, the Boltzmann distribution obtained from the Poisson-Boltzmann (PB) equation is utilized to represent the densities of certain charge species so as to avoid the computationally expensive solution of some Nernst-Planck (NP) equations. Consequently, the coupled Laplace-Beltrami and Poisson-Boltzmann-Nernst-Planck (LB-PBNP) equations are proposed for charge transport in heterogeneous systems. A major emphasis of the present formulation is the consistency between equilibrium LB-PB theory and non-equilibrium LB-PNP theory at equilibrium. Another major emphasis is the capability of the reduced LB-PBNP model to fully recover the prediction of the LB-PNP model at non-equilibrium settings. To account for the fluid impact on the charge transport, we derive coupled Laplace-Beltrami, Poisson-Nernst-Planck and Navier-Stokes equations from the variational principle for chemo-electro-fluid systems. A number of computational algorithms is developed to implement the proposed new variational multiscale models in an efficient manner. A set of ten protein molecules and a realistic ion channel, Gramicidin A, are employed to confirm the consistency and verify the capability. Extensive numerical experiment is designed to validate the proposed variational multiscale models. A good quantitative agreement between our model prediction and the experimental measurement of current-voltage curves is observed for the Gramicidin A channel transport. This paper also provides a brief review of the field.

Variational multiscale models for charge transport

PubMed Central

Wei, Guo-Wei; Zheng, Qiong; Chen, Zhan; Xia, Kelin

2012-01-01

This work presents a few variational multiscale models for charge transport in complex physical, chemical and biological systems and engineering devices, such as fuel cells, solar cells, battery cells, nanofluidics, transistors and ion channels. An essential ingredient of the present models, introduced in an earlier paper (Bulletin of Mathematical Biology, 72, 1562-1622, 2010), is the use of differential geometry theory of surfaces as a natural means to geometrically separate the macroscopic domain from the microscopic domain, meanwhile, dynamically couple discrete and continuum descriptions. Our main strategy is to construct the total energy functional of a charge transport system to encompass the polar and nonpolar free energies of solvation, and chemical potential related energy. By using the Euler-Lagrange variation, coupled Laplace-Beltrami and Poisson-Nernst-Planck (LB-PNP) equations are derived. The solution of the LB-PNP equations leads to the minimization of the total free energy, and explicit profiles of electrostatic potential and densities of charge species. To further reduce the computational complexity, the Boltzmann distribution obtained from the Poisson-Boltzmann (PB) equation is utilized to represent the densities of certain charge species so as to avoid the computationally expensive solution of some Nernst-Planck (NP) equations. Consequently, the coupled Laplace-Beltrami and Poisson-Boltzmann-Nernst-Planck (LB-PBNP) equations are proposed for charge transport in heterogeneous systems. A major emphasis of the present formulation is the consistency between equilibrium LB-PB theory and non-equilibrium LB-PNP theory at equilibrium. Another major emphasis is the capability of the reduced LB-PBNP model to fully recover the prediction of the LB-PNP model at non-equilibrium settings. To account for the fluid impact on the charge transport, we derive coupled Laplace-Beltrami, Poisson-Nernst-Planck and Navier-Stokes equations from the variational principle for chemo-electro-fluid systems. A number of computational algorithms is developed to implement the proposed new variational multiscale models in an efficient manner. A set of ten protein molecules and a realistic ion channel, Gramicidin A, are employed to confirm the consistency and verify the capability. Extensive numerical experiment is designed to validate the proposed variational multiscale models. A good quantitative agreement between our model prediction and the experimental measurement of current-voltage curves is observed for the Gramicidin A channel transport. This paper also provides a brief review of the field. PMID:23172978

Effects of sorption kinetics on the fate and transport of pharmaceuticals in estuaries.

PubMed

Liu, Dong; Lung, Wu-Seng; Colosi, Lisa M

2013-08-01

Many current fate and transport models based on the assumption of instantaneous sorption equilibrium of contaminants in the water column may not be valid for certain pharmaceuticals with long times to reach sorption equilibrium. In this study, a sorption kinetics model was developed and incorporated into a water quality model for the Patuxent River Estuary to evaluate the effect of sorption kinetics. Model results indicate that the assumption of instantaneous sorption equilibrium results in significant under-prediction of water column concentrations for some pharmaceuticals. The relative difference between predicted concentrations for the instantaneous versus kinetic approach is as large as 150% at upstream locations in the Patuxent Estuary. At downstream locations, where sorption processes have had sufficient time to reach equilibrium, the relative difference decreases to roughly 25%. This indicates that sorption kinetics affect a model's ability to capture accumulation of pharmaceuticals into riverbeds and the transport of pharmaceuticals in estuaries. These results offer strong evidence that chemicals are not removed from the water column as rapidly as has been assumed on the basis of equilibrium-based analyses. The findings are applicable not only for pharmaceutical compounds, but also for diverse contaminants that reach sorption equilibrium slowly. Copyright © 2013 Elsevier Ltd. All rights reserved.

Comparison of DNA decatenation by Escherichia coli topoisomerase IV and topoisomerase III: implications for non-equilibrium topology simplification

PubMed Central

Seol, Yeonee; Hardin, Ashley H.; Strub, Marie-Paule; Charvin, Gilles; Neuman, Keir C.

2013-01-01

Type II topoisomerases are essential enzymes that regulate DNA topology through a strand-passage mechanism. Some type II topoisomerases relax supercoils, unknot and decatenate DNA to below thermodynamic equilibrium. Several models of this non-equilibrium topology simplification phenomenon have been proposed. The kinetic proofreading (KPR) model postulates that strand passage requires a DNA-bound topoisomerase to collide twice in rapid succession with a second DNA segment, implying a quadratic relationship between DNA collision frequency and relaxation rate. To test this model, we used a single-molecule assay to measure the unlinking rate as a function of DNA collision frequency for Escherichia coli topoisomerase IV (topo IV) that displays efficient non-equilibrium topology simplification activity, and for E. coli topoisomerase III (topo III), a type IA topoisomerase that unlinks and unknots DNA to equilibrium levels. Contrary to the predictions of the KPR model, topo IV and topo III unlinking rates were linearly related to the DNA collision frequency. Furthermore, topo III exhibited decatenation activity comparable with that of topo IV, supporting proposed roles for topo III in DNA segregation. This study enables us to rule out the KPR model for non-equilibrium topology simplification. More generally, we establish an experimental approach to systematically control DNA collision frequency. PMID:23460205

Learning of Chemical Equilibrium through Modelling-Based Teaching

ERIC Educational Resources Information Center

Maia, Poliana Flavia; Justi, Rosaria

2009-01-01

This paper presents and discusses students' learning process of chemical equilibrium from a modelling-based approach developed from the use of the "Model of Modelling" diagram. The investigation was conducted in a regular classroom (students 14-15 years old) and aimed at discussing how modelling-based teaching can contribute to students…

Trapped ion system for sympathetic cooling and non-equilibrium dynamics

NASA Astrophysics Data System (ADS)

Doret, Charlie; Jubin, Sierra; Stevenson, Sarah

2017-04-01

Atomic systems are superbly suited to the study of non-equilibrium dynamics. These systems' exquisite isolation from environmental perturbations leads to long relaxation times that enable exploration of far-from-equilibrium phenomena. We present progress towards trapping chains of multiple co-trapped calcium isotopes geared towards measuring thermal equilibration and sympathetic cooling rates. We also discuss plans for future experiments in non-equilibrium statistical mechanics, including exploration of the quantum-to-classical crossover between ballistic transport and diffusive, Fourier's Law conduction. This work is supported by Cottrell College Science Award from the Research Corporation for Science Advancement and by Williams College.

