Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

NASA Astrophysics Data System (ADS)

Dousset, S.; Thevenot, M.; Pot, V.; Šimunek, J.; Andreux, F.

2007-12-01

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.

CFD analysis of laboratory scale phase equilibrium cell operation

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

CFD analysis of laboratory scale phase equilibrium cell operation.

PubMed

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

2017-10-01

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

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.

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…

Towards ultrafast dynamics with split-pulse X-ray photon correlation spectroscopy at free electron laser sources

DOE PAGES

Roseker, W.; Hruszkewycz, S. O.; Lehmkuhler, F.; ...

2018-04-27

One of the important challenges in condensed matter science is to understand ultrafast, atomic-scale fluctuations that dictate dynamic processes in equilibrium and non-equilibrium materials. Here, we report an important step towards reaching that goal by using a state-of-the-art perfect crystal based split-and-delay system, capable of splitting individual X-ray pulses and introducing femtosecond to nanosecond time delays. We show the results of an ultrafast hard X-ray photon correlation spectroscopy experiment at LCLS where split X-ray pulses were used to measure the dynamics of gold nanoparticles suspended in hexane. We show how reliable speckle contrast values can be extracted even from verymore » low intensity free electron laser (FEL) speckle patterns by applying maximum likelihood fitting, thus demonstrating the potential of a split-and-delay approach for dynamics measurements at FEL sources. This will enable the characterization of equilibrium and, importantly also reversible non-equilibrium processes in atomically disordered materials.« less

Towards ultrafast dynamics with split-pulse X-ray photon correlation spectroscopy at free electron laser sources

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

Roseker, W.; Hruszkewycz, S. O.; Lehmkuhler, F.

One of the important challenges in condensed matter science is to understand ultrafast, atomic-scale fluctuations that dictate dynamic processes in equilibrium and non-equilibrium materials. Here, we report an important step towards reaching that goal by using a state-of-the-art perfect crystal based split-and-delay system, capable of splitting individual X-ray pulses and introducing femtosecond to nanosecond time delays. We show the results of an ultrafast hard X-ray photon correlation spectroscopy experiment at LCLS where split X-ray pulses were used to measure the dynamics of gold nanoparticles suspended in hexane. We show how reliable speckle contrast values can be extracted even from verymore » low intensity free electron laser (FEL) speckle patterns by applying maximum likelihood fitting, thus demonstrating the potential of a split-and-delay approach for dynamics measurements at FEL sources. This will enable the characterization of equilibrium and, importantly also reversible non-equilibrium processes in atomically disordered materials.« 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.

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.

Equilibrium stochastic dynamics of a Brownian particle in inhomogeneous space: Derivation of an alternative model

NASA Astrophysics Data System (ADS)

Bhattacharyay, A.

2018-03-01

An alternative equilibrium stochastic dynamics for a Brownian particle in inhomogeneous space is derived. Such a dynamics can model the motion of a complex molecule in its conformation space when in equilibrium with a uniform heat bath. The derivation is done by a simple generalization of the formulation due to Zwanzig for a Brownian particle in homogeneous heat bath. We show that, if the system couples to different number of bath degrees of freedom at different conformations then the alternative model gets derived. We discuss results of an experiment by Faucheux and Libchaber which probably has indicated possible limitation of the Boltzmann distribution as equilibrium distribution of a Brownian particle in inhomogeneous space and propose experimental verification of the present theory using similar methods.

Experimental identification and mathematical modeling of viscoplastic material behavior

NASA Astrophysics Data System (ADS)

Haupt, P.; Lion, A.

1995-03-01

Uniaxial torsion and biaxial torsion-tension experiments on thin-walled tubes were carried out to investigate the viscoplastic behavior of stainless steel XCrNi18.9. A series of monotonic tests under strain and stress control shows nonlinear rate dependence and suggests the existence of equilibrium states, which are asymptotically approached during relaxation and creep processes. Strain controlled cyclic experiments display various hardening and softening phenomena that depend on strain amplitude and mean strain. All experiments indicate that the equilibrium states within the material depend on the history of the input process, whereas the history-dependence of the relaxation and creep behavior appears less significant. From the experiments the design of a constitutive model of viscoplasticity is motivated: The basic assumption is a decomposition of the total stress into an equilibrium stress and a non-equilibrium overstress: At constant strain, the overstress relaxes to zero, where the relaxation time depends on the overstress in order to account for the nonlinear rate-dependence. The equilibrium stress is assumed to be a rate independent functional of the total strain history. Classical plasticity is utilized with a kinematic hardening rule of the Armstrong-Frederick type. In order to incorporate the amplitude-dependent hardening and softening behavior, a generalized arc length representation is applied [14]. The introduction of an additional kinematic hardening variable facilitates consideration of additional hardening effects resulting from the non-radiality of the input process. Apart from the common yield and loading criterion of classical plasticity, the proposed constitutive model does not contain any further distinction of different cases. The experimental data are sufficient to identify the material parameters of the constitutive model. The results of the identification procedure demonstrate the ability of the model to represent the observed phenomena with satisfactory approximation.

The Comparative Performance of Batteries: The Lead-Acid and the Aluminum-Air Cells.

ERIC Educational Resources Information Center

LeRoux, Xavier; And Others

1996-01-01

Describes a teaching program that shows how electrochemical principles can be conveyed by means of hands-on experiences of student-centered teaching experiments. Employs the readily available lead-acid cell and the simple aluminum-air cell. Discusses the batteries, equilibrium cell potential, performance comparison, current, electrode separation,…

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

Communication: Introducing prescribed biases in out-of-equilibrium Markov models

NASA Astrophysics Data System (ADS)

Dixit, Purushottam D.

2018-03-01

Markov models are often used in modeling complex out-of-equilibrium chemical and biochemical systems. However, many times their predictions do not agree with experiments. We need a systematic framework to update existing Markov models to make them consistent with constraints that are derived from experiments. Here, we present a framework based on the principle of maximum relative path entropy (minimum Kullback-Leibler divergence) to update Markov models using stationary state and dynamical trajectory-based constraints. We illustrate the framework using a biochemical model network of growth factor-based signaling. We also show how to find the closest detailed balanced Markov model to a given Markov model. Further applications and generalizations are discussed.

Mechanism of α-ketol-type rearrangement of benzoin derivatives under basic conditions.

PubMed

Karino, Masahiro; Kubouchi, Daiki; Hamaoka, Kazuki; Umeyama, Shintaro; Yamataka, Hiroshi

2013-07-19

The mechanism of base-catalyzed rearrangement of ring-substituted benzoins in aqueous methanol was examined by kinetic and product analyses. Substituent effects on the rate and equilibrium constants revealed that the kinetic process has a different electron demand compared to the equilibrium process. Reactions in deuterated solvents showed that the rate of H/D exchange of the α-hydrogen is similar to the overall rate toward the equilibrium state. A proton-inventory experiment using partially deuterated solvents showed a linear dependence of the rate on the deuterium fraction of the solvent, indicating that only one deuterium isotope effect contributes to the overall rate process. All these results point to a mechanism in which the rearrangement is initiated by the rate-determining α-hydrogen abstraction rather than a mechanism with initial hydroxyl hydrogen abstraction as in the general α-ketol rearrangement.

Compressive Failure of Fiber Composites under Multi-Axial Loading

NASA Technical Reports Server (NTRS)

Basu, Shiladitya; Waas, Anthony M.; Ambur, Damodar R.

2006-01-01

This paper examines the compressive strength of a fiber reinforced lamina under multi-axial stress states. An equilibrium analysis is carried out in which a kinked band of rotated fibers, described by two angles, is sandwiched between two regions in which the fibers are nominally straight. Proportional multi-axial stress states are examined. The analysis includes the possibility of bifurcation from the current equilibrium state. The compressive strength of the lamina is contingent upon either attaining a load maximum in the equilibrium response or satisfaction of a bifurcation condition, whichever occurs first. The results show that for uniaxial loading a non-zero kink band angle beta produces the minimum limit load. For multi-axial loading, different proportional loading paths show regimes of bifurcation dominated and limit load dominated behavior. The present results are able to capture the beneficial effect of transverse compression in raising the composite compressive strength as observed in experiments.

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

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.

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

Impact of rainfall intensity on the transport of two herbicides in undisturbed grassed filter strip soil cores

NASA Astrophysics Data System (ADS)

Pot, V.; Šimůnek, J.; Benoit, P.; Coquet, Y.; Yra, A.; Martínez-Cordón, M.-J.

2005-12-01

Two series of displacement experiments with isoproturon and metribuzin herbicides were performed on two undisturbed grassed filter strip soil cores, under unsaturated steady-state flow conditions. Several rainfall intensities (0.070, 0.147, 0.161, 0.308 and 0.326 cm h - 1 ) were used. A water tracer (bromide) was simultaneously injected in each displacement experiment. A descriptive analysis of experimental breakthrough curves of bromide and herbicides combined with a modeling analysis showed an impact of rainfall intensity on the solute transport. Two contrasting physical non-equilibrium transport processes occurred. Multiple (three) porosity domains contributed to flow at the highest rainfall intensities, including preferential flow through macropore pathways. Macropores were not active any longer at intermediate and lowest velocities, and the observed preferential transport was described using dual-porosity-type models with a zero or low flow in the matrix domain. Chemical non-equilibrium transport of herbicides was found at all rainfall intensities. Significantly higher estimated values of degradation rate parameters as compared to batch data were correlated with the degree of non-equilibrium sorption. Experimental breakthrough curves were analyzed using different physical and chemical equilibrium and non-equilibrium transport models: convective-dispersive model (CDE), dual-porosity model (MIM), dual-permeability model (DP), triple-porosity, dual permeability model (DP-MIM); each combined with both chemical instantaneous and kinetic sorption.

Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

NASA Astrophysics Data System (ADS)

Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

2015-12-01

In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

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.

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.

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.

Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

NASA Technical Reports Server (NTRS)

Grodzka, P.; Facemire, B.

1977-01-01

Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

Investigation of the S1/ICT equilibrium in fucoxanthin by ultrafast pump-dump-probe and femtosecond stimulated Raman scattering spectroscopy.

PubMed

Redeckas, Kipras; Voiciuk, Vladislava; Vengris, Mikas

2016-05-01

Time-resolved multi-pulse spectroscopic methods-pump-dump-probe (PDP) and femtosecond stimulated Raman spectroscopy-were used to investigate the excited state photodynamics of the carbonyl group containing carotenoid fucoxanthin (FX). PDP experiments show that S1 and ICT states in FX are strongly coupled and that the interstate equilibrium is rapidly (<5 ps) reestablished after one of the interacting states is deliberately depopulated. Femtosecond stimulated Raman scattering experiments indicate that S1 and ICT are vibrationally distinct species. Identification of the FSRS modes on the S1 and ICT potential energy surfaces allows us to predict a possible coupling channel for the state interaction.

Experimental investigation on V isotope equilibrium fractionation factor between metal and silicate melt

NASA Astrophysics Data System (ADS)

Zhang, S.; Zhang, H.; Huang, F.

2017-12-01

Equilibrium fractionation factors of stable isotopes between metal and silicate melt are of vital importance for understanding the isotope variations within meteorites and planetary bodies. The V isotope composition (reported as δ51V = 1000 × [(51V/50Vsample/51V/50VAA)-1] ) of the bulk silicate Earth (BSE) has been estimated as δ51V = -0.7 ± 0.2‰ (2sd) [1], which is significantly heavier than most meteorites by 1‰ [2]. Such isotopic offset may provide insights for the core formation and core-mantle segregation. Therefore, it is important to understand V isotope equilibrium fractionation factor between silicate melt and metal. Nielsen et al. (2014) [2] had performed 3 experiments using starting materials of pure Fe metal and An50Di28Fo22 composition, revealing no resolvable V isotope fractionation. However, it is not clear whether chemical compositions in the melts can affect V isotope fractionations. Therefore, we experimentally calibrated equilibrium V isotope fractionation between Fe metallic and basaltic melt, with particular focus on the effect of Ni and other light elements. Experiments were performed at 1 GPa and 1600 oC using a 3/4″ end-loaded piston cylinder. The starting materials consisted of 1:1 mixture of pure Fe metal and basaltic composition [3]. The isotope equilibrium was assessed using time series experiments combined with the reverse reaction method. Carbon saturation and C-free experiments were achieved by using graphite and silica capsules, respectively. The Ni series experiments were doped with 6 wt% Ni into the starting Fe metal. The metal and silicate phases of samples were mechanically separated, V was purified using a chromatographic technique, and V isotope ratios were measured using MC-ICP-MS [4]. Carbon saturation, C-free experiments and Ni series experiment all show non-resolvable V isotope fractionation between metal and basaltic melt, which indicates that the presence of C and Ni could not affect V isotope fractionation during core formation. More experiments will be performed to explore the effect of Si and S in the metal on V isotope fractionation between metal and silicate melt.References: [1] Prytulak et al. (2013) EPSL 365, 177-189 [2] Nielsen et al. (2014) EPSL 389, 167-175 [3] Cottrell et al. (2009) CG 268, 167-179 [4] Wu et al. (2016) CG 421, 17-25

Chloride removal from recycled cooling water using ultra-high lime with aluminum process.

PubMed

Abdel-Wahab, Ahmed; Batchelor, Bill

2002-01-01

Chloride is a deleterious ionic species in cooling water systems because it promotes corrosion, and most of the scale and corrosion inhibitors are sensitive to chloride concentration in the water. Chloride can be removed from cooling water by precipitation as calcium chloroaluminate [Ca4Al2Cl2(OH)12]. A set of equilibrium experiments and one kinetic experiment were conducted to evaluate chloride removal using the ultra-high lime with aluminum (UHLA) process and to characterize the equilibrium conditions of calcium chloroaluminate precipitation. A total of 48 batch-equilibrium experiments were conducted on a 30 mM NaCl solution over a range of values for lime dose (0 to 200 mM) and sodium aluminate dose (0 to 100 mM). Experimental results showed that the UHLA process can remove chloride and that the formation of a calcium chloroaluminate solid phase is a reasonable mechanism that is able to adequately describe experimental results. An average value of the ion activity product of 10(-94.75) was obtained and can be used as an estimate of the solubility product for Ca4Al2Cl2(OH)12.

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

NASA Astrophysics Data System (ADS)

Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-02-01

Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Sensitivity of the equilibrium surface temperature of a GCM to systematic changes in atmospheric carbon dioxide

NASA Technical Reports Server (NTRS)

Oglesby, Robert J.; Saltzman, Barry

1990-01-01

The equilibrium response of surface temperature to atmospheric CO2 concentration, for six values between 100 and 1000 ppm, is calculated from a series of GCM experiments. This response is nonlinear, showing greater sensitivity for lower values of CO2 than for the higher values. It is suggested that changes in CO2 concentration of a given magnitude (e.g., 100 ppm) played a larger role in the Pleistocene ice-age-type temperature variations than in causing global temperature changes due to anthropogenic increases.

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)

[Preparation and evaluation of novel mesoporous molecular sieve of baicalin surface molecularly imprinted polymers].

PubMed

Gu, Xia-li; He, Hong-liang; Shi, Li-ying; Gao, Yan-kun; Chen, Li-na

2015-05-01

Taking mesoporous molecular sieve MCM-41 as a substrate, baicalin (BA) as template, acrylamide (AM) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, ethanol as solvent, under thermal polymerization initiator of azobis isobutyronitrilo (AIBN) , a kind of selective recognition of baicalin surface molecularly imprinted polymer was synthesized. The surface morphologies and characteristics of the MIPs were characterized by infrared spectroscopy (IR) and transmission electron microscope (TEM). The adsorption properties of polymer microsphere for the template were tested by the dynamic adsorption equilibrium experiments and static adsorption equilibrium experiments. The experiment showed that the imprinting process was successfully and the well-ordered one-dimensional pore structure of MCM-41 was still preserved. Furthermore, molecularly imprinted polymers had higher selective ability for BA, then provided a new method for the efficient separation and enrichment of baicalin active ingredients from medicinal plants Scutellaria baicalensis.

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.

Dynamic scaling for the growth of non-equilibrium fluctuations during thermophoretic diffusion in microgravity

DOE PAGES

Cerbino, Roberto; Sun, Yifei; Donev, Aleksandar; ...

2015-09-30

Diffusion processes are widespread in biological and chemical systems, where they play a fundamental role in the exchange of substances at the cellular level and in determining the rate of chemical reactions. Recently, the classical picture that portrays diffusion as random uncorrelated motion of molecules has been revised, when it was shown that giant non-equilibrium fluctuations develop during diffusion processes. Under microgravity conditions and at steady-state, non-equilibrium fluctuations exhibit scale invariance and their size is only limited by the boundaries of the system. Here in this work, we investigate the onset of non-equilibrium concentration fluctuations induced by thermophoretic diffusion inmore » microgravity, a regime not accessible to analytical calculations but of great relevance for the understanding of several natural and technological processes. A combination of state of the art simulations and experiments allows us to attain a fully quantitative description of the development of fluctuations during transient diffusion in microgravity. Both experiments and simulations show that during the onset the fluctuations exhibit scale invariance at large wave vectors. In a broader range of wave vectors simulations predict a spinodal-like growth of fluctuations, where the amplitude and length-scale of the dominant mode are determined by the thickness of the diffuse layer.« less

Dynamic scaling for the growth of non-equilibrium fluctuations during thermophoretic diffusion in microgravity

PubMed Central

Cerbino, Roberto; Sun, Yifei; Donev, Aleksandar; Vailati, Alberto

2015-01-01

Diffusion processes are widespread in biological and chemical systems, where they play a fundamental role in the exchange of substances at the cellular level and in determining the rate of chemical reactions. Recently, the classical picture that portrays diffusion as random uncorrelated motion of molecules has been revised, when it was shown that giant non-equilibrium fluctuations develop during diffusion processes. Under microgravity conditions and at steady-state, non-equilibrium fluctuations exhibit scale invariance and their size is only limited by the boundaries of the system. In this work, we investigate the onset of non-equilibrium concentration fluctuations induced by thermophoretic diffusion in microgravity, a regime not accessible to analytical calculations but of great relevance for the understanding of several natural and technological processes. A combination of state of the art simulations and experiments allows us to attain a fully quantitative description of the development of fluctuations during transient diffusion in microgravity. Both experiments and simulations show that during the onset the fluctuations exhibit scale invariance at large wave vectors. In a broader range of wave vectors simulations predict a spinodal-like growth of fluctuations, where the amplitude and length-scale of the dominant mode are determined by the thickness of the diffuse layer. PMID:26419420

Dynamic scaling for the growth of non-equilibrium fluctuations during thermophoretic diffusion in microgravity.

PubMed

Cerbino, Roberto; Sun, Yifei; Donev, Aleksandar; Vailati, Alberto

2015-09-30

Diffusion processes are widespread in biological and chemical systems, where they play a fundamental role in the exchange of substances at the cellular level and in determining the rate of chemical reactions. Recently, the classical picture that portrays diffusion as random uncorrelated motion of molecules has been revised, when it was shown that giant non-equilibrium fluctuations develop during diffusion processes. Under microgravity conditions and at steady-state, non-equilibrium fluctuations exhibit scale invariance and their size is only limited by the boundaries of the system. In this work, we investigate the onset of non-equilibrium concentration fluctuations induced by thermophoretic diffusion in microgravity, a regime not accessible to analytical calculations but of great relevance for the understanding of several natural and technological processes. A combination of state of the art simulations and experiments allows us to attain a fully quantitative description of the development of fluctuations during transient diffusion in microgravity. Both experiments and simulations show that during the onset the fluctuations exhibit scale invariance at large wave vectors. In a broader range of wave vectors simulations predict a spinodal-like growth of fluctuations, where the amplitude and length-scale of the dominant mode are determined by the thickness of the diffuse layer.

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…

Nonequilibrium thermodynamics of dilute polymer solutions in flow.

PubMed

Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M

2014-11-07

Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

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

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments.

PubMed

Emerson, H P; Zengotita, F; Richmann, M; Katsenovich, Y; Reed, D T; Dittrich, T M

2018-10-01

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium K d 's > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Unfolding single RNA molecules: bridging the gap between equilibrium and non-equilibrium statistical thermodynamics.

PubMed

Bustamante, Carlos

2005-11-01

During the last 15 years, scientists have developed methods that permit the direct mechanical manipulation of individual molecules. Using this approach, they have begun to investigate the effect of force and torque in chemical and biochemical reactions. These studies span from the study of the mechanical properties of macromolecules, to the characterization of molecular motors, to the mechanical unfolding of individual proteins and RNA. Here I present a review of some of our most recent results using mechanical force to unfold individual molecules of RNA. These studies make it possible to follow in real time the trajectory of each molecule as it unfolds and characterize the various intermediates of the reaction. Moreover, if the process takes place reversibly it is possible to extract both kinetic and thermodynamic information from these experiments at the same time that we characterize the forces that maintain the three-dimensional structure of the molecule in solution. These studies bring us closer to the biological unfolding processes in the cell as they simulate in vitro, the mechanical unfolding of RNAs carried out in the cell by helicases. If the unfolding process occurs irreversibly, I show here that single-molecule experiments can still provide equilibrium, thermodynamic information from non-equilibrium data by using recently discovered fluctuation theorems. Such theorems represent a bridge between equilibrium and non-equilibrium statistical mechanics. In fact, first derived in 1997, the first experimental demonstration of the validity of fluctuation theorems was obtained by unfolding mechanically a single molecule of RNA. It is perhaps a sign of the times that important physical results are these days used to extract information about biological systems and that biological systems are being used to test and confirm fundamental new laws in physics.

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.

Inevitable power-law behavior of isolated many-body quantum systems and how it anticipates thermalization

NASA Astrophysics Data System (ADS)

Távora, Marco; Torres-Herrera, E. J.; Santos, Lea F.

2016-10-01

Despite being ubiquitous, out-of-equilibrium quantum systems are much less understood than systems at equilibrium. Progress in the field has benefited from a symbiotic relationship between theoretical studies and new experiments on coherent dynamics. The present work strengthens this connection by providing a general picture of the relaxation process of isolated lattice many-body quantum systems that are routinely studied in experiments with cold atoms, ions traps, and nuclear magnetic resonance. We show numerically and analytically that the long-time decay of the probability for finding the system in its initial state necessarily shows a power-law behavior ∝t-γ . This happens independently of the details of the system, such as integrability, level repulsion, and the presence or absence of disorder. Information about the spectrum, the structure of the initial state, and the number of particles that interact simultaneously is contained in the value of γ . From it, we can anticipate whether the initial state will or will not thermalize.

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

Phase transformation pathways of Ln2O3 irradiated by ultrafast laser

NASA Astrophysics Data System (ADS)

Rittman, Dylan; Solomon, Jonathan; Chen, Curtis; Tracy, Cameron; Yalisove, Steven; Asta, Mark; Mao, Wendy; Ewing, Rodney

Ultrafast laser irradiation induces highly non-equilibrium conditions in materials through intense electronic excitation over very short timescales. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln2O3 (Ln = Er-Lu). A combination of grazing incidence X-ray diffraction and transmission electron microscopy is used to characterize the amount and depth-dependence of the phase transformation. Results indicate that-although all materials experience the same transformation-it is achieved through different damage mechanisms (pressure vs. thermal), and the short timescales associated with damage provides non-equilibrium routes of material modification. Ab initio molecular dynamics are used to isolate the effects of electronic excitations, and results are shown to be consistent with the trend in radiation resistance observed experimentally. Overall, this study provides a path to gain insight into the relationship between a material's equilibrium phase diagram and its behavior under highly non-equilibrium conditions. DOE/BES.

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.

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.

Effect of neutrino rest mass on ionization equilibrium freeze-out

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

Grohs, Evan Bradley; Fuller, George M.; Kishimoto, Chad T.

2015-12-23

We show how small neutrino rest masses can increase the expansion rate near the photon decoupling epoch in the early Universe, causing an earlier, higher temperature freeze-out for ionization equilibrium compared to the massless neutrino case. This yields a larger free-electron fraction, thereby affecting the photon diffusion length differently than the sound horizon at photon decoupling. This neutrino-mass and recombination effect depends strongly on the neutrino rest masses. Ultimately, though below current sensitivity, this effect could be probed by next-generation cosmic microwave background experiments, giving another observational handle on neutrino rest mass.

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

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…

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

USGS Publications Warehouse

Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-01-01

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

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.

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.

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.

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→∞.

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.

Complexometric Determination of Mercury Based on a Selective Masking Reaction

ERIC Educational Resources Information Center

Romero, Mercedes; Guidi, Veronica; Ibarrolaza, Agustin; Castells, Cecilia

2009-01-01

In the first analytical chemistry course, students are introduced to the concepts of equilibrium in water solutions and classical (non-instrumental) analytical methods. Our teaching experience shows that "real samples" stimulate students' enthusiasm for the laboratory work. From this diagnostic, we implemented an optional activity at the end of…

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.

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.

Characteristics of ring type traveling wave ultrasonic motor in vacuum.

PubMed

Qu, Jianjun; Zhou, Ningning; Tian, Xiu; Jin, Long; Xu, Zhike

2009-03-01

The characteristics of ultrasonic motor strongly depend on the properties of stator/rotor contact interface which are affected by ambient environment. With the developed apparatus, load properties of two ring type traveling wave ultrasonic motors in atmosphere, low vacuum and high vacuum were studied, respectively. Wear of friction material, variations of vacuum degree and the temperature of motor during the experiment were also measured. The results show that load properties of motor A in vacuum were poorer than those in atmosphere, when load torque M(f) was less than 0.55 N m. Compared to motor A, load properties of motor B were affected a little by environmental pressure. Wear of friction material in vacuum was more severe than wear in atmosphere. The temperature of motor in vacuum rose more quickly than it in atmosphere and had not reached equilibrium in 2 h experiment. However, the temperature of motor in atmosphere had reached equilibrium in about forth minutes. Furthermore, outgas was also observed during experiment under vacuum conditions.

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.

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.

Controlling self-assembly of microtubule spools via kinesin motor density

PubMed Central

Lam, A.T.; Curschellas, C.; Krovvidi, D.; Hess, H.

2014-01-01

Active self-assembly, in which non-thermal energy is consumed by the system to put together building blocks, allows the creation of non-equilibrium structures and active materials. Microtubule spools assembled in gliding assays are one example of such non-equilibrium structures, capable of storing bending energies on the order of 105 kT. Although these structures arise spontaneously in experiments, the origin of microtubule spooling has long been debated. Here, using a stepwise kinesin gradient, we demonstrate that spool assembly can be controlled by the surface density of kinesin motors, showing that pinning of microtubules due to dead motors plays a dominant role in spool initiation. PMID:25269076

Controlling self-assembly of microtubule spools via kinesin motor density.

PubMed

Lam, A T; Curschellas, C; Krovvidi, D; Hess, H

2014-11-21

Active self-assembly, in which non-thermal energy is consumed by the system to put together building blocks, allows the creation of non-equilibrium structures and active materials. Microtubule spools assembled in gliding assays are one example of such non-equilibrium structures, capable of storing bending energies on the order of 10(5) kT. Although these structures arise spontaneously in experiments, the origin of microtubule spooling has long been debated. Here, using a stepwise kinesin gradient, we demonstrate that spool assembly can be controlled by the surface density of kinesin motors, showing that pinning of microtubules due to dead motors plays a dominant role in spool initiation.

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.

Competitive adsorption of ibuprofen and amoxicillin mixtures from aqueous solution on activated carbons.

PubMed

Mansouri, Hayet; Carmona, Rocio J; Gomis-Berenguer, Alicia; Souissi-Najar, Souad; Ouederni, Abdelmottaleb; Ania, Conchi O

2015-07-01

This work investigates the competitive adsorption under dynamic and equilibrium conditions of ibuprofen (IBU) and amoxicillin (AMX), two widely consumed pharmaceuticals, on nanoporous carbons of different characteristics. Batch adsorption experiments of pure components in water and their binary mixtures were carried out to measure both adsorption equilibrium and kinetics, and dynamic tests were performed to validate the simultaneous removal of the mixtures in breakthrough experiments. The equilibrium adsorption capacities evaluated from pure component solutions were higher than those measured in dynamic conditions, and were found to depend on the porous features of the adsorbent and the nature of the specific/dispersive interactions that are controlled by the solution pH, density of surface change on the carbon and ionization of the pollutant. A marked roll-up effect was observed for AMX retention on the hydrophobic carbons, not seen for the functionalized adsorbent likely due to the lower affinity of amoxicillin towards the carbon adsorbent. Dynamic adsorption of binary mixtures from wastewater of high salinity and alkalinity showed a slight increase in IBU uptake and a reduced adsorption of AMX, demonstrating the feasibility of the simultaneous removal of both compounds from complex water matrices. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

The dynamics of single protein molecules is non-equilibrium and self-similar over thirteen decades in time

NASA Astrophysics Data System (ADS)

Hu, Xiaohu; Hong, Liang; Dean Smith, Micholas; Neusius, Thomas; Cheng, Xiaolin; Smith, Jeremy C.

2016-02-01

Internal motions of proteins are essential to their function. The time dependence of protein structural fluctuations is highly complex, manifesting subdiffusive, non-exponential behaviour with effective relaxation times existing over many decades in time, from ps up to ~102 s (refs ,,,). Here, using molecular dynamics simulations, we show that, on timescales from 10-12 to 10-5 s, motions in single proteins are self-similar, non-equilibrium and exhibit ageing. The characteristic relaxation time for a distance fluctuation, such as inter-domain motion, is observation-time-dependent, increasing in a simple, power-law fashion, arising from the fractal nature of the topology and geometry of the energy landscape explored. Diffusion over the energy landscape follows a non-ergodic continuous time random walk. Comparison with single-molecule experiments suggests that the non-equilibrium self-similar dynamical behaviour persists up to timescales approaching the in vivo lifespan of individual protein molecules.

Plasma MRI Experiments at UW-Madison

NASA Astrophysics Data System (ADS)

Flanagan, K.; Clark, M.; Desangles, V.; Siller, R.; Wallace, J.; Weisberg, D.; Forest, C. B.

2015-11-01

Experiments for driving Keplerian-like flow profiles on both the Plasma Couette Experiment Upgrade (PCX-U) and the Wisconsin Plasma Astrophysics Laboratory (WiPAL) user facility are described. Instead of driving flow at the boundaries, as is typical in many liquid metal Couette experiments, a global drive is implemented. A large radial current is drawn across a small axial field generating torque across the whole profile. This global electrically driven flow is capable of producing profiles similar to Keplerian flow. PCX-U has been purposely constructed for MRI experiments, while similar experiments on the WiPAL device show the versatility of the user facility and provide a larger plasma volume. Numerical calculations show the predicted parameter spaces for exciting the MRI in these plasmas and the equilibrium flow profiles expected. In both devices, relevant MRI parameters appear to be within reach of typical operating characteristics.

Confinement effect on the dynamics of non-equilibrium concentration fluctuations far from the onset of convection.

PubMed

Giraudet, Cédric; Bataller, Henri; Sun, Yifei; Donev, Aleksandar; Ortiz de Zárate, José M; Croccolo, Fabrizio

2016-12-01

In a recent letter (C. Giraudet et al., EPL 111, 60013 (2015)) we reported preliminary data showing evidence of a slowing-down of non-equilibrium fluctuations of the concentration in thermodiffusion experiments on a binary mixture of miscible fluids. The reason for this slowing-down was attributed to the effect of confinement. Such tentative explanation is here experimentally corroborated by new measurements and theoretically substantiated by studying analytically and numerically the relevant fluctuating hydrodynamics equations. In the new experiments presented here, the magnitude of the temperature gradient is changed, confirming that the system is controlled solely by the solutal Rayleigh number, and that the slowing-down is dominated by a combined effect of the driving force of buoyancy, the dissipating force of diffusion and the confinement provided by the vertical extension of the sample cell. Moreover, a compact phenomenological interpolating formula is proposed for easy analysis of experimental results.

Photo-generated carriers lose energy during extraction from polymer-fullerene solar cells

PubMed Central

Melianas, Armantas; Etzold, Fabian; Savenije, Tom J.; Laquai, Frédéric; Inganäs, Olle; Kemerink, Martijn

2015-01-01

In photovoltaic devices, the photo-generated charge carriers are typically assumed to be in thermal equilibrium with the lattice. In conventional materials, this assumption is experimentally justified as carrier thermalization completes before any significant carrier transport has occurred. Here, we demonstrate by unifying time-resolved optical and electrical experiments and Monte Carlo simulations over an exceptionally wide dynamic range that in the case of organic photovoltaic devices, this assumption is invalid. As the photo-generated carriers are transported to the electrodes, a substantial amount of their energy is lost by continuous thermalization in the disorder broadened density of states. Since thermalization occurs downward in energy, carrier motion is boosted by this process, leading to a time-dependent carrier mobility as confirmed by direct experiments. We identify the time and distance scales relevant for carrier extraction and show that the photo-generated carriers are extracted from the operating device before reaching thermal equilibrium. PMID:26537357

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…

Development of the PARVMEC Code for Rapid Analysis of 3D MHD Equilibrium

NASA Astrophysics Data System (ADS)

Seal, Sudip; Hirshman, Steven; Cianciosa, Mark; Wingen, Andreas; Unterberg, Ezekiel; Wilcox, Robert; ORNL Collaboration

2015-11-01

The VMEC three-dimensional (3D) MHD equilibrium has been used extensively for designing stellarator experiments and analyzing experimental data in such strongly 3D systems. Recent applications of VMEC include 2D systems such as tokamaks (in particular, the D3D experiment), where application of very small (delB/B ~ 10-3) 3D resonant magnetic field perturbations render the underlying assumption of axisymmetry invalid. In order to facilitate the rapid analysis of such equilibria (for example, for reconstruction purposes), we have undertaken the task of parallelizing the VMEC code (PARVMEC) to produce a scalable and temporally rapidly convergent equilibrium code for use on parallel distributed memory platforms. The parallelization task naturally splits into three distinct parts 1) radial surfaces in the fixed-boundary part of the calculation; 2) two 2D angular meshes needed to compute the Green's function integrals over the plasma boundary for the free-boundary part of the code; and 3) block tridiagonal matrix needed to compute the full (3D) pre-conditioner near the final equilibrium state. Preliminary results show that scalability is achieved for tasks 1 and 3, with task 2 still nearing completion. The impact of this work on the rapid reconstruction of D3D plasmas using PARVMEC in the V3FIT code will be discussed. Work supported by U.S. DOE under Contract DE-AC05-00OR22725 with UT-Battelle, LLC.

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.

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

2013-10-01

Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

The erosion of carbonate stone by acid rain: Laboratory and field investigations

USGS Publications Warehouse

Baedecker, P.A.; Reddy, M.M.

1993-01-01

One of the goals of research on the effects of acidic deposition on carbonate stone surfaces is to define the incremental impact of acidic deposition relative to natural weathering processes on the rate of carbonate stone erosion. If rain that impacts carbonate stone surfaces is resident on the surface long enough to approach chemical equilibrium, the incremental effect of hydrogen ion is expected to be small (i.e., 6% for a rain of pH 4.0). Under nonequilibrium (i.e., high flow rate) conditions, kinetic considerations suggest that the incremental effect of hydrogen ion deposition could be quite significant. Field run-off experiments involving the chemical analysis of rain collected from inclined stone slabs have been used to evaluate stone dissolution processes under ambient conditions of wet and dry deposition of acidic species. The stoichiometry of the reaction of stone with hydrogen ion is difficult to define from the field data due to scatter in the data attributed to hydrodynamic effects. Laboratory run-off experiments show that the stoichiometry is best defined by a reaction with H+ in which CO2 is released from the system. The baseline effect caused by water in equilibrium with atmospheric CO2 is identical in the field and in laboratory simulation. The experiments show that the solutions are close enough to equilibrium for the incremental effect of hydrogen ion to be minor (i.e., 24% for marble for a rain of pH 4.0) relative to dissolution due to water and carbonic acid reactions. Stone erosion rates based on physical measurement are approximately double the recession rates that are due to dissolution (estimated from the observed calcium content of the run-off solutions). The difference may reflect the loss of granular material not included in recession estimates based on the run-off data. Neither the field nor the laboratory run-off experiments indicate a pH dependence for the grain-removal process.

Effects of g-Jitter on Diffusion in Binary Liquids

NASA Technical Reports Server (NTRS)

Duval, Walter M. B.

1999-01-01

The microgravity environment offers the potential to measure the binary diffusion coefficients in liquids without the masking effects introduced by buoyancy-induced flows due to Earth s gravity. However, the background g-jitter (vibrations from the shuttle, onboard machinery, and crew) normally encountered in many shuttle experiments may alter the benefits of the microgravity environment and introduce vibrations that could offset its intrinsic advantages. An experiment during STS-85 (August 1997) used the Microgravity Vibration Isolation Mount (MIM) to isolate and introduce controlled vibrations to two miscible liquids inside a cavity to study the effects of g-jitter on liquid diffusion. Diffusion in a nonhomogeneous liquid system is caused by a nonequilibrium condition that results in the transport of mass (dispersion of the different kinds of liquid molecules) to approach equilibrium. The dynamic state of the system tends toward equilibrium such that the system becomes homogeneous. An everyday example is the mixing of cream and coffee (a nonhomogeneous system) via stirring. The cream diffuses into the coffee, thus forming a homogeneous system. At equilibrium the system is said to be mixed. However, during stirring, simple observations show complex flow field dynamics-stretching and folding of material interfaces, thinning of striation thickness, self-similar patterns, and so on. This example illustrates that, even though mixing occurs via mass diffusion, stirring to enhance transport plays a major role. Stirring can be induced either by mechanical means (spoon or plastic stirrer) or via buoyancy-induced forces caused by Earth s gravity. Accurate measurements of binary diffusion coefficients are often inhibited by buoyancy-induced flows. The microgravity environment minimizes the effect of buoyancy-induced flows and allows the true diffusion limit to be achieved. One goal of this experiment was to show that the microgravity environment suppresses buoyancy-induced convection, thereby mass diffusion becomes the dominant mechanism for transport. Since g-jitter transmitted by the shuttle to the experiment can potentially excite buoyancy-induced flows, we also studied the effects of controlled vibrations on the system.

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.

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.

Entropy production in a fluid-solid system far from thermodynamic equilibrium.

PubMed

Chung, Bong Jae; Ortega, Blas; Vaidya, Ashwin

2017-11-24

The terminal orientation of a rigid body in a moving fluid is an example of a dissipative system, out of thermodynamic equilibrium and therefore a perfect testing ground for the validity of the maximum entropy production principle (MaxEP). Thus far, dynamical equations alone have been employed in studying the equilibrium states in fluid-solid interactions, but these are far too complex and become analytically intractable when inertial effects come into play. At that stage, our only recourse is to rely on numerical techniques which can be computationally expensive. In our past work, we have shown that the MaxEP is a reliable tool to help predict orientational equilibrium states of highly symmetric bodies such as cylinders, spheroids and toroidal bodies. The MaxEP correctly helps choose the stable equilibrium in these cases when the system is slightly out of thermodynamic equilibrium. In the current paper, we expand our analysis to examine i) bodies with fewer symmetries than previously reported, for instance, a half-ellipse and ii) when the system is far from thermodynamic equilibrium. Using two-dimensional numerical studies at Reynolds numbers ranging between 0 and 14, we examine the validity of the MaxEP. Our analysis of flow past a half-ellipse shows that overall the MaxEP is a good predictor of the equilibrium states but, in the special case of the half-ellipse with aspect ratio much greater than unity, the MaxEP is replaced by the Min-MaxEP, at higher Reynolds numbers when inertial effects come into play. Experiments in sedimentation tanks and with hinged bodies in a flow tank confirm these calculations.

Using Visible Spectrophotometers and pH Measurements to Study Speciation in a Guided-Inquiry Laboratory

ERIC Educational Resources Information Center

Otto, William H.; Larive, Cynthia K.; Mason, Susan L.; Robinson, Janet B.; Heppert Joseph A.; Ellis, James D.

2005-01-01

An experiment to perform a simple initial investigation that illustrates concepts of speciation and equilibrium, using the instrument and chemical resources in the laboratory is presented. The investigation showed that the presence of multiple chemical species in a reaction mixture (phenol red solution) reflects the acid and base conditions…

Investigation of the hydrochlorination of SiCL4

NASA Technical Reports Server (NTRS)

Mui, J. Y. P.

1982-01-01

Reaction kinetic measurements on the hydrochlorination of SiCl4 and metallurgical grade (m.g.) silicon metal were made at a wide range of experimental variables. The effect of pressure on the reaction rate was studied at 25 psig, 100 psig, 150 psig and 200 psig, respectively. Results of these experiments show a large pressure effect on the hydrochlorination reaction. As expected, higher pressures produce a higher equilibrium SiHC13 conversion, since the hydrochlorination reaction results in a net volume contraction as product SiHC1 is formed. However, the reaction rate, namely, the rate at which the hydrochlorination reaction reaches its equilibrium SiHC13 conversion, was found to be much faster at low pressures.

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.

Effect made by the colloids to the sorption behavior of strontium on granite fracture-fillings

NASA Astrophysics Data System (ADS)

Wang, L.; Zuo, R.

2017-12-01

The objective of this study was to investigate the effects made by the colloid to the sorption capacity of colloids in granite fracture-fillings in aqueous solutions. The granite fracture-fillings were collected from three different depth of the research mine in Gansu province. According to the composition of the local soil and groundwater, two colloids were chosen to investigate this sorption process. Batch tests had been investigated at 27° under the air atmosphere as a function of pH(3 11), initial uranium concentration(5 400 mg/L) and water-rock ratio on the sorption of Sr on granite fracture-fillings. The batch experimental results showed that the sorption capacity presented a positive relationship with pH value, which may be caused by the hydrolytic adsorption raised by the reaction between Sr(OH)+ and OH- groups on the surface on the adsorbent. Initial strontium concentration also showed a positive relationship with sorption capacity when the concentration was lower than 200mg/mL, when the concentration was higher than 200mg/ml sorption reached the equilibrium. Sorption percentage showed a positive relationship with water/solid ratios, when the ratio was lower than 1:100 the system got equilibrium. When other experiment parameters were fixed and only the solid-liquid ratio changed, the adsorption capacity increased with the increasing solid-water ratio. The reason was that the total amount of Sr in the adsorption system remained unchanged, the adsorption sites increased with the solid-liquid ratio, and the adsorption capacity increased gradually with the increasing adsorption sites. The experiments data were interpreted in terms of Freundlich and Langmuir isotherms and the data fitted the former better. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of colloid.

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.

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…

Dynamic Processes of Conceptual Change: Analysis of Constructing Mental Models of Chemical Equilibrium.

ERIC Educational Resources Information Center

Chiu, Mei-Hung; Chou, Chin-Cheng; Liu, Chia-Ju

2002-01-01

Investigates students' mental models of chemical equilibrium using dynamic science assessments. Reports that students at various levels have misconceptions about chemical equilibrium. Involves 10th grade students (n=30) in the study doing a series of hands-on chemical experiments. Focuses on the process of constructing mental models, dynamic…

A Graphical Simulation of Vapor-Liquid Equilibrium for Use as an Undergraduate Laboratory Experiment and to Demonstrate the Concept of Mathematical Modeling.

ERIC Educational Resources Information Center

Whitman, David L.; Terry, Ronald E.

1985-01-01

Demonstrating petroleum engineering concepts in undergraduate laboratories often requires expensive and time-consuming experiments. To eliminate these problems, a graphical simulation technique was developed for junior-level laboratories which illustrate vapor-liquid equilibrium and the use of mathematical modeling. A description of this…

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)

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.

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.

Dye-induced aggregation of single stranded RNA: a mechanistic approach.

PubMed

Biver, Tarita; Ciatto, Carlo; Secco, Fernando; Venturini, Marcella

2006-08-15

The binding of proflavine (D) to single stranded poly(A) (P) was investigated at pH 7.0 and 25 degrees C using T-jump, stopped-flow and spectrophotometric methods. Equilibrium measurements show that an external complex PD(I) and an internal complex PD(II) form upon reaction between P and D and that their concentrations depend on the polymer/dye concentration ratio (C(P)/C(D)). For C(P)/C(D)<2.5, cooperative formation of stacks external to polymer strands prevails (PD(I)). Equilibria and T-jump experiments, performed at I=0.1M and analyzed according to the Schwarz theory for cooperative binding, provide the values of site size (g=1), equilibrium constant for the nucleation step (K( *)=(1.4+/-0.6)x10(3)M(-1)), equilibrium constant for the growth step (K=(1.2+/-0.6)x10(5)M(-1)), cooperativity parameter (q=85) and rate constants for the growth step (k(r)=1.2x10(7)M(-1)s(-1), k(d)=1.1 x 10(2)s(-1)). Stopped-flow experiments, performed at low ionic strength (I=0.01 M), indicate that aggregation of stacked poly(A) strands do occur provided that C(P)/C(D)<2.5.

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

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

Delayed, disequilibrium degassing in rhyolite magma: Decompression experiments and implications for explosive volcanism

USGS Publications Warehouse

Mangan, M.; Sisson, T.

2000-01-01

Recent numerical models and analog shock tube experiments show that disequilibrium degassing during magma ascent may lead to violent vesiculation very near the surface. In this study a series of decompression experiments using crystal-free, rhyolite melt were conducted to examine the development of large supersaturations due to delayed, homogenous (spontaneous) bubble nucleation. Melts were saturated at 900??C and 200 MPa with either 5.2 wt% dissolved H2O, or with 4.2 wt% H2O and 640 ppm CO2, and isothermally decompressed at linear rates of either 0.003, 0.025, or 8.5 MPa/s to final pressures between 25 and 175 MPa. Additional isobaric saturation experiments (900??C, 200-25 MPa) using pure H2O or mixed H2O-CO2 fluids establish reference equilibrium solubility curves/values. Homogenous nucleation is triggered in both H2O-only and H2O-CO2 experiments once the supersaturation pressure (??Pss) reaches ?? 120-150 MPa and the melt contains ?? two times its equilibrium water contents. Bubble number density and nucleation rate depend on the supersaturation pressure, with values on the order of 102/cm3 and < 1/cm3/s for ??Pss~120 MPa; 106/cm3 and 103-105/cm3/s for ??Pss??~130-150 MPa; and 107/cm3 and 106/cm3/s for ??Pss??160-175 MPa. Nucleation rates are consistent with classical nucleation theory, and infer an activation energy for nucleation of 1.5 x 10-18 J/nucleus, a critical bubble radius of 2 x 10-9 m, and an effective surface tension for rhyolite at 5.2 wt% H2O and 900??C of 0.10-0.11 N/m. The long nucleation delay limits the time available for subsequent diffusion such that disequilibrium dissolved H2O and CO2 contents persist to the end of our runs. The disequilibrium degassing paths inferred from our experiments contrast markedly with the equilibrium or quasi-equilibrium paths found in other studies where bubble nucleation occurs heterogenously on crystals or other discontinuities in the melt at low ??Pss. Homogenous and heterogenous nucleation rates are comparable, however, as are bubble number densities, so that at a given decompression rate it appears that nucleation mechanism, rather than nucleation rate, determines degassing efficiency by fixing the pressure (depth) at which vesiculation commences and hence the time available for equilibration prior to eruption. Although real systems are probably never truly crystal-free, our results show that rhyolitic magmas containing up to 104 crystals/cm3, and perhaps as high as 106 crystals/cm3, are controlled by homogenous, rather than heterogenous, nucleation during ascent. ?? 2000 Elsevier Science B.V. All rights reserved.

Thermodynamics of Surface Nanobubbles.

PubMed

Zargarzadeh, Leila; Elliott, Janet A W

2016-11-01

In this paper, we examine the thermodynamic stability of surface nanobubbles. The appropriate free energy is defined for the system of nanobubbles on a solid surface submerged in a supersaturated liquid solution at constant pressure and temperature, under conditions where an individual nanobubble is not in diffusive contact with a gas phase outside of the system or with other nanobubbles on the time scale of the experiment. The conditions under which plots of free energy versus the radius of curvature of the nanobubbles show a global minimum, which denotes the stable equilibrium state, are explored. Our investigation shows that supersaturation and an anomalously high contact angle (measured through the liquid) are required to have stable surface nanobubbles. In addition, the anomalously high contact angle of surface nanobubbles is discussed from the standpoint of a framework recently proposed by Koch, Amirfazli, and Elliott that relates advancing and receding contact angles to thermodynamic equilibrium contact angles, combined with the existence of a gas enrichment layer.

Integrated fusion simulation with self-consistent core-pedestal coupling

DOE PAGES

Meneghini, O.; Snyder, P. B.; Smith, S. P.; ...

2016-04-20

In this study, accurate prediction of fusion performance in present and future tokamaks requires taking into account the strong interplay between core transport, pedestal structure, current profile and plasma equilibrium. An integrated modeling workflow capable of calculating the steady-state self- consistent solution to this strongly-coupled problem has been developed. The workflow leverages state-of-the-art components for collisional and turbulent core transport, equilibrium and pedestal stability. Validation against DIII-D discharges shows that the workflow is capable of robustly pre- dicting the kinetic profiles (electron and ion temperature and electron density) from the axis to the separatrix in good agreement with the experiments.more » An example application is presented, showing self-consistent optimization for the fusion performance of the 15 MA D-T ITER baseline scenario as functions of the pedestal density and ion effective charge Z eff.« less

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.

Apiaceae Family Plants as Low-Cost Adsorbents for the Removal of Lead Ion from Water Environment

NASA Astrophysics Data System (ADS)

Boontham, W.; Babel, S.

2017-06-01

Adsorbents prepared from the three selected plants from Apiaceae famaily commonly known as parsley, coriander and culantro were observed to remove lead from aqueous solutions. Batch experiments were conducted to study the effect of dosage, pH, contact time and agitation speed at 10 mg L-1 initial Pb(II) concentration. Results revealed that three selected plants showed high adsorption capacity for removal of lead from aqueous solutions. The maximum biosorption of Pb2+ was found to be more than 97% with 1.0 g/l dosage for all three adsorbents under optimum pH of 3-5. The adsorption equilibrium was established after about 1 hr. The equilibrium adsorption capacity of parsley and coriander were found to fit well with the Langmuir isotherm whereas the Freundlich isotherm was better fit for culantro. The studies showed that the adsorbents can be used for removing lead ions from contaminated waters.

Full Field Deformation Measurements in Tensile Kolsky Bar Experiments: Studies and Detailed Analysis of the Early Time History

NASA Astrophysics Data System (ADS)

Sutton, M. A.; Gilat, A.; Seidt, J.; Rajan, S.; Kidane, A.

2018-01-01

The very early stages of high rate tensile loading are important when attempting to characterize the response of materials during the transient loading time. To improve understanding of the conditions imposed on the specimen during the transient stage, a series of high rate loading experiments are performed using a Kolsky tensile bar system. Specimen forces and velocities during the high rate loading experiment are obtained by performing a thorough method of characteristics analysis of the system employed in the experiments. The in-situ full-field specimen displacements, velocities and accelerations during the loading process are quantified using modern ultra-high-speed imaging systems to provide detailed measurements of specimen response, with emphasis on the earliest stages of loading. Detailed analysis of the image-based measurements confirms that conditions are nominally consistent with those necessary for use of the one-dimensional wave equation within the relatively thin, dog-bone shaped tensile specimen. Specifically, measurements and use of the one-dimensional wave equation show clearly that the specimen has low inertial stresses in comparison to the applied transmitted force. Though the accelerations of the specimen continue for up to 50 μs, measurements show that the specimen is essentially in force equilibrium beginning a few microseconds after initial loading. These local measurements contrast with predictions based on comparison of the wave-based incident force measurements, which suggest that equilibrium occurs much later, on the order of 40-50 μs .

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.

Development of safe mechanism for surgical robots using equilibrium point control method.

PubMed

Park, Shinsuk; Lim, Hokjin; Kim, Byeong-sang; Song, Jae-bok

2006-01-01

This paper introduces a novel mechanism for surgical robotic systems to generate human arm-like compliant motion. The mechanism is based on the idea of the equilibrium point control hypothesis which claims that multi-joint limb movements are achieved by shifting the limbs' equilibrium positions defined by neuromuscular activity. The equilibrium point control can be implemented on a robot manipulator by installing two actuators at each joint of the manipulator, one to control the joint position, and the other to control the joint stiffness. This double-actuator mechanism allows us to arbitrarily manipulate the stiffness (or impedance) of a robotic manipulator as well as its position. Also, the force at the end-effector can be estimated based on joint stiffness and joint angle changes without using force transducers. A two-link manipulator and a three-link manipulator with the double-actuator units have been developed, and experiments and simulation results show the potential of the proposed approach. By creating the human arm-like behavior, this mechanism can improve the performance of robot manipulators to execute stable and safe movement in surgical environments by using a simple control scheme.

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.

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.

Simulations in support of the T4B experiment

NASA Astrophysics Data System (ADS)

Qerushi, Artan; Ross, Patrick; Lohff, Chriss; Raymond, Anthony; Montecalvo, Niccolo

2017-10-01

Simulations in support of the T4B experiment are presented. These include a Grad-Shafranov equilibrium solver and equilibrium reconstruction from flux-loop measurements, collision radiative models for plasma spectroscopy (determination of electron density and temperature from line ratios) and fast ion test particle codes for neutral beam - plasma coupling. ©2017 Lockheed Martin Corporation. All Rights Reserved.

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.

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.

Rational and Empirical Play in the Simple Hot Potato Game

ERIC Educational Resources Information Center

Butts, Carter T.; Rode, David C.

2007-01-01

We define a "hot potato" to be a good that may be traded a finite number of times, but which becomes a bad if and when it can no longer be exchanged. We describe a game involving such goods, and show that non-acceptance is a unique subgame perfect Nash equilibrium for rational egoists. Contrastingly, experiments with human subjects show…

Twisting Anderson pseudospins with light: Quench dynamics in THz-pumped BCS superconductors

NASA Astrophysics Data System (ADS)

Chou, Yang-Zhi; Liao, Yunxiang; Foster, Matthew

We study the preparation and the detection of coherent far-from-equilibrium BCS superconductor dynamics in THz pump-probe experiments. In a recent experiment, an intense monocycle THz pulse with center frequency ω = Δ was injected into a superconductor with BCS gap Δ the post-pump evolution was detected via the optical conductivity. It was argued that nonlinear coupling of the pump to the Anderson pseudospins of the superconductor induces coherent dynamics of the Higgs mode Δ (t) . We validate this picture in a 2D BCS model with a combination of exact numerics and the Lax reduction, and we compute the dynamical phase diagram. The main effect of the pump is to scramble the orientations of Anderson pseudospins along the Fermi surface by twisting them in the xy-plane. We show that more intense pulses can induce a far-from-equilibrium gapless phase (phase I), originally predicted in the context of interaction quenches. We show that the THz pump can reach phase I at much lower energy densities than an interaction quench, and we demonstrate that Lax reduction provides a quantitative tool for computing coherent BCS dynamics. We also compute the optical conductivity for the states discussed here.

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.

The dynamics of single protein molecules is non-equilibrium and self-similar over thirteen decades in time

DOE PAGES

Hu, Xiaohu; Hong, Liang; Smith, Micholas Dean; ...

2015-11-23

Here, internal motions of proteins are essential to their function. The time dependence of protein structural fluctuations is highly complex, manifesting subdiffusive, non-exponential behavior with effective relaxation times existing over many decades in time, from ps up to ~10 2s (refs 1-4). Here, using molecular dynamics simulations, we show that, on timescales from 10 –12 to 10 –5s, motions in single proteins are self-similar, non-equilibrium and exhibit ageing. The characteristic relaxation time for a distance fluctuation, such as inter-domain motion, is observation-time-dependent, increasing in a simple, power-law fashion, arising from the fractal nature of the topology and geometry of themore » energy landscape explored. Diffusion over the energy landscape follows a non-ergodic continuous time random walk. Comparison with single-molecule experiments suggests that the non-equilibrium self-similar dynamical behavior persists up to timescales approaching the in vivo lifespan of individual protein molecules.« less

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

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.

Non-equilibrium coherence dynamics in one-dimensional Bose gases.

PubMed

Hofferberth, S; Lesanovsky, I; Fischer, B; Schumm, T; Schmiedmayer, J

2007-09-20

Low-dimensional systems provide beautiful examples of many-body quantum physics. For one-dimensional (1D) systems, the Luttinger liquid approach provides insight into universal properties. Much is known of the equilibrium state, both in the weakly and strongly interacting regimes. However, it remains a challenge to probe the dynamics by which this equilibrium state is reached. Here we present a direct experimental study of the coherence dynamics in both isolated and coupled degenerate 1D Bose gases. Dynamic splitting is used to create two 1D systems in a phase coherent state. The time evolution of the coherence is revealed through local phase shifts of the subsequently observed interference patterns. Completely isolated 1D Bose gases are observed to exhibit universal sub-exponential coherence decay, in excellent agreement with recent predictions. For two coupled 1D Bose gases, the coherence factor is observed to approach a non-zero equilibrium value, as predicted by a Bogoliubov approach. This coupled-system decay to finite coherence is the matter wave equivalent of phase-locking two lasers by injection. The non-equilibrium dynamics of superfluids has an important role in a wide range of physical systems, such as superconductors, quantum Hall systems, superfluid helium and spin systems. Our experiments studying coherence dynamics show that 1D Bose gases are ideally suited for investigating this class of phenomena.

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.

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

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.

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.

Transport of citrate-coated silver nanoparticles in unsaturated sand

NASA Astrophysics Data System (ADS)

Kumahor, Samuel; Hron, Pavel; Metreveli, George; Schaumann, Gabriele; Vogel, Hans-Jörg

2015-04-01

Chemical factors and physical constraints lead to coupled effects during particle transport in unsaturated porous media. Unlike for saturated transport, studies on unsaturated transport as typical for soil are currently scarce. We investigated the mobility of citrate-coated Ag NPs in unsaturated sand (grain diameter: 0.1-0.3 mm). For three flux rates and a given pore-water ionic strength (1 mM KNO3), the citrate-coated Ag NPs were less mobile at pH = 5 compared to pH = 9. The classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory suggests unfavorable deposition conditions at both, the air-water interface and solid-water interface. Breakthrough curves measured under quasi-steady state unsaturated flow showed retardation of the citrate-coated Ag NPs compared to inert solute (KBr). After flushing with nanoparticle-free 1 mM KNO3 solution (pH-adjusted), retention was much lower in deeper depths compared to the surface where the particles entered the flow field. The results show a non-linear dependence of nanoparticle (NP) mobility on flux rate and water content. Especially the observed retardation similar to equilibrium sorption is in contrast to observations under saturated flow conditions. A convection-dispersion and reaction model that combines a reversible equilibrium process and a non-equilibrium interaction process reproduced the measured breakthrough curves reasonably well. From comparison between saturated and unsaturated experiments we conclude that the air-water interface is responsible for the reversible equilibrium process while the water-solid interface accounts for irreversible soption.

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.

Water ordering controls the dynamic equilibrium of micelle-fibre formation in self-assembly of peptide amphiphiles.

PubMed

Deshmukh, Sanket A; Solomon, Lee A; Kamath, Ganesh; Fry, H Christopher; Sankaranarayanan, Subramanian K R S

2016-08-24

Understanding the role of water in governing the kinetics of the self-assembly processes of amphiphilic peptides remains elusive. Here, we use a multistage atomistic-coarse-grained approach, complemented by circular dichroism/infrared spectroscopy and dynamic light scattering experiments to highlight the dual nature of water in driving the self-assembly of peptide amphiphiles (PAs). We show computationally that water cage formation and breakage near the hydrophobic groups control the fusion dynamics and aggregation of PAs in the micellar stage. Simulations also suggest that enhanced structural ordering of vicinal water near the hydrophilic amino acids shifts the equilibrium towards the fibre phase and stimulates structure and order during the PA assembly into nanofibres. Experiments validate our simulation findings; the measured infrared O-H bond stretching frequency is reminiscent of an ice-like bond which suggests that the solvated water becomes increasingly ordered with time in the assembled peptide network, thus shedding light on the role of water in a self-assembly process.

Bridging the gap between ionic liquids and molten salts: group 1 metal salts of the bistriflamide anion in the gas phase.

PubMed

Leal, João P; da Piedade, Manuel E Minas; Canongia Lopes, José N; Tomaszowska, Alina A; Esperança, José M S S; Rebelo, Luís Paulo N; Seddon, Kenneth R

2009-03-19

Fourier transform ion cyclotron resonance mass spectrometry experiments showed that liquid Group 1 metal salts of the bistriflamide anion undergoing reduced-pressure distillation exhibit a remarkable behavior that is in transition between that of the vapor-liquid equilibrium characteristics of aprotic ionic liquids and that of the Group 1 metal halides: the unperturbed vapors resemble those of aprotic ionic liquids, in the sense that they are essentially composed of discrete ion pairs. However, the formation of large aggregates through a succession of ion-molecule reactions is closer to what might be expected for Group 1 metal halides. Similar experiments were also carried out with bis{(trifluoromethyl)sulfonyl}amine to investigate the effect of H(+), which despite being the smallest Group 1 cation, is generally regarded as a nonmetal species. In this case, instead of the complex ion-molecule reaction pattern found for the vapors of Group 1 metal salts, an equilibrium similar to those observed for aprotic ionic liquids was observed.

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.

Silicon Isotopes doping experiments to measure quartz dissolution and precipitation rates at equilibrium and test the principle of detailed balance

NASA Astrophysics Data System (ADS)

Zhu, C.; Rimstidt, J. D.; Liu, Z.; Yuan, H.

2016-12-01

The principle of detailed balance (PDB) has been a cornerstone for irreversible thermodynamics and chemical kinetics for a long time, and its wide application in geochemistry has mostly been implicit and without experimental testing of its applicability. Nevertheless, many extrapolations based on PDB without experimental validation have far reaching impacts on society's mega environmental enterprises. Here we report an isotope doping method that independently measures simultaneous dissolution and precipitation rates and can test this principle. The technique reacts a solution enriched in a rare isotope of an element with a solid having natural isotopic abundances (Beck et al., 1992; Gaillardet, 2008; Gruber et al., 2013). Dissolution and precipitation rates are found from the changing isotopic ratios. Our quartz experiment doped with 29Si showed that the equilibrium dissolution rate remains unchanged at all degrees of undersaturation. We recommend this approach to test the validity of using the detailed balance relationship in rate equations for other substances.

Protein Folding Mechanism of the Dimeric AmphiphysinII/Bin1 N-BAR Domain

PubMed Central

Gruber, Tobias; Balbach, Jochen

2015-01-01

The human AmphyphisinII/Bin1 N-BAR domain belongs to the BAR domain superfamily, whose members sense and generate membrane curvatures. The N-BAR domain is a 57 kDa homodimeric protein comprising a six helix bundle. Here we report the protein folding mechanism of this protein as a representative of this protein superfamily. The concentration dependent thermodynamic stability was studied by urea equilibrium transition curves followed by fluorescence and far-UV CD spectroscopy. Kinetic unfolding and refolding experiments, including rapid double and triple mixing techniques, allowed to unravel the complex folding behavior of N-BAR. The equilibrium unfolding transition curve can be described by a two-state process, while the folding kinetics show four refolding phases, an additional burst reaction and two unfolding phases. All fast refolding phases show a rollover in the chevron plot but only one of these phases depends on the protein concentration reporting the dimerization step. Secondary structure formation occurs during the three fast refolding phases. The slowest phase can be assigned to a proline isomerization. All kinetic experiments were also followed by fluorescence anisotropy detection to verify the assignment of the dimerization step to the respective folding phase. Based on these experiments we propose for N-BAR two parallel folding pathways towards the homodimeric native state depending on the proline conformation in the unfolded state. PMID:26368922

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.

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.

Dark soliton decay due to trap anharmonicity in atomic Bose-Einstein condensates

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

Parker, N. G.; Department of Physics and Astronomy, McMaster University, Hamilton, Ontario L8S 4M1; School of Food Science and Nutrition, University of Leeds, Leeds LS2 9JT

2010-03-15

A number of recent experiments with nearly pure atomic Bose-Einstein condensates have confirmed the predicted dark soliton oscillations when under harmonic trapping. However, a dark soliton propagating in an inhomogeneous condensate has also been predicted to be unstable to the emission of sound waves. Although harmonic trapping supports an equilibrium between the coexisting soliton and sound, we show that the ensuing dynamics are sensitive to trap anharmonicities. Such anharmonicities can break the soliton-sound equilibrium and lead to the net decay of the soliton on a considerably shorter time scale than other dissipation mechanisms. Thus, we propose that small realistic modificationsmore » to existing experimental setups could enable the experimental observation of this decay channel.« less

Nonlinear analogue of the May−Wigner instability transition

PubMed Central

Fyodorov, Yan V.; Khoruzhenko, Boris A.

2016-01-01

We study a system of N≫1 degrees of freedom coupled via a smooth homogeneous Gaussian vector field with both gradient and divergence-free components. In the absence of coupling, the system is exponentially relaxing to an equilibrium with rate μ. We show that, while increasing the ratio of the coupling strength to the relaxation rate, the system experiences an abrupt transition from a topologically trivial phase portrait with a single equilibrium into a topologically nontrivial regime characterized by an exponential number of equilibria, the vast majority of which are expected to be unstable. It is suggested that this picture provides a global view on the nature of the May−Wigner instability transition originally discovered by local linear stability analysis. PMID:27274077

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.

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.

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.

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.

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.

Requirements for Initiation and Sustained Propagation of Fuel-Air Explosives

DTIC Science & Technology

1983-06-01

of single-head spin gives the limiting composition for stable propagation of a detonation wave. I. INTRODUCTION which the effects of blockage ratio...Ihu. Dateanle;otd) equivalent chemical times derived from it) provide a much more useful parameter as input to the required theories and empirical...dimensional steady state equilibrium theory (hence static). Experience shows that the dynamic parameters reflect more intimately the detonation properties

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.

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...

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…

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.

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

Understanding the Structural Ensembles of a Highly Extended Disordered Protein†

PubMed Central

Daughdrill, Gary W.; Kashtanov, Stepan; Stancik, Amber; Hill, Shannon E.; Helms, Gregory; Muschol, Martin

2013-01-01

Developing a comprehensive description of the equilibrium structural ensembles for intrinsically disordered proteins (IDPs) is essential to understanding their function. The p53 transactivation domain (p53TAD) is an IDP that interacts with multiple protein partners and contains numerous phosphorylation sites. Multiple techniques were used to investigate the equilibrium structural ensemble of p53TAD in its native and chemically unfolded states. The results from these experiments show that the native state of p53TAD has dimensions similar to a classical random coil while the chemically unfolded state is more extended. To investigate the molecular properties responsible for this behavior, a novel algorithm that generates diverse and unbiased structural ensembles of IDPs was developed. This algorithm was used to generate a large pool of plausible p53TAD structures that were reweighted to identify a subset of structures with the best fit to small angle X-ray scattering data. High weight structures in the native state ensemble show features that are localized to protein binding sites and regions with high proline content. The features localized to the protein binding sites are mostly eliminated in the chemically unfolded ensemble; while, the regions with high proline content remain relatively unaffected. Data from NMR experiments support these results, showing that residues from the protein binding sites experience larger environmental changes upon unfolding by urea than regions with high proline content. This behavior is consistent with the urea-induced exposure of nonpolar and aromatic side-chains in the protein binding sites that are partially excluded from solvent in the native state ensemble. PMID:21979461

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.

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

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.

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.

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.

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.

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.

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.

Real-Time NMR Studies of Oxyamine Ligations of Reducing Carbohydrates under Equilibrium Conditions.

PubMed

Baudendistel, Oliver R; Wieland, Daniel E; Schmidt, Magnus S; Wittmann, Valentin

2016-11-21

Ligation reactions at the anomeric center of carbohydrates have gained increasing importance in the field of glycobiology. Oxyamines are frequently used in labeling, immobilization, and bioconjugation of reducing carbohydrates. Herein, we present a systematic investigation of these ligation reactions under aqueous conditions. A series of four unprotected monosaccharides (glucose, N-acetylglucosamine, mannose, and 2-deoxyglucose) and one disaccharide (N,N'-diacetylchitobiose) was reacted with three primary and one secondary oxyamine. We monitored the concentrations of the starting materials and products by 1 H NMR spectroscopy and determined reaction times and equilibrium yields. Our experiments show that the outcome of the ligation reaction is not only dependent on the sugar and oxyamine used but also strongly on the reaction conditions. In the case of glucose, lowering the pH from 6 to 3 led to steadily increasing reaction rates, whereas the yields were decreasing at the same time. Variation of the temperature did not only influence the product ratio in equilibrium but can also have a strong impact on the equilibrium yield. In the case of reactions of a primary oxyamine, increased temperatures led to a higher proportion of acyclic products. Reaction of the secondary oxyamine with glucose unexpectedly led to lower yields at higher temperatures. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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)

Thermodynamics of enzyme-catalyzed esterifications: II. Levulinic acid esterification with short-chain alcohols.

PubMed

Altuntepe, Emrah; Emel'yanenko, Vladimir N; Forster-Rotgers, Maximilian; Sadowski, Gabriele; Verevkin, Sergey P; Held, Christoph

2017-10-01

Levulinic acid was esterified with methanol, ethanol, and 1-butanol with the final goal to predict the maximum yield of these equilibrium-limited reactions as function of medium composition. In a first step, standard reaction data (standard Gibbs energy of reaction Δ R g 0 ) were determined from experimental formation properties. Unexpectedly, these Δ R g 0 values strongly deviated from data obtained with classical group contribution methods that are typically used if experimental standard data is not available. In a second step, reaction equilibrium concentrations obtained from esterification catalyzed by Novozym 435 at 323.15 K were measured, and the corresponding activity coefficients of the reacting agents were predicted with perturbed-chain statistical associating fluid theory (PC-SAFT). The so-obtained thermodynamic activities were used to determine Δ R g 0 at 323.15 K. These results could be used to cross-validate Δ R g 0 from experimental formation data. In a third step, reaction-equilibrium experiments showed that equilibrium position of the reactions under consideration depends strongly on the concentration of water and on the ratio of levulinic acid: alcohol in the initial reaction mixtures. The maximum yield of the esters was calculated using Δ R g 0 data from this work and activity coefficients of the reacting agents predicted with PC-SAFT for varying feed composition of the reaction mixtures. The use of the new Δ R g 0 data combined with PC-SAFT allowed good agreement to the measured yields, while predictions based on Δ R g 0 values obtained with group contribution methods showed high deviations to experimental yields.

The fundamental role of quantized vibrations in coherent light harvesting by cryptophyte algae

NASA Astrophysics Data System (ADS)

Kolli, Avinash; O'Reilly, Edward J.; Scholes, Gregory D.; Olaya-Castro, Alexandra

2012-11-01

The influence of fast vibrations on energy transfer and conversion in natural molecular aggregates is an issue of central interest. This article shows the important role of high-energy quantized vibrations and their non-equilibrium dynamics for energy transfer in photosynthetic systems with highly localized excitonic states. We consider the cryptophyte antennae protein phycoerythrin 545 and show that coupling to quantized vibrations, which are quasi-resonant with excitonic transitions is fundamental for biological function as it generates non-cascaded transport with rapid and wider spatial distribution of excitation energy. Our work also indicates that the non-equilibrium dynamics of such vibrations can manifest itself in ultrafast beating of both excitonic populations and coherences at room temperature, with time scales in agreement with those reported in experiments. Moreover, we show that mechanisms supporting coherent excitonic dynamics assist coupling to selected modes that channel energy to preferential sites in the complex. We therefore argue that, in the presence of strong coupling between electronic excitations and quantized vibrations, a concrete and important advantage of quantum coherent dynamics is precisely to tune resonances that promote fast and effective energy distribution.

Sinking during earthquakes: Critical acceleration criteria control drained soil liquefaction

NASA Astrophysics Data System (ADS)

Clément, C.; Toussaint, R.; Stojanova, M.; Aharonov, E.

2018-02-01

This article focuses on liquefaction of saturated granular soils, triggered by earthquakes. Liquefaction is defined here as the transition from a rigid state, in which the granular soil layer supports structures placed on its surface, to a fluidlike state, in which structures placed initially on the surface sink to their isostatic depth within the granular layer. We suggest a simple theoretical model for soil liquefaction and show that buoyancy caused by the presence of water inside a granular medium has a dramatic influence on the stability of an intruder resting at the surface of the medium. We confirm this hypothesis by comparison with laboratory experiments and discrete-element numerical simulations. The external excitation representing ground motion during earthquakes is simulated via horizontal sinusoidal oscillations of controlled frequency and amplitude. In the experiments, we use particles only slightly denser than water, which as predicted theoretically increases the effect of liquefaction and allows clear depth-of-sinking measurements. In the simulations, a micromechanical model simulates grains using molecular dynamics with friction between neighbors. The effect of the fluid is captured by taking into account buoyancy effects on the grains when they are immersed. We show that the motion of an intruder inside a granular medium is mainly dependent on the peak acceleration of the ground motion and establish a phase diagram for the conditions under which liquefaction happens, depending on the soil bulk density, friction properties, presence of water, and peak acceleration of the imposed large-scale soil vibrations. We establish that in liquefaction conditions, most cases relax toward an equilibrium position following an exponential in time. We also show that the equilibrium position itself, for most liquefaction regimes, corresponds to the isostatic equilibrium of the intruder inside a medium of effective density. The characteristic time to relaxation is shown to be essentially a function of the peak ground velocity.

Sinking during earthquakes: Critical acceleration criteria control drained soil liquefaction.

PubMed

Clément, C; Toussaint, R; Stojanova, M; Aharonov, E

2018-02-01

This article focuses on liquefaction of saturated granular soils, triggered by earthquakes. Liquefaction is defined here as the transition from a rigid state, in which the granular soil layer supports structures placed on its surface, to a fluidlike state, in which structures placed initially on the surface sink to their isostatic depth within the granular layer. We suggest a simple theoretical model for soil liquefaction and show that buoyancy caused by the presence of water inside a granular medium has a dramatic influence on the stability of an intruder resting at the surface of the medium. We confirm this hypothesis by comparison with laboratory experiments and discrete-element numerical simulations. The external excitation representing ground motion during earthquakes is simulated via horizontal sinusoidal oscillations of controlled frequency and amplitude. In the experiments, we use particles only slightly denser than water, which as predicted theoretically increases the effect of liquefaction and allows clear depth-of-sinking measurements. In the simulations, a micromechanical model simulates grains using molecular dynamics with friction between neighbors. The effect of the fluid is captured by taking into account buoyancy effects on the grains when they are immersed. We show that the motion of an intruder inside a granular medium is mainly dependent on the peak acceleration of the ground motion and establish a phase diagram for the conditions under which liquefaction happens, depending on the soil bulk density, friction properties, presence of water, and peak acceleration of the imposed large-scale soil vibrations. We establish that in liquefaction conditions, most cases relax toward an equilibrium position following an exponential in time. We also show that the equilibrium position itself, for most liquefaction regimes, corresponds to the isostatic equilibrium of the intruder inside a medium of effective density. The characteristic time to relaxation is shown to be essentially a function of the peak ground velocity.

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.

Localization and Symmetry Breaking in the Quantum Quasiperiodic Ising Glass

NASA Astrophysics Data System (ADS)

Chandran, A.; Laumann, C. R.

2017-07-01

Quasiperiodic modulation can prevent isolated quantum systems from equilibrating by localizing their degrees of freedom. In this article, we show that such systems can exhibit dynamically stable long-range orders forbidden in equilibrium. Specifically, we show that the interplay of symmetry breaking and localization in the quasiperiodic quantum Ising chain produces a quasiperiodic Ising glass stable at all energy densities. The glass order parameter vanishes with an essential singularity at the melting transition with no signatures in the equilibrium properties. The zero-temperature phase diagram is also surprisingly rich, consisting of paramagnetic, ferromagnetic, and quasiperiodically alternating ground-state phases with extended, localized, and critically delocalized low-energy excitations. The system exhibits an unusual quantum Ising transition whose properties are intermediate between those of the clean and infinite randomness Ising transitions. Many of these results follow from a geometric generalization of the Aubry-André duality that we develop. The quasiperiodic Ising glass may be realized in near-term quantum optical experiments.

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.

Experimental verification of the thermodynamic properties for a jet-A fuel

NASA Technical Reports Server (NTRS)

Graciasalcedo, Carmen M.; Brabbs, Theodore A.; Mcbride, Bonnie J.

1988-01-01

Thermodynamic properties for a Jet-A fuel were determined by Shell Development Company in 1970 under a contract for NASA Lewis Research Center. The polynomial fit necessary to include Jet-A fuel (liquid and gaseous phases) in the library of thermodynamic properties of the NASA Lewis Chemical Equilibrium Program is calculated. To verify the thermodynamic data, the temperatures of mixtures of liquid Jet-A injected into a hot nitrogen stream were experimentally measured and compared to those calculated by the program. Iso-octane, a fuel for which the thermodynamic properties are well known, was used as a standard to calibrate the apparatus. The measured temperatures for the iso-octane/nitrogen mixtures reproduced the calculated temperatures except for a small loss due to the non-adiabatic behavior of the apparatus. The measurements for Jet-A were corrected for this heat loss and showed excellent agreement with the calculated temperatures. These experiments show that this process can be adequately described by the thermodynamic properties fitted for the Chemical Equilibrium Program.