Role of delay and screening in controlling AIDS

NASA Astrophysics Data System (ADS)

Chauhan, Sudipa; Bhatia, Sumit Kaur; Gupta, Surbhi

2016-06-01

We propose a non-linear HIV/ AIDS model to analyse the spread and control of HIV/AIDS. The population is divided into three classes, susceptible, infective and AIDS patients. The model is developed under the assumptions of vertical transmission and time delay in infective class. Time delay is also included to show sexual maturity period of infected newborns. We study dynamics of the model and obtain the reproduction number. Now to control the epidemic, we study the model where aware infective class is also added, i.e., people are made aware of their medical status by way of screening. To make the model more realistic, we consider the situation where aware infective class also interacts with other people. The model is analysed qualitatively by stability theory of ODE. Stability analysis of both disease-free and endemic equilibrium is studied based on reproduction number. Also, it is proved that if (R0)1, R1 ≤ 1 then, disease free equilibrium point is locally asymptotically stable and if (R0)1, R1 > 1 then, disease free equilibrium is unstable. Also, the stability analysis of endemic equilibrium point has been done and it is shown that for (R0)1 > 1 endemic equilibrium point is stable. Global stability analysis of endemic equilibrium point has also been done. At last, it is shown numerically that the delay in sexual maturity of infected individuals result in less number of AIDS patients.

Improving high-altitude emp modeling capabilities by using a non-equilibrium electron swarm model to monitor conduction electron evolution

NASA Astrophysics Data System (ADS)

Pusateri, Elise Noel

An Electromagnetic Pulse (EMP) can severely disrupt the use of electronic devices in its path causing a significant amount of infrastructural damage. EMP can also cause breakdown of the surrounding atmosphere during lightning discharges. This makes modeling EMP phenomenon an important research effort in many military and atmospheric physics applications. EMP events include high-energy Compton electrons or photoelectrons that ionize air and produce low energy conduction electrons. A sufficient number of conduction electrons will damp or alter the EMP through conduction current. Therefore, it is important to understand how conduction electrons interact with air in order to accurately predict the EMP evolution and propagation in the air. It is common for EMP simulation codes to use an equilibrium ohmic model for computing the conduction current. Equilibrium ohmic models assume the conduction electrons are always in equilibrium with the local instantaneous electric field, i.e. for a specific EMP electric field, the conduction electrons instantaneously reach steady state without a transient process. An equilibrium model will work well if the electrons have time to reach their equilibrium distribution with respect to the rise time or duration of the EMP. If the time to reach equilibrium is comparable or longer than the rise time or duration of the EMP then the equilibrium model would not accurately predict the conduction current necessary for the EMP simulation. This is because transport coefficients used in the conduction current calculation will be found based on equilibrium reactions rates which may differ significantly from their non-equilibrium values. We see this deficiency in Los Alamos National Laboratory's EMP code, CHAP-LA (Compton High Altitude Pulse-Los Alamos), when modeling certain EMP scenarios at high altitudes, such as upward EMP, where the ionization rate by secondary electrons is over predicted by the equilibrium model, causing the EMP to short abruptly. The objective of the PhD research is to mitigate this effect by integrating a conduction electron model into CHAP-LA which can calculate the conduction current based on a non-equilibrium electron distribution. We propose to use an electron swarm model to monitor the time evolution of conduction electrons in the EMP environment which is characterized by electric field and pressure. Swarm theory uses various collision frequencies and reaction rates to study how the electron distribution and the resultant transport coefficients change with time, ultimately reaching an equilibrium distribution. Validation of the swarm model we develop is a necessary step for completion of the thesis work. After validation, the swarm model is integrated in the air chemistry model CHAP-LA employs for conduction electron simulations. We test high altitude EMP simulations with the swarm model option in the air chemistry model to show improvements in the computational capability of CHAP-LA. A swarm model has been developed that is based on a previous swarm model developed by Higgins, Longmire and O'Dell 1973, hereinafter HLO. The code used for the swarm model calculation solves a system of coupled differential equations for electric field, electron temperature, electron number density, and drift velocity. Important swarm parameters, including the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are recalculated and compared to the previously reported empirical results given by HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford 2005. BOLSIG+ utilizes updated electron scattering cross sections that are defined over an expanded energy range found in the atomic and molecular cross section database published by Phelps in the Phelps Database 2014 on the LXcat website created by Pancheshnyi et al. 2012. The swarm model is also updated from the original HLO model by including additional physical parameters such as the O2 electron attachment rate, recombination rate, and mutual neutralization rate. This necessitates tracking the positive and negative ion densities in the swarm model. Adding these parameters, especially electron attachment, is important at lower EMP altitudes where atmospheric density is high. We compare swarm model equilibrium temperatures and times using the HLO and BOLSIG+ coefficients for a uniform electric field of 1 StatV/cm for a range of atmospheric heights. This is done in order to test sensitivity to the swarm parameters used in the swarm model. It is shown that the equilibrium temperature and time are sensitive to the modifications in the collision frequency and ionization rate based on the updated electron interaction cross sections. We validate the swarm model by comparing ionization coefficients and equilibrium drift velocities to experimental results over a wide range of reduced electric field values. The final part of the PhD thesis work includes integrating the swarm model into CHAP-LA. We discuss the physics included in the CHAP-LA EMP model and demonstrate EMP damping behavior caused by the ohmic model at high altitudes. We report on numerical techniques for incorporation of the swarm model into CHAP-LA's Maxwell solver. This includes a discussion of integration techniques for Maxwell's equations in CHAP-LA using the swarm model calculated conduction current. We show improvements on EMP parameter calculations when modeling a high altitude, upward EMP scenario. This provides a novel computational capability that will have an important impact on the atmospheric and EMP research community.