Evolution of Cooperation in Public Goods Games

NASA Astrophysics Data System (ADS)

Xia, Cheng-Yi; Zhang, Juan-Juan; Wang, Yi-Ling; Wang, Jin-Song

2011-10-01

We investigate the evolution of cooperation with evolutionary public goods games based on finite populations, where four pure strategies: cooperators, defectors, punishers and loners who are unwilling to participate are considered. By adopting approximate best response dynamics, we show that the magnitude of rationality not only quantitatively explains the experiment results in [Nature (London) 425 (2003) 390], but also it will heavily influence the evolution of cooperation. Compared with previous results of infinite populations, which result in two equilibriums, we show that there merely exists a special equilibrium and the relevant high value of bounded rationality will sustain cooperation. In addition, we characterize that loner's payoff plays an active role in the maintenance of cooperation, which will only be warranted for the low and moderate values of loner's payoff. It thus indicates the effects of rationality and loner's payoff will influence the cooperation. Finally, we highlight the important result that the introduction of voluntary participation and punishment will facilitate cooperation greatly.

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

Thermodynamic versus non-equilibrium stability of palmitic acid monolayers in calcium-enriched sea spray aerosol proxy systems.

PubMed

Wellen Rudd, Bethany A; Vidalis, Andrew S; Allen, Heather C

2018-04-16

Of the major cations in seawater (Na+, Mg2+, Ca2+, K+), Ca2+ is found to be the most enriched in fine sea spray aerosols (SSA). In this work, we investigate the binding of Ca2+ to the carboxylic acid headgroup of palmitic acid (PA), a marine-abundant fatty acid, and the impact such binding has on the stability of PA monolayers in both equilibrium and non-equilibrium systems. A range of Ca2+ conditions from 10 μM to 300 mM was utilized to represent the relative concentration of Ca2+ in high and low relative humidity aerosol environments. The CO2- stretching modes of PA detected by surface-sensitive infrared reflection-absorption spectroscopy (IRRAS) reveal ionic binding motifs of the Ca2+ ion to the carboxylate group with varying degrees of hydration. Surface tensiometry was used to determine the thermodynamic equilibrium spreading pressure (ESP) of PA on the various aqueous CaCl2 subphases. Up to concentrations of 1 mM Ca2+, each system reached equilibrium, and Ca2+:PA surface complexation gave rise to a lower energy state revealed by elevated surface pressures relative to water. We show that PA films are not thermodynamically stable at marine aerosol-relevant Ca2+ concentrations ([Ca2+] ≥ 10 mM). IRRAS and vibrational sum frequency generation (VSFG) spectroscopy were used to investigate the surface presence of PA on high concentration Ca2+ aqueous subphases. Non-equilibrium relaxation (NER) experiments were also conducted and monitored by Brewster angle microscopy (BAM) to determine the effect of the Ca2+ ions on PA stability. At high surface pressures, the relaxation mechanisms of PA varied among the systems and were dependent on Ca2+ concentration.

On violations of Le Chatelier's principle for a temperature change in small systems observed for short times

NASA Astrophysics Data System (ADS)

Dasmeh, Pouria; Searles, Debra J.; Ajloo, Davood; Evans, Denis J.; Williams, Stephen R.

2009-12-01

Le Chatelier's principle states that when a system is disturbed, it will shift its equilibrium to counteract the disturbance. However for a chemical reaction in a small, confined system, the probability of observing it proceed in the opposite direction to that predicted by Le Chatelier's principle, can be significant. This work gives a molecular level proof of Le Chatelier's principle for the case of a temperature change. Moreover, a new, exact mathematical expression is derived that is valid for arbitrary system sizes and gives the relative probability that a single experiment will proceed in the endothermic or exothermic direction, in terms of a microscopic phase function. We show that the average of the time integral of this function is the maximum possible value of the purely irreversible entropy production for the thermal relaxation process. Our result is tested against computer simulations of the unfolding of a polypeptide. We prove that any equilibrium reaction mixture on average responds to a temperature increase by shifting its point of equilibrium in the endothermic direction.

Numerical simulation of a non-equilibrium electrokinetic micro/nano fluidic mixer

NASA Astrophysics Data System (ADS)

Hadidi, H.; Kamali, R.

2016-03-01

In this study we numerically simulate a novel micromixer that utilizes vortex generation from the non-equilibrium electrokinetics near the micro/nanochannels interface. After mixing in combined pressure-driven and electroosmotic flows was compared with mixing in a pure pressure-driven flow, the superior mixing performance of the former was evident: for a specific case study, 90% mixing of two fluid streams for a short mixing length was achieved. The results of our numerical study were very similar to those of previously reported experiments. In this paper we explain the phenomenon occurring adjacent to the nano-junctions by plotting the electrical field components, the velocity contours and the concentration distribution in the micromixer. The vortices at the micro/nanochannel interface were obviously indicators of non-equilibrium behaviour in these regions. At the end, the mixing performance was evaluated by the investigation of different applied voltages, Reynolds numbers and surface charge densities using the mixing index parameter, and the results showed that more efficient mixing occurred when the applied voltage and surface charge density magnitude were increased and the Reynolds number was decreased.

Dynamical quantum phase transitions: a review

NASA Astrophysics Data System (ADS)

Heyl, Markus

2018-05-01

Quantum theory provides an extensive framework for the description of the equilibrium properties of quantum matter. Yet experiments in quantum simulators have now opened up a route towards the generation of quantum states beyond this equilibrium paradigm. While these states promise to show properties not constrained by equilibrium principles, such as the equal a priori probability of the microcanonical ensemble, identifying the general properties of nonequilibrium quantum dynamics remains a major challenge, especially in view of the lack of conventional concepts such as free energies. The theory of dynamical quantum phase transitions attempts to identify such general principles by lifting the concept of phase transitions to coherent quantum real-time evolution. This review provides a pedagogical introduction to this field. Starting from the general setting of nonequilibrium dynamics in closed quantum many-body systems, we give the definition of dynamical quantum phase transitions as phase transitions in time with physical quantities becoming nonanalytic at critical times. We summarize the achieved theoretical advances as well as the first experimental observations, and furthermore provide an outlook to major open questions as well as future directions of research.

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.

Dynamical quantum phase transitions: a review.

PubMed

Heyl, Markus

2018-05-01

Quantum theory provides an extensive framework for the description of the equilibrium properties of quantum matter. Yet experiments in quantum simulators have now opened up a route towards the generation of quantum states beyond this equilibrium paradigm. While these states promise to show properties not constrained by equilibrium principles, such as the equal a priori probability of the microcanonical ensemble, identifying the general properties of nonequilibrium quantum dynamics remains a major challenge, especially in view of the lack of conventional concepts such as free energies. The theory of dynamical quantum phase transitions attempts to identify such general principles by lifting the concept of phase transitions to coherent quantum real-time evolution. This review provides a pedagogical introduction to this field. Starting from the general setting of nonequilibrium dynamics in closed quantum many-body systems, we give the definition of dynamical quantum phase transitions as phase transitions in time with physical quantities becoming nonanalytic at critical times. We summarize the achieved theoretical advances as well as the first experimental observations, and furthermore provide an outlook to major open questions as well as future directions of research.

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

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.

Contrasting Effects of Carbon and Sulfur on Fe-Isotope Fractionation between Metal and Silicate Melt during Planetary Core Formation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.

2015-12-01

There are numerous studies that show well-resolved Fe isotope fractionations in igneous materials from different planetary bodies. Potential explanations for these fractionations include a non-chondritic bulk planetary Fe isotopic composition, and equilibrium fractionation between Fe-alloys or minerals and silicate melts during planetary differentiation, mantle melting, or fractional crystallization. This is further complicated by the fact that these processes are not mutually exclusive, making the interpretation of Fe isotope data a complex task. Here we present new experimental results investigating the effect of C on Fe isotope fractionation between molten peridotite and an Fe-alloy. Experiments were conducted at 1 GPa and 1850° C for 0.5 - 3 hours on a mixture of an 54Fe-spiked peridotite and Fe-metal with and without Ni metal in an end-loaded piston cylinder at the Geophysical Laboratory. Carbon saturation was achieved with a graphite capsule, and resulted in C contents of the Fe-alloy in our experiments ranging from 3.8 - 4.9 wt. %. The metal and silicate phases from half of each experiment were separated manually and dissolved in concentrated acids. Iron was separated from matrix elements by anion exchange chromatagraphy. Iron-isotopic compositions were determined with the Nu Plasma II MC-ICP-MS at GL. The other half of each experiment was used for quantitative microbeam analysis. Equilibrium was assessed with a time series and the three-isotope exchange method. The Ni-free experiments resulted in no resolvable Fe isotope fractionation between the Fe-C-alloy and molten silicate. This is in contrast to the results of Shahar et al. (2015) which showed a fractionation for Δ57Fe of ~0.18 ‰ between a peridotite and an Fe-alloy with a similar S abundance to C in these experiments. The one experiment thus far that contained Ni (~4 wt. % in the alloy) showed a resolvable fractionation between the Fe-Ni-C alloy and silicate of ~0.10 ‰. Shahar et al. found a similar magnitude fractionation to our Ni bearing experiment in experiments with no C or S. The difference in temperature (1650° C in Shahar et al. vs. 1850° C here) may be partially responsible for these discrepancies. Ongoing experiments will further investigate the effects of C and other light elements on Fe isotope fractionation during core segregation.

Dissipative Dynamics of Enzymes

NASA Astrophysics Data System (ADS)

Ariyaratne, Amila; Wu, Chenhao; Tseng, Chiao-Yu; Zocchi, Giovanni

2014-11-01

We explore enzyme conformational dynamics at sub-Å resolution, specifically, temperature effects. The ensemble-averaged mechanical response of the folded enzyme is viscoelastic in the whole temperature range between the warm and cold denaturation transitions. The dissipation parameter γ of the viscoelastic description decreases by a factor of 2 as the temperature is raised from 10 to 45 °C ; the elastic parameter K shows a similar decrease. Thus, when probed dynamically, the enzyme softens for increasing temperature. Equilibrium mechanical experiments with the DNA spring (and a different enzyme) also show, qualitatively, a small softening for increasing temperature.

Dissipative Dynamics of Enzymes

NASA Astrophysics Data System (ADS)

Ariyaratne, Amila; Wu, Chenhao; Tseng, Chiao-Yu; Zocchi, Giovanni; Zocchi LabMolecular Biophysics Team

2015-03-01

We explore enzyme conformational dynamics at sub - Å resolution, specifically temperature effects. The ensemble averaged mechanical response of the folded enzyme is viscoelastic in the whole temperature range between the warm and cold denaturation transitions. The dissipation parameter γ of the viscoelastic description decreases by a factor 2 as the temperature is raised from 10 C to 45 C; the elastic parameter K shows a similar decrease. Thus when probed dynamically, the enzyme softens for increasing temperature. Equilibrium mechanical experiments with the DNA spring (and a different enzyme) also show, qualitatively, a small softening for increasing temperature.

Dissipative dynamics of enzymes.

PubMed

Ariyaratne, Amila; Wu, Chenhao; Tseng, Chiao-Yu; Zocchi, Giovanni

2014-11-07

We explore enzyme conformational dynamics at sub-Å resolution, specifically, temperature effects. The ensemble-averaged mechanical response of the folded enzyme is viscoelastic in the whole temperature range between the warm and cold denaturation transitions. The dissipation parameter γ of the viscoelastic description decreases by a factor of 2 as the temperature is raised from 10 to 45 °C; the elastic parameter K shows a similar decrease. Thus, when probed dynamically, the enzyme softens for increasing temperature. Equilibrium mechanical experiments with the DNA spring (and a different enzyme) also show, qualitatively, a small softening for increasing temperature.

Correlation buildup during recrystallization in three-dimensional dusty plasma clusters

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

Schella, André; Mulsow, Matthias; Melzer, André

2014-05-15

The recrystallization process of finite three-dimensional dust clouds after laser heating is studied experimentally. The time-dependent Coulomb coupling parameter is presented, showing that the recrystallization starts with an exponential cooling phase where cooling is slower than damping by the neutral gas friction. At later times, the coupling parameter oscillates into equilibrium. It is found that a large fraction of cluster states after recrystallization experiments is in metastable states. The temporal evolution of the correlation buildup shows that correlation occurs on even slower time scale than cooling.

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

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.

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.

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.

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.

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.

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.

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

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.

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

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.

Convergence to equilibrium of renormalised solutions to nonlinear chemical reaction–diffusion systems

NASA Astrophysics Data System (ADS)

Fellner, Klemens; Tang, Bao Quoc

2018-06-01

The convergence to equilibrium for renormalised solutions to nonlinear reaction-diffusion systems is studied. The considered reaction-diffusion systems arise from chemical reaction networks with mass action kinetics and satisfy the complex balanced condition. By applying the so-called entropy method, we show that if the system does not have boundary equilibria, i.e. equilibrium states lying on the boundary of R_+^N, then any renormalised solution converges exponentially to the complex balanced equilibrium with a rate, which can be computed explicitly up to a finite-dimensional inequality. This inequality is proven via a contradiction argument and thus not explicitly. An explicit method of proof, however, is provided for a specific application modelling a reversible enzyme reaction by exploiting the specific structure of the conservation laws. Our approach is also useful to study the trend to equilibrium for systems possessing boundary equilibria. More precisely, to show the convergence to equilibrium for systems with boundary equilibria, we establish a sufficient condition in terms of a modified finite-dimensional inequality along trajectories of the system. By assuming this condition, which roughly means that the system produces too much entropy to stay close to a boundary equilibrium for infinite time, the entropy method shows exponential convergence to equilibrium for renormalised solutions to complex balanced systems with boundary equilibria.

Adsorption and desorption of hexavalent chromium in an alluvial aquifer near Telluride, Colorado

USGS Publications Warehouse

Stollenwerk, K.G.; Grove, D.B.

1985-01-01

A laboratory investigation of reactions between hexavalent chromium [Cr(VI)] and alluvium was conducted to evaluate reactions of Cr(VI) contaminating an alluvial aquifer near Telluride, CO and to determine the mechanisms responsible for these reactions. Uncontaminated alluvium and groundwater (spiked with CrO42-) from the study site were used in batch and column experiments. Results of these experiments show that Cr(VI) was adsorbed by the alluvium. Distribution coefficients from batch experiments ranged from 52 L/kg at an equilibrium CrO42- concentration of 0.4 ??mol/L to 1.7 L/kg at an equilibrium concentration of 1400 ??mol/L. The zero point of charge for the alluvium was approximately 8.3, and the alluvium had a positive net charge at the groundwater pH of 6.8. Visual and chemical evidence indicated that Fe oxide and hydroxide coatings on the alluvial particles principally were responsible for the absorption of Cr(VI). During column experiments, Cr(VI) initially was desorbed easily from the alluvium by Cr-free groundwater; however, the rate of desorption decreased rapidly, and > 60 pore volumes of groundwater were required to decrease the effluent concentration of Cr(VI) to 3 ??mol/L [drinking water standard for Cr(VI) = 1 ??mol/L]. The quantity of Cr(VI) adsorbed varied with the type and concentration of other anions in solution.

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.

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.

Quantum Sensors for the Generating Functional of Interacting Quantum Field Theories

NASA Astrophysics Data System (ADS)

Bermudez, A.; Aarts, G.; Müller, M.

2017-10-01

Difficult problems described in terms of interacting quantum fields evolving in real time or out of equilibrium abound in condensed-matter and high-energy physics. Addressing such problems via controlled experiments in atomic, molecular, and optical physics would be a breakthrough in the field of quantum simulations. In this work, we present a quantum-sensing protocol to measure the generating functional of an interacting quantum field theory and, with it, all the relevant information about its in- or out-of-equilibrium phenomena. Our protocol can be understood as a collective interferometric scheme based on a generalization of the notion of Schwinger sources in quantum field theories, which make it possible to probe the generating functional. We show that our scheme can be realized in crystals of trapped ions acting as analog quantum simulators of self-interacting scalar quantum field theories.

Molecular weight and oligomerization of rabbit thrombomodulin as assessed by sedimentation equilibrium

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

Winnard, P.T.; Esmon, C.T.; Laue, T.M.

1989-02-15

Lubrol-solubilized rabbit thrombomodulin has been examined by equilibrium sedimentation in buffers that include sufficient D/sub 2/O to make the detergent neutrally buoyant. Data were acquired at rotor speeds from 12,000 to 28,000 rpm from two thrombomodulin preparations, at protein concentrations from 0.01 to 0.07%, and in buffer containing 0.01 to 0.23% Lubrol. Examination of the data from different rotor speeds shows that the thrombomodulin exists as a heterogeneous mixture containing monomer (Mr 65,000), trimer, and higher oligomers. The oligomers do not equilibrate over the time scale of the experiment. The weight fraction as monomer varies from preparation to preparation, andmore » appears to be independent of detergent concentration. Thus, experimenters should be cautious when interpreting binding or kinetic results obtained under similar buffer conditions.« less

Out-of-equilibrium spin transport in mesoscopic superconductors.

PubMed

Quay, C H L; Aprili, M

2018-08-06

The excitations in conventional superconductors, Bogoliubov quasi-particles, are spin-[Formula: see text] fermions but their charge is energy-dependent and, in fact, zero at the gap edge. Therefore, in superconductors (unlike normal metals) spin and charge degrees of freedom may be separated. In this article, we review spin injection into conventional superconductors and focus on recent experiments on mesoscopic superconductors. We show how quasi-particle spin transport and out-of-equilibrium spin-dependent superconductivity can be triggered using the Zeeman splitting of the quasi-particle density of states in thin-film superconductors with small spin-mixing scattering. Finally, we address the spin dynamics and the feedback of quasi-particle spin imbalances on the amplitude of the superconducting energy gap.This article is part of the theme issue 'Andreev bound states'. © 2018 The Author(s).

Atwood and Poggendorff: an insightful analogy

NASA Astrophysics Data System (ADS)

Coelho, R. L.; Borges, P. F.; Karam, R.

2016-11-01

Atwood’s treatise, in which the Atwood machine appears, was published in 1784. About 70 years later, Poggendorff showed experimentally that the weight of an Atwood machine is reduced when it is brought to motion. In the present paper, a twofold connection between this experiment and the Atwood machine is established. Firstly, if the Poggendorff apparatus is taken as an ideal one, the equations of motion of the apparatus coincide with the equations of motion of the compound Atwood machine. Secondly, if the Poggendorff apparatus, which works as a lever, is rebalanced, the equations of this equilibrium provide us with the solution for a compound Atwood machine with the same bodies. This analogy is pedagogically useful because it illustrates a common strategy to transform a dynamic in a static situation improving students’ comprehension of Newton’s laws and equilibrium.

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.

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.

Haloing in bimodal magnetic colloids: The role of field-induced phase separation

NASA Astrophysics Data System (ADS)

Magnet, C.; Kuzhir, P.; Bossis, G.; Meunier, A.; Suloeva, L.; Zubarev, A.

2012-07-01

If a suspension of magnetic micrometer-sized and nanosized particles is subjected to a homogeneous magnetic field, the nanoparticles are attracted to the microparticles and form thick anisotropic halos (clouds) around them. Such clouds can hinder the approach of microparticles and result in effective repulsion between them [M. T. López-López, A. Yu. Zubarev, and G. Bossis, Soft Matter10.1039/c0sm00261e 6, 4346 (2010)]. In this paper, we present detailed experimental and theoretical studies of nanoparticle concentration profiles and of the equilibrium shapes of nanoparticle clouds around a single magnetized microsphere, taking into account interactions between nanoparticles. We show that at a strong enough magnetic field, the ensemble of nanoparticles experiences a gas-liquid phase transition such that a dense liquid phase is condensed around the magnetic poles of a microsphere while a dilute gas phase occupies the rest of the suspension volume. Nanoparticle accumulation around a microsphere is governed by two dimensionless parameters—the initial nanoparticle concentration (φ0) and the magnetic-to-thermal energy ratio (α)—and the three accumulation regimes are mapped onto a α-φ0 phase diagram. Our local thermodynamic equilibrium approach gives a semiquantitative agreement with the experiments on the equilibrium shapes of nanoparticle clouds. The results of this work could be useful for the development of the bimodal magnetorheological fluids and of the magnetic separation technologies used in bioanalysis and water purification systems.

Pore-scale supercritical CO2 dissolution and mass transfer under imbibition conditions

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

Chang, Chun; Zhou, Quanlin; Kneafsey, Timothy J.

2016-06-01

In modeling of geological carbon storage, dissolution of supercritical CO2 (scCO2) is often assumed to be instantaneous with equilibrium phase partitioning. In contrast, recent core-scale imbibition experiments have shown a prolonged depletion of residual scCO2 by dissolution, implying a non-equilibrium mechanism. In this study, eight pore-scale scCO2 dissolution experiments in a 2D heterogeneous, sandstone-analogue micromodel were conducted at supercritical conditions (9 MPa and 40 °C). The micromodel was first saturated with deionized (DI) water and drained by injecting scCO2 to establish a stable scCO2 saturation. DI water was then injected at constant flow rates after scCO2 drainage was completed. Highmore » resolution time-lapse images of scCO2 and water distributions were obtained during imbibition and dissolution, aided by a scCO2-soluble fluorescent dye introduced with scCO2 during drainage. These images were used to estimate scCO2 saturations and scCO2 depletion rates. Experimental results show that (1) a time-independent, varying number of water-flow channels are created during imbibition and later dominant dissolution by the random nature of water flow at the micromodel inlet, and (2) a time-dependent number of water-flow channels are created by coupled imbibition and dissolution following completion of dominant imbibition. The number of water-flow paths, constant or transient in nature, greatly affects the overall depletion rate of scCO2 by dissolution. The average mass fraction of dissolved CO2 (dsCO2) in water effluent varies from 0.38% to 2.72% of CO2 solubility, indicating non-equilibrium scCO2 dissolution in the millimeter-scale pore network. In general, the transient depletion rate decreases as trapped, discontinuous scCO2 bubbles and clusters within water-flow paths dissolve, then remains low with dissolution of large bypassed scCO2 clusters at their interfaces with longitudinal water flow, and finally increases with coupled transverse water flow and enhanced dissolution of large scCO2 clusters. The three stages of scCO2 depletion, common to experiments with time-independent water-flow paths, are revealed by zoom-in image analysis of individual scCO2 bubbles and clusters. The measured relative permeability of water, affected by scCO2 dissolution and bi-modal permeability, shows a non-monotonic dependence on saturation. The results for experiments with different injection rates imply that the non-equilibrium nature of scCO2 dissolution becomes less important when water flow is relatively low and the time scale for dissolution is large, and more pronounced when heterogeneity is strong.« less

Reconnection Scaling Experiment (RSX): Magnetic Reconnection in Linear Geometry

NASA Astrophysics Data System (ADS)

Intrator, T.; Sovinec, C.; Begay, D.; Wurden, G.; Furno, I.; Werley, C.; Fisher, M.; Vermare, L.; Fienup, W.

2001-10-01

The linear Reconnection Scaling Experiment (RSX) at LANL is a qualitatively different way of creating MHD relevant plasmas to look at the physics of magnetic reconnection. We show here an overview of the experiment and initial electrostatic and magnetic probe data. Plasma creation using plasma guns is independent of equilibrium or force balance, so we can scale many relevant parameters. As the magnetic reconnection region between two parallel current channels sweeps down a long plasma column we can generate 3D movies of magnetic reconnection from many repetitive shots. If two current channels were to move because of kink instabilities instead of mutual J x B forces and reconnection effects, each shot would less reproducible. Our data show the kink stability boundary for a single current channel. We compare this with MHD 2 fluid NIMROD simulations of the single current channel kink stability boundary for a variety of experimental conditions.

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.

Regime-dependence of Impacts of Radar Rainfall Data Assimilation

NASA Astrophysics Data System (ADS)

Craig, G. C.; Keil, C.

2009-04-01

Experience from the first operational trials of assimilation of radar data in kilometre scale numerical weather prediction models (operating without cumulus parameterisation) shows that the positive impact of the radar data on convective precipitation forecasts typically decay within a few hours, although certain cases show much longer impacts. Here the impact time of radar data assimilation is related to characteristics of the meteorological environment. This QPF uncertainty is investigated using an ensemble of 10 forecasts at 2.8 km horizontal resolution based on different initial and boundary conditions from a global forecast ensemble. Control forecasts are compared with forecasts where radar reflectivity data is assimilated using latent heat nudging. Examination of different cases of convection in southern Germany suggests that the forecasts can be separated into two regimes using a convective timescale. Short impact times are associated with short convective timescales that are characteristic of equilibrium convection. In this regime the statistical properties of the convection are constrained by the large-scale forcing, and effects of the radar data are lost within a few hours as the convection rapidly returns to equilibrium. When the convective timescale is large (non-equilibrium conditions), the impact of the radar data is longer since convective systems are triggered by the latent heat nudging and are able to persist for many hours in the very unstable conditions present in these cases.

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.

Experimental testing of olivine-melt equilibrium models at high temperatures

NASA Astrophysics Data System (ADS)

Krasheninnikov, S. P.; Sobolev, A. V.; Batanova, V. G.; Kargaltsev, A. A.; Borisov, A. A.

2017-08-01

Data are presented on the equilibrium compositions of olivine and melts in the products of 101 experiments performed at 1300-1600°C, atmospheric pressure, and controlled oxygen fugacity by means of new equipment at the Vernadsky Institute. It was shown that the available models of the olivine-melt equilibrium describe with insufficient adequacy the natural systems at temperatures over 1400°C. The most adequate is the model by Ford et al. (1983). However, this model overestimates systematically the equilibrium temperature with underestimating by 20-40°C at 1450-1600°C. These data point to the need for developing a new, improved quantitative model of the olivine-melt equilibrium for high-temperature magnesian melts, as well as to the possibility of these studies on the basis of the equipment presented.

Run-Reversal Equilibrium for Clinical Trial Randomization

PubMed Central

Grant, William C.

2015-01-01

In this paper, we describe a new restricted randomization method called run-reversal equilibrium (RRE), which is a Nash equilibrium of a game where (1) the clinical trial statistician chooses a sequence of medical treatments, and (2) clinical investigators make treatment predictions. RRE randomization counteracts how each investigator could observe treatment histories in order to forecast upcoming treatments. Computation of a run-reversal equilibrium reflects how the treatment history at a particular site is imperfectly correlated with the treatment imbalance for the overall trial. An attractive feature of RRE randomization is that treatment imbalance follows a random walk at each site, while treatment balance is tightly constrained and regularly restored for the overall trial. Less predictable and therefore more scientifically valid experiments can be facilitated by run-reversal equilibrium for multi-site clinical trials. PMID:26079608

Ehrenfest's Lottery--Time and Entropy Maximization

ERIC Educational Resources Information Center

Ashbaugh, Henry S.

2010-01-01

Successful teaching of the Second Law of Thermodynamics suffers from limited simple examples linking equilibrium to entropy maximization. I describe a thought experiment connecting entropy to a lottery that mixes marbles amongst a collection of urns. This mixing obeys diffusion-like dynamics. Equilibrium is achieved when the marble distribution is…

Surprises from quenches in long-range-interacting systems: temperature inversion and cooling

NASA Astrophysics Data System (ADS)

Gupta, Shamik; Casetti, Lapo

2016-10-01

What happens when one of the parameters governing the dynamics of a long-range interacting system of particles in thermal equilibrium is abruptly changed (quenched) to a different value? While a short-range system, under the same conditions, will relax in time to a new thermal equilibrium with a uniform temperature across the system, a long-range system shows a fast relaxation to a non-equilibrium quasistationary state (QSS). The lifetime of such an off-equilibrium state diverges with the system size, and the temperature is non-uniform across the system. Quite surprisingly, the density profile in the QSS obtained after the quench is anticorrelated with the temperature profile in space, thus exhibiting the phenomenon of temperature inversion: denser regions are colder than sparser ones. We illustrate with extensive molecular dynamics simulations the ubiquity of this scenario in a prototypical long-range interacting system subject to a variety of quenching protocols, and in a model that mimics an experimental setup of atoms interacting with light in an optical cavity. We further demonstrate how a procedure of iterative quenching combined with filtering out the high-energy particles in the system may be employed to cool the system. Temperature inversion is observed in nature in some astrophysical settings; our results imply that such a phenomenon should be observable, and could even be exploitable to advantage, also in controlled laboratory experiments.

Outgassing rate analysis of a velvet cathode and a carbon fiber cathode

NASA Astrophysics Data System (ADS)

Li, An-Kun; Fan, Yu-Wei; Qian, Bao-Liang; Zhang, Zi-cheng; Xun, Tao

2017-11-01

In this paper, the outgassing-rates of a carbon fiber array cathode and a polymer velvet cathode are tested and discussed. Two different methods of measurements are used in the experiments. In one scheme, a method based on dynamic equilibrium of pressure is used. Namely, the cathode works in the repetitive mode in a vacuum diode, a dynamic equilibrium pressure would be reached when the outgassing capacity in the chamber equals the pumping capacity of the pump, and the outgassing rate could be figured out according to this equilibrium pressure. In another scheme, a method based on static equilibrium of pressure is used. Namely, the cathode works in a closed vacuum chamber (a hard tube), and the outgassing rate could be calculated from the pressure difference between the pressure in the chamber before and after the work of the cathode. The outgassing rate is analyzed from the real time pressure evolution data which are measured using a magnetron gauge in both schemes. The outgassing rates of the carbon fiber array cathode and the velvet cathode are 7.3 ± 0.4 neutrals/electron and 85 ± 5 neutrals/electron in the first scheme and 9 ± 0.5 neutrals/electron and 98 ± 7 neutrals/electron in the second scheme. Both the results of two schemes show that the outgassing rate of the carbon fiber array cathode is an order smaller than that of the velvet cathode under similar conditions, which shows that this carbon fiber array cathode is a promising replacement of the velvet cathode in the application of magnetically insulated transmission line oscillators and relativistic magnetrons.

A modified experimental setup for sedimentation equilibrium experiments with gels. Part 2: Technical developments.

PubMed

Cölfen, H; Borchard, W

1994-06-01

This part of the paper trilogy describes technical developments for an efficient experimental setup to investigate gels with equilibrium analytical ultracentrifugation. New 10-channel centerpieces for the Schlieren optics, a new programmable multiplexer, a modified Schlieren optical system, and a photo pickup with impulse transformer are introduced as major developments. Also, some new centerpieces suitable for equilibrium experiments with solutions using the Rayleigh interference and the uv-absorption optics are presented. These centerpieces allow the investigation of 10, 12, or even 26 samples per centerpiece. The problem to find suitable materials for cell centerpieces and windows in the case of adhering samples is discussed for the system gelatin/water. A phase volume calculation for circular sample channels as a correction for the case of broadened menisci is presented. The method described allows an accurate measurement of up to 70 samples simultaneously in an equilibrium experiment if the 8-hole rotor presented in part 1 of the trilogy is used. The number of samples is sufficient to characterize a gel/solvent system in the experimentally accessible range under identical conditions, which is not possible by means of any of the methods known before. All parts described are also applicable for the investigation of solutions.

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

Nanostructure Formation by controlled dewetting on patterned substrates: A combined theoretical, modeling and experimental study.

PubMed

Lu, Liang-Xing; Wang, Ying-Min; Srinivasan, Bharathi Madurai; Asbahi, Mohamed; Yang, Joel K W; Zhang, Yong-Wei

2016-09-01

We perform systematic two-dimensional energetic analysis to study the stability of various nanostructures formed by dewetting solid films deposited on patterned substrates. Our analytical results show that by controlling system parameters such as the substrate surface pattern, film thickness and wetting angle, a variety of equilibrium nanostructures can be obtained. Phase diagrams are presented to show the complex relations between these system parameters and various nanostructure morphologies. We further carry out both phase field simulations and dewetting experiments to validate the analytically derived phase diagrams. Good agreements between the results from our energetic analyses and those from our phase field simulations and experiments verify our analysis. Hence, the phase diagrams presented here provide guidelines for using solid-state dewetting as a tool to achieve various nanostructures.

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.

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:

DNA-cisplatin binding mechanism peculiarities studied with single molecule stretching experiments

NASA Astrophysics Data System (ADS)

Crisafuli, F. A. P.; Cesconetto, E. C.; Ramos, E. B.; Rocha, M. S.

2012-02-01

We propose a method to determine the DNA-cisplatin binding mechanism peculiarities by monitoring the mechanical properties of these complexes. To accomplish this task, we have performed single molecule stretching experiments by using optical tweezers, from which the persistence and contour lengths of the complexes can be promptly measured. The persistence length of the complexes as a function of the drug total concentration in the sample was used to deduce the binding data, from which we show that cisplatin binds cooperatively to the DNA molecule, a point which so far has not been stressed in binding equilibrium studies of this ligand.

Does the nervous system use equilibrium-point control to guide single and multiple joint movements?

PubMed

Bizzi, E; Hogan, N; Mussa-Ivaldi, F A; Giszter, S

1992-12-01

The hypothesis that the central nervous system (CNS) generates movement as a shift of the limb's equilibrium posture has been corroborated experimentally in studies involving single- and multijoint motions. Posture may be controlled through the choice of muscle length-tension curve that set agonist-antagonist torque-angle curves determining an equilibrium position for the limb and the stiffness about the joints. Arm trajectories seem to be generated through a control signal defining a series of equilibrium postures. The equilibrium-point hypothesis drastically simplifies the requisite computations for multijoint movements and mechanical interactions with complex dynamic objects in the environment. Because the neuromuscular system is springlike, the instantaneous difference between the arm's actual position and the equilibrium position specified by the neural activity can generate the requisite torques, avoiding the complex "inverse dynamic" problem of computing the torques at the joints. The hypothesis provides a simple, unified description of posture and movement as well as contact control task performance, in which the limb must exert force stably and do work on objects in the environment. The latter is a surprisingly difficult problem, as robotic experience has shown. The prior evidence for the hypothesis came mainly from psychophysical and behavioral experiments. Our recent work has shown that microstimulation of the frog spinal cord's premotoneural network produces leg movements to various positions in the frog's motor space. The hypothesis can now be investigated in the neurophysiological machinery of the spinal cord.

Determination of thermodynamic and transport parameters of naphthenic acids and organic process chemicals in oil sand tailings pond water.

PubMed

Wang, Xiaomeng; Robinson, Lisa; Wen, Qing; Kasperski, Kim L

2013-07-01

Oil sand tailings pond water contains naphthenic acids and process chemicals (e.g., alkyl sulphates, quaternary ammonium compounds, and alkylphenol ethoxylates). These chemicals are toxic and can seep through the foundation of the tailings pond to the subsurface, potentially affecting the quality of groundwater. As a result, it is important to measure the thermodynamic and transport parameters of these chemicals in order to study the transport behavior of contaminants through the foundation as well as underground. In this study, batch adsorption studies and column experiments were performed. It was found that the transport parameters of these chemicals are related to their molecular structures and other properties. The computer program (CXTFIT) was used to further evaluate the transport process in the column experiments. The results from this study show that the transport of naphthenic acids in a glass column is an equilibrium process while the transport of process chemicals seems to be a non-equilibrium process. At the end of this paper we present a real-world case study in which the transport of the contaminants through the foundation of an external tailings pond is calculated using the lab-measured data. The results show that long-term groundwater monitoring of contaminant transport at the oil sand mining site may be necessary to avoid chemicals from reaching any nearby receptors.

[Preparation and performance investigation of Trichoderma viride-modified corn stalk as sorbent materials for oil spills].

PubMed

Lan, Zhou-Lin; Peng, Dan; Guo, Chu-Ling; Zhu, Chao-Fei; Xue, Xiu-Ling; Dang, Zhi

2013-04-01

This work aims at preparing oil spill sorbent (TCS, Trichoderma viride-modified corn stalk) through solid-state fermentation of corn stalk by Trichoderma viride. Single-factor experiments, including the effect of modification time, solid-liquid ratio of modification and modification temperature, and adsorption experiments simulating oil spill condition, were carried out. The results indicated that the maximum oil adsorption of TCS, 13.84 g x g(-1), could be obtained under the conditions of 6 days of modification, with a solid-liquid ratio of 1:4 and a modification temperature of 25 degrees C. This oil absorption was 110.33% of that of the raw material (RCS, Raw Corn Stalk). Comparing RCS and TCS by means of Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Diffraction (XRD), the results separately showed that TCS had rougher surface, lower cellulose content and higher instability, which explains the increase of oil absorption. Also, the component analysis indicated that bio-modification could reduce the contents of celluloses and hemicelluloses from corn stalk. Besides, sorption kinetics and oil retention performance test showed that, TCS, which could reach adsorption equilibrium after 1 h of 80 r x min(-1) oscillating, had fast oil adsorption rate, and it also had good oil retention performance, which could keep 74. 87% of the initial adsorption rate when trickling 10 min after reaching adsorption equilibrium.

TitaniQ in reverse: backing out the equilibrium solubility of titanium in quartz

NASA Astrophysics Data System (ADS)

Thomas, J. B.

2014-12-01

There is close agreement among three of the four experimental studies that have 'calibrated' the P-T dependencies of Ti-in-quartz solubility. New experiments were conducted to identify potential experimental disequilibrium, and determine which Ti-in-quartz solubility calibration is most accurate. Quartz and rutile were synthesized from SiO2- and TiO2saturated aqueous fluids in a forward-type experiment at 925°C and 10 kbar in a piston-cylinder apparatus. A range of crystal sizes was examined to determine if growth rate affected Ti incorporation in quartz. Cathodoluminescence (CL) images and electron microprobe measurements show that intercrystalline and intracrystalline variations in Ti concentrations are remarkably small regardless of crystal size. The average Ti-in-quartz concentration from the forward-type experiment is 392±1 ppm Ti, which is within 95% confidence interval of data from the 10 kbar isobar of Wark and Watson (2006) and Thomas et al. (2010). Quartz from the forward-type experiment was used as starting material for reversal-type experiments. The high-Ti quartz starting material was recrystallized at 925°C and 20 kbar to reduce the solubility of Ti in recrystallized quartz to the equilibrium solubility concentration of the reversed P-T condition. The 'dry' and 'wet' reversal experiments produced polycrystalline quartzites. Rutile occurs as inclusions in quartz, and as individual crystals dispersed along quartz/quartz grain boundaries. Quartz that recrystallized during the reversal-type experiment has substantially lower Ti concentrations than the quartz starting material because Ti solubility at 20 kbar is significantly lower than at 10 kbar. Dark cathodoluminescent quartz with low Ti concentrations shows that extensive quartz recrystallization occurred at the reversal P-T condition. The average Ti concentration in quartz from reversal experiments is 94±2 ppm Ti, which is within the 95% confidence interval of a linear fit to the 20 kbar data of Thomas et al. (2010). Thomas JB, Watson EB, Spear FS, Shemella FS, Nayak SK, Lanzirotti A (2010) Contrib Mineral Petrol 160:743-759 Wark DA, Watson EB (2006) Contrib Mineral Petrol 152:743-754

3D equilibrium reconstruction with islands

NASA Astrophysics Data System (ADS)

Cianciosa, M.; Hirshman, S. P.; Seal, S. K.; Shafer, M. W.

2018-04-01

This paper presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wall limited L-mode case with an n = 1 error field applied. Flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase. ).

Verification and rectification of the physical analogy of simulated annealing for the solution of the traveling salesman problem.

PubMed

Hasegawa, M

2011-03-01

The aim of the present study is to elucidate how simulated annealing (SA) works in its finite-time implementation by starting from the verification of its conventional optimization scenario based on equilibrium statistical mechanics. Two and one supplementary experiments, the design of which is inspired by concepts and methods developed for studies on liquid and glass, are performed on two types of random traveling salesman problems. In the first experiment, a newly parameterized temperature schedule is introduced to simulate a quasistatic process along the scenario and a parametric study is conducted to investigate the optimization characteristics of this adaptive cooling. In the second experiment, the search trajectory of the Metropolis algorithm (constant-temperature SA) is analyzed in the landscape paradigm in the hope of drawing a precise physical analogy by comparison with the corresponding dynamics of glass-forming molecular systems. These two experiments indicate that the effectiveness of finite-time SA comes not from equilibrium sampling at low temperature but from downward interbasin dynamics occurring before equilibrium. These dynamics work most effectively at an intermediate temperature varying with the total search time and thus this effective temperature is identified using the Deborah number. To test directly the role of these relaxation dynamics in the process of cooling, a supplementary experiment is performed using another parameterized temperature schedule with a piecewise variable cooling rate and the effect of this biased cooling is examined systematically. The results show that the optimization performance is not only dependent on but also sensitive to cooling in the vicinity of the above effec-tive temperature and that this feature is interpreted as a consequence of the presence or absence of the workable interbasin dynamics. It is confirmed for the present instances that the effectiveness of finite-time SA derives from the glassy relaxation dynamics occurring in the "landscape-influenced" temperature regime and that its naive optimization scenario should be rectified by considering the analogy with vitrification phenomena. A comprehensive guideline for the design of finite-time SA and SA-related algorithms is discussed on the basis of this rectified analogy.

Precipitation of Inner-Zone Electrons by Whistler-Mode Waves from the VLF Transmitters UMS and NWC

DTIC Science & Technology

1980-12-01

model plasmasphere in diffusive equilibrium [ Angerami and Thomas ,1964]. The diffusive-equilibrium model used a 90 to 10 percent H+ to O mixture at 16000...Experiments with the Kosmos- 142 and Kosmos-Z59 artificial satellites, Izv. Vyssh. Uchebn. Zaved., Radiofiz, Engl. Transl., 18, 996, 1975. Angerami

Using Think-Aloud Protocols to Investigate Secondary School Chemistry Teachers' Misconceptions about Chemical Equilibrium

ERIC Educational Resources Information Center

Cheung, Derek

2009-01-01

Secondary school chemistry teachers' understanding of chemical equilibrium was investigated through interviews using the think-aloud technique. The interviews were conducted with twelve volunteer chemistry teachers in Hong Kong. Their teaching experience ranged from 3 to 18 years. They were asked to predict what would happen to the equilibrium…

Estimating soil hydraulic parameters from transient flow experiments in a centrifuge using parameter optimization technique

USGS Publications Warehouse

Šimůnek, Jirka; Nimmo, John R.

2005-01-01

A modified version of the Hydrus software package that can directly or inversely simulate water flow in a transient centrifugal field is presented. The inverse solver for parameter estimation of the soil hydraulic parameters is then applied to multirotation transient flow experiments in a centrifuge. Using time‐variable water contents measured at a sequence of several rotation speeds, soil hydraulic properties were successfully estimated by numerical inversion of transient experiments. The inverse method was then evaluated by comparing estimated soil hydraulic properties with those determined independently using an equilibrium analysis. The optimized soil hydraulic properties compared well with those determined using equilibrium analysis and steady state experiment. Multirotation experiments in a centrifuge not only offer significant time savings by accelerating time but also provide significantly more information for the parameter estimation procedure compared to multistep outflow experiments in a gravitational field.

Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

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

Li, Tanping, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu; Kumar, Revati, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu

2015-11-07

We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaksmore » down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids.« less

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.

Slope-velocity equilibrium and evolution of surface roughness on a stony hillslope

NASA Astrophysics Data System (ADS)

Nearing, Mark A.; Polyakov, Viktor O.; Nichols, Mary H.; Hernandez, Mariano; Li, Li; Zhao, Ying; Armendariz, Gerardo

2017-06-01

Slope-velocity equilibrium is hypothesized as a state that evolves naturally over time due to the interaction between overland flow and surface morphology, wherein steeper areas develop a relative increase in physical and hydraulic roughness such that flow velocity is a unique function of overland flow rate independent of slope gradient. This study tests this hypothesis under controlled conditions. Artificial rainfall was applied to 2 m by 6 m plots at 5, 12, and 20 % slope gradients. A series of simulations were made with two replications for each treatment with measurements of runoff rate, velocity, rock cover, and surface roughness. Velocities measured at the end of each experiment were a unique function of discharge rates, independent of slope gradient or rainfall intensity. Physical surface roughness was greater at steeper slopes. The data clearly showed that there was no unique hydraulic coefficient for a given slope, surface condition, or rainfall rate, with hydraulic roughness greater at steeper slopes and lower intensities. This study supports the hypothesis of slope-velocity equilibrium, implying that use of hydraulic equations, such as Chezy and Manning, in hillslope-scale runoff models is problematic because the coefficients vary with both slope and rainfall intensity.

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.

A Simple Organic Microscale Experiment Illustrating the Equilibrium Aspect of the Aldol Condensation

NASA Astrophysics Data System (ADS)

Harrison, Ernest A., Jr.

1998-05-01

A simple microscale experiment has been developed that illustrates the equilibrium aspect of the aldol condensation by using two versions of the standard preparation of tetraphenylcyclopentadienone (5) from benzil (1) and 1,3-diphenyl-2-propanone (2). In version (high base concentration) a mixture of 5 and the diastereomeric 4-hydroxy-2,3,4,5-tetraphenyl-2-cyclopenten-1-ones 3 and 4 are produced, while in the other (low base concentration) a mixture of 1, 2, 3, and 4 results. The experiment is typically carried out in conjunction with the previously reported preparation/dehydration of 3, thus the students provide themselves with authentic samples of 3 and 5. Using these, plus authentic samples of 1 and 2 which are made available, students are able to identify all of the components in the equilibrium mixtures, except 4, by TLC analysis. In the case of 4, students are expected to propose a reasonable structure for this compound based on the observed chemistry and the spectroscopic evidence which is provided (i.e., NMR, IR and mass spectra). The experiment lends itself nicely to either the traditional or problem-solving approach, and it also opens up opportunities for collaborative learning.

Grinding kinetics and equilibrium states

NASA Technical Reports Server (NTRS)

Opoczky, L.; Farnady, F.

1984-01-01

The temporary and permanent equilibrium occurring during the initial stage of cement grinding does not indicate the end of comminution, but rather an increased energy consumption during grinding. The constant dynamic equilibrium occurs after a long grinding period indicating the end of comminution for a given particle size. Grinding equilibrium curves can be constructed to show the stages of comminution and agglomeration for certain particle sizes.

Is Equilibrium Floc Size a Function of Concentration?

NASA Astrophysics Data System (ADS)

Tran, D. A.; Strom, K.

2014-12-01

Flocculation is the process in which cohesive sediments amalgamate to form larger aggregates or flocs. The two factors that strongly influence the flocculation of mud are the turbulent shear rate and the suspended sediment concentration. Increases in turbulent shear rate are known to decrease the time to equilibrium and limit floc size. Increases in concentration are typically thought to decrease the time to equilibrium and increase the final equilibrium floc size. In this laboratory study, the effect of concentration on the growth rate and equilibrium size of flocs is systematically investigated. A camera system and image processing program were used to observe and analyze the evolution of flocs created by of a mixture of 80% kaolinite and 20% montmorillonite clay at six different concentrations (25, 50, 100, 200, 300 and 400 mg/L). Each mixture was first sonicated for 15 minutes before being introduced to a tank of tap water being mixed at an turbulent shear rate of G = 58 s-1. Flocs were then allowed to grow for two hours. During the following hour, a much higher shear rate of G = 1200 s-1 was applied to break the flocs. The shear rate was then reduced back to and maintained at G = 58 s-1 for another six hours. Running the experiments in this way allowed for the observation of floc growth from two different initial particle states at each concentration, resulting in a total of 12 floc growth experiments. The primary conclusions from this set of experiments are: (1) higher suspended sediment concentration is correlated with a higher rate of floc growth, and (2) at equilibrium, the average floc size stabilizes at ≈ 100 µm independent of the initial particle state or the suspended sediment concentration. Therefor, for the sediment mixture tested, the results imply that the effect of concentration on flocculation was restricted to the floc growth rate. This is contrary to what would be predicted using typical mud settling velocity equations.

Tubular lipid membranes pulled from vesicles: Dependence of system equilibrium on lipid bilayer curvature

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

Golushko, I. Yu., E-mail: vaniagolushko@yandex.ru; Rochal, S. B.

2016-01-15

Conditions of joint equilibrium and stability are derived for a spherical lipid vesicle and a tubular lipid membrane (TLM) pulled from this vesicle. The obtained equations establish relationships between the geometric and physical characteristics of the system and the external parameters, which have been found to be controllable in recent experiments. In particular, the proposed theory shows that, in addition to the pressure difference between internal and external regions of the system, the variable spontaneous average curvature of the lipid bilayer (forming the TLM) also influences the stability of the lipid tube. The conditions for stability of the cylindrical phasemore » of TLMs after switching off the external force that initially formed the TLM from a vesicle are discussed. The loss of system stability under the action of a small axial force compressing the TLM is considered.« less

Mechanisms of Phosphorus Removal by Recycled Crushed Concrete.

PubMed

Deng, Yihuan; Wheatley, Andrew

2018-02-17

Due to urbanisation, there are large amounts of waste concrete, particularly in rapidly industrialising countries. Currently, demolished concrete is mainly recycled as aggregate for reconstruction. This study has shown that larger sizes (2-5 mm) of recycled concrete aggregate (RCA) removed more than 90% of P from effluent when at pH 5. Analysis of the data, using equilibrium models, indicated a best fit with the Langmuir which predicated an adsorption capacity of 6.88 mg/g. Kinetic analysis indicated the equilibrium adsorption time was 12 h, with pseudo second-order as the best fit. The thermal dynamic tests showed that the adsorption was spontaneous and, together with the evidence from the sequential extraction and desorption experiments, indicated the initial mechanism was physical attraction to the surface followed by chemical reactions which prevented re-release. These results suggested that RCA could be used for both wastewater treatment and P recovery.

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.

Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

PubMed Central

Rice, James W.; Suuberg, Eric M.

2010-01-01

To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

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.

Mechanisms of Phosphorus Removal by Recycled Crushed Concrete

PubMed Central

Wheatley, Andrew

2018-01-01

Due to urbanisation, there are large amounts of waste concrete, particularly in rapidly industrialising countries. Currently, demolished concrete is mainly recycled as aggregate for reconstruction. This study has shown that larger sizes (2–5 mm) of recycled concrete aggregate (RCA) removed more than 90% of P from effluent when at pH 5. Analysis of the data, using equilibrium models, indicated a best fit with the Langmuir which predicated an adsorption capacity of 6.88 mg/g. Kinetic analysis indicated the equilibrium adsorption time was 12 h, with pseudo second-order as the best fit. The thermal dynamic tests showed that the adsorption was spontaneous and, together with the evidence from the sequential extraction and desorption experiments, indicated the initial mechanism was physical attraction to the surface followed by chemical reactions which prevented re-release. These results suggested that RCA could be used for both wastewater treatment and P recovery. PMID:29462987

Benchmark Shock Tube Experiments for Radiative Heating Relevant to Earth Re-Entry

NASA Technical Reports Server (NTRS)

Brandis, A. M.; Cruden, B. A.

2017-01-01

Detailed spectrally and spatially resolved radiance has been measured in the Electric Arc Shock Tube (EAST) facility for conditions relevant to high speed entry into a variety of atmospheres, including Earth, Venus, Titan, Mars and the Outer Planets. The tests that measured radiation relevant for Earth re-entry are the focus of this work and are taken from campaigns 47, 50, 52 and 57. These tests covered conditions from 8 km/s to 15.5 km/s at initial pressures ranging from 0.05 Torr to 1 Torr, of which shots at 0.1 and 0.2 Torr are analyzed in this paper. These conditions cover a range of points of interest for potential fight missions, including return from Low Earth Orbit, the Moon and Mars. The large volume of testing available from EAST is useful for statistical analysis of radiation data, but is problematic for identifying representative experiments for performing detailed analysis. Therefore, the intent of this paper is to select a subset of benchmark test data that can be considered for further detailed study. These benchmark shots are intended to provide more accessible data sets for future code validation studies and facility-to-facility comparisons. The shots that have been selected as benchmark data are the ones in closest agreement to a line of best fit through all of the EAST results, whilst also showing the best experimental characteristics, such as test time and convergence to equilibrium. The EAST data are presented in different formats for analysis. These data include the spectral radiance at equilibrium, the spatial dependence of radiance over defined wavelength ranges and the mean non-equilibrium spectral radiance (so-called 'spectral non-equilibrium metric'). All the information needed to simulate each experimental trace, including free-stream conditions, shock time of arrival (i.e. x-t) relation, and the spectral and spatial resolution functions, are provided.

Model of DNA topology simplification has come full (supercoiled) circle after two decades of research. Comment on "Disentangling DNA molecules" by Alexander Vologodskii

NASA Astrophysics Data System (ADS)

Stasiak, Andrzej

2016-09-01

Being a geek of DNA topology, I remember very well the stir caused by 1997 Science paper showing that DNA topoisomerases have the ability to simplify DNA topology below the topological equilibrium values [1]. In their seminal experiments Rybenkov et al. [1] started with linear double-stranded DNA molecules with cohesive ends. The mutual cohesiveness of DNA ends was due to mutual complementarity of single-stranded extensions at both ends of linear double-stranded DNA molecules. When such DNA molecules were heated up and then slowly cooled down the single-stranded ends eventually annealed with each other causing DNA circularization. This experimental protocol permitted the authors to establish topological/thermodynamic equilibrium within samples of circularized DNA molecules. Among simple unknotted circles one also observed knotted and catenated DNA molecules. The fraction of knotted molecules in DNA samples at topological equilibrium was increasing with the length of DNA molecules undergoing slow circularization. The fraction of catenated molecules was increasing with the length and the concentration of the molecules undergoing slow circularization. Rybenkov et al. incubated then such equilibrated DNA samples with type II DNA topoisomerases, which pass DNA duplex regions through each other, and observed that as the result of it the fraction of knotted and catenated DNA molecules was dramatically decreased (up to 80-fold). This elegant experiment indicated for the first time that type II DNA topoisomerases acting on knotted or catenated DNA molecules have the ability to select among many potential sites of DNA-DNA passages these that result in DNA unknotting or decatenation. Without such a selection topoisomerases could only maintain the original topological equilibrium obtained during the slow cyclization. The big question was how DNA topoisomerases can be directed to do DNA-DNA passages that preferentially result in DNA unknotting and decatenation.

Enhancement of superexchange pairing in the periodically driven Hubbard model

NASA Astrophysics Data System (ADS)

Coulthard, J. R.; Clark, S. R.; Al-Assam, S.; Cavalleri, A.; Jaksch, D.

2017-08-01

Recent experiments performed on cuprates and alkali-doped fullerides have demonstrated that key signatures of superconductivity can be induced above the equilibrium critical temperature by optical modulation. These observations in disparate physical systems may indicate a general underlying mechanism. Multiple theories have been proposed, but these either consider specific features, such as competing instabilities, or focus on conventional BCS-type superconductivity. Here we show that periodic driving can enhance electron pairing in strongly correlated systems. Focusing on the strongly repulsive limit of the doped Hubbard model, we investigate in-gap, spatially inhomogeneous, on-site modulations. We demonstrate that such modulations substantially reduce electronic hopping, while simultaneously sustaining superexchange interactions and pair hopping via driving-induced virtual charge excitations. We calculate real-time dynamics for the one-dimensional case, starting from zero- and finite-temperature initial states, and we show that enhanced singlet-pair correlations emerge quickly and robustly in the out-of-equilibrium many-body state. Our results reveal a fundamental pairing mechanism that might underpin optically induced superconductivity in some strongly correlated quantum materials.

Active nematic emulsions

PubMed Central

Hardoüin, Jérôme; Sagués, Francesc

2018-01-01

The formation of emulsions from multiple immiscible fluids is governed by classical concepts such as surface tension, differential chemical affinity and viscosity, and the action of surface-active agents. Much less is known about emulsification when one of the components is active and thus inherently not constrained by the laws of thermodynamic equilibrium. We demonstrate one such realization consisting in the encapsulation of an active liquid crystal (LC)–like gel, based on microtubules and kinesin molecular motors, into a thermotropic LC. These active nematic emulsions exhibit a variety of dynamic behaviors that arise from the cross-talk between topological defects separately residing in the active and passive components. Using numerical simulations, we show a feedback mechanism by which active flows continuously drive the passive defects that, in response, resolve the otherwise degenerated trajectories of the active defects. Our experiments show that the choice of surfactant, which stabilizes the active/passive interface, allows tuning the regularity of the self-sustained dynamic events. The hybrid active-passive system demonstrated here provides new perspectives for dynamic self-assembly driven by an active material but regulated by the equilibrium properties of the passive component. PMID:29740605

Active nematic emulsions.

PubMed

Guillamat, Pau; Kos, Žiga; Hardoüin, Jérôme; Ignés-Mullol, Jordi; Ravnik, Miha; Sagués, Francesc

2018-04-01

The formation of emulsions from multiple immiscible fluids is governed by classical concepts such as surface tension, differential chemical affinity and viscosity, and the action of surface-active agents. Much less is known about emulsification when one of the components is active and thus inherently not constrained by the laws of thermodynamic equilibrium. We demonstrate one such realization consisting in the encapsulation of an active liquid crystal (LC)-like gel, based on microtubules and kinesin molecular motors, into a thermotropic LC. These active nematic emulsions exhibit a variety of dynamic behaviors that arise from the cross-talk between topological defects separately residing in the active and passive components. Using numerical simulations, we show a feedback mechanism by which active flows continuously drive the passive defects that, in response, resolve the otherwise degenerated trajectories of the active defects. Our experiments show that the choice of surfactant, which stabilizes the active/passive interface, allows tuning the regularity of the self-sustained dynamic events. The hybrid active-passive system demonstrated here provides new perspectives for dynamic self-assembly driven by an active material but regulated by the equilibrium properties of the passive component.

Drop dynamics on a thin film: Thin film rupture

NASA Astrophysics Data System (ADS)

Carlson, Andreas; Kim, Pilnam; Stone, Howard A.

2011-11-01

The spreading of a water drop on an oil film that covers a solid substrate is a common event in many industrial processes. We study in experiments the dynamics of a water drop on a thin silicone oil film and quantify its interaction with the solid substrate that supports the film. The oil film becomes unstable and ruptures for solids that are hydrophilic. We determine the ``waiting time,'' the time it takes the water drop to drain the silicone film. This timescale is found to highly depend on how well water wets the solid, illustrating the interplay between intermolecular and hydrodynamic forces in the phenomenon. A phase diagram for the thin film stability is extracted based on waters equilibrium contact angle on the solid, which shows that we can either promote or inhibit de-wetting. As water comes in direct contact with the solid, it spreads and peels off the silicone film. We show the influence of viscosity, equilibrium contact angle and film height on the opening radius of the hole formed as the solid de-wets.

Interfacial Alloy Hydride Destabilization in Mg/Pd Thin Films

NASA Astrophysics Data System (ADS)

Chung, C.-J.; Lee, Sang-Chul; Groves, James R.; Brower, Edwin N.; Sinclair, Robert; Clemens, Bruce M.

2012-03-01

Recently, a large increase in the equilibrium hydrogen pressure has been reported for MG thin films capped with a Pd layer. We show that this increase is due to intermixing of Mg and Pd, as opposed to a strain effect as previously claimed. Transmission electron microscopy and depth profiling x-ray photoemission spectroscopy are used to directly measure interfacial intermixing between Mg and Pd, and we find that intermixing and equilibrium hydrogen pressure both increase with annealing. We present a thermodynamic model of the effect of alloying on equilibrium pressure, and find that the observed equilibrium pressure increase is consistent with the observed thickness of the intermixed region, which is of the order of a few nm. We also show that stress measured during hydrogenation corresponds to a negligible increase in equilibrium pressure.

Free energy surfaces from nonequilibrium processes without work measurement

NASA Astrophysics Data System (ADS)

Adib, Artur B.

2006-04-01

Recent developments in statistical mechanics have allowed the estimation of equilibrium free energies from the statistics of work measurements during processes that drive the system out of equilibrium. Here a different class of processes is considered, wherein the system is prepared and released from a nonequilibrium state, and no external work is involved during its observation. For such "clamp-and-release" processes, a simple strategy for the estimation of equilibrium free energies is offered. The method is illustrated with numerical simulations and analyzed in the context of tethered single-molecule experiments.

Control Model for Dampening Hand Vibrations Using Information of Internal and External Coordinates

PubMed Central

Togo, Shunta; Kagawa, Takahiro; Uno, Yoji

2015-01-01

In the present study, we investigate a control mechanism that dampens hand vibrations. Here, we propose a control method with two components to suppress hand vibrations. The first is a passive suppression method that lowers the joint stiffness to passively dampen the hand vibrations. The second is an active suppression method that adjusts an equilibrium point based on skyhook control to actively dampen the hand vibrations. In a simulation experiment, we applied these two methods to dampen hand vibrations during the shoulder’s horizontal oscillation. We also conducted a measurement experiment wherein a subject’s shoulder was sinusoidally oscillated by a platform that generated horizontal oscillations. The results of the measurement experiments showed that the jerk of each part of the arm in a task using a cup filled with water was smaller than the shoulder jerk and that in a task with a cup filled with stones was larger than the shoulder jerk. Moreover, the amplitude of the hand trajectory in both horizontal and vertical directions was smaller in a task using a cup filled with water than in a task using a cup filled with stones. The results of the measurement experiments were accurately reproduced by the active suppression method based on skyhook control. These results suggest that humans dampen hand vibrations by controlling the equilibrium point through the information of the external workspace and the internal body state rather than by lowering joint stiffness only by using internal information. PMID:25876037

3D equilibrium reconstruction with islands

DOE PAGES

Cianciosa, M.; Hirshman, S. P.; Seal, S. K.; ...

2018-02-15

This study presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wallmore » limited L-mode case with an n = 1 error field applied. Finally, flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase.« less

3D equilibrium reconstruction with islands

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

Cianciosa, M.; Hirshman, S. P.; Seal, S. K.

This study presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wallmore » limited L-mode case with an n = 1 error field applied. Finally, flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase.« less

Detached Bridgman Growth of Germanium and Germanium-Silicon Alloy Crystals

NASA Technical Reports Server (NTRS)

Szofran, F. R.; Volz, M. P.; Schweizer, M.; Cobb, S. D.; Motakef, S.; Croell, A.; Dold, P.; Curreri, Peter A. (Technical Monitor)

2002-01-01

Earth based experiments on the science of detached crystal growth are being conducted on germanium and germanium-silicon alloys (2 at% Si average composition) in preparation for a series of experiments aboard the International Space Station (ISS). The purpose of the microgravity experiments includes differentiating among proposed mechanisms contributing to detachment, and confirming or refining our understanding of the detachment mechanism. Because large contact angle are critical to detachment, sessile drop measurements were used to determine the contact angles as a function of temperature and composition for a large number of substrates made of potential ampoule materials. Growth experiments have used pyrolytic boron nitride (pBN) and fused silica ampoules with the majority of the detached results occurring predictably in the pBN. The contact angles were 173 deg (Ge) and 165 deg (GeSi) for pBN. For fused silica, the contact angle decreases from 150 deg to an equilibrium value of 117 deg (Ge) or from 129 deg to an equilibrium value of 100 deg (GeSi) over the duration of the experiment. The nature and extent of detachment is determined by using profilometry in conjunction with optical and electron microscopy. The stability of detachment has been analyzed, and an empirical model for the conditions necessary to achieve sufficient stability to maintain detached growth for extended periods has been developed. Results in this presentation will show that we have established the effects on detachment of ampoule material, pressure difference above and below the melt, and silicon concentration; samples that are nearly completely detached can be grown repeatedly in pBN.

Rapid reduction of MORB glass in piston cylinder experiments with graphite capsule - a XANES study

NASA Astrophysics Data System (ADS)

Ni, P.; Zhang, Y.; Fiege, A.; Newville, M.; Lanzirotti, A.

2017-12-01

Graphite capsules have been widely used in high-pressure, high-temperature experiments to prevent iron loss from iron-bearing samples. One common uncertainty with this experimental setup is the oxygen fugacity (fO2) inside the capsule imposed by the presence of graphite. As Holloway et al. (1992) pointed out, the use of graphite capsule places an upper limit on the fO2 in the experiment to be below CCO (graphite-CO-CO2 buffer). More recently, Medard et al. (2015) estimated the fO2 for their experiments using Pt-graphite or graphite-only capsules to be CCO-0.8. Despite the improved understanding on the fO2 using graphite capsule, the mechanism and kinetics of fO2 control in graphite capsule is still poorly understood. Such knowledge is especially important to understand whether equilibrium fO2 is reached in the sample when short experiment durations are needed (e.g. for kinetic experiments). In this study, MORB glasses after olivine dissolution (Chen and Zhang 2008) and plagioclase dissolution (Yu et al. 2016) experiments at 0.5 GPa and 1300 ºC with durations ranging from 10 s to 30 min are analyzed by XANES to obtain Fe3+/Fetotal profiles from their contact with the graphite capsule. The results show rapid Fe reduction away from the graphite-melt interface, causing a decrease of Fe3+/Fetotal from 12% to 3%. In a duration of 30 min, the 1200-µm-thick and 2000-µm-diameter basaltic glass reached near equilibrium in its iron oxidation state, with Fe3+/Fetotal ranging from 3% to 4% throughout the run product. The equilibrium Fe3+/Fetotal ratio corresponds to an fO2 of CCO-1.4, which is within error compared to the result in Medard et al. (2015). Even in the shortest experiment with an effective duration of only 10 s, a 60 µm long reduction profile was detected. Such a rapid fO2 change can be explained by rapid H2 diffusion in melt and its reaction with ferric iron: H2+Fe2O3=2FeO+H2O, which is also supported by the H2O concentration profiles measured along the reduction profile. Our results indicate rapid fO2 equilibration in MORB-glass-composition samples during nominally anhydrous graphite capsule experiments at 1300°C, and can be used to guide experimental designs.

DC electrophoresis and viscosity of realistic salt-free concentrated suspensions: non-equilibrium dissociation-association processes.

PubMed

Ruiz-Reina, Emilio; Carrique, Félix; Lechuga, Luis

2014-03-01

Most of the suspensions usually found in industrial applications are concentrated, aqueous and in contact with the atmospheric CO2. The case of suspensions with a high concentration of added salt is relatively well understood and has been considered in many studies. In this work we are concerned with the case of concentrated suspensions that have no ions different than: (1) those stemming from the charged colloidal particles (the added counterions, that counterbalance their surface charge); (2) the H(+) and OH(-) ions from water dissociation, and (3) the ions generated by the atmospheric CO2 contamination. We call this kind of systems "realistic salt-free suspensions". We show some theoretical results about the electrophoretic mobility of a colloidal particle and the electroviscous effect of realistic salt-free concentrated suspensions. The theoretical framework is based on a cell model that accounts for particle-particle interactions in concentrated suspensions, which has been successfully applied to many different phenomena in concentrated suspensions. On the other hand, the water dissociation and CO2 contamination can be described following two different levels of approximation: (a) by local equilibrium mass-action equations, because it is supposed that the reactions are so fast that chemical equilibrium is attained everywhere in the suspension, or (b) by non-equilibrium dissociation-association kinetic equations, because it is considered that some reactions are not rapid enough to ensure local chemical equilibrium. Both approaches give rise to different results in the range from dilute to semidilute suspensions, causing possible discrepancies when comparing standard theories and experiments concerning transport properties of realistic salt-free suspensions. Copyright © 2013 Elsevier Inc. All rights reserved.

Two-wave photon Doppler velocimetry measurements in direct impact Hopkinson pressure bar experiments

NASA Astrophysics Data System (ADS)

Lea, Lewis J.; Jardine, Andrew P.

2015-09-01

Direct impact Hopkinson pressure bar systems offer many potential advantages over split Hopkinson pressure bars, including access to higher strain rates, higher strains for equivalent striker velocity and system length, lower dispersion and faster achievement of force equilibrium. Currently advantages are gained at a significant cost: the fact that input bar data is unavailable removes all information about the striker impacted specimen face, preventing the determination of force equilibrium, and requiring approximations to be made on the sample deformation history. Recently photon Doppler velocimetry methods have been developed, which can replace strain gauges on Hopkinson bars. In this paper we discuss an experimental method and complementary data analysis for using Doppler velocimetry to measure surface velocities of the striker and output bars in a direct impact bar experiment, allowing similar data to be recorded as in a split bar system, with the same level of convenience. We discuss extracting velocity and force measurements, and improving the accuracy and convenience of Doppler velocimetry on Hopkinson bars. Results obtained using the technique are compared to equivalent split bar tests, showing improved stress measurements for the lowest and highest strains.

Preparation and Characterization of Activated Cow Bone Powder for the Adsorption of Cadmium from Palm Oil Mill Effluent

NASA Astrophysics Data System (ADS)

AbdulRahman, A.; Latiff, A. A. A.; Daud, Z.; Ridzuan, M. B.; D, N. F. M.; Jagaba, A. H.

2016-07-01

Several studies have been conducted on the removal of heavy metals from palm oil mill effluent. In this study, cow bones were developed as an adsorbent for the removal of cadmium II from POME. A batch experiment was conducted to investigate the effectiveness of the prepared activated cow bone powder for the sorption of cadmium II from raw POME. The experiment was carried out under fixed conditions using 100mg/L raw POME combined with different adsorbent dosage of CBP of 184.471 Ra(nm) surface roughness. The equilibrium adsorption capacity of the hydrophobic CBP of average contact angle 890 was determined from the relationship between the initial and equilibrium liquid phase concentrations of POME. The optimum adsorption of cadmium II on CBP was at 10g adsorbent dosage for sample 1 and 2 at 97.8% and 96.93% respectively. The least uptake was at 30g adsorbent weight for both samples at average of 95.1% for both samples. The effective removal of cadmium ion showed that CBP has a great potential for the treatment of heavy metal in POME.

Dissolution of multi-component LNAPL gasolines: The effects of weathering and composition

NASA Astrophysics Data System (ADS)

Lekmine, Greg; Bastow, Trevor P.; Johnston, Colin D.; Davis, Greg B.

2014-05-01

The composition of light non-aqueous phase liquid (LNAPL) gasoline and other petroleum products changes profoundly over their life once released into aquifers. However limited attention has been given to how such changes affect key parameters such as the activity coefficients which control partitioning of components of petroleum fuel into groundwater and are used to predict long-term risk from fuel releases. Laboratory experiments were conducted on a range of fresh, weathered and synthetic gasoline mixtures designed to mimic the expected changes in composition in an aquifer. Weathered gasoline created under controlled evaporation and water washing, and naturally weathered gasoline, were investigated. Equilibrium concentrations in water and molar fractions in the gasoline mixtures were compared with equilibrium concentrations predicted by Raoult's law assuming ideal behaviour of the solutions. The experiments carried out allowed the relative sensitivity of the activity coefficients of key risk drivers such as benzene, toluene, ethylbenzene and xylene (BTEX) compounds to be quantified with respect to the presence of other types of compounds and where the source LNAPL had undergone different types of weathering. Results differed for the mixtures examined but in some cases higher than predicted dissolved equilibrium concentrations showed non-ideal behaviour for toluene, benzene and xylenes. Comparison of the activity coefficients showed that the naturally weathered gasoline and a 50% evaporated unleaded gasoline present a similar range of values varying between 1.0 and 1.2, suggesting close to ideal partitioning between the LNAPL and water. The fresh and water-washed gasoline had higher values for the activity coefficient, from 1.2 to 1.4, indicating non-ideal partitioning. Results from synthetic mixtures demonstrated that these differences could be due to the different molar fractions of the nC5 and nC6 aliphatic hydrocarbons acting on the molecular interactions, while differences in molar volumes seemed to have less of an influence on ideality.

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.

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.

AN ASSESSMENT OF THE ABILITY OF 3-D AIR QUALITY MODELS WITH CURRENT THERMODYNAMIC EQUILIBRIUM MODELS TO PREDICT AEROSOL NO3

EPA Science Inventory

The partitioning of total nitrate (TNO3) and total ammonium (TNH4) between gas and aerosol phases is studied with two thermodynamic equilibrium models, ISORROPIA and AIM, and three datasets: high time-resolution measurement data from the 1999 Atlanta SuperSite Experiment and from...

Understanding the Nernst Equation and Other Electrochemical Concepts: An Easy Experimental Approach for Students

ERIC Educational Resources Information Center

Vidal-Iglesias, Francisco J.; Solla-Gullon, Jose; Rodes, Antonio; Herrero, Enrique; Aldaz, Antonio

2012-01-01

The goal of the present laboratory experiment is to deepen the understanding of the Nernst equation and some other concepts that are essential in electrochemistry. In this practical laboratory session, students first learn that the equilibrium potential of an electrode is related to the difference between two equilibrium inner electric potentials…

A simple apparatus for controlling nucleation and size in protein crystal growth

NASA Technical Reports Server (NTRS)

Gernert, Kim M.; Smith, Robert; Carter, Daniel C.

1988-01-01

A simple device is described for controlling vapor equilibrium in macromolecular crystallization as applied to the protein crystal growth technique commonly referred to as the 'hanging drop' method. Crystal growth experiments with hen egg white lysozyme have demonstrated control of the nucleation rate. Nucleation rate and final crystal size have been found to be highly dependent upon the rate at which critical supersaturation is approached. Slower approaches show a marked decrease in the nucleation rate and an increase in crystal size.

Simulations for Teaching Chemical Equilibrium

NASA Astrophysics Data System (ADS)

Huddle, Penelope A.; White, Margaret Dawn; Rogers, Fiona

2000-07-01

This paper outlines a systematic approach to teaching chemical equilibrium using simulation experiments that address most known alternate conceptions in the topic. Graphs drawn using the data from the simulations are identical to those obtained using real experimental data for reactions that go to equilibrium. This allows easy mapping of the analogy to the target. The requirements for the simulations are simple and inexpensive, making them accessible to even the poorest schools. The simulations can be adapted for all levels, from pupils who are first encountering equilibrium through students in tertiary education to qualified teachers who have experienced difficulty in teaching the topic. The simulations were piloted on four very different audiences. Minor modifications were then made before the Equilibrium Games as reported in this paper were tested on three groups of subjects: a Grade 12 class, college students, and university Chemistry I students. Marked improvements in understanding of the concept were shown in two of the three sets of subjects.

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.

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.

An Oligomeric Equilibrium Intermediate as the Precursory Nucleus of Globular and Fibrillar Supramacromolecular Assemblies in a PDZ Domain

PubMed Central

Murciano-Calles, Javier; Cobos, Eva S.; Mateo, Pedro L.; Camara-Artigas, Ana; Martinez, Jose C.

2010-01-01

Abstract The equilibrium unfolding at neutral pH of the third PDZ domain of PSD95, as followed by DSC, is characterized by the presence of an equilibrium intermediate with clear signs of oligomerization. DLS and SEC measurements indicate that at 60–70°C small oligomers populate, showing a typical β-sheet far-UV CD spectrum. These intermediate species lead to the formation of rodlike particulates of ∼12 nm, which remain in solution after 2 weeks incubation and grow until they adopt annular/spherical shapes of ∼50 nm and protofibrils, which are subsequently fully transformed into fibrils. The fibrils can also disaggregate after the addition of 1:1 buffer dilution followed by cooling to room temperature, thus returning to the initial monomeric state. Growth kinetics, as shown by ThT and ANS fluorescence, show that the organization of the different supramacromolecular structures comes from a common nucleation unit, the small oligomers, which organize themselves before reaching the incubation temperature of 60°C. Our experiments point toward the existence of a well-defined reversible, stepwise, and downhill organization of the processes involved in the association-dissociation of the intermediate. We estimate the enthalpy change accompanying the association-dissociation equilibria to be 130 kJ × mol−1. Furthermore, the coalescence under essentially reversible conditions of different kinds of supramacromolecular assemblies renders this protein system highly interesting for biophysical studies aimed at our further understanding of amyloid pathological conditions. PMID:20655855

Children's strategic theory of mind.

PubMed

Sher, Itai; Koenig, Melissa; Rustichini, Aldo

2014-09-16

Human strategic interaction requires reasoning about other people's behavior and mental states, combined with an understanding of their incentives. However, the ontogenic development of strategic reasoning is not well understood: At what age do we show a capacity for sophisticated play in social interactions? Several lines of inquiry suggest an important role for recursive thinking (RT) and theory of mind (ToM), but these capacities leave out the strategic element. We posit a strategic theory of mind (SToM) integrating ToM and RT with reasoning about incentives of all players. We investigated SToM in 3- to 9-y-old children and adults in two games that represent prevalent aspects of social interaction. Children anticipate deceptive and competitive moves from the other player and play both games in a strategically sophisticated manner by 7 y of age. One game has a pure strategy Nash equilibrium: In this game, children achieve equilibrium play by the age of 7 y on the first move. In the other game, with a single mixed-strategy equilibrium, children's behavior moved toward the equilibrium with experience. These two results also correspond to two ways in which children's behavior resembles adult behavior in the same games. In both games, children's behavior becomes more strategically sophisticated with age on the first move. Beyond the age of 7 y, children begin to think about strategic interaction not myopically, but in a farsighted way, possibly with a view to cooperating and capitalizing on mutual gains in long-run relationships.