A model on CME/Flare initiation: Loss of Equilibrium caused by mass loss of quiescent prominences

NASA Astrophysics Data System (ADS)

Miley, George; Chon Nam, Sok; Kim, Mun Song; Kim, Jik Su

2015-08-01

Coronal Mass Ejections (CMEs) model should give an answer to enough energy storage for giant bulk plasma into interplanetary space to escape against the sun’s gravitation and its explosive eruption. Advocates of ‘Mass Loading’ model (e.g. Low, B. 1996, SP, 167, 217) suggested a simple mechanism of CME initiation, the loss of mass from a prominence anchoring magnetic flux rope, but they did not associate the mass loss with the loss of equilibrium. The catastrophic loss of equilibrium model is considered as to be a prospective CME/Flare model to explain sudden eruption of magnetic flux systems. Isenberg, P. A., et al (1993, ApJ, 417, 368)developed ideal magnetohydrodynamic theory of the magnetic flux rope to show occurrence of catastrophic loss of equilibrium according to increasing magnetic flux transported into corona.We begin with extending their study including gravity on prominence’s material to obtain equilibrium curves in case of given mass parameters, which are the strengths of the gravitational force compared with the characteristic magnetic force. Furthermore, we study quasi-static evolution of the system including massive prominence flux rope and current sheet below it to obtain equilibrium curves of prominence’s height according to decreasing mass parameter in a properly fixed magnetic environment. The curves show equilibrium loss behaviors to imply that mass loss result in equilibrium loss. Released fractions of magnetic energy are greater than corresponding zero-mass case. This eruption mechanism is expected to be able to apply to the eruptions of quiescent prominences, which is located in relatively weak magnetic environment with 105 km of scale length and 10G of photospheric magnetic field.

Response of a channel with alternate bars to a decrease in supple of mixed-size bedload: A flume experiment

Treesearch

Thomas E. Lisle; Fujiko Iseya; Hiroshi Ikeda

1993-01-01

The response of a channel with a topography and modeled bed material size typical of gravel bed rivers to reductions in sediment supply was investigated in a laboratory flume filled and fed with a sand-gravel mixture. After a series of quasi-stationary alternate bars were formed under equilibrium sediment transport, feed rate was reduced in two steps to one third and...

Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments

PubMed Central

Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

2015-01-01

In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0–2.2 M) than the formation of the native state (0–1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7–2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin. PMID:26244984

Dynamics of a Delayed HIV-1 Infection Model with Saturation Incidence Rate and CTL Immune Response

NASA Astrophysics Data System (ADS)

Guo, Ting; Liu, Haihong; Xu, Chenglin; Yan, Fang

2016-12-01

In this paper, we investigate the dynamics of a five-dimensional virus model incorporating saturation incidence rate, CTL immune response and three time delays which represent the latent period, virus production period and immune response delay, respectively. We begin this model by proving the positivity and boundedness of the solutions. Our model admits three possible equilibrium solutions, namely the infection-free equilibrium E0, the infectious equilibrium without immune response E1 and the infectious equilibrium with immune response E2. Moreover, by analyzing corresponding characteristic equations, the local stability of each of the feasible equilibria and the existence of Hopf bifurcation at the equilibrium point E2 are established, respectively. Further, by using fluctuation lemma and suitable Lyapunov functionals, it is shown that E0 is globally asymptotically stable when the basic reproductive numbers for viral infection R0 is less than unity. When the basic reproductive numbers for immune response R1 is less than unity and R0 is greater than unity, the equilibrium point E1 is globally asymptotically stable. Finally, some numerical simulations are carried out for illustrating the theoretical results.

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

NASA Technical Reports Server (NTRS)

Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

2014-01-01

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

A Harris-Todaro Agent-Based Model to Rural-Urban Migration

NASA Astrophysics Data System (ADS)

Espíndola, Aquino L.; Silveira, Jaylson J.; Penna, T. J. P.

2006-09-01

The Harris-Todaro model of the rural-urban migration process is revisited under an agent-based approach. The migration of the workers is interpreted as a process of social learning by imitation, formalized by a computational model. By simulating this model, we observe a transitional dynamics with continuous growth of the urban fraction of overall population toward an equilibrium. Such an equilibrium is characterized by stabilization of rural-urban expected wages differential (generalized Harris-Todaro equilibrium condition), urban concentration and urban unemployment. These classic results obtained originally by Harris and Todaro are emergent properties of our model.

Non-equilibrium Quasi-Chemical Nucleation Model

NASA Astrophysics Data System (ADS)

Gorbachev, Yuriy E.

2018-04-01

Quasi-chemical model, which is widely used for nucleation description, is revised on the basis of recent results in studying of non-equilibrium effects in reacting gas mixtures (Kolesnichenko and Gorbachev in Appl Math Model 34:3778-3790, 2010; Shock Waves 23:635-648, 2013; Shock Waves 27:333-374, 2017). Non-equilibrium effects in chemical reactions are caused by the chemical reactions themselves and therefore these contributions should be taken into account in the corresponding expressions for reaction rates. Corrections to quasi-equilibrium reaction rates are of two types: (a) spatially homogeneous (caused by physical-chemical processes) and (b) spatially inhomogeneous (caused by gas expansion/compression processes and proportional to the velocity divergency). Both of these processes play an important role during the nucleation and are included into the proposed model. The method developed for solving the generalized Boltzmann equation for chemically reactive gases is applied for solving the set of equations of the revised quasi-chemical model. It is shown that non-equilibrium processes lead to essential deviation of the quasi-stationary distribution and therefore the nucleation rate from its traditional form.

A rumor transmission model with incubation in social networks

NASA Astrophysics Data System (ADS)

Jia, Jianwen; Wu, Wenjiang

2018-02-01

In this paper, we propose a rumor transmission model with incubation period and constant recruitment in social networks. By carrying out an analysis of the model, we study the stability of rumor-free equilibrium and come to the local stable condition of the rumor equilibrium. We use the geometric approach for ordinary differential equations for showing the global stability of the rumor equilibrium. And when ℜ0 = 1, the new model occurs a transcritical bifurcation. Furthermore, numerical simulations are used to support the analysis. At last, some conclusions are presented.

Derivation of Pitzer Interaction Parameters for an Aqueous Species Pair of Sodium and Iron(II)-Citrate Complex

NASA Astrophysics Data System (ADS)

Jang, J. H.; Nemer, M.

2015-12-01

The U.S. DOE Waste Isolation Pilot Plant (WIPP) is a deep underground repository for the permanent disposal of transuranic (TRU) radioactive waste. The WIPP is located in the Permian Delaware Basin near Carlsbad, New Mexico, U.S.A. The TRU waste includes, but is not limited to, iron-based alloys and the complexing agent, citric acid. Iron is also present from the steel used in the waste containers. The objective of this analysis is to derive the Pitzer activity coefficients for the pair of Na+ and FeCit- complex to expand current WIPP thermodynamic database. An aqueous model for the dissolution of Fe(OH)2(s) in a Na3Cit solution was fitted to the experimentally measured solubility data. The aqueous model consists of several chemical reactions and related Pitzer interaction parameters. Specifically, Pitzer interaction parameters for the Na+ and FeCit- pair (β(0), β(1), and Cφ) plus the stability constant for species of FeCit- were fitted to the experimental data. Anoxic gloveboxes were used to keep the oxygen level low (<1 ppm) throughout the experiments due to redox sensitivity. EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations, packaged in EQ3/6 v.8.0a, calculates the aqueous speciation and saturation index using an aqueous model addressed in EQ3/6's database. The saturation index indicates how far the system is from equilibrium with respect to the solid of interest. Thus, the smaller the sum of squared saturation indices that the aqueous model calculates for the given number of experiments, the more closely the model attributes equilibrium to each individual experiment with respect to the solid of interest. The calculation of aqueous speciation and saturation indices was repeated by adjusting stability constant of FeCit-, β(0), β(1), and Cφ in the database until the values are found that make the sum of squared saturation indices the smallest for the given number of experiments. Results will be presented at the time of conference.