Children’s strategic theory of mind

PubMed Central

Sher, Itai; Koenig, Melissa; Rustichini, Aldo

2014-01-01

Human strategic interaction requires reasoning about other people’s behavior and mental states, combined with an understanding of their incentives. However, the ontogenic development of strategic reasoning is not well understood: At what age do we show a capacity for sophisticated play in social interactions? Several lines of inquiry suggest an important role for recursive thinking (RT) and theory of mind (ToM), but these capacities leave out the strategic element. We posit a strategic theory of mind (SToM) integrating ToM and RT with reasoning about incentives of all players. We investigated SToM in 3- to 9-y-old children and adults in two games that represent prevalent aspects of social interaction. Children anticipate deceptive and competitive moves from the other player and play both games in a strategically sophisticated manner by 7 y of age. One game has a pure strategy Nash equilibrium: In this game, children achieve equilibrium play by the age of 7 y on the first move. In the other game, with a single mixed-strategy equilibrium, children’s behavior moved toward the equilibrium with experience. These two results also correspond to two ways in which children’s behavior resembles adult behavior in the same games. In both games, children’s behavior becomes more strategically sophisticated with age on the first move. Beyond the age of 7 y, children begin to think about strategic interaction not myopically, but in a farsighted way, possibly with a view to cooperating and capitalizing on mutual gains in long-run relationships. PMID:25197065

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.

Conversion of Chemical Reaction Energy into Useful Work in the Van't Hoff Equilibrium Box

ERIC Educational Resources Information Center

Bazhin, N. M.; Parmon, V. N.

2007-01-01

The ideal van't Hoff equilibrium box is described in detail. It shows that van't Hoff equilibrium box divided in two parts can simultaneously produce heat and useful work without violation of the first law of thermodynamics.

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.

Adiabatic out-of-equilibrium solutions to the Boltzmann equation in warm inflation

NASA Astrophysics Data System (ADS)

Bastero-Gil, Mar; Berera, Arjun; Ramos, Rudnei O.; Rosa, João G.

2018-02-01

We show that, in warm inflation, the nearly constant Hubble rate and temperature lead to an adiabatic evolution of the number density of particles interacting with the thermal bath, even if thermal equilibrium cannot be maintained. In this case, the number density is suppressed compared to the equilibrium value but the associated phase-space distribution retains approximately an equilibrium form, with a smaller amplitude and a slightly smaller effective temperature. As an application, we explicitly construct a baryogenesis mechanism during warm inflation based on the out-of-equilibrium decay of particles in such an adiabatically evolving state. We show that this generically leads to small baryon isocurvature perturbations, within the bounds set by the Planck satellite. These are correlated with the main adiabatic curvature perturbations but exhibit a distinct spectral index, which may constitute a smoking gun for baryogenesis during warm inflation. Finally, we discuss the prospects for other applications of adiabatically evolving out-of-equilibrium states.

Radiative heat transfer and nonequilibrium Casimir-Lifshitz force in many-body systems with planar geometry

NASA Astrophysics Data System (ADS)

Latella, Ivan; Ben-Abdallah, Philippe; Biehs, Svend-Age; Antezza, Mauro; Messina, Riccardo

2017-05-01

A general theory of photon-mediated energy and momentum transfer in N -body planar systems out of thermal equilibrium is introduced. It is based on the combination of the scattering theory and the fluctuational-electrodynamics approach in many-body systems. By making a Landauer-like formulation of the heat transfer problem, explicit formulas for the energy transmission coefficients between two distinct slabs as well as the self-coupling coefficients are derived and expressed in terms of the reflection and transmission coefficients of the single bodies. We also show how to calculate local equilibrium temperatures in such systems. An analogous formulation is introduced to quantify momentum transfer coefficients describing Casimir-Lifshitz forces out of thermal equilibrium. Forces at thermal equilibrium are readily obtained as a particular case. As an illustration of this general theoretical framework, we show on three-body systems how the presence of a fourth slab can impact equilibrium temperatures in heat-transfer problems and equilibrium positions resulting from the forces acting on the system.

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

Experiments for Modern Introductory Chemistry.

ERIC Educational Resources Information Center

Kildahl, Nicholas; Berka, Ladislav H.

1995-01-01

Presents a headspace gas chromatography experiment that enables discovery of the temperature dependence of the vapor pressure of a pure liquid. Illustrates liquid-vapor phase equilibrium of pure liquids. Contains 22 references. (JRH)

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.

High-pressure phase transitions of α-quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

NASA Astrophysics Data System (ADS)

Carl, Eva-Regine; Mansfeld, Ulrich; Liermann, Hanns-Peter; Danilewsky, Andreas; Langenhorst, Falko; Ehm, Lars; Trullenque, Ghislain; Kenkmann, Thomas

2017-07-01

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high-pressure polymorphs in rock-forming minerals are known from meteorites and terrestrial impact craters. Here, we investigate the formation of high-pressure polymorphs of α-quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α-quartz in situ by synchrotron powder X-ray diffraction. Phase transitions of α-quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s-1, experiments reveal that α-quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO6 octahedra rather than the rearrangement of the SiO4 tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.

Statistical investigation of simulated intestinal fluid composition on the equilibrium solubility of biopharmaceutics classification system class II drugs.

PubMed

Khadra, Ibrahim; Zhou, Zhou; Dunn, Claire; Wilson, Clive G; Halbert, Gavin

2015-01-25

A drug's solubility and dissolution behaviour within the gastrointestinal tract is a key property for successful administration by the oral route and one of the key factors in the biopharmaceutics classification system. This property can be determined by investigating drug solubility in human intestinal fluid (HIF) but this is difficult to obtain and highly variable, which has led to the development of multiple simulated intestinal fluid (SIF) recipes. Using a statistical design of experiment (DoE) technique this paper has investigated the effects and interactions on equilibrium drug solubility of seven typical SIF components (sodium taurocholate, lecithin, sodium phosphate, sodium chloride, pH, pancreatin and sodium oleate) within concentration ranges relevant to human intestinal fluid values. A range of poorly soluble drugs with acidic (naproxen, indomethacin, phenytoin, and piroxicam), basic (aprepitant, carvedilol, zafirlukast, tadalafil) or neutral (fenofibrate, griseofulvin, felodipine and probucol) properties have been investigated. The equilibrium solubility results determined are comparable with literature studies of the drugs in either HIF or SIF indicating that the DoE is operating in the correct space. With the exception of pancreatin, all of the factors individually had a statistically significant influence on equilibrium solubility with variations in magnitude of effect between the acidic and basic or neutral compounds and drug specific interactions were evident. Interestingly for the neutral compounds pH was the factor with the second largest solubility effect. Around one third of all the possible factor combinations showed a significant influence on equilibrium solubility with variations in interaction significance and magnitude of effect between the acidic and basic or neutral compounds. The least number of significant media component interactions were noted for the acidic compounds with three and the greatest for the neutral compounds at seven, with again drug specific effects evident. This indicates that a drug's equilibrium solubility in SIF is influenced depending upon drug type by between eight to fourteen individual or combinations of media components with some of these drug specific. This illustrates the complex nature of these fluids and provides for individual drugs a visualisation of the possible solubility envelope within the gastrointestinal tract, which may be of importance for modelling in vivo behaviour. In addition the results indicate that the design of experiment approach can be employed to provide greater detail of drug solubility behaviour, possible drug specific interactions and influence of variations in gastrointestinal media components due to disease. The approach is also feasible and amenable to adaptation for high throughput screening of drug candidates. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanostructure Formation by controlled dewetting on patterned substrates: A combined theoretical, modeling and experimental study

PubMed Central

Lu, Liang-Xing; Wang, Ying-Min; Srinivasan, Bharathi Madurai; Asbahi, Mohamed; Yang, Joel K. W.; Zhang, Yong-Wei

2016-01-01

We perform systematic two-dimensional energetic analysis to study the stability of various nanostructures formed by dewetting solid films deposited on patterned substrates. Our analytical results show that by controlling system parameters such as the substrate surface pattern, film thickness and wetting angle, a variety of equilibrium nanostructures can be obtained. Phase diagrams are presented to show the complex relations between these system parameters and various nanostructure morphologies. We further carry out both phase field simulations and dewetting experiments to validate the analytically derived phase diagrams. Good agreements between the results from our energetic analyses and those from our phase field simulations and experiments verify our analysis. Hence, the phase diagrams presented here provide guidelines for using solid-state dewetting as a tool to achieve various nanostructures. PMID:27580943

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

Balanced Electrostatic and Structural Forces Guide the Large Conformational Change Associated with Maturation of T = 4 Virus

PubMed Central

Matsui, Tsutomu; Tsuruta, Hiro; Johnson, John E.

2010-01-01

Nudaurelia capensis omega virus has a well-characterized T = 4 capsid that undergoes a pH-dependent large conformational changes (LCC) and associated auto-catalytic cleavage of the subunit. We examined previously the particle size at different pH values and showed that maturation occurred at pH 5.5. We now characterized the LCC with time-resolved small-angle x-ray scattering and showed that there were three kinetic stages initiated with an incremental drop in pH: 1), a rapid (<10 ms) collapse to an incrementally smaller particle; 2), a continuous size reduction over the next 5 s; and 3), a smaller final transition occurring in 2–3 min. Equilibrium measurements similar to those reported previously, but now more precise, showed that the particle dimension between pH 5.5 and 5 requires the autocatalytic cleavage to achieve its final compact size. A balance of electrostatic and structural forces shapes the energy landscape of the LCC with the latter requiring annealing of portions of the subunit. Equilibrium experiments showed that many intermediate states could be populated with a homogeneous ensemble of particles by carefully controlling the pH. A titration curve for the LCC was generated that showed that the virtual pKa (i.e., the composite of all titratable residues that contribute to the LCC) is 5.8. PMID:20371334

Materials Laboratory Classes for First Year Undergraduates

ERIC Educational Resources Information Center

Fahy, F. W.

1975-01-01

Describes a combined demonstration and student experiment course to illustrate fundamental techniques, instrumentation, and concise report writing. Describes experiments including tensile tests, heat treatment, equilibrium diagram, microexamination, strain measurement, and recrystallization. (GH)

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

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

The Solubility of Nickel Sulfate-6-Water: A General Chemistry Experiment.

ERIC Educational Resources Information Center

Pacer, Richard A.

1984-01-01

Background information, procedures used, and typical results are provided for a solubility experiment. Among the 12 objectives of the experiment are: acquiring understanding of the terms "saturated,""unsaturated," and "supersaturated;" learning meaning of the expression "to approach equilibrium;" gaining…

Overshoot in biological systems modelled by Markov chains: a non-equilibrium dynamic phenomenon.

PubMed

Jia, Chen; Qian, Minping; Jiang, Daquan

2014-08-01

A number of biological systems can be modelled by Markov chains. Recently, there has been an increasing concern about when biological systems modelled by Markov chains will perform a dynamic phenomenon called overshoot. In this study, the authors found that the steady-state behaviour of the system will have a great effect on the occurrence of overshoot. They showed that overshoot in general cannot occur in systems that will finally approach an equilibrium steady state. They further classified overshoot into two types, named as simple overshoot and oscillating overshoot. They showed that except for extreme cases, oscillating overshoot will occur if the system is far from equilibrium. All these results clearly show that overshoot is a non-equilibrium dynamic phenomenon with energy consumption. In addition, the main result in this study is validated with real experimental data.

The solubility of platinum in silicate melt under reducing conditions: Results from experiments without metal inclusions

NASA Astrophysics Data System (ADS)

Bennett, N. R.; Brenan, J. M.; Koga, K. T.

2014-05-01

The solubility of Pt in silicate melt was investigated at conditions of 2073-2573 K, 2 GPa and ˜IW -1.5 to +3.5. These are the first measurements of Pt solubility under conditions more reducing than the iron-wüstite buffer (IW) which are demonstrably free from contamination by metal-inclusions. Pt solubility increases with increasing temperature and decreasing oxygen fugacity. The ability of carbon to enhance Pt solubility under reducing conditions (3500 K. Under these conditions however, the estimated Pt/Os ratio is ˜40,000 times higher than that estimated for the PUM (Brandon et al., 2006). Instead, the PUM composition is generated most readily by metal-silicate equilibrium at more modest temperatures (˜3100 K), followed by a late accretion of chondritic material subsequent to core formation.

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;…

Using Beads and Divided Containers to Study Kinetic and Equilibrium Isotope Effects in the Laboratory and in the Classroom

ERIC Educational Resources Information Center

Campbell, Dean J.; Brewer, Emily R.; Martinez, Keri A.; Fitzjarrald, Tamara J.

2017-01-01

The purpose of this laboratory experiment is to study fundamental concepts of kinetics and equilibria and the isotope effects associated with both of these concepts. The concepts of isotopes in introductory and general chemistry courses are typically used within the contexts of atomic weights and radioactivity. Kinetic and equilibrium isotope…

Investigating the Magnetic Interaction with Geomag and Tracker Video Analysis: Static Equilibrium and Anharmonic Dynamics

ERIC Educational Resources Information Center

Onorato, P.; Mascheretti, P.; DeAmbrosis, A.

2012-01-01

In this paper, we describe how simple experiments realizable by using easily found and low-cost materials allow students to explore quantitatively the magnetic interaction thanks to the help of an Open Source Physics tool, the Tracker Video Analysis software. The static equilibrium of a "column" of permanents magnets is carefully investigated by…

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

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

Using Controlled Landslide Initiation Experiments to Test Limit-Equilibrium Analyses of Slope Stability

NASA Astrophysics Data System (ADS)

Reid, M. E.; Iverson, R. M.; Brien, D. L.; Iverson, N. R.; Lahusen, R. G.; Logan, M.

2004-12-01

Most studies of landslide initiation employ limit equilibrium analyses of slope stability. Owing to a lack of detailed data, however, few studies have tested limit-equilibrium predictions against physical measurements of slope failure. We have conducted a series of field-scale, highly controlled landslide initiation experiments at the USGS debris-flow flume in Oregon; these experiments provide exceptional data to test limit equilibrium methods. In each of seven experiments, we attempted to induce failure in a 0.65m thick, 2m wide, 6m3 prism of loamy sand placed behind a retaining wall in the 31° sloping flume. We systematically investigated triggering of sliding by groundwater injection, by prolonged moderate-intensity sprinkling, and by bursts of high intensity sprinkling. We also used vibratory compaction to control soil porosity and thereby investigate differences in failure behavior of dense and loose soils. About 50 sensors were monitored at 20 Hz during the experiments, including nests of tiltmeters buried at 7 cm spacing to define subsurface failure geometry, and nests of tensiometers and pore-pressure sensors to define evolving pore-pressure fields. In addition, we performed ancillary laboratory tests to measure soil porosity, shear strength, hydraulic conductivity, and compressibility. In loose soils (porosity of 0.52 to 0.55), abrupt failure typically occurred along the flume bed after substantial soil deformation. In denser soils (porosity of 0.41 to 0.44), gradual failure occurred within the soil prism. All failure surfaces had a maximum length to depth ratio of about 7. In even denser soil (porosity of 0.39), we could not induce failure by sprinkling. The internal friction angle of the soils varied from 28° to 40° with decreasing porosity. We analyzed stability at failure, given the observed pore-pressure conditions just prior to large movement, using a 1-D infinite-slope method and a more complete 2-D Janbu method. Each method provides a static Factor of Safety (FS), and in theory failure occurs when FS ≤ 1. Using the 1-D analysis, all experiments having failure had FS well below 1 (typically 0.5-0.8). Using the 2-D analysis for these same conditions, FS was less than but closer to 1 (typically 0.8-0.9). For the experiment with no failure, the 2-D FS was, reassuringly, > 1. These results indicate that the 2-D Janbu analysis is more accurate than the 1-D infinite-slope method for computing limit-equilibrium slope stability in shallow slides with limited areal extent.

Effects of resident water and non-equilibrium adsorption on the primary and enhanced coalbed methane gas recovery

NASA Astrophysics Data System (ADS)

Jahediesfanjani, Hossein

The major part of the gas in coalbed methane and shale gas reservoirs is stored as the adsorbed gas in the coal and organic materials of the black shale internal surfaces. The sorption sites in both reservoirs are composed of several macropores that contain very small pore sizes. Therefore, the adsorption/desorption is very slow process and follows a non-equilibrium trend. The time-dependency of the sorption process is further affected by the reservoir resident water. Water can diffuse into the matrix and adsorption sites, plug the pores and affect the reservoir gas production. This study presents an experimental and theoretical procedure to investigate the effects of the resident water and time-dependency of the sorption process on coalbed and shale gas primary and enhanced recovery by simultaneous CO 2/N2 injection. Series of the experiments are conducted to construct both equilibrium and non-equilibrium single and multi-component isotherms with the presence of water. A novel and rapid data interpretation technique is developed based on the nonequilibrium adsorption/desorption thermodynamics, mass conservation law, and volume filling adsorption theory. The developed technique is implemented to construct both equilibrium and non-equilibrium multi-component multi-phase isotherms from the early time experimental measurements. The non-equilibrium isotherms are incorporated in the coalbed methane/shale gas reservoir simulations to account for the time-dependency of the sorption process. The experimental results indicate that the presence of water in the sorption system reduces both carbon dioxide and nitrogen adsorption rates. Reduction in the adsorption rate for carbon dioxide is more than nitrogen. The results also indicate that the resident water reduces the adsorption ability of low rank coals more than high rank ones. The results of the multi-component sorption tests indicate that increasing the initial mole fraction of the nitrogen gas in the injected CO2/N2 mixture will increase the net carbon dioxide sequestration rate on coals in the presence of water. The optimum CO2/N2 ratio that can result in the maximum carbon dioxide sequestration rate can be obtained by conducting the experiments for various CO2/N2 ratios. The results of applying the developed non-equilibrium interpretation technique for several literature and in-house data indicate that both the equilibrium and non-equilibrium isotherms can be constructed in shorter time period (around 70 times less than the time required with the equilibrium techniques) and with higher accuracy using this method. (Abstract shortened by UMI.)

Application of Van Der Waals Density Functional Theory to Study Physical Properties of Energetic Materials

NASA Astrophysics Data System (ADS)

Conroy, M. W.; Budzevich, M. M.; Lin, Y.; Oleynik, I. I.; White, C. T.

2009-12-01

An empirical correction to account for van der Waals interactions based on the work of Neumann and Perrin [J. Phys. Chem. B 109, 15531 (2005)] was applied to density functional theory calculations of energetic molecular crystals. The calculated equilibrium unit-cell volumes of FOX-7, β-HMX, solid nitromethane, PETN-I, α-RDX, and TATB show a significant improvement in the agreement with experimental results. Hydrostatic-compression simulations of β-HMX, PETN-I, and α-RDX were also performed. The isothermal equations of state calculated from the results show increased agreement with experiment in the pressure intervals studied.

Effects of dispersal on total biomass in a patchy, heterogeneous system: analysis and experiment.

USGS Publications Warehouse

Zhang, Bo; Liu, Xin; DeAngelis, Donald L.; Ni, Wei-Ming; Wang, G Geoff

2015-01-01

An intriguing recent result from mathematics is that a population diffusing at an intermediate rate in an environment in which resources vary spatially will reach a higher total equilibrium biomass than the population in an environment in which the same total resources are distributed homogeneously. We extended the current mathematical theory to apply to logistic growth and also showed that the result applies to patchy systems with dispersal among patches, both for continuous and discrete time. This allowed us to make specific predictions, through simulations, concerning the biomass dynamics, which were verified by a laboratory experiment. The experiment was a study of biomass growth of duckweed (Lemna minor Linn.), where the resources (nutrients added to water) were distributed homogeneously among a discrete series of water-filled containers in one treatment, and distributed heterogeneously in another treatment. The experimental results showed that total biomass peaked at an intermediate, relatively low, diffusion rate, higher than the total carrying capacity of the system and agreeing with the simulation model. The implications of the experiment to dynamics of source, sink, and pseudo-sink dynamics are discussed.

Thermal equilibrium concentrations and effects of negatively charged Ga vacancies in n-type GaAs

NASA Astrophysics Data System (ADS)

Tan, T. Y.; You, H.-M.; Gösele, U. M.

1993-03-01

We have calculated the thermal equilibrium concentrations of the various negatively charged Ga vacancy species in GaAs. The triply-negatively-charged Ga vacancy, V {Ga/3-}, has been emphasized, since it dominates Ga self-diffusion and Ga-Al interdiffusion under intrinsic and n-doping conditions, as well as the diffusion of Si donor atoms occupying Ga sites. Under strong n-doping conditions, the thermal equilibrium V {Ga/3-}concentration, C_{V_{_{Ga} }^{3 - } }^{eq} (n), has been found to exhibit a temperature independence or a negative temperature dependence, i.e., the C_{V_{_{Ga} }^{3 - } }^{eq} (n) value is either unchanged or increases as the temperature is lowered. This is quite contrary to the normal point defect behavior for which the point defect thermal equilibrium concentration decreases as the temperature is lowered. This C_{V_{_{Ga} }^{3 - } }^{eq} (n) property provides explanations to a number of outstanding experimental results, either requiring the interpretation that V {Ga/3-}has attained its thermal equilibrium concentration at the onset of each experiment, or requiring mechanisms involving point defect non-equilibrium phenomena.

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.

Notes on Experiments.

ERIC Educational Resources Information Center

Physics Education, 1985

1985-01-01

Describes: (1) two experiments using a laser (resonant cavity for light and pinhole camera effect with a hologram); (2) optical differaction patterns displayed by microcomputer; and (3) automating the Hall effect (with comments on apparatus needed and computer program used); and (4) an elegant experiment in mechanical equilibrium. (JN)

The Chemistry Involved in the Preparation of a Paint Pigment: An Experiment for the Freshman Laboratory

ERIC Educational Resources Information Center

Daines, Terri L.; Morse, Karen W.

1976-01-01

Describes an experiment that demonstrates the following principles and reactions: amphoterism, oxidation-reduction, equilibrium dependence on pH, solubility, and polymerization. The experiment involves the oxidation of chromium and the precipitation of a chromate salt. (MLH)

On gamesmen and fair men: explaining fairness in non-cooperative bargaining games.

PubMed

Suleiman, Ramzi

2018-02-01

Experiments on bargaining games have repeatedly shown that subjects fail to use backward induction, and that they only rarely make demands in accordance with the subgame perfect equilibrium. In a recent paper, we proposed an alternative model, termed 'economic harmony' in which we modified the individual's utility by defining it as a function of the ratio between the actual and aspired pay-offs. We also abandoned the notion of equilibrium, in favour of a new notion of 'harmony', defined as the intersection of strategies, at which all players are equally satisfied. We showed that the proposed model yields excellent predictions of offers in the ultimatum game, and requests in the sequential common pool resource dilemma game. Strikingly, the predicted demand in the ultimatum game is equal to the famous Golden Ratio (approx. 0.62 of the entire pie). The same prediction was recently derived independently by Schuster (Schuster 2017. Sci. Rep. 7 , 5642). In this paper, we extend the solution to bargaining games with alternating offers. We show that the derived solution predicts the opening demands reported in several experiments, on games with equal and unequal discount factors and game horizons. Our solution also predicts several unexplained findings, including the puzzling 'disadvantageous counter-offers', and the insensitivity of opening demands to variations in the players' discount factors, and game horizon. Strikingly, we find that the predicted opening demand in the alternating offers game is also equal to the Golden Ratio.

On gamesmen and fair men: explaining fairness in non-cooperative bargaining games

PubMed Central

2018-01-01

Experiments on bargaining games have repeatedly shown that subjects fail to use backward induction, and that they only rarely make demands in accordance with the subgame perfect equilibrium. In a recent paper, we proposed an alternative model, termed ‘economic harmony’ in which we modified the individual's utility by defining it as a function of the ratio between the actual and aspired pay-offs. We also abandoned the notion of equilibrium, in favour of a new notion of ‘harmony’, defined as the intersection of strategies, at which all players are equally satisfied. We showed that the proposed model yields excellent predictions of offers in the ultimatum game, and requests in the sequential common pool resource dilemma game. Strikingly, the predicted demand in the ultimatum game is equal to the famous Golden Ratio (approx. 0.62 of the entire pie). The same prediction was recently derived independently by Schuster (Schuster 2017. Sci. Rep. 7, 5642). In this paper, we extend the solution to bargaining games with alternating offers. We show that the derived solution predicts the opening demands reported in several experiments, on games with equal and unequal discount factors and game horizons. Our solution also predicts several unexplained findings, including the puzzling ‘disadvantageous counter-offers’, and the insensitivity of opening demands to variations in the players' discount factors, and game horizon. Strikingly, we find that the predicted opening demand in the alternating offers game is also equal to the Golden Ratio. PMID:29515877

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.

Quantum irreversible decoherence behaviour in open quantum systems with few degrees of freedom: Application to 1H NMR reversion experiments in nematic liquid crystals

NASA Astrophysics Data System (ADS)

Segnorile, H. H.; Zamar, R. C.

2013-10-01

An experimental study of NMR spin decoherence in nematic liquid crystals is presented. Decoherence dynamics can be put in evidence by means of refocusing experiments of the dipolar interactions. The experimental technique used in this work is based on the MREV8 pulse sequence. The aim of the work is to detect the main features of the irreversible quantum decoherence in liquid crystals, on the basis of the theory presented by the authors recently. The focus is laid on experimentally probing the eigen-selection process in the intermediate time scale, between quantum interference of a closed system and thermalization, as a signature of the quantum spin decoherence of the open quantum system, as well as on quantifying the effects of non-idealities as possible sources of signal decays which could mask the intrinsic decoherence. In order to contrast experiment and theory, the theory was adapted to obtain the decoherence function corresponding to the MREV8 reversion experiments. Non-idealities of the experimental setting, like external field inhomogeneity, pulse misadjustments, and the presence of non-reverted spin interaction terms are analysed in detail within this framework, and their effects on the observed signal decay are numerically estimated. It is found that though all these non-idealities could in principle affect the evolution of the spin dynamics, their influence can be mitigated and they do not present the characteristic behaviour of the irreversible spin decoherence. As unique characteristic of decoherence, the experimental results clearly show the occurrence of eigen-selectivity in the intermediate timescale, in complete agreement with the theoretical predictions. We conclude that the eigen-selection effect is the fingerprint of decoherence associated with a quantum open spin system in liquid crystals. Besides, these features of the results account for the quasi-equilibrium states of the spin system, which were observed previously in these mesophases, and lead to conclude that the quasi-equilibrium is a definite stage of the spin dynamics during its evolution towards equilibrium.

Accelerating Multiagent Reinforcement Learning by Equilibrium Transfer.

PubMed

Hu, Yujing; Gao, Yang; An, Bo

2015-07-01

An important approach in multiagent reinforcement learning (MARL) is equilibrium-based MARL, which adopts equilibrium solution concepts in game theory and requires agents to play equilibrium strategies at each state. However, most existing equilibrium-based MARL algorithms cannot scale due to a large number of computationally expensive equilibrium computations (e.g., computing Nash equilibria is PPAD-hard) during learning. For the first time, this paper finds that during the learning process of equilibrium-based MARL, the one-shot games corresponding to each state's successive visits often have the same or similar equilibria (for some states more than 90% of games corresponding to successive visits have similar equilibria). Inspired by this observation, this paper proposes to use equilibrium transfer to accelerate equilibrium-based MARL. The key idea of equilibrium transfer is to reuse previously computed equilibria when each agent has a small incentive to deviate. By introducing transfer loss and transfer condition, a novel framework called equilibrium transfer-based MARL is proposed. We prove that although equilibrium transfer brings transfer loss, equilibrium-based MARL algorithms can still converge to an equilibrium policy under certain assumptions. Experimental results in widely used benchmarks (e.g., grid world game, soccer game, and wall game) show that the proposed framework: 1) not only significantly accelerates equilibrium-based MARL (up to 96.7% reduction in learning time), but also achieves higher average rewards than algorithms without equilibrium transfer and 2) scales significantly better than algorithms without equilibrium transfer when the state/action space grows and the number of agents increases.

The determination of density and molecular weight distributions of lipoproteins by sedimentation equilibrium.

PubMed

Jeffrey, P D; Nichol, L W; Smith, G D

1975-01-25

A method is presented by which an experimental record of total concentration as a function of radial distance, obtained in a sedimentation equilibrium experiment conducted with a noninteracting mixture in the absence of a density gradient, may be analyzed to obtain the unimodal distributions of molecular weight and of partial molar volume when these vary concomitantly and continuously. Particular attention is given to the caracterization of classes of lipoproteins exhibiting Gaussian distributions of these quantities, although the analysis is applicable to other types of unimodal distribution. Equations are also formulated permitting the definition of the corresponding distributions of partial specific volume and of density. The analysis procedure is based on a method (employing Laplace transforms) developed previously, but differs from it in that it avoids the necessity of differentiating experimental results, which introduces error. The method offers certain advantages over other procedures used to characterize and compare lipoprotein samples (exhibiting unimodal distributions) with regard to the duration of the experiment, economy of the sample, and, particularly, the ability to define in principle all of the relevant distributions from one sedimentation equilibrium experiment and an external measurement of the weight average partial specific volume. These points and the steps in the analysis procedure are illustrated with experimental results obtained in the sedimentation equilibrium of a sample of human serum low density lipoprotein. The experimental parameters (such as solution density, column height, and angular velocity) used in the conduction of these experiments were selected on the basis of computer-simulated examples, which are also presented. These provide a guide for other workers interested in characterizing lipoproteins of this class.

Thermal conductance at the interface between crystals using equilibrium and nonequilibrium molecular dynamics

NASA Astrophysics Data System (ADS)

Merabia, Samy; Termentzidis, Konstantinos

2012-09-01

In this article, we compare the results of nonequilibrium (NEMD) and equilibrium (EMD) molecular dynamics methods to compute the thermal conductance at the interface between solids. We propose to probe the thermal conductance using equilibrium simulations measuring the decay of the thermally induced energy fluctuations of each solid. We also show that NEMD and EMD give generally speaking inconsistent results for the thermal conductance: Green-Kubo simulations probe the Landauer conductance between two solids which assumes phonons on both sides of the interface to be at equilibrium. On the other hand, we show that NEMD give access to the out-of-equilibrium interfacial conductance consistent with the interfacial flux describing phonon transport in each solid. The difference may be large and reaches typically a factor 5 for interfaces between usual semiconductors. We analyze finite size effects for the two determinations of the interfacial thermal conductance, and show that the equilibrium simulations suffer from severe size effects as compared to NEMD. We also compare the predictions of the two above-mentioned methods—EMD and NEMD—regarding the interfacial conductance of a series of mass mismatched Lennard-Jones solids. We show that the Kapitza conductance obtained with EMD can be well described using the classical diffuse mismatch model (DMM). On the other hand, NEMD simulation results are consistent with an out-of-equilibrium generalization of the acoustic mismatch model (AMM). These considerations are important in rationalizing previous results obtained using molecular dynamics, and help in pinpointing the physical scattering mechanisms taking place at atomically perfect interfaces between solids, which is a prerequisite to understand interfacial heat transfer across real interfaces.

Trapped nonneutral plasmas, liquids, and crystals (the thermal equilibrium states)

NASA Astrophysics Data System (ADS)

Dubin, Daniel H.; O'neil, T. M.

1999-01-01

Plasmas consisting exclusively of particles with a single sign of charge (e.g., pure electron plasmas and pure ion plasmas) can be confined by static electric and magnetic fields (in a Penning trap) and also be in a state of global thermal equilibrium. This important property distinguishes these totally unneutralized plasmas from neutral and quasineutral plasmas. This paper reviews the conditions for, and the structure of, the thermal equilibrium states. Both theory and experiment are discussed, but the emphasis is decidedly on theory. It is a huge advantage to be able to use thermal equilibrium statistical mechanics to describe the plasma state. Such a description is easily obtained and complete, including for example the details of the plasma shape and microscopic order. Pure electron and pure ion plasmas are routinely confined for hours and even days, and thermal equilibrium states are observed. These plasmas can be cooled to the cryogenic temperature range, where liquid and crystal-like states are realized. The authors discuss the structure of the correlated states separately for three plasma sizes: large plasmas, in which the free energy is dominated by the bulk plasma; mesoscale plasmas, in which the free energy is strongly influenced by the surface; and Coulomb clusters, in which the number of particles is so small that the canonical ensemble is not a good approximation for the microcanonical ensemble. All three cases have been studied through numerical simulations, analytic theory, and experiment. In addition to describing the structure of the thermal equilibrium states, the authors develop a thermodynamic theory of the trapped plasma system. Thermodynamic inequalities and Maxwell relations provide useful bounds on and general relationships between partial derivatives of the various thermodynamic variables.

Using nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) for simultaneous determination of concentration and equilibrium constant.

PubMed

Kanoatov, Mirzo; Galievsky, Victor A; Krylova, Svetlana M; Cherney, Leonid T; Jankowski, Hanna K; Krylov, Sergey N

2015-03-03

Nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) is a versatile tool for studying affinity binding. Here we describe a NECEEM-based approach for simultaneous determination of both the equilibrium constant, K(d), and the unknown concentration of a binder that we call a target, T. In essence, NECEEM is used to measure the unbound equilibrium fraction, R, for the binder with a known concentration that we call a ligand, L. The first set of experiments is performed at varying concentrations of T, prepared by serial dilution of the stock solution, but at a constant concentration of L, which is as low as its reliable quantitation allows. The value of R is plotted as a function of the dilution coefficient, and dilution corresponding to R = 0.5 is determined. This dilution of T is used in the second set of experiments in which the concentration of T is fixed but the concentration of L is varied. The experimental dependence of R on the concentration of L is fitted with a function describing their theoretical dependence. Both K(d) and the concentration of T are used as fitting parameters, and their sought values are determined as the ones that generate the best fit. We have fully validated this approach in silico by using computer-simulated NECEEM electropherograms and then applied it to experimental determination of the unknown concentration of MutS protein and K(d) of its interactions with a DNA aptamer. The general approach described here is applicable not only to NECEEM but also to any other method that can determine a fraction of unbound molecules at equilibrium.

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.

On structural transitions, thermodynamic equilibrium, and the phase diagram of DNA and RNA duplexes under torque and tension.

PubMed

Wereszczynski, Jeff; Andricioaei, Ioan

2006-10-31

A precise understanding of the flexibility of double stranded nucleic acids and the nature of their deformed conformations induced by external forces is important for a wide range of biological processes including transcriptional regulation, supercoil and catenane removal, and site-specific recombination. We present, at atomic resolution, a simulation of the dynamics involved in the transitions from B-DNA and A-RNA to Pauling (P) forms and to denatured states driven by application of external torque and tension. We then calculate the free energy profile along a B- to P-transition coordinate and from it, compute a reversible pathway, i.e., an isotherm of tension and torque pairs required to maintain P-DNA in equilibrium. The reversible isotherm maps correctly onto a phase diagram derived from single molecule experiments, and yields values of elongation, twist, and twist-stretch coupling in agreement with measured values. We also show that configurational entropy compensates significantly for the large electrostatic energy increase due to closer-packed P backbones. A similar set of simulations applied to RNA are used to predict a novel structure, P-RNA, with its associated free energy, equilibrium tension, torque and structural parameters, and to assign the location, on the phase-diagram, of a putative force-torque-dependent RNA "triple point."

Classical evolution of fractal measures on the lattice

NASA Astrophysics Data System (ADS)

Antoniou, N. G.; Diakonos, F. K.; Saridakis, E. N.; Tsolias, G. A.

2007-04-01

We consider the classical evolution of a lattice of nonlinear coupled oscillators for a special case of initial conditions resembling the equilibrium state of a macroscopic thermal system at the critical point. The displacements of the oscillators define initially a fractal measure on the lattice associated with the scaling properties of the order parameter fluctuations in the corresponding critical system. Assuming a sudden symmetry breaking (quench), leading to a change in the equilibrium position of each oscillator, we investigate in some detail the deformation of the initial fractal geometry as time evolves. In particular, we show that traces of the critical fractal measure can be sustained for large times, and we extract the properties of the chain that determine the associated time scales. Our analysis applies generally to critical systems for which, after a slow developing phase where equilibrium conditions are justified, a rapid evolution, induced by a sudden symmetry breaking, emerges on time scales much shorter than the corresponding relaxation or observation time. In particular, it can be used in the fireball evolution in a heavy-ion collision experiment, where the QCD critical point emerges, or in the study of evolving fractals of astrophysical and cosmological scales, and may lead to determination of the initial critical properties of the Universe through observations in the symmetry-broken phase.

Hot super-dense compact object with particular EoS

NASA Astrophysics Data System (ADS)

Tito, E. P.; Pavlov, V. I.

2018-03-01

We show the possibility of existence of a self-gravitating spherically-symmetric equilibrium configuration for a neutral matter with neutron-like density, small mass M ≪ M_{⊙}, and small radius R ≪ R_{⊙}. We incorporate the effects of both the special and general theories of relativity. Such object may be formed in a cosmic cataclysm, perhaps an exotic one. Since the base equations of hydrostatic equilibrium are completed by the equation of state (EoS) for the matter of the object, we offer a novel, interpolating experimental data from high-energy physics, EoS which permits the existence of such compact system of finite radius. This EoS model possesses a critical state characterized by density ρc and temperature Tc. For such an object, we derive a radial distribution for the super-dense matter in "liquid" phase using Tolman-Oppenheimer-Volkoff equations for hydrostatic equilibrium. We demonstrate that a stable configuration is indeed possible (only) for temperatures smaller than the critical one. We derive the mass-radius relation (adjusted for relativistic corrections) for such small (M ≪ M_{⊙}) super-dense compact objects. The results are within the constraints established by both heavy-ion collision experiments and theoretical studies of neutron-rich matter.

Dynamical control of electron-phonon interactions with high-frequency light

NASA Astrophysics Data System (ADS)

Dutreix, C.; Katsnelson, M. I.

2017-01-01

This work addresses the one-dimensional problem of Bloch electrons when they are rapidly driven by a homogeneous time-periodic light and linearly coupled to vibrational modes. Starting from a generic time-periodic electron-phonon Hamiltonian, we derive a time-independent effective Hamiltonian that describes the stroboscopic dynamics up to the third order in the high-frequency limit. This yields nonequilibrium corrections to the electron-phonon coupling that are controllable dynamically via the driving strength. This shows in particular that local Holstein interactions in equilibrium are corrected by antisymmetric Peierls interactions out of equilibrium, as well as by phonon-assisted hopping processes that make the dynamical Wannier-Stark localization of Bloch electrons impossible. Subsequently, we revisit the Holstein polaron problem out of equilibrium in terms of effective Green's functions, and specify explicitly how the binding energy and effective mass of the polaron can be controlled dynamically. These tunable properties are reported within the weak- and strong-coupling regimes since both can be visited within the same material when varying the driving strength. This work provides some insight into controllable microscopic mechanisms that may be involved during the multicycle laser irradiations of organic molecular crystals in ultrafast pump-probe experiments, although it should also be suitable for realizations in shaken optical lattices of ultracold atoms.

Infinite-mode squeezed coherent states and non-equilibrium statistical mechanics (phase-space-picture approach)

NASA Technical Reports Server (NTRS)

Yeh, Leehwa

1993-01-01

The phase-space-picture approach to quantum non-equilibrium statistical mechanics via the characteristic function of infinite-mode squeezed coherent states is introduced. We use quantum Brownian motion as an example to show how this approach provides an interesting geometrical interpretation of quantum non-equilibrium phenomena.

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.

The Nature of the Interplay among Components of Pedagogical Content Knowledge in Reaction Rate and Chemical Equilibrium Topics of Novice and Experienced Chemistry Teachers

ERIC Educational Resources Information Center

Akin, Fatma Nur; Uzuntiryaki-Kondakci, Esen

2018-01-01

We examined the interactions among pedagogical content knowledge (PCK) components of novice and experienced chemistry teachers in teaching reaction rate and chemical equilibrium topics in this qualitative multiple-case design study. For this aim, three chemistry teachers who had different levels of teaching experience in chemistry teaching were…

Studying Equilibrium in the Chemical Reaction between Ferric and Iodide Ions in Solution Using a Simple and Inexpensive Approach

ERIC Educational Resources Information Center

Nikolaychuk, Pavel Anatolyevich; Kuvaeva, Alyona Olegovna

2016-01-01

A laboratory experiment on the study of the chemical equilibrium based on the reaction between ferric and iodide ions in solution with the formation of ferrous ions, free iodine, and triiodide ions is developed. The total concentration of iodide and triiodide ions in the reaction mixture during the reaction is determined by the argentometric…

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.

Remnant Geometric Hall Response in a Quantum Quench.

PubMed

Wilson, Justin H; Song, Justin C W; Refael, Gil

2016-12-02

Out-of-equilibrium systems can host phenomena that transcend the usual restrictions of equilibrium systems. Here, we unveil how out-of-equilibrium states, prepared via a quantum quench in a two-band system, can exhibit a nonzero Hall-type current-a remnant Hall response-even when the instantaneous Hamiltonian is time reversal symmetric (in contrast to equilibrium Hall currents). Interestingly, the remnant Hall response arises from the coherent dynamics of the wave function that retain a remnant of its quantum geometry postquench, and can be traced to processes beyond linear response. Quenches in two-band Dirac systems are natural venues for realizing remnant Hall currents, which exist when either mirror or time-reversal symmetry are broken (before or after the quench). Its long time persistence, sensitivity to symmetry breaking, and decoherence-type relaxation processes allow it to be used as a sensitive diagnostic of the complex out-of-equilibrium dynamics readily controlled and probed in cold-atomic optical lattice experiments.

Application of acidic treated pumice as an adsorbent for the removal of azo dye from aqueous solutions: kinetic, equilibrium and thermodynamic studies

PubMed Central

2012-01-01

Colored effluents are one of the important environment pollution sources since they contain unused dye compounds which are toxic and less-biodegradable. In this work removal of Acid Red 14 and Acid Red 18 azo dyes was investigated by acidic treated pumice stone as an efficient adsorbent at various experimental conditions. Removal of dye increased with increase in contact time and initial dye concentration, while decreased for increment in solution temperature and pH. Results of the equilibrium study showed that the removal of AR14 and AR18 followed Freundlich (r2>0.99) and Langmuir (r2>0.99) isotherm models. Maximum sorption capacities were 3.1 and 29.7 mg/g for AR 14 and AR18, namely significantly higher than those reported in the literature, even for activated carbon. Fitting of experimental data onto kinetic models showed the relevance of the pseudo-second order (r2>0.99) and intra-particle diffusion (r2>0.98) models for AR14 and AR18, respectively. For both dyes, the values of external mass transfer coefficient decreased for increasing initial dye concentrations, showing increasing external mass transfer resistance at solid/liquid layer. Desorption experiments confirmed the relevance of pumice stone for dye removal, since the pH regeneration method showed 86% and 89% regeneration for AR14 and AR18, respectively. PMID:23369579

Pore Scale Dynamics of Microemulsion Formation.

PubMed

Unsal, Evren; Broens, Marc; Armstrong, Ryan T

2016-07-19

Experiments in various porous media have shown that multiple parameters come into play when an oleic phase is displaced by an aqueous solution of surfactant. In general, the displacement efficiency is improved when the fluids become quasi-miscible. Understanding the phase behavior oil/water/surfactant systems is important because microemulsion has the ability to generate ultralow interfacial tension (<10(-2) mN m(-1)) that is required for miscibility to occur. Many studies focus on microemulsion formation and the resulting properties under equilibrium conditions. However, the majority of applications where microemulsion is present also involve flow, which has received relatively less attention. It is commonly assumed that the characteristics of an oil/water/surfactant system under flowing conditions are identical to the one under equilibrium conditions. Here, we show that this is not necessarily the case. We studied the equilibrium phase behavior of a model system consisting of n-decane and an aqueous solution of olefin sulfonate surfactant, which has practical applications for enhanced oil recovery. The salt content of the aqueous solution was varied to provide a range of different microemulsion compositions and oil-water interfacial tensions. We then performed microfluidic flow experiments to study the dynamic in situ formation of microemulsion by coinjecting bulk fluids of n-decane and surfactant solution into a T-junction capillary geometry. A solvatochromatic fluorescent dye was used to obtain spatially resolved compositional information. In this way, we visualized the microemulsion formation and the flow of it along with the excess phases. A complex interaction between the flow patterns and the microemulsion properties was observed. The formation of microemulsion influenced the flow regimes, and the flow regimes affected the characteristics of the microemulsion formation. In particular, at low flow rates, slug flow was observed, which had profound consequences on the pore scale mixing behavior and resulting microemulsion properties.

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.

Absence of jamming in ant trails: feedback control of self-propulsion and noise.

PubMed

Chaudhuri, Debasish; Nagar, Apoorva

2015-01-01

We present a model of ant traffic considering individual ants as self-propelled particles undergoing single-file motion on a one-dimensional trail. Recent experiments on unidirectional ant traffic in well-formed natural trails showed that the collective velocity of ants remains approximately unchanged, leading to the absence of jamming even at very high densities [John et al., Phys. Rev. Lett. 102, 108001 (2009)]. Assuming a feedback control mechanism of self-propulsion force generated by each ant using information about the distance from the ant in front, our model captures all the main features observed in the experiment. The distance headway distribution shows a maximum corresponding to separations within clusters. The position of this maximum remains independent of average number density. We find a non-equilibrium first-order transition, with the formation of an infinite cluster at a threshold density where all the ants in the system suddenly become part of a single cluster.

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).

[Synthesis and Study on Adsorption Property of Congo Red Molecularly Imprinted Polymer Nanospheres].

PubMed

Chang, Zi-qiang; Chen, Fu-bin; Zhang, Yu; Shi, Zuo-long; Yang, Chun-yan; Zhang, Zhu-jun

2015-07-01

Molecularly imprinted polymer nanospheres (MIP) were prepared with Congo red as the template, methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross linker, azodiisobutyronitrile (AIBN) as an initiator, and acetonitrile as the porogen by precipitation polymerization. The morphology of MIP was characterized by SEM and TEM which showed that the diameter of MIP was nanometer grade (90 nm) and the shape was homogeneous. The specific surface area and pore volumes of MIP and NIP were examined through Brunauer-Emett-Teller method of nitrogen adsorption experiments. Then, the adsorption and selective recognition ability of MIPs were evaluated using the equilibrium rebinding experiments. The results indicated that the prepared MIP showed a good selectivity recognition ability to its template. It concluded that MIP could be employed as an effective material for removing Congo red from waste water.

Generation of cavitation luminescence by laser-induced exothermic chemical reaction

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

Jung Park, Han; Diebold, Gerald J.

2013-08-14

Absorption of high power laser radiation by aqueous carbon suspensions is known to result in the formation of highly compressed bubbles of hydrogen and carbon monoxide through the endothermic carbon-steam reaction. The bubbles expand rapidly, overreaching their equilibrium diameter, and then collapse tens to hundreds of microseconds after formation to give a flash of radiation. Here we report on the effects of laser-initiated exothermic chemical reaction on cavitation luminescence. Experiments with hydrogen peroxide added to colloidal carbon suspensions show that both the time of the light flash following the laser pulse and the intensity of luminescence increase with hydrogen peroxidemore » concentration, indicating that large, highly energetic gas bubbles are produced. Additional experiments with colloidal carbon suspensions show the effects of high pressure on the luminescent intensity and its time of appearance following firing of the laser.« less

Experimental and theoretical investigation of the role of clay in subaqueous sediment flows and its effect on run-out distance

NASA Astrophysics Data System (ADS)

Hermidas, Navid; Luthi, Stefan; Eggenhuisen, Joris; Silva Jacinto, Ricardo; Toth, Ferenc; Pohl, Florian; de Leeuw, Jan

2016-04-01

Debris flows are driven by gravity, which in the tail region is overcome by the yield strength of the flow, forcing it to freeze. These flows are capable of achieving staggeringly large run-out distances on low gradients. The case in point, described in previous publications, is the flow which resulted in the deposit of Bed 5 of the Agadir megaslide on the north-west African margin. Debrites of this flow have been recorded several hundred kilometres away from the original landslide. Previous studies have attributed such long run-out distances to hydroplaning, low yield strength, and flow transformation. It is known that the net force acting on a volume of fluid in equilibrium is zero. In this work we show that clay-laden flows are capable of approaching equilibrium. The flows which can achieve the maximum run-out distance are cohesive enough to resist some of the surrounding disturbances, that can upset the equilibrium, and reach close to equilibrium conditions, yet are dilute enough to have low viscous stress, and relatively low yield strength and lose little sediment due to deposition. A flow that is not in equilibrium will always seek to approach equilibrium conditions by speeding up or slowing down, depositing sediment, eroding the substrate, contracting in the form of the tail approaching the head, stretching, entraining water and growing in height, or dewatering and collapsing. Here we present a theory that shows that two dimensional (2D) flows in equilibrium do not grow in height. 2D flume experiments were conducted on different mixtures of kaolinite, sand, silt, and water, on varying slopes and a transitionally rough bed (sand glued), and using various discharge rates, in order to map out different stages in the evolution of a density flow from a cohesive plug flow into a turbidity current. The following flow types were observed: high density turbidity currents, plug flows, and no flow. From the velocity profiles, certain runs demonstrated close to equilibrium behaviour. For these flows, very little flow height growth and velocity variation was observed over the length of the flume. In all cases the flow appeared to be laminar within the boundary layer with Kelvin-Helmholtz instabilities at the top which were suppressed to a large extent for higher sediment concentrations. A deposit consisting of thick muddy sand, with approximately uniform thickness, was observed for higher sediment concentrations, indicating relatively higher yield strength values, while a thinner more sandy deposit was observed for more dilute flows. It was concluded that high sediment concentrations on more moderate slopes result in slower moving plug flows which are capable of suppressing turbulence at the top, while lower sediment concentrations on steeper slopes result in faster moving, more turbulent currents. The flows which can achieve the largest run-out distance are located between these two extremes.

Extracting physics of life at the molecular level: A review of single-molecule data analyses.

PubMed

Colomb, Warren; Sarkar, Susanta K

2015-06-01

Studying individual biomolecules at the single-molecule level has proved very insightful recently. Single-molecule experiments allow us to probe both the equilibrium and nonequilibrium properties as well as make quantitative connections with ensemble experiments and equilibrium thermodynamics. However, it is important to be careful about the analysis of single-molecule data because of the noise present and the lack of theoretical framework for processes far away from equilibrium. Biomolecular motion, whether it is free in solution, on a substrate, or under force, involves thermal fluctuations in varying degrees, which makes the motion noisy. In addition, the noise from the experimental setup makes it even more complex. The details of biologically relevant interactions, conformational dynamics, and activities are hidden in the noisy single-molecule data. As such, extracting biological insights from noisy data is still an active area of research. In this review, we will focus on analyzing both fluorescence-based and force-based single-molecule experiments and gaining biological insights at the single-molecule level. Inherently nonequilibrium nature of biological processes will be highlighted. Simulated trajectories of biomolecular diffusion will be used to compare and validate various analysis techniques. Copyright © 2015 Elsevier B.V. All rights reserved.

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

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

Aggregation of 2-aminobenzimidazole--a combined experimental and theoretical investigation.

PubMed

Angelova, Silvia E; Spassova, Milena I; Deneva, Vera V; Rogojerov, Marin I; Antonov, Liudmil M

2011-06-20

An investigation of 2-aminobenzimidazole was carried out by calculations at HF, MP2, and DFT levels of theory and also by UV and IR spectroscopy. The quantum chemical calculations predict a full shift of the equilibrium towards the amino form, but the absorption spectra in different solvents distinctly show a two-component equilibrium system. Examination of possible equilibria in solution shows that an equilibrium between two dimeric forms of the amino tautomer of 2-aminobenzimidazole explains the spectral observations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

MHD Equilibrium with Reversed Current Density and Magnetic Islands Revisited: the Vacuum Vector Potential Calculus

NASA Astrophysics Data System (ADS)

L. Braga, F.

2013-10-01

The solution of Grad-Shafranov equation determines the stationary behavior of fusion plasma inside a tokamak. To solve the equation it is necessary to know the toroidal current density profile. Recent works show that it is possible to determine a magnetohydrodynamic (MHD) equilibrium with reversed current density (RCD) profiles that presents magnetic islands. In this work we show analytical MHD equilibrium with a RCD profile and analyze the structure of the vacuum vector potential associated with these equilibria using the virtual casing principle.

Silicon isotope fractionations in pure Si and Fe-Si systems and their geological implications

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Beard, B. L.; Reddy, T. R.; Roden, E. E.; Johnson, C.

2016-12-01

Amorphous Si or Si-bearing materials are ubiquitous in nature, and are likely precursors to various rock types, such as cherts and banded iron formations (BIFs). Si isotope exchange kinetics and fractionation factors between these materials and aqueous Si, however, are poorly constrained, preventing a mechanistic or quantitative understanding of geological δ30Si records. A series of laboratory experiments were conducted to provide better estimates on Si isotope exchange kinetics and fractionation factors. Equilibrium Si isotope fractionation factors between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aq) in artificial Archean seawater (AAS), determined by a three-isotope method with a 29Si tracer, are -2.3‰ where Fe2+ is absent from the solution, and -3.2‰ where Fe2+ is present in the solution[1]. Aqueous Fe2+ catalyzes Si isotope exchange, and causes larger Si isotope fractionation due to incorporation into the solid that may have changed Si bonding. In contrast, our preliminary results show that Δ30Sigel-aq between pure Si gel and aqueous Si at equilibrium is -0.13‰. Ongoing experiments are intended to approach the isotope equilibrium from multiple directions to resolve potential kinetic effects, and to explore temperature dependence. Nonetheless, the contrast in Δ30Sigel-aq between Fe-Si and pure Si systems highlights a significant impact of Fe on Si isotope fractionations. These results have important implications for Si isotopes in Precambrian cherts and BIFs, as well as in weathering systems in general. Silicon isotope fractionation was also studied in experiments that involved dissimilatory iron reduction of Fe(III)-Si gel by Desulfuromonas acetoxidans in AAS[2], and was found to become larger with progression of Fe reduction. A Δ30Sigel-aq of -3.5‰ was observed at 32% reduction of Fe3+. This result explains lower δ30Si values in magnetite-associated quartz that those in hematite-associated quartz in some BIFs. The large Si isotope fractionation produced in the microbial experiment, even larger than that seen in our Fe(II)-bearing abiologic experiments, suggests that δ30Si can be a potential tracer for magnetite of a microbial origin, or, vice versa, for microbial activities in magnetite. [1] Zheng et al., 2016, GCA 187, 102-122. [2] Reddy et al., 2016, GCA 190, 85-99.

EXPERIMENTS WITH A RESIN-IN-PULP PROCESS FOR TREATING LEAD-CONTAMINATED SOIL

EPA Science Inventory

This paper presents the results of experiments to evaluate the potential for using a resin-in-pulp process to remove lead contamination from soil. These experiments examined the kinetics and equilibrium partitioning of lead, lead carbonate, lead oxide, and lead sulfate in resin-s...

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.

A demonstration experiment for studying the properties of saturated vapor

NASA Astrophysics Data System (ADS)

Grebenev, Igor V.; Lebedeva, Olga V.; Polushkina, Svetlana V.

2017-11-01

The paper proposes an important demonstration experiment that can be used at secondary schools in physics. The described experiment helps students learn the main concepts of the topic ‘saturated vapor’, namely, evaporation, condensation, dynamic equilibrium, saturation vapor, partial pressure, and the dependence of saturated vapor pressure on temperature.

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.

Stochastic Evolution Dynamic of the Rock-Scissors-Paper Game Based on a Quasi Birth and Death Process

NASA Astrophysics Data System (ADS)

Yu, Qian; Fang, Debin; Zhang, Xiaoling; Jin, Chen; Ren, Qiyu

2016-06-01

Stochasticity plays an important role in the evolutionary dynamic of cyclic dominance within a finite population. To investigate the stochastic evolution process of the behaviour of bounded rational individuals, we model the Rock-Scissors-Paper (RSP) game as a finite, state dependent Quasi Birth and Death (QBD) process. We assume that bounded rational players can adjust their strategies by imitating the successful strategy according to the payoffs of the last round of the game, and then analyse the limiting distribution of the QBD process for the game stochastic evolutionary dynamic. The numerical experiments results are exhibited as pseudo colour ternary heat maps. Comparisons of these diagrams shows that the convergence property of long run equilibrium of the RSP game in populations depends on population size and the parameter of the payoff matrix and noise factor. The long run equilibrium is asymptotically stable, neutrally stable and unstable respectively according to the normalised parameters in the payoff matrix. Moreover, the results show that the distribution probability becomes more concentrated with a larger population size. This indicates that increasing the population size also increases the convergence speed of the stochastic evolution process while simultaneously reducing the influence of the noise factor.

Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS

NASA Astrophysics Data System (ADS)

Hait, Diptarka; Head-Gordon, Martin

2018-05-01

Double hybrid (DH) density functionals are amongst the most accurate density functional approximations developed so far, largely due to the incorporation of correlation effects from unoccupied orbitals via second order perturbation theory (PT2). The xDH family of DH functionals calculate energy directly from orbitals optimized by a lower level approach like B3LYP, without self-consistent optimization. XYG3 and XYGJ-OS are two widely used xDH functionals that are known to be quite accurate at equilibrium geometries. Here, we show that the XYG3 and XYGJ-OS functionals can be ill behaved for stretched bonds well beyond the Coulson-Fischer point, predicting unphysical dipole moments and humps in potential energy curves for some simple systems like the hydrogen fluoride molecule. Numerical experiments and analysis show that these failures are not due to PT2. Instead, a large mismatch at stretched bond-lengths between the reference B3LYP orbitals and the optimized orbitals associated with the non-PT2 part of XYG3 leads to an unphysically large non-Hellman-Feynman contribution to first order properties like forces and electron densities.

Study on the conformational equilibrium of the alanine dipeptide in water solution by using the averaged solvent electrostatic potential from molecular dynamics methodology.

PubMed

García-Prieto, Francisco F; Fdez Galván, Ignacio; Aguilar, Manuel A; Martín, M Elena

2011-11-21

The ASEP/MD method has been employed for studying the solvent effect on the conformational equilibrium of the alanine dipeptide in water solution. MP2 and density functional theory (DFT) levels of theory were used and results were compared. While in gas phase cyclic structures showing intramolecular hydrogen bonds were found to be the most stable, the stability order is reversed in water solution. Intermolecular interaction with the solvent causes the predominance of extended structures as the stabilizing contacts dipeptide-water are favoured. Free-energy differences in solution were calculated and PPII, α(R), and C5 conformers were identified as the most stable at MP2 level. Experimental data from Raman and IR techniques show discrepancies about the relative abundance of α(R) y C5, our results support the Raman data. The DFT level of theory agrees with MP2 in the location and stability of PPII and α(R) forms but fails in the location of C5. MP2 results suggest the possibility of finding traces of C7eq conformer in water solution, in agreement with recent experiments.

Scalar model for frictional precursors dynamics

PubMed Central

Taloni, Alessandro; Benassi, Andrea; Sandfeld, Stefan; Zapperi, Stefano

2015-01-01

Recent experiments indicate that frictional sliding occurs by nucleation of detachment fronts at the contact interface that may appear well before the onset of global sliding. This intriguing precursory activity is not accounted for by traditional friction theories but is extremely important for friction dominated geophysical phenomena as earthquakes, landslides or avalanches. Here we simulate the onset of slip of a three dimensional elastic body resting on a surface and show that experimentally observed frictional precursors depend in a complex non-universal way on the sample geometry and loading conditions. Our model satisfies Archard's law and Amontons' first and second laws, reproducing with remarkable precision the real contact area dynamics, the precursors' envelope dynamics prior to sliding, and the normal and shear internal stress distributions close to the interfacial surface. Moreover, it allows to assess which features can be attributed to the elastic equilibrium, and which are attributed to the out-of-equilibrium dynamics, suggesting that precursory activity is an intrinsically quasi-static physical process. A direct calculation of the evolution of the Coulomb stress before and during precursors nucleation shows large variations across the sample, explaining why earthquake forecasting methods based only on accumulated slip and Coulomb stress monitoring are often ineffective. PMID:25640079

Scalar model for frictional precursors dynamics.

PubMed

Taloni, Alessandro; Benassi, Andrea; Sandfeld, Stefan; Zapperi, Stefano

2015-02-02

Recent experiments indicate that frictional sliding occurs by nucleation of detachment fronts at the contact interface that may appear well before the onset of global sliding. This intriguing precursory activity is not accounted for by traditional friction theories but is extremely important for friction dominated geophysical phenomena as earthquakes, landslides or avalanches. Here we simulate the onset of slip of a three dimensional elastic body resting on a surface and show that experimentally observed frictional precursors depend in a complex non-universal way on the sample geometry and loading conditions. Our model satisfies Archard's law and Amontons' first and second laws, reproducing with remarkable precision the real contact area dynamics, the precursors' envelope dynamics prior to sliding, and the normal and shear internal stress distributions close to the interfacial surface. Moreover, it allows to assess which features can be attributed to the elastic equilibrium, and which are attributed to the out-of-equilibrium dynamics, suggesting that precursory activity is an intrinsically quasi-static physical process. A direct calculation of the evolution of the Coulomb stress before and during precursors nucleation shows large variations across the sample, explaining why earthquake forecasting methods based only on accumulated slip and Coulomb stress monitoring are often ineffective.

Illuminating the Mechanistic Roles of Enzyme Conformational Dynamics

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

Hanson, Jeffrey A.; Dunderstadt, Karl; Watkins, Lucas P.

2007-11-13

Many enzymes mold their structures to enclose substrates in their active sites such that conformational remodeling may be required during each catalytic cycle. In adenylate kinase (AK), this involves a large-amplitude rearrangement of the enzyme’s lid domain. Using our method of high-resolution single-molecule FRET, we directly followed AK’s domain movements on its catalytic time scale. To quantitatively measure the enzyme’s entire conformational distribution, we have applied maximum entropy-based methods to remove photon-counting noise from single-molecule data. This analysis shows unambiguously that AK is capable of dynamically sampling two distinct states, which correlate well with those observed by x-ray crystallography. Unexpectedly,more » the equilibrium favors the closed, active-site-forming configurations even in the absence of substrates. Our experiments further showed that interaction with substrates, rather than locking the enzyme into a compact state, restricts the spatial extent of conformational fluctuations and shifts the enzyme’s conformational equilibrium toward the closed form by increasing the closing rate of the lid. Integrating these microscopic dynamics into macroscopic kinetics allows us to model lid opening-coupled product release as the enzyme’s rate-limiting step.« less

Stochastic Evolution Dynamic of the Rock-Scissors-Paper Game Based on a Quasi Birth and Death Process.

PubMed

Yu, Qian; Fang, Debin; Zhang, Xiaoling; Jin, Chen; Ren, Qiyu

2016-06-27

Stochasticity plays an important role in the evolutionary dynamic of cyclic dominance within a finite population. To investigate the stochastic evolution process of the behaviour of bounded rational individuals, we model the Rock-Scissors-Paper (RSP) game as a finite, state dependent Quasi Birth and Death (QBD) process. We assume that bounded rational players can adjust their strategies by imitating the successful strategy according to the payoffs of the last round of the game, and then analyse the limiting distribution of the QBD process for the game stochastic evolutionary dynamic. The numerical experiments results are exhibited as pseudo colour ternary heat maps. Comparisons of these diagrams shows that the convergence property of long run equilibrium of the RSP game in populations depends on population size and the parameter of the payoff matrix and noise factor. The long run equilibrium is asymptotically stable, neutrally stable and unstable respectively according to the normalised parameters in the payoff matrix. Moreover, the results show that the distribution probability becomes more concentrated with a larger population size. This indicates that increasing the population size also increases the convergence speed of the stochastic evolution process while simultaneously reducing the influence of the noise factor.

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

Vaezi, P.; Holland, C.; Thakur, S. C.

The Controlled Shear Decorrelation Experiment (CSDX) linear plasma device provides a unique platform for investigating the underlying physics of self-regulating drift-wave turbulence/zonal flow dynamics. A minimal model of 3D drift-reduced nonlocal cold ion fluid equations which evolves density, vorticity, and electron temperature fluctuations, with proper sheath boundary conditions, is used to simulate dynamics of the turbulence in CSDX and its response to changes in parallel boundary conditions. These simulations are then carried out using the BOUndary Turbulence (BOUT++) framework and use equilibrium electron density and temperature profiles taken from experimental measurements. The results show that density gradient-driven drift-waves are themore » dominant instability in CSDX. However, the choice of insulating or conducting endplate boundary conditions affects the linear growth rates and energy balance of the system due to the absence or addition of Kelvin-Helmholtz modes generated by the sheath-driven equilibrium E × B shear and sheath-driven temperature gradient instability. Moreover, nonlinear simulation results show that the boundary conditions impact the turbulence structure and zonal flow formation, resulting in less broadband (more quasi-coherent) turbulence and weaker zonal flow in conducting boundary condition case. These results are qualitatively consistent with earlier experimental observations.« less

Equilibrium and out-of-equilibrium mechanics of living mammalian cytoplasm

NASA Astrophysics Data System (ADS)

Gupta, Satish Kumar; Guo, Ming

2017-10-01

Living cells are intrinsically non-equilibrium systems. They are driven out of equilibrium by the activity of the molecular motors and other enzymatic processes. This activity along with the ever present thermal agitation results in intracellular fluctuations inside the cytoplasm. In analogy to Brownian motion, the material property of the cytoplasm also influences the characteristics of these fluctuations. In this paper, through a combination of experimentation and theoretical analysis, we show that intracellular fluctuations are indeed due to non-thermal forces at relatively long time-scales, however, are dominated solely by thermal forces at relatively short time-scales. Thus, the cytoplasm of living mammalian cells behaves as an equilibrium material at short time-scales. The mean square displacement of these intracellular fluctuations scales inversely with the cytoplasmic shear modulus in this short time-scale equilibrium regime, and is inversely proportional to the square of the cytoplasmic shear modulus in the long time-scale out-of-equilibrium regime. Furthermore, we deploy passive microrheology based on these fluctuations to extract the mechanical property of the cytoplasm at the high-frequency regime. We show that the cytoplasm of living mammalian cells is a weak elastic gel in this regime; this is in an excellent agreement with an independent micromechanical measurement using optical tweezers.

Transitions of tethered chain molecules under tension.

PubMed

Luettmer-Strathmann, Jutta; Binder, Kurt

2014-09-21

An applied tension force changes the equilibrium conformations of a polymer chain tethered to a planar substrate and thus affects the adsorption transition as well as the coil-globule and crystallization transitions. Conversely, solvent quality and surface attraction are reflected in equilibrium force-extension curves that can be measured in experiments. To investigate these effects theoretically, we study tethered chains under tension with Wang-Landau simulations of a bond-fluctuation lattice model. Applying our model to pulling experiments on biological molecules we obtain a good description of experimental data in the intermediate force range, where universal features dominate and finite size effects are small. For tethered chains in poor solvent, we observe the predicted two-phase coexistence at transitions from the globule to stretched conformations and also discover direct transitions from crystalline to stretched conformations. A phase portrait for finite chains constructed by evaluating the density of states for a broad range of solvent conditions and tensions shows how increasing tension leads to a disappearance of the globular phase. For chains in good solvents tethered to hard and attractive surfaces we find the predicted scaling with the chain length in the low-force regime and show that our results are well described by an analytical, independent-bond approximation for the bond-fluctuation model for the highest tensions. Finally, for a hard or slightly attractive surface the stretching of a tethered chain is a conformational change that does not correspond to a phase transition. However, when the surface attraction is sufficient to adsorb a chain it will undergo a desorption transition at a critical value of the applied force. Our results for force-induced desorption show the transition to be discontinuous with partially desorbed conformations in the coexistence region.

Effects of initial saturation on properties modification and displacement of tetrachloroethene with aqueous isobutanol.

PubMed

Boyd, Glen R; Ocampo-Gómez, Ana M; Li, Minghua; Husserl, Johana

2006-11-20

Packed column experiments were conducted to study effects of initial saturation of tetrachloroethene (PCE) in the range of 1.0-14% pore volume (PV) on mobilization and downward migration of the non-aqueous phase liquid (NAPL) product upon contact with aqueous isobutanol ( approximately 10 vol.%). This study focused on the consequences of swelling beyond residual saturation. Columns were packed with mixtures of neat PCE, water and glass beads and waterflooded to establish a desired homogeneous residual saturation, and then flooded with aqueous isobutanol under controlled hydraulic conditions. Results showed a critical saturation of approximately 8% PV for these packed column experimental conditions. At low initial PCE saturations (<8% PV), experimental results showed reduced risk of NAPL-product migration upon contact with aqueous isobutanol. At higher initial PCE saturations (>8% PV), results showed NAPL-product mobilization and downward migration which was attributed to interfacial tension (IFT) reduction, swelling of the NAPL-product, and reduced density modification. Packed column results were compared with good agreement to theoretical predictions of NAPL-product mobilization using the total trapping number, N(T). In addition to the packed column study, preliminary batch experiments were conducted to study the effects of PCE volumetric fraction in the range of 0.5-20% on density, viscosity, and IFT modification as a function of time following contact with aqueous isobutanol ( approximately 10 vol.%). Modified NAPL-product fluid properties approached equilibrium within approximately 2 h of contact for density and viscosity. IFT reduction occurred immediately as expected. Measured fluid properties were compared with good agreement to theoretical equilibrium predictions based on UNIQUAC. Overall, this study demonstrates the importance of initial DNAPL saturation, and the associated risk of downward NAPL-product migration, in applying alcohol flooding for remediation of DNAPL contaminated ground water sites.

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.

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

Nonequilibrium dynamic critical scaling of the quantum Ising chain.

PubMed

Kolodrubetz, Michael; Clark, Bryan K; Huse, David A

2012-07-06

We solve for the time-dependent finite-size scaling functions of the one-dimensional transverse-field Ising chain during a linear-in-time ramp of the field through the quantum critical point. We then simulate Mott-insulating bosons in a tilted potential, an experimentally studied system in the same equilibrium universality class, and demonstrate that universality holds for the dynamics as well. We find qualitatively athermal features of the scaling functions, such as negative spin correlations, and we show that they should be robustly observable within present cold atom experiments.

Equilibrium-point control hypothesis examined by measured arm stiffness during multijoint movement.

PubMed

Gomi, H; Kawato

1996-04-05

For the last 20 years, it has been hypothesized that well-coordinated, multijoint movements are executed without complex computation by the brain, with the use of springlike muscle properties and peripheral neural feedback loops. However, it has been technically and conceptually difficult to examine this "equilibrium-point control" hypothesis directly in physiological or behavioral experiments. A high-performance manipulandum was developed and used here to measure human arm stiffness, the magnitude of which during multijoint movement is important for this hypothesis. Here, the equilibrium-point trajectory was estimated from the measured stiffness, the actual trajectory, and the generated torque. Its velocity profile differed from that of the actual trajectory. These results argue against the hypothesis that the brain sends as a motor command only an equilibrium-point trajectory similar to the actual trajectory.

Critical fluid thermal equilibration experiment (19-IML-1)

NASA Technical Reports Server (NTRS)

Wilkinson, R. Allen

1992-01-01

Gravity sometimes blocks all experimental techniques of making a desired measurement. Any pure fluid possesses a liquid-vapor critical point. It is defined by a temperature, pressure, and density state in thermodynamics. The critical issue that this experiment attempts to understand is the time it takes for a sample to reach temperature and density equilibrium as the critical point is approached; is it infinity due to mass and thermal diffusion, or do pressure waves speed up energy transport while mass is still under diffusion control. The objectives are to observe: (1) large phase domain homogenization without and with stirring; (2) time evolution of heat and mass after temperature step is applied to a one phase equilibrium sample; (3) phase evolution and configuration upon going two phase from a one phase equilibrium state; (4) effects of stirring on a low g two phase configuration; (5) two phase to one phase healing dynamics starting from a two phase low g configuration; and (6) effects of shuttle acceleration events on spatially and temporally varying compressible critical fluid dynamics.

Simulations of plasmas pentrating magnetic barriers

NASA Astrophysics Data System (ADS)

Gunell, Herbert; Hurtig, Tomas; Koepke, Mark; Brenning, Nils; Nilsson, Hans

2007-11-01

Perturbed currents perpendicular to the magnetic are generated by plasma motions in which the equilibrium magnetic field (and the corresponding equilibrium currents) are compressed, stretched, and deformed. One example of this is the Earth's magnetopause with its ever-present equilibrium transverse currents and its strong perturbations. Experiments have recently been performed using a plasma gun to shoot a plasma at a magnetic barrier (Brenning, et al., PoP, 2005). It was found that, at a critical drift that is about 2-3 times the ion thermal speed, non-linear oscillations in the lower hybrid range give rise to a resistivity which is at least 200-300 times the Spitzer resistivity. We present simulations of the above scenario for different values of the plasma kinetic energy density. We find waves with frequencies on the order of the plasma frequency. These waves contribute to the electron heating that has been observed both in the experiments and in previous simulations (Hurtig, et al., PoP, 2003).

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.

Atrazine Adsorption Potential of Leonardite from Mae Moh Power Plant

NASA Astrophysics Data System (ADS)

Rittirat, A.; Chokejaroenrat, C.; Watcharenwong, A.

2018-01-01

Leonardite is an immature coal from the power plant, which we obtained from Lampang province, Thailand. It is known to contain relatively high humic substance making it suitable as the soil conditioner in agricultural aspect and as an adsorbent. Our objectives were: [1] to determine the leonardite physical and chemical properties (e.g., cation exchange capacity, organic matter content, and electron microscope imaging), and (2) to quantify the adsorption efficiency of atrazine from the soil. We used varied amount of leonardite ranging from 0.05 to 1.60 g to adsorb 8 mg L-1 of atrazine from aqueous solution in a batch experiment. This experiment was achieved within 48 hours so that the equilibrium time and isotherm parameters can be determined. The uncarbonized leonardite characteristic revealed that it could adsorb atrazine as its surface possesses mesopore type, relatively high cation exchange capacity (59.89 cmol Kg-1), and high organic matter of 21.62 %. The isotherm study showed the equilibrium time of 24 hours and adsorption isotherm was Langmuir with qmax of 3.9683 mg g-1. This study provides proof that leonardite used in the agricultural field can also be useful to adsorb atrazine and simultaneously slow the percolating process of atrazine before contaminating groundwater.

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.

Adsorption of cadmium and lead onto oxidized nitrogen-doped multiwall carbon nanotubes in aqueous solution: equilibrium and kinetics

NASA Astrophysics Data System (ADS)

Perez-Aguilar, Nancy Veronica; Muñoz-Sandoval, Emilio; Diaz-Flores, Paola Elizabeth; Rangel-Mendez, Jose Rene

2010-02-01

Nitrogen-doped multiwall carbon nanotubes (CNx) were chemically oxidized and tested to adsorb cadmium and lead from aqueous solution. Physicochemical characterization of carbon nanotubes included morphological analysis, textural properties, and chemical composition. In addition, the cadmium adsorption capacity of oxidized-CNx was compared with commercially available activated carbon and single wall carbon nanotubes. Carboxylic and nitro groups on the surface of oxidized CNx shifted the point of zero charge from 6.6 to 3.1, enhancing their adsorption capacity for cadmium and lead to 0.083 and 0.139 mmol/g, respectively, at pH 5 and 25 °C. Moreover, oxidized-CNx had higher selectivity for lead when both metal ions were in solution. Kinetic experiments for adsorption of cadmium showed that the equilibrium was reached at about 4 min. Finally, the small size, geometry, and surface chemical composition of oxidized-CNx are the key factors for their higher adsorption capacity than activated carbon.

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.

Microcalorimetric study of the adsorption of PEGylated lysozyme and PEG on a mildly hydrophobic resin: influence of ammonium sulfate.

PubMed

Werner, Albert; Blaschke, Tim; Hasse, Hans

2012-08-07

Adsorption of native as well as mono-, di-, and tri-PEGylated lysozyme on Toyopearl PPG-600M, a mildly hydrophobic resin is studied by isothermal titration calorimetry and by independent adsorption equilibrium measurements in sodium phosphate buffer at pH 7.0 and 25 °C. For PEGylation two different PEG sizes are used (5 and 10 kDa) which leads to six different forms of PEGylated lysozyme all of which are systematically studied. Additionally, the adsorption of five pure PEGs is explored. The ammonium sulfate concentration is varied from 600 to 1200 mM. The molar enthalpy of adsorption Δh(p)(ads) is determined from the calorimetric and the adsorption equilibrium data. It is found to be endothermic in all experiments. The comparison of the adsorption of different PEGylated forms shows that the adsorption of PEGylated lysozyme is driven by the adsorption of the PEG chain. The results provide insight into the adsorption mechanisms of polymer-modified proteins on hydrophobic chromatographic resins.

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.

Energy landscape-driven non-equilibrium evolution of inherent structure in disordered material

DOE PAGES

Fan, Yue; Iwashita, Takuya; Egami, Takeshi

2017-05-19

Complex states in glasses can be neatly expressed by the potential energy landscape (PEL). But, because PEL is highly multi-dimensional it is difficult to describe how the system moves around in PEL. We demonstrate that it is possible to predict the evolution of macroscopic state in a metallic glass, such as ageing and rejuvenation, through a set of simple equations describing excitations in the PEL. The key to this simplification is the realization that the step of activation from the initial state to the saddle point in PEL and the following step of relaxation to the final state are essentiallymore » decoupled. Furthermore, the model shows that the interplay between activation and relaxation in PEL is the key driving force that simultaneously explains both the equilibrium of supercooled liquid and the thermal hysteresis observed in experiments. It further predicts anomalous peaks in truncated thermal scanning, validated by independent molecular dynamics simulation.« less

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.