Analyses of 1/15 scale Creare bypass transient experiments. [PWR

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

Kmetyk, L.N.; Buxton, L.D.; Cole, R.K. Jr.

1982-09-01

RELAP4 analyses of several 1/15 scale Creare H-series bypass transient experiments have been done to investigate the effect of using different downcomer nodalizations, physical scales, slip models, and vapor fraction donoring methods. Most of the analyses were thermal equilibrium calculations performed with RELAP4/MOD5, but a few such calculations were done with RELAP4/MOD6 and RELAP4/MOD7, which contain improved slip models. In order to estimate the importance of nonequilibrium effects, additional analyses were performed with TRAC-PD2, RELAP5 and the nonequilibrium option of RELAP4/MOD7. The purpose of these studies was to determine whether results from Westinghouse's calculation of the Creare experiments, which weremore » done with a UHI-modified version of SATAN, were sufficient to guarantee SATAN would be conservative with respect to ECC bypass in full-scale plant analyses.« less

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

Magnetic diagnostics for equilibrium reconstructions with eddy currents on the lithium tokamak experiment

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

Schmitt, J. C., E-mail: jschmitt@pppl.gov; Lazerson, S.; Majeski, R.

2014-11-15

The Lithium Tokamak eXperiment is a spherical tokamak with a close-fitting low-recycling wall composed of thin lithium layers evaporated onto a stainless steel-lined copper shell. Long-lived non-axisymmetric eddy currents are induced in the shell and vacuum vessel by transient plasma and coil currents and these eddy currents influence both the plasma and the magnetic diagnostic signals that are used as constraints for equilibrium reconstruction. A newly installed set of re-entrant magnetic diagnostics and internal saddle flux loops, compatible with high-temperatures and lithium environments, is discussed. Details of the axisymmetric (2D) and non-axisymmetric (3D) treatments of the eddy currents and themore » equilibrium reconstruction are presented.« less

A general equilibrium model of a production economy with asset markets

NASA Astrophysics Data System (ADS)

Raberto, Marco; Teglio, Andrea; Cincotti, Silvano

2006-10-01

In this paper, a general equilibrium model of a monetary production economy is presented. The model is characterized by three classes of agents: a representative firm, heterogeneous households, and the government. Two markets (i.e., a labour market and a goods market, are considered) and two assets are traded in exchange of money, namely, government bonds and equities. Households provide the labour force and decide on consumption and savings, whereas the firm provides consumption goods and demands labour. The government receives taxes from households and pays interests on debt. The Walrasian equilibrium is derived analytically. The dynamics through quantity constrained equilibria out from the Walrasian equilibrium is also studied by means of computer simulations.

Raoult's law revisited: accurately predicting equilibrium relative humidity points for humidity control experiments.

PubMed

Bowler, Michael G; Bowler, David R; Bowler, Matthew W

2017-04-01

The humidity surrounding a sample is an important variable in scientific experiments. Biological samples in particular require not just a humid atmosphere but often a relative humidity (RH) that is in equilibrium with a stabilizing solution required to maintain the sample in the same state during measurements. The controlled dehydration of macromolecular crystals can lead to significant increases in crystal order, leading to higher diffraction quality. Devices that can accurately control the humidity surrounding crystals while monitoring diffraction have led to this technique being increasingly adopted, as the experiments become easier and more reproducible. Matching the RH to the mother liquor is the first step in allowing the stable mounting of a crystal. In previous work [Wheeler, Russi, Bowler & Bowler (2012). Acta Cryst. F 68 , 111-114], the equilibrium RHs were measured for a range of concentrations of the most commonly used precipitants in macromolecular crystallography and it was shown how these related to Raoult's law for the equilibrium vapour pressure of water above a solution. However, a discrepancy between the measured values and those predicted by theory could not be explained. Here, a more precise humidity control device has been used to determine equilibrium RH points. The new results are in agreement with Raoult's law. A simple argument in statistical mechanics is also presented, demonstrating that the equilibrium vapour pressure of a solvent is proportional to its mole fraction in an ideal solution: Raoult's law. The same argument can be extended to the case where the solvent and solute molecules are of different sizes, as is the case with polymers. The results provide a framework for the correct maintenance of the RH surrounding a sample.

Thermal and Mechanical Non-Equilibrium Effects on Turbulent Flows: Fundamental Studies of Energy Exchanges Through Direct Numerical Simulations, Molecular Simulations and Experiments

DTIC Science & Technology

2016-02-26

AFRL-AFOSR-VA-TR-2016-0104 Thermal and mechanical non-equilibrium effects on turbulent flows:fundamental studies of energy exchanges through direct...flows: fundamental studies of energy exchanges through direct numerical simulations, molecular simulations and experiments 5a.  CONTRACT NUMBER 5b...AVAILABILITY STATEMENT A DISTRIBUTION UNLIMITED: PB Public Release 13. SUPPLEMENTARY NOTES 14. ABSTRACT Utilizing internal energy exchange for intelligent

Utilization of unconventional lignocellulosic waste biomass for the biosorption of toxic triphenylmethane dye malachite green from aqueous solution.

PubMed

Selvasembian, Rangabhashiyam; P, Balasubramanian

2018-05-12

Biosorption potential of novel lignocellulosic biosorbents Musa sp. peel (MSP) and Aegle marmelos shell (AMS) was investigated for the removal of toxic triphenylmethane dye malachite green (MG), from aqueous solution. Batch experiments were performed to study the biosorption characteristics of malachite green onto lignocellulosic biosorbents as a function of initial solution pH, initial malachite green concentration, biosorbents dosage, and temperature. Biosorption equilibrium data were fitted to two and three parameters isotherm models. Three-parameter isotherm models better described the equilibrium data. The maximum monolayer biosorption capacities obtained using the Langmuir model for MG removal using MSP and AMS was 47.61 and 18.86 mg/g, respectively. The biosorption kinetic data were analyzed using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The pseudo-second-order kinetic model best fitted the experimental data, indicated the MG biosorption using MSP and AMS as chemisorption process. The removal of MG using AMS was found as highly dependent on the process temperature. The removal efficiency of MG showed declined effect at the higher concentrations of NaCl and CaCl 2 . The regeneration test of the biosorbents toward MG removal was successful up to three cycles.

An extension of ASM2d including pH calculation.