Relaxation of nonequilibrium populations after a pump: the breaking of Mathiessen's rule

NASA Astrophysics Data System (ADS)

Freericks, J. K.; Abdurazakov, O.; Kemper, A. F.

2017-05-01

From the early days of many-body physics, it was realized that the self-energy governs the relaxation or lifetime of the retarded Green's function. So it seems reasonable to directly extend those results into the nonequilibrium domain. But experiments and calculations of the response of quantum materials to a pump show that the relationship between the relaxation and the self-energy only holds in special cases. Experimentally, the decay time for a population to relax back to equilibrium and the linewidth measured in a linear-response angle-resolved photoemission spectroscopy differ by large amounts. Theoretically, aside from the weak-coupling regime where the relationship holds, one also finds deviations and additionally one sees violations of Mathiessen's rule. In this work, we examine whether looking at an effective transport relaxation time helps to analyze the decay times of excited populations as they relax back to equilibrium. We conclude that it may do a little better, but it has a fitting parameter for the overall scale which must be determined.

Calculating the mean time to capture for tethered ligands and its effect on the chemical equilibrium of bound ligand pairs

NASA Astrophysics Data System (ADS)

Shen, Lu; Decker, Caitlin; Maynard, Heather; Levine, Alex

Cells interact with a number of extracellular proteins including growth factors, which are essential for e.g., wound healing and development. Some of these growth factors must form dimers on the cell surface to initiate their signaling pathway. This suggests one can more efficiently induce signaling via polymer-linked proteins. Motivated by experiments on a family of fibroblast growth factors linked by polymers of varying molecular weight we investigate theoretically the effect of the length of the linking polymer on the binding kinetics of the dimers to a receptor-covered surface. We show, through a first-passage time calculation, how the number of bound dimers in chemical equilibrium depends on the linker molecular weight. We discuss more broadly the implications for a variety of signaling molecules. This work was supported by the NSF-DMR-1309188. HDM thanks the NIH NIBIB (R01EB013674) for support of the cell assay data.

Application of photon Doppler velocimetry to direct impact Hopkinson pressure bars

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

Lea, Lewis J., E-mail: ll379@cam.ac.uk; Jardine, Andrew P.

2016-02-15

Direct impact Hopkinson pressure bar systems offer many potential advantages over split Hopkinson pressure bars, including access to higher strain rates, higher strains for equivalent striker velocity and system length, lower dispersion, and faster achievement of force equilibrium. Currently, these advantages are gained at the expense of all information about the striker impacted specimen face, preventing the experimental determination of force equilibrium, and requiring approximations to be made on the sample deformation history. In this paper, we discuss an experimental method and complementary data analysis for using photon Doppler velocimetry to measure surface velocities of the striker and output barsmore » in a direct impact bar experiment, allowing similar data to be recorded as in a split bar system. We discuss extracting velocity and force measurements, and the precision of measurements. Results obtained using the technique are compared to equivalent split bar tests, showing improved stress measurements for the lowest and highest strains in fully dense metals, and improvement for all strains in slow and non-equilibrating materials.« less

Reconstruction of Pressure Profile Evolution during Levitated Dipole Experiments

NASA Astrophysics Data System (ADS)

Mauel, M.; Garnier, D.; Boxer, A.; Ellsworth, J.; Kesner, J.

2008-11-01

Magnetic levitation of the LDX superconducting dipole causes significant changes in the measured diamagnetic flux and what appears to be an isotropic plasma pressure profile (p˜p||). This poster describes the reconstruction of plasma current and plasma pressure profiles from external measurements of the equilibrium magnetic field, which vary substantially as a function of time depending upon variations in neutral pressure and multifrequency ECRH power levels. Previous free-boundary reconstructions of plasma equilibrium showed the plasma to be anisotropic and highly peaked at the location of the cyclotron resonance of the microwave heating sources. Reconstructions of the peaked plasma pressures confined by a levitated dipole incorporate the small axial motion of the dipole (±5 mm), time varying levitation coil currents, eddy currents flowing in the vacuum vessel, constant magnetic flux linking the superconductor, and new flux loops located near the hot plasma in order to closely couple to plasma current and dipole current variations. I. Karim, et al., J. Fusion Energy, 26 (2007) 99.

Removal of hexavalent chromium from wastewater using a new composite chitosan biosorbent.

PubMed

Boddu, Veera M; Abburi, Krishnaiah; Talbott, Jonathan L; Smith, Edgar D

2003-10-01

A new composite chitosan biosorbent was prepared by coating chitosan, a glucosamine biopolymer, onto ceramic alumina. The composite bioadsorbent was characterized by high-temperature pyrolysis, porosimetry, scanning electron microscopy, and X-ray photoelectron spectroscopy. Batch isothermal equilibrium and continuous column adsorption experiments were conducted at 25 degrees C to evaluate the biosorbent for the removal of hexavalent chromium from synthetic as well as field samples obtained from chrome plating facilities. The effect of pH, sulfate, and chloride ion on adsorption was also investigated. The biosorbent loaded with Cr(VI) was regenerated using 0.1 M sodium hydroxide solution. A comparison of the results of the present investigation with those reported in the literature showed that chitosan coated on alumina exhibits greater adsorption capacity for chromium(VI). Further, experimental equilibrium data were fitted to Langmuir and Freundlich adsorption isotherms, and values of the parameters of the isotherms are reported. The ultimate capacity obtained from the Langmuir model is 153.85 mg/g chitosan.

Time-resolved absorbance changes induced by fast acidification of bacteriorhodopsin in vesicle systems.

PubMed Central

Druckmann, S; Ottolenghi, M; Korenstein, R

1985-01-01

The direction of the accessibility to protons of the binding site in bacteriorhodopsin is of primary importance in elucidating the proton-pump mechanism. The problem is approached via the pH-dependent equilibrium bR560 in equilibrium bR605 in vesicles with preferentially oriented purple membranes. Fast acidification (stopped-flow) experiments with inside-out, monomeric, bR vesicles were carried out with and without a buffer enclosed in the vesicle interior. The results, showing a buffer-induced delay in the formation of bR605, indicate that the binding site is accessible to protons from the inside of the vesicles. We arrive at this conclusion also by working with inside-out trimeric vesicles in the presence and in the absence of H+ (and K+) ionophores. The results suggest that in Halobacterium halobium, the binding site and thus the retinal Schiff base are exposed to the outside of the cell. This conclusion is consistent with a pumping mechanism based on a light-induced pK change. PMID:3978185

Using NMR to Determine the Boiling Point Diagram for a Non-Ideal Solution

ERIC Educational Resources Information Center

Allen, Fritz S.; And Others

1975-01-01

Describes an experiment that enables the student to concentrate on the fundamentals of the non-ideal liquid-vapor equilibrium. Presents typical student data and suggests features which might be added to the experiment. (GS)

High-pressure phase transitions of α-quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

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

Carl, Eva-Regine; Mansfeld, Ulrich; Liermann, Hanns-Peter

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high-pressure polymorphs in rock-forming minerals are known from meteorites and terrestrial impact craters. In this paper, we investigate the formation of high-pressure polymorphs of α-quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α-quartz in situ by synchrotron powder X-ray diffraction. Phase transitions ofmore » α-quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s -1, experiments reveal that α-quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO 6 octahedra rather than the rearrangement of the SiO 4 tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.« less

High-pressure phase transitions of α-quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

DOE PAGES

Carl, Eva-Regine; Mansfeld, Ulrich; Liermann, Hanns-Peter; ...

2017-03-27

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high-pressure polymorphs in rock-forming minerals are known from meteorites and terrestrial impact craters. In this paper, we investigate the formation of high-pressure polymorphs of α-quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α-quartz in situ by synchrotron powder X-ray diffraction. Phase transitions ofmore » α-quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s -1, experiments reveal that α-quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO 6 octahedra rather than the rearrangement of the SiO 4 tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.« 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).

Implementation and simulation of a cone dielectric elastomer actuator

NASA Astrophysics Data System (ADS)

Wang, Huaming; Zhu, Jianying

2008-11-01

The purpose is to investigate the performance of cone dielectric elastomer actuator (DEA) by experiment and FEM simulation. Two working equilibrium positions of cone DEA, which correspond to its initial displacement and displacement output with voltage off and on respectively, are determined through the analysis on its working principle. Experiments show that analytical results accord with experimental ones, and work output in a workcycle is hereby calculated. Actuator can respond quickly when voltage is applied and can return to its original position rapidly when voltage is released. Also, FEM simulation is used to obtain the movement of cone DEA in advance. Simulation results agree well with experimental ones and prove the feasibility of simulation. Also, causes for small difference between them in displacement output are analyzed.

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.

Invariant structures of magnetic flux tubes

NASA Astrophysics Data System (ADS)

Solovev, A. A.

1982-04-01

The basic properties of a screened magnetic flux tube possessing a finite radius of curvature are discussed in order to complement the findings of Parker (1974, 1976) and improve their accuracy. Conditions of equilibrium, twisting equilibrium, and twisting oscillations are discussed, showing that a twisted magnetic loop or arch is capable of executing elastic oscillations about an equilibrium state. This property can in particular be used in the theory of solar flares. Invariant structures of a force-free magnetic tube are analyzed, showing that invariant structures of the field preserve their form when the geometrical parameters of the flux tube are changed. In a quasi-equilibrium transition of the tube from one state to another the length and pitch of the tube spiral change in proportion to the radius of its cross section.

Temperature effect on behaviour, oxygen consumption, ammonia excretion and tolerance limit of the post larvae of shrimp Penaeus indicus.

PubMed

Krishnamoorthy, R; Mohamed, E H Syed; Rao, T Subba; Venugopalanj, V P; Hameed, P Shahul

2008-01-01

The present study has been carried out to know the effect of temperature on behaviour, equilibrium loss and tolerance limit of the post larvae of shrimp Penaeus indicus. The experimental temperatures were selected based on the thermal tolerance limit. The experiments were conducted at a specific temperature for duration of 48 hr. The thermal tolerance experiments were conducted in two ways: in direct exposure and in gradually increasing temperature. The upper and lower lethal temperatures for the post larvae of shrimp P. indicus were 43.5 degrees C and 8 degrees C respectively. During tolerance experiment, no mortality was observed at 33 degrees C and 35 degrees C. But at 38 degrees C with gradual increase in temperature, 30% loss of equilibrium and mortality were recorded in 24.31 hrs and 25.07 hrs, and the remaining 70% were alive. On the contrary, when the post larvae of shrimps were directly exposed to 38 degrees C, almost 80% loss of equilibrium and mortality were recorded in 30.22 hrs and 30.40 hrs, remaining 20% were alive. At 40 degrees C with gradual increase in temperature, 100% loss of equilibrium and mortality were recorded in 25.32 hrs and 25.56 hrs. On the other hand, when the post larvae of shrimps were directly exposed to 40 degrees C, 100% loss of equilibrium was observed in 0.37 hrs and mortality in 1.40 hrs. These behavioral responses include an elevated temperature of 12 degrees C, surfacing, dashing against glass wall, jumping out of the water, etc. In general, the rate of oxygen consumption and ammonia excretion was found to enhance with increasing temperature. In the present study, it was found that gradual increase in temperature favours the shellfish population to escape from the thermal exposure as compared to direct exposure.

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.

EAST kinetic equilibrium reconstruction combining with Polarimeter-Interferometer internal measurement constraints

NASA Astrophysics Data System (ADS)

Lian, H.; Liu, H. Q.; Li, K.; Zou, Z. Y.; Qian, J. P.; Wu, M. Q.; Li, G. Q.; Zeng, L.; Zang, Q.; Lv, B.; Jie, Y. X.; EAST Team

2017-12-01

Plasma equilibrium reconstruction plays an important role in the tokamak plasma research. With a high temporal and spatial resolution, the POlarimeter-INTerferometer (POINT) system on EAST has provided effective measurements for 102s H-mode operation. Based on internal Faraday rotation measurements provided by the POINT system, the equilibrium reconstruction with a more accurate core current profile constraint has been demonstrated successfully on EAST. Combining other experimental diagnostics and external magnetic fields measurement, the kinetic equilibrium has also been reconstructed on EAST. Take the pressure and edge current information from kinetic EFIT into the equilibrium reconstruction with Faraday rotation constraint, the new equilibrium reconstruction not only provides a more accurate internal current profile but also contains edge current and pressure information. One time slice result using new kinetic equilibrium reconstruction with POINT data constraints is demonstrated in this paper and the result shows there is a reversed shear of q profile and the pressure profile is also contained. The new improved equilibrium reconstruction is greatly helpful to the future theoretical analysis.

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.

New phenomena in non-equilibrium quantum physics

NASA Astrophysics Data System (ADS)

Kitagawa, Takuya

From its beginning in the early 20th century, quantum theory has become progressively more important especially due to its contributions to the development of technologies. Quantum mechanics is crucial for current technology such as semiconductors, and also holds promise for future technologies such as superconductors and quantum computing. Despite of the success of quantum theory, its applications have been mostly limited to equilibrium or static systems due to 1. lack of experimental controllability of non-equilibrium quantum systems 2. lack of theoretical frameworks to understand non-equilibrium dynamics. Consequently, physicists have not yet discovered too many interesting phenomena in non-equilibrium quantum systems from both theoretical and experimental point of view and thus, non-equilibrium quantum physics did not attract too much attentions. The situation has recently changed due to the rapid development of experimental techniques in condensed matter as well as cold atom systems, which now enables a better control of non-equilibrium quantum systems. Motivated by this experimental progress, we constructed theoretical frameworks to study three different non-equilibrium regimes of transient dynamics, steady states and periodically drives. These frameworks provide new perspectives for dynamical quantum process, and help to discover new phenomena in these systems. In this thesis, we describe these frameworks through explicit examples and demonstrate their versatility. Some of these theoretical proposals have been realized in experiments, confirming the applicability of the theories to realistic experimental situations. These studies have led to not only the improved fundamental understanding of non-equilibrium processes in quantum systems, but also suggested entirely different venues for developing quantum technologies.

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

Direct Determination of the Equilibrium Unbinding Potential Profile for a Short DNA Duplex from Force Spectroscopy Data

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

Noy, A

2004-05-04

Modern force microscopy techniques allow researchers to use mechanical forces to probe interactions between biomolecules. However, such measurements often happen in non-equilibrium regime, which precludes straightforward extraction of the equilibrium energy information. Here we use the work averaging method based on Jarzynski equality to reconstruct the equilibrium interaction potential from the unbinding of a complementary 14-mer DNA duplex from the results of non-equilibrium single-molecule measurements. The reconstructed potential reproduces most of the features of the DNA stretching transition, previously observed only in equilibrium stretching of long DNA sequences. We also compare the reconstructed potential with the thermodynamic parameters of DNAmore » duplex unbinding and show that the reconstruction accurately predicts duplex melting enthalpy.« less

Achieving Radiation Tolerance through Non-Equilibrium Grain Boundary Structures.

PubMed

Vetterick, Gregory A; Gruber, Jacob; Suri, Pranav K; Baldwin, Jon K; Kirk, Marquis A; Baldo, Pete; Wang, Yong Q; Misra, Amit; Tucker, Garritt J; Taheri, Mitra L

2017-09-25

Many methods used to produce nanocrystalline (NC) materials leave behind non-equilibrium grain boundaries (GBs) containing excess free volume and higher energy than their equilibrium counterparts with identical 5 degrees of freedom. Since non-equilibrium GBs have increased amounts of both strain and free volume, these boundaries may act as more efficient sinks for the excess interstitials and vacancies produced in a material under irradiation as compared to equilibrium GBs. The relative sink strengths of equilibrium and non-equilibrium GBs were explored by comparing the behavior of annealed (equilibrium) and as-deposited (non-equilibrium) NC iron films on irradiation. These results were coupled with atomistic simulations to better reveal the underlying processes occurring on timescales too short to capture using in situ TEM. After irradiation, NC iron with non-equilibrium GBs contains both a smaller number density of defect clusters and a smaller average defect cluster size. Simulations showed that excess free volume contribute to a decreased survival rate of point defects in cascades occurring adjacent to the GB and that these boundaries undergo less dramatic changes in structure upon irradiation. These results suggest that non-equilibrium GBs act as more efficient sinks for defects and could be utilized to create more radiation tolerant materials in future.

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.

Evolution of recombination rates in a multi-locus, haploid-selection, symmetric-viability model.

PubMed

Chasnov, J R; Ye, Felix Xiaofeng

2013-02-01

A fast algorithm for computing multi-locus recombination is extended to include a recombination-modifier locus. This algorithm and a linear stability analysis is used to investigate the evolution of recombination rates in a multi-locus, haploid-selection, symmetric-viability model for which stable equilibria have recently been determined. When the starting equilibrium is symmetric with two selected loci, we show analytically that modifier alleles that reduce recombination always invade. When the starting equilibrium is monomorphic, and there is a fixed nonzero recombination rate between the modifier locus and the selected loci, we determine analytical conditions for which a modifier allele can invade. In particular, we show that a gap exists between the recombination rates of modifiers that can invade and the recombination rate that specifies the lower stability boundary of the monomorphic equilibrium. A numerical investigation shows that a similar gap exists in a weakened form when the starting equilibrium is fully polymorphic but asymmetric. Copyright © 2012 Elsevier Inc. All rights reserved.

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.

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

NASA Astrophysics Data System (ADS)

Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

2016-08-01

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium Si isotope fractionation for Fe-Si gel systems is significantly larger in magnitude than estimates of a near-zero solid-aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si-O bonds, and hence the isotopic properties, of Fe-Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe-Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe-Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides.

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.

Equilibrium expert: an add-in to Microsoft Excel for multiple binding equilibrium simulations and parameter estimations.

PubMed

Raguin, Olivier; Gruaz-Guyon, Anne; Barbet, Jacques

2002-11-01

An add-in to Microsoft Excel was developed to simulate multiple binding equilibriums. A partition function, readily written even when the equilibrium is complex, describes the experimental system. It involves the concentrations of the different free molecular species and of the different complexes present in the experiment. As a result, the software is not restricted to a series of predefined experimental setups but can handle a large variety of problems involving up to nine independent molecular species. Binding parameters are estimated by nonlinear least-square fitting of experimental measurements as supplied by the user. The fitting process allows user-defined weighting of the experimental data. The flexibility of the software and the way it may be used to describe common experimental situations and to deal with usual problems such as tracer reactivity or nonspecific binding is demonstrated by a few examples. The software is available free of charge upon request.

Adaptive Chemical Networks under Non-Equilibrium Conditions: The Evaporating Droplet.

PubMed

Armao, Joseph J; Lehn, Jean-Marie

2016-10-17

Non-volatile solutes in an evaporating drop experience an out-of-equilibrium state due to non-linear concentration effects and complex flow patterns. Here, we demonstrate a small molecule chemical reaction network that undergoes a rapid adaptation response to the out-of-equilibrium conditions inside the droplet leading to control over the molecular constitution and spatial arrangement of the deposition pattern. Adaptation results in a pronounced coffee stain effect and coupling to chemical concentration gradients within the drop is demonstrated. Amplification and suppression of network species are readily identifiable with confocal fluorescence microscopy. We anticipate that these observations will contribute to the design and exploration of out-of-equilibrium chemical systems, as well as be useful towards the development of point-of-care medical diagnostics and controlled deposition of small molecules through inkjet printing. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chimpanzee choice rates in competitive games match equilibrium game theory predictions.

PubMed

Martin, Christopher Flynn; Bhui, Rahul; Bossaerts, Peter; Matsuzawa, Tetsuro; Camerer, Colin

2014-06-05

The capacity for strategic thinking about the payoff-relevant actions of conspecifics is not well understood across species. We use game theory to make predictions about choices and temporal dynamics in three abstract competitive situations with chimpanzee participants. Frequencies of chimpanzee choices are extremely close to equilibrium (accurate-guessing) predictions, and shift as payoffs change, just as equilibrium theory predicts. The chimpanzee choices are also closer to the equilibrium prediction, and more responsive to past history and payoff changes, than two samples of human choices from experiments in which humans were also initially uninformed about opponent payoffs and could not communicate verbally. The results are consistent with a tentative interpretation of game theory as explaining evolved behavior, with the additional hypothesis that chimpanzees may retain or practice a specialized capacity to adjust strategy choice during competition to perform at least as well as, or better than, humans have.

Twisting Anderson pseudospins with light: Quench dynamics in terahertz-pumped BCS superconductors

NASA Astrophysics Data System (ADS)

Chou, Yang-Zhi; Liao, Yunxiang; Foster, Matthew S.

2017-03-01

We study the preparation (pump) and the detection (probe) of far-from-equilibrium BCS superconductor dynamics in THz pump-probe experiments. In a recent experiment [R. Matsunaga, Y. I. Hamada, K. Makise, Y. Uzawa, H. Terai, Z. Wang, and R. Shimano, Phys. Rev. Lett. 111, 057002 (2013), 10.1103/PhysRevLett.111.057002], an intense monocycle THz pulse with center frequency ω ≃Δ was injected into a superconductor with BCS gap Δ ; the subsequent postpump evolution was detected via the optical conductivity. It was argued that nonlinear coupling of the pump to the Anderson pseudospins of the superconductor induces coherent dynamics of the Higgs (amplitude) mode Δ (t ) . We validate this picture in a two-dimensional BCS model with a combination of exact numerics and the Lax reduction method, and we compute the nonequilibrium phase diagram as a function of the pump intensity. The main effect of the pump is to scramble the orientations of Anderson pseudospins along the Fermi surface by twisting them in the x y plane. We show that more intense pump pulses can induce a far-from-equilibrium phase of gapless superconductivity ("phase I"), originally predicted in the context of interaction quenches in ultracold atoms. We show that the THz pump method can reach phase I at much lower energy densities than an interaction quench, and we demonstrate that Lax reduction (tied to the integrability of the BCS Hamiltonian) provides a general quantitative tool for computing coherent BCS dynamics. We also calculate the Mattis-Bardeen optical conductivity for the nonequilibrium states discussed here.

Energy Flow in Dense Off-Equilibrium Plasma

DTIC Science & Technology

2016-07-15

akT e in our system100 i e T T Teller 1966 Smoking Gun Experiment: Laser Breakdown in COLD gas In going from room to liquid Nitrogen temperature...oflaser breakdown have revealed a new phase of off-equilibrium plasma that has a tensile strength similar to a liquid , and reduced ion-electron...approved for public release. Part 1: Energy Balance in Sonoluminescing Dense Plasma Sonoluminescence occurs from rapid implosion of gas bubbles caused to

Finite-Difference Solution for Laminar or Turbulent Boundary Layer Flow over Axisymmetric Bodies with Ideal Gas, CF4, or Equilibrium Air Chemistry

NASA Technical Reports Server (NTRS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-01-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Finite-difference solution for laminar or turbulent boundary layer flow over axisymmetric bodies with ideal gas, CF4, or equilibrium air chemistry

NASA Astrophysics Data System (ADS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-12-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Phase Equilibrium Investigations of Planetary Materials

NASA Technical Reports Server (NTRS)

Grove, T. L.

2005-01-01

This grant provided funds to carry out phase equilibrium studies on the processes of chemical differentiation of the moon and the meteorite parent bodies, during their early evolutionary history. Several experimental studies examined processes that led to the formation of lunar ultramafic glasses. Phase equilibrium studies were carried out on selected low-Ti and high-Ti lunar ultramafic glass compositions to provide constraints on the depth range, temperature and processes of melt generation and/or assimilation. A second set of experiments examined the role of sulfide melts in core formation processes in the earth and terrestrial planets. The major results of each paper are discussed, and copies of the papers are attached as Appendix I.

A Nonlinear, Multiinput, Multioutput Process Control Laboratory Experiment

ERIC Educational Resources Information Center

Young, Brent R.; van der Lee, James H.; Svrcek, William Y.

2006-01-01

Experience in using a user-friendly software, Mathcad, in the undergraduate chemical reaction engineering course is discussed. Example problems considered for illustration deal with simultaneous solution of linear algebraic equations (kinetic parameter estimation), nonlinear algebraic equations (equilibrium calculations for multiple reactions and…

Theory of the Protein Equilibrium Population Snapshot by H/D Exchange Electrospray Ionization Mass Spectrometry (PEPS-HDX-ESI-MS) Method used to obtain Protein Folding Energies/Rates and Selected Supporting Experimental Evidence.

PubMed

Liyanage, Rohana; Devarapalli, Nagarjuna; Pyland, Derek B; Puckett, Latisha M; Phan, N H; Starch, Joel A; Okimoto, Mark R; Gidden, Jennifer; Stites, Wesley E; Lay, Jackson O

2012-12-15

Protein equilibrium snapshot by hydrogen/deuterium exchange electrospray ionization mass spectrometry (PEPS-HDX-ESI-MS or PEPS) is a method recently introduced for estimating protein folding energies and rates. Herein we describe the basis for this method using both theory and new experiments. Benchmark experiments were conducted using ubiquitin because of the availability of reference data for folding and unfolding rates from NMR studies. A second set of experiments was also conducted to illustrate the surprising resilience of the PEPS to changes in HDX time, using staphylococcal nuclease and time frames ranging from a few seconds to several minutes. Theory suggests that PEPS experiments should be conducted at relatively high denaturant concentrations, where the protein folding/unfolding rates are slow with respect to HDX and the life times of both the closed and open states are long enough to be sampled experimentally. Upon deliberate denaturation, changes in folding/unfolding are correlated with associated changes in the ESI-MS signal upon fast HDX. When experiments are done quickly, typically within a few seconds, ESI-MS signals, corresponding to the equilibrium population of the native (closed) and denatured (open) states can both be detected. The interior of folded proteins remains largely un-exchanged. Amongst MS methods, the simultaneous detection of both states in the spectrum is unique to PEPS and provides a "snapshot" of these populations. The associated ion intensities are used to estimate the protein folding equilibrium constant (or the free energy change, ΔG). Linear extrapolation method (LEM) plots of derived ΔG values for each denaturant concentration can then be used to calculate ΔG in the absence of denaturant, ΔG(H(2)O). In accordance with the requirement for detection of signals for both the folded and unfolded states, this theoretical framework predicts that PEPS experiments work best at the middle of the denaturation curve where natured and denatured protein molecules are equilibrated at easily detectable ratios, namely 1:1. It also requires that closed and open states have lifetimes measurable in the time frame of the HDX experiment. Because both conditions are met by PEPS, these measurements can provide an accurate assessment of closed/open state populations and thus protein folding energies/rates.

Effects of dispersal on total biomass in a patchy, heterogeneous system: Analysis and experiment.

PubMed

Zhang, Bo; Liu, Xin; DeAngelis, D L; Ni, Wei-Ming; Wang, G Geoff

2015-06-01

An intriguing recent result from mathematics is that a population diffusing at an intermediate rate in an environment in which resources vary spatially will reach a higher total equilibrium biomass than the population in an environment in which the same total resources are distributed homogeneously. We extended the current mathematical theory to apply to logistic growth and also showed that the result applies to patchy systems with dispersal among patches, both for continuous and discrete time. This allowed us to make specific predictions, through simulations, concerning the biomass dynamics, which were verified by a laboratory experiment. The experiment was a study of biomass growth of duckweed (Lemna minor Linn.), where the resources (nutrients added to water) were distributed homogeneously among a discrete series of water-filled containers in one treatment, and distributed heterogeneously in another treatment. The experimental results showed that total biomass peaked at an intermediate, relatively low, diffusion rate, higher than the total carrying capacity of the system and agreeing with the simulation model. The implications of the experiment to dynamics of source, sink, and pseudo-sink dynamics are discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

International Space Station Attitude Control and Energy Storage Experiment: Effects of Flywheel Torque

NASA Technical Reports Server (NTRS)

Roithmayr, Carlos M.

1999-01-01

The Attitude Control and Energy Storage Experiment is currently under development for the International Space Station; two counter-rotating flywheels will be levitated with magnetic bearings and placed in vacuum housings. The primary objective of the experiment is to store and discharge energy, in combination with existing batteries, into the electrical power system. The secondary objective is to use the flywheels to exert torque on the Station; a simple torque profile has been designed so that the Station's Control Moment Gyroscopes will be assisted in maintaining torque equilibrium attitude. Two energy storage contingencies could result in the inadvertent application of torque by the flywheels to the Station: an emergency shutdown of one flywheel rotor while the other remains spinning, and energy storage with only one rotor instead of the counterrotating pair. Analysis of these two contingencies shows that attitude control and the microgravity environment will not be adversely affected.

Batch-Versuche zur Bestimmung der Sorption und Reaktionskinetik von fluoreszierenden Tracern

NASA Astrophysics Data System (ADS)

Vaitl, Tobias; Wohnlich, Stefan

2018-06-01

For many tracer experiments, prior determination of interaction between solid medium and used tracers is of major interest in order to achieve efficient, economic and successful field experiments. In the present study, three different types of batch experiments were performed with three fluorescent dyes (Na-Fluorescein, Amidorhodamin G and Tinopal CBS-X) and three different rock types (sandstone, claystone and limestone), to determine distribution coefficients and reaction kinetics. All three rock types were analysed for organic carbon content, specific surface area and mineralogical composition to identify the main sorption mechanisms. For all tracers, different sorption properties were found depending on the type of rock. The strongest sorption was observed for Tinopal CBS-X in contact with claystone. Only Na-Fluorescein showed sorption (albeit limited) in contact with the sandstones. The investigated limestones indicated a high sorption for the tracer Tinopal CBS-X. Regarding reaction kinetics, in most cases, thermodynamic equilibrium conditions were reached after two weeks.

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

Energy Cascade in Quantum Gases

NASA Astrophysics Data System (ADS)

Yin, X. Y.; Ho, Tin-Lun

Energy cascade is ubiquitous in systems far from equilibrium. Facilitated by particle interactions and external forces, it can lead to highly complex phenomena like fully developed turbulence, characterized by power law velocity correlation functions. Yet despite decades of research, how these power laws emerge from first principle remains unclear. Recently, experiments show that when a Bose condensate is subjected to periodic shaking, its momentum distribution exhibits a power law behavior. The flexibility of cold atom experiments has provided new opportunities to explore the emergence of these power laws, and to disentangle different sources of energy cascade. Here, we point out that recent experiments in cold atoms imply that classical turbulence is part of a larger family of scale invariant phenomena that include ideal gases. Moreover, the property of the entire family is contained in the structure of its Floquet states. For ideal gases, we show analytically that its momentum distribution acquires a 1 /q2 tail in each dimension when it is shaken periodically. We acknowledge NSF Grant DMR1309615, MURI Grant FP054294-D, and NASA Fundamental Physics Grant 1518233.

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

Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

NASA Astrophysics Data System (ADS)

Deng, Yuying; Li, Yingzhou; Li, Long

2018-04-01

Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

Budget Allocation in a Competitive Communication Spectrum Economy

NASA Astrophysics Data System (ADS)

Lin, Ming-Hua; Tsai, Jung-Fa; Ye, Yinyu

2009-12-01

This study discusses how to adjust "monetary budget" to meet each user's physical power demand, or balance all individual utilities in a competitive "spectrum market" of a communication system. In the market, multiple users share a common frequency or tone band and each of them uses the budget to purchase its own transmit power spectra (taking others as given) in maximizing its Shannon utility or pay-off function that includes the effect of interferences. A market equilibrium is a budget allocation, price spectrum, and tone power distribution that independently and simultaneously maximizes each user's utility. The equilibrium conditions of the market are formulated and analyzed, and the existence of an equilibrium is proved. Computational results and comparisons between the competitive equilibrium and Nash equilibrium solutions are also presented, which show that the competitive market equilibrium solution often provides more efficient power distribution.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Low Temperature Thermodynamic Equilibrium of CO2 Dimer Anion Species in Cryogenic Argon and Krypton Matrices

NASA Astrophysics Data System (ADS)

Goodrich, Michael E.; Moore, David T.

2016-06-01

The separated CO2 dimer anion, (CO2)(CO2-), is observed by FTIR spectroscopy in matrix isolation experiments at 1652 cm-1 upon deposition of high energy argon ions into an argon matrix doped with 0.5% CO2. It has previously been reported by Andrews that upon annealing the matrix to 25K, the separated species converts to an oxalate-like C2O4- species which appears at 1856 cm-1.a We have observed that subsequently holding the matrix at 10K caused the C2O4- species to fully convert back to (CO2)(CO2-). Upon further investigation, we determined that the two species reversibly interconvert between 19K and 23K, suggesting the species are in thermodynamic equilibrium. The associated van't Hoff plot has a linear trend and indicates an endothermic reaction driven by a large increase in entropy. An analogous experiment in a krypton matrix was performed, and the equilibrium was found to occur between 26K and 31K. Interestingly, analysis revealed the reaction in krypton is more endothermic, but has nearly the same entropy value as was observed in the argon experiment. aZhou, M.; Andrews, L.; J. Chem. Phys. 110, 2414 (1999).

Experimental evidence of new tetragonal polymorphs of silicon formed through ultrafast laser-induced confined microexplosion

DOE PAGES

Rapp, L.; Haberl, B.; Pickard, C. J.; ...

2015-06-29

Ordinary materials can transform into novel phases with new crystal structures at extraordinary high pressure and temperature applied under both equilibrium and non-equilibrium conditions 1-6. The recently developed method of ultra-short laser-induced confined microexplosions 7-9 extends the range of possible new phases by initiating a highly non-equilibrium plasma state deep inside a bulk material 7-12. Ultra-high quenching rates can help to overcome kinetic barriers to the formation of new metastable phases, while the surrounding pristine crystal confines the affected material and preserves it for further study 10-12. Here we demonstrate that ultra-rapid pressure release from a completely disordered plasma statemore » in silicon produces several new metastable end phases quenched to ambient conditions. Their structure is determined from comparison to an ab initio random structure search which revealed six new energetically competitive potential phases, four tetragonal and two monoclinic ones. We show the presence of bt8 and st12, which have been predicted theoretically previously 13-15, but have not been observed in nature or in laboratory experiments. Additionally, the presence of the as yet unidentified silicon phase, Si-VIII and two of our other predicted tetragonal phases are highly likely within laser-affected zones. These findings pave the way for new materials with novel and exotic properties.« less

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.

Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

NASA Astrophysics Data System (ADS)

Park, T.; Kyung, D.; Lee, W.

2013-12-01

Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

Fe3O4@Polypyrrole Microspheres with High Magnetization and Superparamagnetism for Efficient and Fast Removal of Pb(II) Ions

NASA Astrophysics Data System (ADS)

Zhang, Wei; Zhu, Wanyan; Xu, Wutong; Wang, Yan; Li, Ning; Zhang, Tingting; Wang, Hui

2017-12-01

Core-shell structured Fe3O4@PPy microspheres are synthesized successfully through a facile polyol reduction method in combination with a modified Stöber method. We show that the as-prepared Fe3O4@PPy microspheres with high saturation magnetization, superparamagnetism, and good dispersibility have a high efficient adsorption capacity for high efficient removal of Pb(II) ions of up to 391.71 mg g-1 and a fast adsorption equilibrium time of 20 min. Furthermore, the lead-adsorbed Fe3O4@PPy microspheres can be rapidly separated from solution because of the excellent superparamagnetic properties. The composite Fe3O4@PPy microspheres are characterized using X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM). The adsorption data from our experiments show that the adsorption process fits well with the pseudosecond- order kinetic model and the adsorption isotherm follows the Langmuir isotherm model. The thermodynamic studies show that the adsorption of Pb(II) on Fe3O4@PPy microspheres is an endothermic and spontaneous process. Comprehensive comparison among adsorbents for the removal of Pb(II) ions that literature reported, reusability, high adsorption efficiency, fast adsorption equilibrium, and rapid magnetic separation make these Fe3O4@PPy microspheres very promising application for removal of Pb(II) ions from contaminated water.

Statistical investigation of simulated fed intestinal media composition on the equilibrium solubility of oral drugs.

PubMed

Zhou, Zhou; Dunn, Claire; Khadra, Ibrahim; Wilson, Clive G; Halbert, Gavin W

2017-03-01

Gastrointestinal fluid is a complex milieu and it is recognised that gut drug solubility is different to that observed in simple aqueous buffers. Simulated gastrointestinal media have been developed covering fasted and fed states to facilitate in vitro prediction of gut solubility and product dissolution. However, the combination of bile salts, phospholipids, fatty acids and proteins in an aqueous buffered system creates multiple phases and drug solubility is therefore a complex interaction between these components, which may create unique environments for each API. The impact on solubility can be assessed through a statistical design of experiment (DoE) approach, to determine the influence and relationships between factors. In this paper DoE has been applied to fed simulated gastrointestinal media consisting of eight components (pH, bile salt, lecithin, sodium oleate, monoglyceride, buffer, salt and pancreatin) using a two level D-optimal design with forty-four duplicate measurements and four centre points. The equilibrium solubility of a range of poorly soluble acidic (indomethacin, ibuprofen, phenytoin, valsartan, zafirlukast), basic (aprepitant, carvedilol, tadalafil, bromocriptine) and neutral (fenofibrate, felodipine, probucol, itraconazole) drugs was investigated. Results indicate that the DoE provides equilibrium solubility values that are comparable to literature results for other simulated fed gastrointestinal media systems or human intestinal fluid samples. For acidic drugs the influence of pH predominates but other significant factors related to oleate and bile salt or interactions between them are present. For basic drugs pH, oleate and bile salt have equal significance along with interactions between pH and oleate and lecithin and oleate. Neutral drugs show diverse effects of the media components particularly with regard to oleate, bile salt, pH and lecithin but the presence of monoglyceride, pancreatin and buffer have significant but smaller effects on solubility. There are fourteen significant interactions between factors mainly related to the surfactant components and pH, indicating that the solubility of neutral drugs in fed simulated media is complex. The results also indicate that the equilibrium solubility of each drug can exhibit individualistic behaviour associated with the drug's chemical structure, physicochemical properties and interaction with media components. The utility of DoE for fed simulated media has been demonstrated providing equilibrium solubility values comparable with similar in vitro systems whilst also providing greater information on the influence of media factors and their interactions. The determination of a drug's gastrointestinal solubility envelope provides useful limits that can potentially be applied to in silico modelling and in vivo experiments. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

13C 18O clumping in speleothems: Observations from natural caves and precipitation experiments

NASA Astrophysics Data System (ADS)

Daëron, M.; Guo, W.; Eiler, J.; Genty, D.; Blamart, D.; Boch, R.; Drysdale, R.; Maire, R.; Wainer, K.; Zanchetta, G.

2011-06-01

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ 18O. Interpreting speleothem δ 18O records in terms of absolute paleotemperatures and δ 18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C 18O bonds in CO 2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation. Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ 18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ 18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ 18O and Δ47 values, probably inherited from prior degassing within the cave system. In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ47 in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ47 in inorganic carbonates.

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.

A Free Entry and Exit Experiment.

ERIC Educational Resources Information Center

Garratt, Rod

2000-01-01

Describes a two-stage experiment where students play the role of farmers who must select one of four markets (corn, wheat, rice, or soybeans). Demonstrates the process leading to equilibrium in a multimarket setting. Includes an appendix with the farmer profit chart and homework exercises. (CMK)

Comparing nonlinear MHD simulations of low-aspect-ratio RFPs to RELAX experiments

NASA Astrophysics Data System (ADS)

McCollam, K. J.; den Hartog, D. J.; Jacobson, C. M.; Sovinec, C. R.; Masamune, S.; Sanpei, A.

2016-10-01

Standard reversed-field pinch (RFP) plasmas provide a nonlinear dynamical system as a validation domain for numerical MHD simulation codes, with applications in general toroidal confinement scenarios including tokamaks. Using the NIMROD code, we simulate the nonlinear evolution of RFP plasmas similar to those in the RELAX experiment. The experiment's modest Lundquist numbers S (as low as a few times 104) make closely matching MHD simulations tractable given present computing resources. Its low aspect ratio ( 2) motivates a comparison study using cylindrical and toroidal geometries in NIMROD. We present initial results from nonlinear single-fluid runs at S =104 for both geometries and a range of equilibrium parameters, which preliminarily show that the magnetic fluctuations are roughly similar between the two geometries and between simulation and experiment, though there appear to be some qualitative differences in their temporal evolution. Runs at higher S are planned. This work is supported by the U.S. DOE and by the Japan Society for the Promotion of Science.

A Printed Equilibrium Dialysis Device with Integrated Membranes for Improved Binding Affinity Measurements.

PubMed

Pinger, Cody W; Heller, Andrew A; Spence, Dana M

2017-07-18

Equilibrium dialysis is a simple and effective technique used for investigating the binding of small molecules and ions to proteins. A three-dimensional (3D) printer was used to create a device capable of measuring binding constants between a protein and a small ion based on equilibrium dialysis. Specifically, the technology described here enables the user to customize an equilibrium dialysis device to fit their own experiments by choosing membranes of various material and molecular-weight cutoff values. The device has dimensions similar to that of a standard 96-well plate, thus being amenable to automated sample handlers and multichannel pipettes. The device consists of a printed base that hosts multiple windows containing a porous regenerated-cellulose membrane with a molecular-weight cutoff of ∼3500 Da. A key step in the fabrication process is a print-pause-print approach for integrating membranes directly into the windows subsequently inserted into the base. The integrated membranes display no leaking upon placement into the base. After characterizing the system's requirements for reaching equilibrium, the device was used to successfully measure an equilibrium dissociation constant for Zn 2+ and human serum albumin (K d = (5.62 ± 0.93) × 10 -7 M) under physiological conditions that is statistically equal to the constants reported in the literature.

Comparison of linear and non-linear method in estimating the sorption isotherm parameters for safranin onto activated carbon.

PubMed

Kumar, K Vasanth; Sivanesan, S

2005-08-31

Comparison analysis of linear least square method and non-linear method for estimating the isotherm parameters was made using the experimental equilibrium data of safranin onto activated carbon at two different solution temperatures 305 and 313 K. Equilibrium data were fitted to Freundlich, Langmuir and Redlich-Peterson isotherm equations. All the three isotherm equations showed a better fit to the experimental equilibrium data. The results showed that non-linear method could be a better way to obtain the isotherm parameters. Redlich-Peterson isotherm is a special case of Langmuir isotherm when the Redlich-Peterson isotherm constant g was unity.

Anticipatory balance control is affected by loadless training experiences.

PubMed

Robert, G; Gueguen, N; Avogadro, P; Mouchnino, L

2004-09-01

The main purpose of this study was to identify whether a lot of sports training had any effect on the balance control associated with a leg movement. The nature of the training experience was also an important concern and we chose subject who had undergone specific training experience in absence of equilibrium constraints. To this end a comparison between control (untrained) subjects, triathletes and swimmers was designed to establish whether a general training in sports (triathletes) or a specific loadless training (swimmers), leads to differences in the balance control. A leg movement is preceded by a shift of the center of mass (CM) towards the supporting side to maintain equilibrium and forward to create the condition for progression. To provide an acceleration of the CM sideward and forward, an initial displacement of the center of pressure (CP) towards the moving limb and in posterior direction was performed. Interestingly, the lateral pressure onto the ground was greater increased in swimmers in both leg raising and obstacle avoidance tasks compared to the control group and/or triathletes whereas the backward CP shift in all group was the same. The initial control of the CM shift is very different in swimmers compared to triathletes and controls. The increased lateral pressure onto the ground in swimmers may be a result of a prolonged training in water. This suggests that prolonged training in the absence of equilibrium constraints has more of an effect on balance control than a prolonged general training. In addition, the lack of differences in the backward CP shift suggests that M/L and A/P controls support two functional goals: equilibrium maintenance and movement initiation.

Effect of Temperature on Acidity and Hydration Equilibrium Constants of Delphinidin-3-O- and Cyanidin-3-O-sambubioside Calculated from Uni- and Multiwavelength Spectroscopic Data.

PubMed

Vidot, Kévin; Achir, Nawel; Mertz, Christian; Sinela, André; Rawat, Nadirah; Prades, Alexia; Dangles, Olivier; Fulcrand, Hélène; Dornier, Manuel

2016-05-25

Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside are the main anthocyanins of Hibiscus sabdariffa calyces, traditionally used to make a bright red beverage by decoction in water. At natural pH, these anthocyanins are mainly in their flavylium form (red) in equilibrium with the quinonoid base (purple) and the hemiketal (colorless). For the first time, their acidity and hydration equilibrium constants were obtained from a pH-jump method followed by UV-vis spectroscopy as a function of temperature from 4 to 37 °C. Equilibrium constant determination was also performed by multivariate curve resolution (MCR). Acidity and hydration constants of cyanidin-3-O-sambubioside at 25 °C were 4.12 × 10(-5) and 7.74 × 10(-4), respectively, and were significantly higher for delphinidin-3-O-sambubioside (4.95 × 10(-5) and 1.21 × 10(-3), respectively). MCR enabled the obtaining of concentration and spectrum of each form but led to overestimated values for the equilibrium constants. However, both methods showed that formations of the quinonoid base and hemiketal were endothermic reactions. Equilibrium constants of anthocyanins in the hibiscus extract showed comparable values as for the isolated anthocyanins.

The influence of kinetics on the oxygen isotope composition of calcium carbonate

NASA Astrophysics Data System (ADS)

Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

2013-08-01

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

Strongly Interacting Fermi Gases: Non-Equilibrium Dynamics and Dimensional Crossover

NASA Astrophysics Data System (ADS)

Sommer, Ariel

2015-05-01

Strongly interacting atomic Fermi gases near Feshbach resonances give access to a rich variety of phenomena in many-fermion physics and superfluidity. This flexible and microscopically well-characterized system provides a pristine platform in which to benchmark many-body theories. I will describe three experiments on gases of fermionic 6Li atoms. In the first experiment, we study spin transport in the return to equilibrium after a spin excitation. From the dynamics near equilibrium, we obtain spin transport coefficients over a range of temperatures and interaction strengths, and observe quantum-limited spin diffusion at unitarity. In separate experiments, we study the effect of dimensionality on the binding of pairs of fermions. We tune the system from three to two dimensions by adjusting the strength of a one-dimensional optical lattice, and measure the binding energy of fermion pairs using radio-frequency spectroscopy. In a third set of experiments, we study nonlinear excitations of a fermionic superfluid. Imprinting a phase jump on the superfluid order parameter causes a long-lived, localized density depletion that oscillates through the cloud. We measure the oscillation period and find that it corresponds to an emergent particle with an effective mass of up to several hundred times the bare mass. This excitation has been identified as a solitonic vortex that results from the decay of a planar soliton. This work was performed at the Massachusetts Institute of Technology under the supervision of Prof. Martin Zwierlein.

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.

Perceptions of job stress.

PubMed

Dearmun, A K

1998-01-01

The experiences of the first graduate children's nurses to qualify on Part 15 of the UKCC Register were drawn on for this study. The literature shows that stress is more prevalent in newly qualified staff nurses. In order to provide optimum support, awareness of the particular factors that create stress at this time is vital. There was a chronological dimension to the stress experience of the children's nurses', which began with an initial feeling of survival and ended with a sense of equilibrium. Situations which would have initially evoked stress were no longer perceived as stressful as their confidence grew. Towards the end of the year, any specific stressful events were associated with increased managerial responsibilities or beginning a new job. The nurses consistently reported increased stress when dealing with a number of specific situations.

Thermodynamic equilibrium with acceleration and the Unruh effect

NASA Astrophysics Data System (ADS)

Becattini, F.

2018-04-01

We address the problem of thermodynamic equilibrium with constant acceleration along the velocity field lines in a quantum relativistic statistical mechanics framework. We show that for a free scalar quantum field, after vacuum subtraction, all mean values vanish when the local temperature T is as low as the Unruh temperature TU=A /2 π where A is the magnitude of the acceleration four-vector. We argue that the Unruh temperature is an absolute lower bound for the temperature of any accelerated fluid at global thermodynamic equilibrium. We discuss the conditions of this bound to be applicable in a local thermodynamic equilibrium situation.

Computations of ideal and real gas high altitude plume flows

NASA Technical Reports Server (NTRS)

Feiereisen, William J.; Venkatapathy, Ethiraj

1988-01-01

In the present work, complete flow fields around generic space vehicles in supersonic and hypersonic flight regimes are studied numerically. Numerical simulation is performed with a flux-split, time asymptotic viscous flow solver that incorporates a generalized equilibrium chemistry model. Solutions to generic problems at various altitude and flight conditions show the complexity of the flow, the equilibrium chemical dissociation and its effect on the overall flow field. Viscous ideal gas solutions are compared against equilibrium gas solutions to illustrate the effect of equilibrium chemistry. Improved solution accuracy is achieved through adaptive grid refinement.

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

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

High-resolution spectroscopy for Doppler-broadening ion temperature measurements of implosions at the National Ignition Facility.

PubMed

Koch, J A; Stewart, R E; Beiersdorfer, P; Shepherd, R; Schneider, M B; Miles, A R; Scott, H A; Smalyuk, V A; Hsing, W W

2012-10-01

Future implosion experiments at the national ignition facility (NIF) will endeavor to simultaneously measure electron and ion temperatures with temporal and spatial resolution in order to explore non-equilibrium temperature distributions and their relaxation toward equilibrium. In anticipation of these experiments, and with understanding of the constraints of the NIF facility environment, we have explored the use of Doppler broadening of mid-Z dopant emission lines, such as krypton He-α at 13 keV, as a diagnostic of time- and potentially space-resolved ion temperature. We have investigated a number of options analytically and with numerical raytracing, and we have identified several promising candidate spectrometer designs that meet the expected requirements of spectral and temporal resolution and data signal-to-noise ratio for gas-filled exploding pusher implosions, while providing maximum flexibility for use on a variety of experiments that potentially include burning plasma.

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.

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

NASA Astrophysics Data System (ADS)

Morgan, G. B., VI; Chou, I.-Ming; Pasteris, J. D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H 2C 2O 4 · 2H 2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750°C, with bulk fluid densities in the range 0.01-0.53 g/cm 3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350°C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3 H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H 2O-CO 2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of SAXENA and FEI (1988). Such disagreement suggests that the formations of CH 4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650°C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H 2O-CO 2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions.

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

USGS Publications Warehouse

Morgan, G.B.; Chou, I.-Ming; Pasteris, J.D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H2C2O4 ?? 2H2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750??C, with bulk fluid densities in the range 0.01-0.53 g/cm3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350??C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H2O-CO2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of Saxena and Fei (1988). Such disagreement suggests that the formations of CH4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650??C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H2O-CO2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions. ?? 1992.

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.

Multi-modal investigations of compressible Rayleigh-Taylor instability in stratified media Project: w17_multirti

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

Livescu, Daniel; Wieland, Scott A.; Reckinger, Scott

The simulations compare, for the first time, three practically important background stratifications under thermal equilibrium and out of equilibrium (isentropic, isopycnic) and show significant differences on the instability growth

Analysis of a Fishery Model with two competing prey species in the presence of a predator species for Optimal Harvesting

NASA Astrophysics Data System (ADS)

Sutimin; Khabibah, Siti; Munawwaroh, Dita Anis

2018-02-01

A harvesting fishery model is proposed to analyze the effects of the presence of red devil fish population, as a predator in an ecosystem. In this paper, we consider an ecological model of three species by taking into account two competing species and presence of a predator (red devil), the third species, which incorporates the harvesting efforts of each fish species. The stability of the dynamical system is discussed and the existence of biological and bionomic equilibrium is examined. The optimal harvest policy is studied and the solution is derived in the equilibrium case applying Pontryagin's maximal principle. The simulation results is presented to simulate the dynamical behavior of the model and show that the optimal equilibrium solution is globally asymptotically stable. The results show that the optimal harvesting effort is obtained regarding to bionomic and biological equilibrium.

Answer Sets in a Fuzzy Equilibrium Logic

NASA Astrophysics Data System (ADS)

Schockaert, Steven; Janssen, Jeroen; Vermeir, Dirk; de Cock, Martine

Since its introduction, answer set programming has been generalized in many directions, to cater to the needs of real-world applications. As one of the most general “classical” approaches, answer sets of arbitrary propositional theories can be defined as models in the equilibrium logic of Pearce. Fuzzy answer set programming, on the other hand, extends answer set programming with the capability of modeling continuous systems. In this paper, we combine the expressiveness of both approaches, and define answer sets of arbitrary fuzzy propositional theories as models in a fuzzification of equilibrium logic. We show that the resulting notion of answer set is compatible with existing definitions, when the syntactic restrictions of the corresponding approaches are met. We furthermore locate the complexity of the main reasoning tasks at the second level of the polynomial hierarchy. Finally, as an illustration of its modeling power, we show how fuzzy equilibrium logic can be used to find strong Nash equilibria.

Classical molecular dynamics simulations for non-equilibrium correlated plasmas

NASA Astrophysics Data System (ADS)

Ferri, S.; Calisti, A.; Talin, B.

2017-03-01

A classical molecular dynamics model was recently extended to simulate neutral multi-component plasmas where various charge states of the same atom and electrons coexist. It is used to investigate the plasma effects on the ion charge and on the ionization potential in dense plasmas. Different simulated statistical properties will show that the concept of isolated particles is lost in such correlated plasmas. The charge equilibration is discussed for a carbon plasma at solid density and investigation on the charge distribution and on the ionization potential depression (IPD) for aluminum plasmas is discussed with reference to existing experiments.

Isolation and characterization of a new zinc-binding protein from albacore tuna plasma

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

Dyke, B.; Hegenauer, J.; Saltman, P.

1987-06-02

The protein responsible for sequestering high levels of zinc in the plasma of the albacore tuna (Thunnus alalunga) has been isolated by sequential chromatography. The glycoprotein has a molecular weight of 66,000. Approximately 8.2% of its amino acid residues are histidines. Equilibrium dialysis experiments show it to bind 3 mol of zinc/mol of protein. The stoichiometric constant for the association of zinc with a binding site containing three histidines was determined to be 10/sup 9.4/. This protein is different from albumin and represents a previously uncharacterized zinc transport protein.

Memory Effect Manifested by a Boson Peak in Metallic Glass.

PubMed

Luo, P; Li, Y Z; Bai, H Y; Wen, P; Wang, W H

2016-04-29

We explore the correlation between a boson peak and structural relaxation in a typical metallic glass. Consistent with enthalpy recovery, a boson peak shows a memory effect in an aging-and-scan procedure. Single-step isothermal aging produces a monotonic decrease of enthalpy and boson peak intensity; for double-step isothermal aging, both enthalpy and boson peak intensity experience, coincidently, an incipient increase to a maximum and a subsequent decrease toward the equilibrium state. Our results indicate a direct link between slow structural relaxation and fast boson peak dynamics, which presents a profound understanding of the two dynamic behaviors in glass.

Existence of k⁻¹ power-law scaling in the equilibrium regions of wall-bounded turbulence explained by Heisenberg's eddy viscosity.

PubMed

Katul, Gabriel G; Porporato, Amilcare; Nikora, Vladimir

2012-12-01

The existence of a "-1" power-law scaling at low wavenumbers in the longitudinal velocity spectrum of wall-bounded turbulence was explained by multiple mechanisms; however, experimental support has not been uniform across laboratory studies. This letter shows that Heisenberg's eddy viscosity approach can provide a theoretical framework that bridges these multiple mechanisms and explains the elusiveness of the "-1" power law in some experiments. Novel theoretical outcomes are conjectured about the role of intermittency and very-large scale motions in modifying the k⁻¹ scaling.

Dynamics of polymers in elongational flow studied by the neutron spin-echo technique

NASA Astrophysics Data System (ADS)

Rheinstädter, Maikel C.; Sattler, Rainer; Häußler, Wolfgang; Wagner, Christian

2010-09-01

The nanoscale fluctuation dynamics of semidilute high molecular weight polymer solutions of polyethylenoxide (PEO) in D 2O under non-equilibrium flow conditions were studied by the neutron spin-echo technique. The sample cell was in contraction flow geometry and provided a pressure driven flow with a high elongational component that stretched the polymers most efficiently. Neutron scattering experiments in dilute polymer solutions are challenging because of the low polymer concentration and corresponding small quasi-elastic signals. A relaxation process with relaxation times of about 10 ps was observed, which shows anisotropic dynamics with applied flow.

Evaluation of indoor radon equilibrium factor using CFD modeling and resulting annual effective dose

NASA Astrophysics Data System (ADS)

Rabi, R.; Oufni, L.

2018-04-01

The equilibrium factor is an important parameter for reasonably estimating the population dose from radon. However, the equilibrium factor value depended mainly on the ventilation rate and the meteorological factors. Therefore, this study focuses on investigating numerically the influence of the ventilation rate, temperature and humidity on equilibrium factor between radon and its progeny. The numerical results showed that ventilation rate, temperature and humidity have significant impacts on indoor equilibrium factor. The variations of equilibrium factor with the ventilation, temperature and relative humidity are discussed. Moreover, the committed equivalent doses due to 218Po and 214Po radon short-lived progeny were evaluated in different tissues of the respiratory tract of the members of the public from the inhalation of indoor air. The annual effective dose due to radon short lived progeny from the inhalation of indoor air by the members of the public was investigated.

Information-theoretic equilibrium and observable thermalization

NASA Astrophysics Data System (ADS)

Anzà, F.; Vedral, V.

2017-03-01

A crucial point in statistical mechanics is the definition of the notion of thermal equilibrium, which can be given as the state that maximises the von Neumann entropy, under the validity of some constraints. Arguing that such a notion can never be experimentally probed, in this paper we propose a new notion of thermal equilibrium, focused on observables rather than on the full state of the quantum system. We characterise such notion of thermal equilibrium for an arbitrary observable via the maximisation of its Shannon entropy and we bring to light the thermal properties that it heralds. The relation with Gibbs ensembles is studied and understood. We apply such a notion of equilibrium to a closed quantum system and show that there is always a class of observables which exhibits thermal equilibrium properties and we give a recipe to explicitly construct them. Eventually, an intimate connection with the Eigenstate Thermalisation Hypothesis is brought to light.

Information-theoretic equilibrium and observable thermalization

PubMed Central

Anzà, F.; Vedral, V.

2017-01-01

A crucial point in statistical mechanics is the definition of the notion of thermal equilibrium, which can be given as the state that maximises the von Neumann entropy, under the validity of some constraints. Arguing that such a notion can never be experimentally probed, in this paper we propose a new notion of thermal equilibrium, focused on observables rather than on the full state of the quantum system. We characterise such notion of thermal equilibrium for an arbitrary observable via the maximisation of its Shannon entropy and we bring to light the thermal properties that it heralds. The relation with Gibbs ensembles is studied and understood. We apply such a notion of equilibrium to a closed quantum system and show that there is always a class of observables which exhibits thermal equilibrium properties and we give a recipe to explicitly construct them. Eventually, an intimate connection with the Eigenstate Thermalisation Hypothesis is brought to light. PMID:28266646

Information-theoretic equilibrium and observable thermalization.

PubMed

Anzà, F; Vedral, V

2017-03-07

A crucial point in statistical mechanics is the definition of the notion of thermal equilibrium, which can be given as the state that maximises the von Neumann entropy, under the validity of some constraints. Arguing that such a notion can never be experimentally probed, in this paper we propose a new notion of thermal equilibrium, focused on observables rather than on the full state of the quantum system. We characterise such notion of thermal equilibrium for an arbitrary observable via the maximisation of its Shannon entropy and we bring to light the thermal properties that it heralds. The relation with Gibbs ensembles is studied and understood. We apply such a notion of equilibrium to a closed quantum system and show that there is always a class of observables which exhibits thermal equilibrium properties and we give a recipe to explicitly construct them. Eventually, an intimate connection with the Eigenstate Thermalisation Hypothesis is brought to light.

Ozone chemical equilibrium in the extended mesopause under the nighttime conditions

NASA Astrophysics Data System (ADS)

Belikovich, M. V.; Kulikov, M. Yu.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-01-01

For retrieval of atomic oxygen and atomic hydrogen via ozone observations in the extended mesopause region (∼70-100 km) under nighttime conditions, an assumption on photochemical equilibrium of ozone is often used in research. In this work, an assumption on chemical equilibrium of ozone near mesopause region during nighttime is proofed. We examine 3D chemistry-transport model (CTM) annual calculations and determine the ratio between the correct (modeled) distributions of the O3 density and its equilibrium values depending on the altitude, latitude, and season. The results show that the retrieval of atomic oxygen and atomic hydrogen distributions using an assumption on ozone chemical equilibrium may lead to large errors below ∼81-87 km. We give simple and clear semi-empirical criterion for practical utilization of the lower boundary of the area with ozone's chemical equilibrium near mesopause.

The Differential Gibbs Free Energy of Activation and its Implications in the Transition-State of Enzymatic Reactions

NASA Astrophysics Data System (ADS)

Maggi, F.; Riley, W. J.

2016-12-01

We propose a mathematical framework to introduce the concept of differential free energy of activation in enzymatically catalyzed reactions, and apply it to N uptake by microalgae and bacteria. This framework extends the thermodynamic capabilities of the classical transition-state theory in and harmonizes the consolidated definitions of kinetic parameters with their thermodynamic and physical meaning. Here, the activation energy is assumed to be a necessary energetic level for equilibrium complexation between reactants and activated complex; however, an additional energy contribution is required for the equilibrium activated complex to release reaction products. We call this "differential free energy of activation"; it can be described by a Boltzmann distribution, and corresponds to a free energy level different from that of complexation. Whether this level is above or below the free energy of activation depends on the reaction, and defines energy domains that correspond to "superactivated", "activated", and "subactivated" complexes. The activated complex reaching one of those states will eventually release the products from an energy level different than that of activation. The concept of differential free energy of activation was tested on 57 independent experiments of NH­4+ and NO3- uptake by various microalgae and bacteria at temperatures ranging between 1 and 45oC. Results showed that the complexation equilibrium always favored the activated complex, but the differential energy of activation led to an apparent energy barrier consistent with observations. Temperature affected all energy levels within this framework but did not alter substantially these thermodynamic features. Overall the approach: (1) provides a thermodynamic and mathematical link between Michaelis-Menten and rate constants; (2) shows that both kinetic parameters can be described or approximated by Arrhenius' like equations; (3) describes the likelihood of formation of sub-, super-, and activated complexes; and (4) shows direction and thermodynamic likelihood of each reaction branch within the transition state. The approach suites particularly well for calibration of kinetic parameters against experimentally acquired reaction dynamics measurements of nutrient biogeochemical cycles.

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.

Experimental study of Fe-Mg- and Ca-distribution between coexisting ortho- and clinopyroxenes at P=294 MPa, T=750 and 800° C

NASA Astrophysics Data System (ADS)

Fonarev, V. I.; Graphchikov, A. A.

1982-07-01

The Fe-Mg-Ca-distribution was investigated in synthesis experiments and with the mineral assemblage orthopyroxene+clinopyroxene+quartz. The phase compositions were identified by X-ray diffraction and, where possible, by electron microprobe. The attainment of equilibrium in the run products was signalled by the compositions from control runs (different solutions) becoming closely similar, by recycling runs, by the attainment of equilibrium from different directions (depending on the composition of starting phases), and by special kinetic experiments. The study produced the following results: (1) the Ca content of the clinopyroxenes decreases with increasing Fe (mol%) from 48.4 at X {Cpx/Fe}=5 to 39.8 at X {Cpx/Fe}=45 (800° C); from 47.6 at X {Cpx/Fe}= 10 to 41.7 at X {Cpx/Fe}=45 (750° C); increasing temperature expands the stability field of the less calcic clinopyroxenes. (2) The Ca content of orthopyroxenes increases slightly with Fe content from 1.8 at X {Opx/Fe}=20.5 to 3.2 at X {Opx/Fe}=75; the temperature effect on the Ca content under the T, P conditions of the experiment was not large. (3) Fe and Mg distribution between the coexisting ortho-and clinopyroxenes is largely temperature-dependent, particularly in the compositional range X {Opx/Fe}=15 75 mol%; as T increases, Fe redistributes from the rhombic to monoclinic mineral. Preliminary estimates of rock formation temperatures using the obtained data show that most of the known two-pyroxene geothermometers overstate the actual values by 50 150° C.

Understanding the impact of insulating and conducting endplate boundary conditions on turbulence in CSDX through nonlocal simulations

DOE PAGES

Vaezi, P.; Holland, C.; Thakur, S. C.; ...

2017-04-01

The Controlled Shear Decorrelation Experiment (CSDX) linear plasma device provides a unique platform for investigating the underlying physics of self-regulating drift-wave turbulence/zonal flow dynamics. A minimal model of 3D drift-reduced nonlocal cold ion fluid equations which evolves density, vorticity, and electron temperature fluctuations, with proper sheath boundary conditions, is used to simulate dynamics of the turbulence in CSDX and its response to changes in parallel boundary conditions. These simulations are then carried out using the BOUndary Turbulence (BOUT++) framework and use equilibrium electron density and temperature profiles taken from experimental measurements. The results show that density gradient-driven drift-waves are themore » dominant instability in CSDX. However, the choice of insulating or conducting endplate boundary conditions affects the linear growth rates and energy balance of the system due to the absence or addition of Kelvin-Helmholtz modes generated by the sheath-driven equilibrium E × B shear and sheath-driven temperature gradient instability. Moreover, nonlinear simulation results show that the boundary conditions impact the turbulence structure and zonal flow formation, resulting in less broadband (more quasi-coherent) turbulence and weaker zonal flow in conducting boundary condition case. These results are qualitatively consistent with earlier experimental observations.« less

Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil.

PubMed

Jiang, Yu Feng; Sun, Hang; Yves, Uwamungu J; Li, Hong; Hu, Xue Fei

2016-02-01

The primary objective of this study was to investigate the effect of biochar, produced from wheat residue at different temperatures, on the adsorption of diesel oil by loess soil. Kinetic and equilibrium data were processed to understand the adsorption mechanism of diesel by biochar-affected loess soil; dynamic and thermodynamic adsorption experiments were conducted to characterize this adsorption. The surface features and chemical structure of biochar, modified at varying pyrolytic temperatures, were investigated using surface scanning electron microscopy and Fourier transform infrared analysis. The kinetic data showed that the adsorption of diesel oil onto loess soil could be described by a pseudo-second-order kinetic model, with the rate-controlling step being intraparticle diffusion. However, in the presence of biochar, boundary layer control and intraparticle diffusion were both involved in the adsorption. Besides, the adsorption equilibrium data were well described by the Freundlich isothermal model. The saturated adsorption capacity weakened as temperature increased, suggesting a spontaneous exothermic process. Thermodynamic parameter analysis showed that adsorption was mainly a physical process and was enhanced by chemical adsorption. The adsorption capacity of loess soil for diesel oil was weakened with increasing pH. The biochar produced by pyrolytic wheat residue increased the adsorption behavior of petroleum pollutants in loess soil.

Distribution of atrazine and its phytoremediation by submerged macrophytes in lake sediments.

PubMed

Qu, Mengjie; Li, Huidong; Li, Na; Liu, Guanglong; Zhao, Jianwei; Hua, Yumei; Zhu, Duanwei

2017-02-01

We investigated sediments with high atrazine accumulation capability from 6 eutrophic lakes in Hubei Province of central China. Almost all lakes have atrazine in their sediments because of human activities. Honghu Lake and Liangzihu Lake were found to have higher levels of atrazine in sediment: 0.171 and 0.114 mg kg -1 , respectively. The results showed that lake sediments could adsorb atrazine six times faster than soils. The equilibrium partition coefficient of atrazine desorption (K Pd ) is much larger than the adsorption equilibrium partition coefficient (K Pa ) of atrazine, indicating that the residue of atrazine in water is easily immobilized by the sediments. Meanwhile, the incubation experiment showed that the removal rateof atrazine in Potamogeton crispus-planted and Myriophyllum spicatum-planted sediments reached >90%, while the rate in unplanted sediments was 77.2 ± 2.12% over 45 d. In unplanted sediment, the half-life of atrazine dissipation was 14.30 d, which was strongly enhanced by P. crispus and M. spicatum, greatly reducing the half-life to 8.60 and 9.72 d, respectively. These two submerged macrophytes are considered to be potential tools in the remediation of atrazine-contaminated sediments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Equilibrium, kinetic and thermodynamic studies on the removal of U(VI) by low cost agricultural waste.

PubMed

Kausar, Abida; Bhatti, Haq Nawaz; MacKinnon, Gillian

2013-11-01

In this research, biosorption efficiency of different agro-wastes was evaluated with rice husk showing maximum biosorption capacity among the selected biosorbents. Optimization of native, SDS-treated and immobilized rice husk adsorption parameters including pH, biosorbent amount, contact time, initial U(VI) concentration and temperature for maximum U(VI) removal was investigated. Maximum biosorption capacity for native (29.56 mg g(-1)) and immobilized biomass (17.59 mg g(-1)) was observed at pH 4 while SDS-treated biomass showed maximum removal (28.08 mg g(-1)) at pH 5. The Langmuir sorption isotherm model correlated best with the U(IV) biosorption equilibrium data for the 10-100 mg L(-1) concentration range. The kinetics of the reaction followed pseudo-second order kinetic model. Thermodynamic parameters like free energy (ΔG(0)) and enthalpy (ΔH°) confirmed the spontaneous and exothermic nature of the process. Experiments to determine the regeneration capacity of the selected biosorbents and the effect of competing metal ions on biosorption capacity were also conducted. The biomass was characterized using scanning electron microscopy, surface area analysis, Fourier transformed infra-red spectroscopy and thermal gravimetric analysis. The study proved that rice husk has potential to treat uranium in wastewater. Copyright © 2013 Elsevier B.V. All rights reserved.

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

Magnetic diagnostics for equilibrium reconstructions with eddy currents on the lithium tokamak experimenta)

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

Schmitt, J. C.; Bialek, J.; Lazerson, S.

2014-11-01

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 diagnositc 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

Serpentinization as a reactive transport process: The brucite silicification reaction

NASA Astrophysics Data System (ADS)

Tutolo, B. M.; Luhmann, A. J.; Tosca, N. J.; Seyfried, W. E., Jr.

2017-12-01

Serpentinization plays a fundamental role in the biogeochemical and tectonic evolution of the Earth and perhaps many other rocky planetary bodies. Yet, geochemical models still fail to produce accurate predictions of the various modes of serpentinization, which limits our ability to predict a variety of related geological phenomena over many spatial and temporal scales. Here, we utilize kinetic and reactive transport experiments to parameterize the brucite silicification reaction and provide fundamental constraints on SiO2 transport during serpentinization. We show that, at temperatures characteristic of the sub-seafloor at the serpentinite-hosted Lost City Hydrothermal Field, the assembly of Si tetrahedra onto MgOH2 (i.e., brucite) surfaces is a rate-limiting elementary reaction in the production of serpentine and/or talc from olivine. Moreover, a kinetic rate law extracted from our laboratory experiments shows that this reaction is exponentially dependent on the activity of aqueous silica (aSiO2(aq)), such that its rate is orders of magnitude slower near-equilibrium than it is far-from-equilibrium. Calculations performed with this rate law demonstrate that both brucite and Si are surprisingly persistent in serpentinizing environments, leading to elevated Si concentrations in fluids that can be transported over comparatively large distances without equilibrating with brucite. Moreover, applying this rate law to an open-system reactive transport experiment indicates that advection, preferential flow pathways, and reactive surface area armoring can diminish the net rate of Si uptake resulting from this reaction even further. Because brucite silicification is a fundamentally rate-limiting elementary reaction for the production of both serpentine and talc from forsterite, our new constraints are applicable across the many environments where serpentinization occurs. The unexpected but highly consequential behavior of this simple reaction emphasizes the need for considering serpentinization and many other hydrothermal processes in a reactive transport framework whereby fluid, solute, and heat transport are intimately coupled to kinetically-controlled reactions.

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.

Light and phosphate competition between Cylindrospermopsis raciborskii and Microcystis aeruginosa is strain dependent.

PubMed

Marinho, Marcelo Manzi; Souza, Maria Betânia Gonçalves; Lürling, Miquel

2013-10-01

The hypothesis that outcomes of phosphorus and light competition between Cylindrospermopsis raciborskii and Microcystis aeruginosa are strain dependent was tested experimentally. Critical requirements of phosphorus (P*) and of light (I*) of two strains of each species were determined through monoculture experiments, which indicated a trade-off between species and also between Microcystis strains. Competition experiments between species were performed using the weakest predicted competitors (with the highest values of P* and of I*) and with the strongest predicted competitors (with the lowest values of P* and of I*). Under light limitation, competition between the weakest competitors led C. raciborskii to dominate. Between the strongest competitors, the opposite was observed, M. aeruginosa displaced C. raciborskii, but both strains co-existed in equilibrium. Under phosphate limitation, competition between the weakest competitors led C. raciborskii to exclude M. aeruginosa, and between the strongest competitors, the opposite was observed, M. aeruginosa displaced C. raciborskii, but the system did not reach an equilibrium and both strains were washed out. Hence, outcomes of the competition depended on the pair of competing strains and not only on species or on type of limitation. We concluded that existence of different trade-offs among strains and between species underlie our results showing that C. raciborskii can either dominate or be displaced by M. aeruginosa when exposed to different conditions of light or phosphate limitation.

On the non-stationary generalized Langevin equation

NASA Astrophysics Data System (ADS)

Meyer, Hugues; Voigtmann, Thomas; Schilling, Tanja

2017-12-01

In molecular dynamics simulations and single molecule experiments, observables are usually measured along dynamic trajectories and then averaged over an ensemble ("bundle") of trajectories. Under stationary conditions, the time-evolution of such averages is described by the generalized Langevin equation. By contrast, if the dynamics is not stationary, it is not a priori clear which form the equation of motion for an averaged observable has. We employ the formalism of time-dependent projection operator techniques to derive the equation of motion for a non-equilibrium trajectory-averaged observable as well as for its non-stationary auto-correlation function. The equation is similar in structure to the generalized Langevin equation but exhibits a time-dependent memory kernel as well as a fluctuating force that implicitly depends on the initial conditions of the process. We also derive a relation between this memory kernel and the autocorrelation function of the fluctuating force that has a structure similar to a fluctuation-dissipation relation. In addition, we show how the choice of the projection operator allows us to relate the Taylor expansion of the memory kernel to data that are accessible in MD simulations and experiments, thus allowing us to construct the equation of motion. As a numerical example, the procedure is applied to Brownian motion initialized in non-equilibrium conditions and is shown to be consistent with direct measurements from simulations.

Crystallisation regimes and kinetics in experimentally decompressed dacitic magma

NASA Astrophysics Data System (ADS)

Blum-Oeste, N.; Schmidt, B. C.; Webb, S. L.

2011-12-01

Kinetic processes during magma ascent may have a strong influence on the eruption style. In water bearing dacitic magmas decompression induced exsolution of water and accompanying crystallisation of plagioclase are the main processes which drive the system towards a new equilibrium state. We present new data on the evolution of residual glass composition and crystal size distributions of plagioclase from decompression experiments. Experiments have been conducted in cold seal pressure vessels at 850°C on a natural dacite composition from Taapaca volcano (N. Chile). After an initial equilibration at 2kbar decompression rates between 6.3 and 450bar/h were applied to final pressures between 50 and 1550bar where samples were rapidly quenched. Complementary equilibrium experiments were done at corresponding pressures. The glass composition evolves from the initial state towards the equilibrium at the final pressure. The completeness of this re-equilibration depends on run duration and reaction rates. We introduce the "re-equilibration index" (REI), a fraction between 0 (initial state) and 1 (final state) which allows comparison of chemical components in terms of re-equilibration at different decompression rates. REI divided by the decompression duration gives the "re-equilibration rate" (RER). The REI varies among oxides and it decreases with increasing decompression rate. The highest REIs of ~0.9 have been found for MgO, K2O and Al2O3 at 6.3bar/h whereas Na2O shows the lowest number with 0.25 at this decompression rate. Towards faster decompression all REIs tend to decrease which shows a decreasing completeness of re-equilibration. At 450bar/h the highest REIs are ~0.25. RERs increase from below ~0.005/h at 6.3bar/h up to almost 0.08/h for Al2O3 at 450bar/h. The variability of RERs of different oxides also increases with decompression rates. At 450bar/h the RERs reach from <0.005/h up to 0.08/h. Although RERs strongly increase from low to high decompression rates, this does not compensate for the decreasing duration available for re-equilibration as REIs clearly show. The volume fraction of plagioclase decreases from ~21% at 6.3bar/h to ~16% at 450bar/h which fits the decrease in REIs. The population density of small crystals decreases whereas the population density of larger crystals increases from slow to fast decompression. This reflects a transition from nucleation controlled crystallisation at slow decompression to a growth dominated regime at fast decompression. As RERs show re-equilibration is faster in the growth dominated regime. Although this transition in nucleation processes might be counter-intuitive it can be explained by the observation of slightly higher water concentrations at fast decompression rates resulting in higher liquidus temperatures and thus lower undercooling.

Using Simple Quadratic Equations to Estimate Equilibrium Concentrations of an Acid

ERIC Educational Resources Information Center

Brilleslyper, Michael A.

2004-01-01

Application of quadratic equations to standard problem in chemistry like finding equilibrium concentrations of ions in an acid solution is explained. This clearly shows that pure mathematical analysis has meaningful applications in other areas as well.

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.