PubMed

Serralta, J; Ferrer, J; Borrás, L; Seco, A

2004-11-01

This paper presents an extension of the Activated Sludge Model No. 2d (ASM2d) including a chemical model able to calculate the pH value in biological processes. The developed chemical model incorporates the complete set of chemical species affecting the pH value to ASM2d describing non-equilibrium biochemical processes. It considers the system formed by one aqueous phase, in which biochemical processes take place, and one gaseous phase, and is based on the assumptions of instantaneous chemical equilibrium under liquid phase and kinetically governed mass transport between the liquid and gas phase. The ASM2d enlargement comprises the addition of every component affecting the pH value and an ion-balance for the calculation of the pH value and the dissociation species. The significant pH variations observed in a sequencing batch reactor operated for enhanced biological phosphorus removal were used to verify the capability of the extended model for predicting the dynamics of pH jointly with concentrations of acetic acid and phosphate. A pH inhibition function for polyphosphate accumulating bacteria has also been included in the model to simulate the behaviour observed. Experimental data obtained in four different experiments (with different sludge retention time and influent phosphorus concentrations) were accurately reproduced.

Large-scale density structures in the outer heliosphere

NASA Technical Reports Server (NTRS)

Belcher, J. W.; Lazarus, A. J.; Mcnutt, R. L., Jr.; Gordon, G. S., Jr.

1993-01-01

The Plasma Science experiment on the Voyager 2 spacecraft has measured the solar wind density from 1 to 38 AU. Over this distance, the solar wind density decreases as the inverse square of the heliocentric distance. However, there are large variations in this density at a given radius. Such changes in density are the dominant cause of changes in the solar wind ram pressure in the outer heliosphere and can cause large perturbations in the location of the termination shock of the solar wind. Following a simple model suggested by Suess, we study the non-equilibrium, dynamic location of the termination shock as it responds to these pressure changes. The results of this study suggest that the termination shock is rarely if ever at its equilibrium distance and may depart from that distance by as much as 50 AU at times.

An Analog Earth Climate Model

NASA Astrophysics Data System (ADS)

Varekamp, J. C.

2010-12-01

The earth climate is broadly governed by the radiative power of the sun as well as the heat retention and convective cooling of the atmosphere. I have constructed an analog earth model for an undergraduate climate class that simulates mean climate using these three parameters. The ‘earth’ is a hollow, black, bronze sphere (4 cm diameter) mounted on a thin insulated rod, and illuminated by two opposite optic fibers, with light focused on the sphere by a set of lenses. The sphere is encased in a large double-walled aluminum cylinder (34 cm diameter by 26 cm high) with separate water cooling jackets at the top, bottom, and sides. The cylinder can be filled with a gas of choice at a variety of pressures or can be run in vacuum. The exterior is cladded with insulation, and the temperature of the sphere, atmosphere and walls is monitored with thermocouples. The temperature and waterflow of the three cooling jackets can be monitored to establish the energy output of the whole system; the energy input is the energy yield of the two optic fibers. A small IR transmissive lens at the top provides the opportunity to hook up the fiber of a hyper spectrometer to monitor the emission spectrum of the black ‘earth’ sphere. A pressure gauge and gas inlet-outlet system for flushing of the cell completes it. The heat yield of the cooling water at the top is the sum of the radiative and convective components, whereas the bottom jacket only carries off the radiative heat of the sphere. Undergraduate E&ES students at Wesleyan University have run experiments with dry air, pure CO2, N2 and Ar at 1 atmosphere, and a low vacuum run was accomplished to calibrate the energy input. For each experiment, the lights are flipped on, the temperature acquisition routine is activated, and the sphere starts to warm up until an equilibrium temperature has been reached. The lights are then flipped off and the cooling sequence towards ambient is registered. The energy input is constant for a given experiment. For each time increment the radiative heat loss of the sphere is calculated from the Stefan Boltzman expression using the observed temperature at that time. The heating of the ‘earth sphere’ is accounted for in the energy balance equation by applying the temperature increase per time increment with the specific heat of bronze. The remaining energy term is the sum of the convective cooling and greenhouse effect. The heat budgets of the cooling trajectories were calculated analogous, with radiative and convective cooling causing the temperature drop per time increment. The greenhouse component again is lumped with the convective term. Equilibrium temperatures of 50-70 C were reached, with ambient temperature at 22 C. Somewhat surprising, experiments with radiatively neutral pure Argon gas yielded the highest equilibrium temperatures. Argon had the lowest specific heat of the gases used, and the observed equilibrium temperatures for different cell gases broadly scaled inversely with the heat capacity of those gases. Apparently, the efficiency of the free convective cooling strongly impacts the equilibrium temperatures. The greenhouse effects possibly have only a minor impact on final temperature as a result of the short cell pathlength. Experiments at higher cell filling pressures may provide more insight in this.

Accounting for natural organic matter in aqueous chemical equilibrium models: a review of the theories and applications

NASA Astrophysics Data System (ADS)

Dudal, Yves; Gérard, Frédéric

2004-08-01

Soil organic matter consists of a highly complex and diversified blend of organic molecules, ranging from low molecular weight organic acids (LMWOAs), sugars, amines, alcohols, etc., to high apparent molecular weight fulvic and humic acids. The presence of a wide range of functional groups on these molecules makes them very reactive and influential in soil chemistry, in regards to acid-base chemistry, metal complexation, precipitation and dissolution of minerals and microbial reactions. Out of these functional groups, the carboxylic and phenolic ones are the most abundant and most influential in regards to metal complexation. Therefore, chemical equilibrium models have progressively dealt with organic matter in their calculations. This paper presents a review of six chemical equilibrium models, namely N ICA-Donnan, E Q3/6, G EOCHEM, M INTEQA2, P HREEQC and W HAM, in light of the account they make of natural organic matter (NOM) with the objective of helping potential users in choosing a modelling approach. The account has taken various faces, mainly by adding specific molecules within the existing model databases (E Q3/6, G EOCHEM, and P HREEQC) or by using either a discrete (W HAM) or a continuous (N ICA-Donnan and M INTEQA2) distribution of the deprotonated carboxylic and phenolic groups. The different ways in which soil organic matter has been integrated into these models are discussed in regards to the model-experiment comparisons that were found in the literature, concerning applications to either laboratory or natural systems. Much of the attention has been focused on the two most advanced models, W HAM and N ICA-Donnan, which are able to reasonably describe most of the experimental results. Nevertheless, a better knowledge of the humic substances metal-binding properties is needed to better constrain model inputs with site-specific parameter values. This represents the main axis of research that needs to be carried out to improve the models. In addition to humic substances, more non-humic compounds should also be introduced in model databases, notably the ones that readily interact with the soil microorganisms. Thermodynamic data are generally available for most of these compounds, such as low molecular-weight organic acids. However, the more complex non-humic substances, exhibiting a ratio of hydrophobic versus hydrophilic bonds lower than humic substances, need to be further characterised for a comprehensive implementation in chemical equilibrium models.

Re-evaluation of the sorption behaviour of Bromide and Sulfamethazine under field conditions using leaching data and modelling methods

NASA Astrophysics Data System (ADS)

Gassmann, Matthias; Olsson, Oliver; Höper, Heinrich; Hamscher, Gerd; Kümmerer, Klaus

2016-04-01

The simulation of reactive transport in the aquatic environment is hampered by the ambiguity of environmental fate process conceptualizations for a specific substance in the literature. Concepts are usually identified by experimental studies and inverse modelling under controlled lab conditions in order to reduce environmental uncertainties such as uncertain boundary conditions and input data. However, since environmental conditions affect substance behaviour, a re-evaluation might be necessary under environmental conditions which might, in turn, be affected by uncertainties. Using a combination of experimental data and simulations of the leaching behaviour of the veterinary antibiotic Sulfamethazine (SMZ; synonym: sulfadimidine) and the hydrological tracer Bromide (Br) in a field lysimeter, we re-evaluated the sorption concepts of both substances under uncertain field conditions. Sampling data of a field lysimeter experiment in which both substances were applied twice a year with manure and sampled at the bottom of two lysimeters during three subsequent years was used for model set-up and evaluation. The total amount of leached SMZ and Br were 22 μg and 129 mg, respectively. A reactive transport model was parameterized to the conditions of the two lysimeters filled with monoliths (depth 2 m, area 1 m²) of a sandy soil showing a low pH value under which Bromide is sorptive. We used different sorption concepts such as constant and organic-carbon dependent sorption coefficients and instantaneous and kinetic sorption equilibrium. Combining the sorption concepts resulted in four scenarios per substance with different equations for sorption equilibrium and sorption kinetics. The GLUE (Generalized Likelihood Uncertainty Estimation) method was applied to each scenario using parameter ranges found in experimental and modelling studies. The parameter spaces for each scenario were sampled using a Latin Hypercube method which was refined around local model efficiency maxima. Results of the cumulative SMZ leaching simulations suggest a best conceptualization combination of instantaneous sorption to organic carbon which is consistent with the literature. The best Nash-Sutcliffe efficiency (Neff) was 0.96 and the 5th and 95th percentile of the uncertainty estimation were 18 and 27 μg. In contrast, both scenarios of kinetic Br sorption had similar results (Neff =0.99, uncertainty bounds 110-176 mg and 112-176 mg) but were clearly better than instantaneous sorption scenarios. Therefore, only the concept of sorption kinetics could be identified for Br modelling whereas both tested sorption equilibrium coefficient concepts performed equally well. The reasons for this specific case of equifinality may be uncertainties of model input data under field conditions or an insensitivity of the sorption equilibrium method due to relatively low adsorption of Br. Our results show that it may be possible to identify or at least falsify specific sorption concepts under uncertain field conditions using a long-term leaching experiment and modelling methods. Cases of environmental fate concept equifinality arouse the possibility of future model structure uncertainty analysis using an ensemble of models with different environmental fate concepts.

Equilibrium-point control of human elbow-joint movement under isometric environment by using multichannel functional electrical stimulation

PubMed Central

Matsui, Kazuhiro; Hishii, Yasuo; Maegaki, Kazuya; Yamashita, Yuto; Uemura, Mitsunori; Hirai, Hiroaki; Miyazaki, Fumio

2014-01-01

Functional electrical stimulation (FES) is considered an effective technique for aiding quadriplegic persons. However, the human musculoskeletal system has highly non-linearity and redundancy. It is thus difficult to stably and accurately control limbs using FES. In this paper, we propose a simple FES method that is consistent with the motion-control mechanism observed in humans. We focus on joint motion by a pair of agonist-antagonist muscles of the musculoskeletal system, and define the “electrical agonist-antagonist muscle ratio (EAA ratio)” and “electrical agonist-antagonist muscle activity (EAA activity)” in light of the agonist-antagonist muscle ratio and agonist-antagonist muscle activity, respectively, to extract the equilibrium point and joint stiffness from electromyography (EMG) signals. These notions, the agonist-antagonist muscle ratio and agonist-antagonist muscle activity, are based on the hypothesis that the equilibrium point and stiffness of the agonist-antagonist motion system are controlled by the central nervous system. We derived the transfer function between the input EAA ratio and force output of the end-point. We performed some experiments in an isometric environment using six subjects. This transfer-function model is expressed as a cascade-coupled dead time element and a second-order system. High-speed, high-precision, smooth control of the hand force were achieved through the agonist-antagonist muscle stimulation pattern determined by this transfer function model. PMID:24987326

Equilibrium-point control of human elbow-joint movement under isometric environment by using multichannel functional electrical stimulation.

PubMed

Matsui, Kazuhiro; Hishii, Yasuo; Maegaki, Kazuya; Yamashita, Yuto; Uemura, Mitsunori; Hirai, Hiroaki; Miyazaki, Fumio

2014-01-01

Functional electrical stimulation (FES) is considered an effective technique for aiding quadriplegic persons. However, the human musculoskeletal system has highly non-linearity and redundancy. It is thus difficult to stably and accurately control limbs using FES. In this paper, we propose a simple FES method that is consistent with the motion-control mechanism observed in humans. We focus on joint motion by a pair of agonist-antagonist muscles of the musculoskeletal system, and define the "electrical agonist-antagonist muscle ratio (EAA ratio)" and "electrical agonist-antagonist muscle activity (EAA activity)" in light of the agonist-antagonist muscle ratio and agonist-antagonist muscle activity, respectively, to extract the equilibrium point and joint stiffness from electromyography (EMG) signals. These notions, the agonist-antagonist muscle ratio and agonist-antagonist muscle activity, are based on the hypothesis that the equilibrium point and stiffness of the agonist-antagonist motion system are controlled by the central nervous system. We derived the transfer function between the input EAA ratio and force output of the end-point. We performed some experiments in an isometric environment using six subjects. This transfer-function model is expressed as a cascade-coupled dead time element and a second-order system. High-speed, high-precision, smooth control of the hand force were achieved through the agonist-antagonist muscle stimulation pattern determined by this transfer function model.

Spontaneous Time Symmetry Breaking in System with Mixed Strategy Nash Equilibrium: Evidences in Experimental Economics Data

NASA Astrophysics Data System (ADS)

Wang, Zhijian; Xu, Bin; Zhejiang Collaboration

2011-03-01

In social science, laboratory experiment with human subjects' interaction is a standard test-bed for studying social processes in micro level. Usually, as in physics, the processes near equilibrium are suggested as stochastic processes with time-reversal symmetry (TRS). To the best of our knowledge, near equilibrium, the breaking time symmetry, as well as the existence of robust time anti-symmetry processes, has not been reported clearly in experimental economics till now. By employing Markov transition method to analysis the data from human subject 2x2 Games with wide parameters and mixed Nash equilibrium, we study the time symmetry of the social interaction process near Nash equilibrium. We find that, the time symmetry is broken, and there exists a robust time anti-symmetry processes. We also report the weight of the time anti-symmetry processes in the total processes of each the games. Evidences in laboratory marketing experiments, at the same time, are provided as one-dimension cases. In these cases, time anti-symmetry cycles can also be captured. The proposition of time anti-symmetry processes is small, but the cycles are distinguishable.

Hydrophobic interaction between contiguous residues in the S6 transmembrane segment acts as a stimuli integration node in the BK channel

PubMed Central

Carrasquel-Ursulaez, Willy; Contreras, Gustavo F.; Sepúlveda, Romina V.; Aguayo, Daniel; González-Nilo, Fernando

2015-01-01

Large-conductance Ca2+- and voltage-activated K+ channel (BK) open probability is enhanced by depolarization, increasing Ca2+ concentration, or both. These stimuli activate modular voltage and Ca2+ sensors that are allosterically coupled to channel gating. Here, we report a point mutation of a phenylalanine (F380A) in the S6 transmembrane helix that, in the absence of internal Ca2+, profoundly hinders channel opening while showing only minor effects on the voltage sensor active–resting equilibrium. Interpretation of these results using an allosteric model suggests that the F380A mutation greatly increases the free energy difference between open and closed states and uncouples Ca2+ binding from voltage sensor activation and voltage sensor activation from channel opening. However, the presence of a bulky and more hydrophobic amino acid in the F380 position (F380W) increases the intrinsic open–closed equilibrium, weakening the coupling between both sensors with the pore domain. Based on these functional experiments and molecular dynamics simulations, we propose that F380 interacts with another S6 hydrophobic residue (L377) in contiguous subunits. This pair forms a hydrophobic ring important in determining the open–closed equilibrium and, like an integration node, participates in the communication between sensors and between the sensors and pore. Moreover, because of its effects on open probabilities, the F380A mutant can be used for detailed voltage sensor experiments in the presence of permeant cations. PMID:25548136

Dynamics of one-state downhill protein folding.

PubMed

Li, Peng; Oliva, Fabiana Y; Naganathan, Athi N; Muñoz, Victor

2009-01-06

The small helical protein BBL has been shown to fold and unfold in the absence of a free energy barrier according to a battery of quantitative criteria in equilibrium experiments, including probe-dependent equilibrium unfolding, complex coupling between denaturing agents, characteristic DSC thermogram, gradual melting of secondary structure, and heterogeneous atom-by-atom unfolding behaviors spanning the entire unfolding process. Here, we present the results of nanosecond T-jump experiments probing backbone structure by IR and end-to-end distance by FRET. The folding dynamics observed with these two probes are both exponential with common relaxation times but have large differences in amplitude following their probe-dependent equilibrium unfolding. The quantitative analysis of amplitude and relaxation time data for both probes shows that BBL folding dynamics are fully consistent with the one-state folding scenario and incompatible with alternative models involving one or several barrier crossing events. At 333 K, the relaxation time for BBL is 1.3 micros, in agreement with previous folding speed limit estimates. However, late folding events at room temperature are an order of magnitude slower (20 micros), indicating a relatively rough underlying energy landscape. Our results in BBL expose the dynamic features of one-state folding and chart the intrinsic time-scales for conformational motions along the folding process. Interestingly, the simple self-averaging folding dynamics of BBL are the exact dynamic properties required in molecular rheostats, thus supporting a biological role for one-state folding.

Incorporation of the equilibrium temperature approach in a Soil and Water Assessment Tool hydroclimatological stream temperature model

NASA Astrophysics Data System (ADS)

Du, Xinzhong; Shrestha, Narayan Kumar; Ficklin, Darren L.; Wang, Junye

2018-04-01

Stream temperature is an important indicator for biodiversity and sustainability in aquatic ecosystems. The stream temperature model currently in the Soil and Water Assessment Tool (SWAT) only considers the impact of air temperature on stream temperature, while the hydroclimatological stream temperature model developed within the SWAT model considers hydrology and the impact of air temperature in simulating the water-air heat transfer process. In this study, we modified the hydroclimatological model by including the equilibrium temperature approach to model heat transfer processes at the water-air interface, which reflects the influences of air temperature, solar radiation, wind speed and streamflow conditions on the heat transfer process. The thermal capacity of the streamflow is modeled by the variation of the stream water depth. An advantage of this equilibrium temperature model is the simple parameterization, with only two parameters added to model the heat transfer processes. The equilibrium temperature model proposed in this study is applied and tested in the Athabasca River basin (ARB) in Alberta, Canada. The model is calibrated and validated at five stations throughout different parts of the ARB, where close to monthly samplings of stream temperatures are available. The results indicate that the equilibrium temperature model proposed in this study provided better and more consistent performances for the different regions of the ARB with the values of the Nash-Sutcliffe Efficiency coefficient (NSE) greater than those of the original SWAT model and the hydroclimatological model. To test the model performance for different hydrological and environmental conditions, the equilibrium temperature model was also applied to the North Fork Tolt River Watershed in Washington, United States. The results indicate a reasonable simulation of stream temperature using the model proposed in this study, with minimum relative error values compared to the other two models. However, the NSE values were lower than those of the hydroclimatological model, indicating that more model verification needs to be done. The equilibrium temperature model uses existing SWAT meteorological data as input, can be calibrated using fewer parameters and less effort and has an overall better performance in stream temperature simulation. Thus, it can be used as an effective tool for predicting the changes in stream temperature regimes under varying hydrological and meteorological conditions. In addition, the impact of the stream temperature simulations on chemical reaction rates and concentrations was tested. The results indicate that the improved performance of the stream temperature simulation could significantly affect chemical reaction rates and the simulated concentrations, and the equilibrium temperature model could be a potential tool to model stream temperature in water quality simulations.

Non-equilibrium STLS approach to transport properties of single impurity Anderson model

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

Rezai, Raheleh, E-mail: R_Rezai@sbu.ac.ir; Ebrahimi, Farshad, E-mail: Ebrahimi@sbu.ac.ir

In this work, using the non-equilibrium Keldysh formalism, we study the effects of the electron–electron interaction and the electron-spin correlation on the non-equilibrium Kondo effect and the transport properties of the symmetric single impurity Anderson model (SIAM) at zero temperature by generalizing the self-consistent method of Singwi, Tosi, Land, and Sjolander (STLS) for a single-band tight-binding model with Hubbard type interaction to out of equilibrium steady-states. We at first determine in a self-consistent manner the non-equilibrium spin correlation function, the effective Hubbard interaction, and the double-occupancy at the impurity site. Then, using the non-equilibrium STLS spin polarization function in themore » non-equilibrium formalism of the iterative perturbation theory (IPT) of Yosida and Yamada, and Horvatic and Zlatic, we compute the spectral density, the current–voltage characteristics and the differential conductance as functions of the applied bias and the strength of on-site Hubbard interaction. We compare our spectral densities at zero bias with the results of numerical renormalization group (NRG) and depict the effects of the electron–electron interaction and electron-spin correlation at the impurity site on the aforementioned properties by comparing our numerical result with the order U{sup 2} IPT. Finally, we show that the obtained numerical results on the differential conductance have a quadratic universal scaling behavior and the resulting Kondo temperature shows an exponential behavior. -- Highlights: •We introduce for the first time the non-equilibrium method of STLS for Hubbard type models. •We determine the transport properties of SIAM using the non-equilibrium STLS method. •We compare our results with order-U2 IPT and NRG. •We show that non-equilibrium STLS, contrary to the GW and self-consistent RPA, produces the two Hubbard peaks in DOS. •We show that the method keeps the universal scaling behavior and correct exponential behavior of Kondo temperature.« less

Emergence of life from multicomponent mixtures of chemicals: the case for experiments with cycling physicochemical gradients.

PubMed

Spitzer, Jan

2013-04-01

The emergence of life from planetary multicomponent mixtures of chemicals is arguably the most complicated and least understood natural phenomenon. The fact that living cells are non-equilibrium systems suggests that life can emerge only from non-equilibrium chemical systems. From an astrobiological standpoint, non-equilibrium chemical systems arise naturally when solar irradiation strikes rotating surfaces of habitable planets: the resulting cycling physicochemical gradients persistently drive planetary chemistries toward "embryonic" living systems and an eventual emergence of life. To better understand the factors that lead to the emergence of life, I argue for cycling non-equilibrium experiments with multicomponent chemical systems designed to represent the evolving chemistry of Hadean Earth ("prebiotic soups"). Specifically, I suggest experimentation with chemical engineering simulators of Hadean Earth to observe and analyze (i) the appearances and phase separations of surface active and polymeric materials as precursors of the first "cell envelopes" (membranes) and (ii) the accumulations, commingling, and co-reactivity of chemicals from atmospheric, oceanic, and terrestrial locations.

Assembly of hard spheres in a cylinder: a computational and experimental study.

PubMed

Fu, Lin; Bian, Ce; Shields, C Wyatt; Cruz, Daniela F; López, Gabriel P; Charbonneau, Patrick

2017-05-14

Hard spheres are an important benchmark of our understanding of natural and synthetic systems. In this work, colloidal experiments and Monte Carlo simulations examine the equilibrium and out-of-equilibrium assembly of hard spheres of diameter σ within cylinders of diameter σ≤D≤ 2.82σ. Although phase transitions formally do not exist in such systems, marked structural crossovers can nonetheless be observed. Over this range of D, we find in simulations that structural crossovers echo the structural changes in the sequence of densest packings. We also observe that the out-of-equilibrium self-assembly depends on the compression rate. Slow compression approximates equilibrium results, while fast compression can skip intermediate structures. Crossovers for which no continuous line-slip exists are found to be dynamically unfavorable, which is the main source of this difference. Results from colloidal sedimentation experiments at low diffusion rate are found to be consistent with the results of fast compressions, as long as appropriate boundary conditions are used.

Interfacial self-healing of nanocomposite hydrogels: Theory and experiment

NASA Astrophysics Data System (ADS)

Wang, Qiming; Gao, Zheming; Yu, Kunhao

2017-12-01

Polymers with dynamic bonds are able to self-heal their fractured interfaces and restore the mechanical strengths. It is largely elusive how to analytically model this self-healing behavior to construct the mechanistic relationship between the self-healing properties (e.g., healed interfacial strength and equilibrium healing time) and the material compositions and healing conditions. Here, we take a self-healable nanocomposite hydrogel as an example to illustrate an interfacial self-healing theory for hydrogels with dynamic bonds. In the theory, we consider the free polymer chains diffuse across the interface and reform crosslinks to bridge the interface. We analytically reveal that the healed strengths of nanocomposite hydrogels increase with the healing time in an error-function-like form. The equilibrium self-healing time of the full-strength recovery decreases with the temperature and increases with the nanoparticle concentration. We further analytically reveal that the healed interfacial strength decreases with increasing delaying time before the healing process. The theoretical results quantitatively match with our experiments on nanosilica hydrogels, and also agree well with other researchers' experiments on nanoclay hydrogels. We expect that this theory would open promising avenues for quantitative understanding of the self-healing mechanics of various polymers with dynamic bonds, and offer insights for designing high-performance self-healing polymers.

Nonequilibrium quantum field dynamics from the two-particle-irreducible effective action

NASA Astrophysics Data System (ADS)

Laurie, Nathan S.

The two-particle-irreducible effective action offers a powerful approach to the study of quantum field dynamics far from equilibrium. Recent and upcoming heavy ion collision experiments motivate the study of such nonequilibrium dynamics in an expanding space-time background. For the O(N) model I derive exact, causal evolution equations for the statistical and spectral functions in a longitudinally expanding system. It is followed by an investigation into how the expansion affects the prospect of the system reaching equilibrium. Results are obtained in 1+1 dimensions at next-to- leading order in loop- and 1/N-expansions of the 2PI effective action. I focus on the evolution of the statistical function from highly nonequilibrium initial conditions, presenting a detailed analysis of early, intermediate and late-time dynamics. It is found that dynamics at very early times is attracted by a nonthermal fixed point of the mean field equations, after which interactions attempt to drive the system to equilibrium. The competition between the interactions and the expansion is eventually won by the expansion, with so-called freeze-out emerging naturally in this description. In order to investigate the convergence of the 2PI-1/N expansion in the 0(N) model, I compare results obtained numerically in 1+1 dimensions at leading, next- to-leading and next-to-next-to-leading order in 1/N. Convergence with increasing N, and also with decreasing coupling are discussed. A comparison is also made in the classical statistical field theory limit, where exact numerical results are available. I focus on early-time dynamics and quasi-particle properties far from equilibrium and observe rapid effective convergence already for moderate values of 1/N or the coupling strength.

Preliminary Simulations of the Ullage Dynamics in Microgravity During the Jet Mixing Portion of Tank Pressure Control Experiments

NASA Technical Reports Server (NTRS)

Breisacher, Kevin; Moder, Jeffrey

2015-01-01

The results of CFD simulations of microgravity tank pressure control experiments performed on the Space Shuttle are presented. A 13.7 liter acrylic model tank was used in these experiments. The tank was filled to an 83 percent fill fraction with Freon refrigerant to simulate cryogenic propellants stored in space. In the experiments, a single liquid jet near the bottom of the tank was used for mixing the tank. Simulations at a range of jet Weber numbers were performed. Qualitative comparisons of the liquid and gas interface dynamics observed and recorded in the experiments and those computed are shown and discussed. The simulations were able to correctly capture jet penetration of the ullage, qualitatively reproduce ullage shapes and dynamics, as well as the final equilibrium position of the ullage.

Preliminary Simulations of the Ullage Dynamics in Microgravity during the Jet Mixing Portion of Tank Pressure Control Experiments

NASA Technical Reports Server (NTRS)

Breisacher, Kevin; Moder, Jeffrey

2015-01-01

The results of CFD simulations of microgravity tank pressure control experiments performed on the Space Shuttle are presented. A 13.7 liter acrylic model tank was used in these experiments. The tank was filled to an 83 percent fill fraction with Freon refrigerant to simulate cryogenic propellants stored in space. In the experiments, a single liquid jet near the bottom of the tank was used for mixing the tank. Simulations at a range of jet Weber numbers were performed. Qualitative comparisons of the liquid and gas interface dynamics observed and recorded in the experiments and those computed are shown and discussed. The simulations were able to correctly capture jet penetration of the ullage, qualitatively reproduce ullage shapes and dynamics, as well as the final equilibrium position of the ullage.

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar

PubMed Central

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm3 at a gasification temperature of 1500 K and equivalence ratio of 0.15. PMID:27433487

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar.

PubMed

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm(3) at a gasification temperature of 1500 K and equivalence ratio of 0.15.