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Sample records for eranos based equilibrium

  1. YALINA analytical benchmark analyses using the deterministic ERANOS code system.

    SciTech Connect

    Gohar, Y.; Aliberti, G.; Nuclear Engineering Division

    2009-08-31

    The growing stockpile of nuclear waste constitutes a severe challenge for the mankind for more than hundred thousand years. To reduce the radiotoxicity of the nuclear waste, the Accelerator Driven System (ADS) has been proposed. One of the most important issues of ADSs technology is the choice of the appropriate neutron spectrum for the transmutation of Minor Actinides (MA) and Long Lived Fission Products (LLFP). This report presents the analytical analyses obtained with the deterministic ERANOS code system for the YALINA facility within: (a) the collaboration between Argonne National Laboratory (ANL) of USA and the Joint Institute for Power and Nuclear Research (JIPNR) Sosny of Belarus; and (b) the IAEA coordinated research projects for accelerator driven systems (ADS). This activity is conducted as a part of the Russian Research Reactor Fuel Return (RRRFR) Program and the Global Threat Reduction Initiative (GTRI) of DOE/NNSA.

  2. MCNPX, MONK, and ERANOS analyses of the YALINA booster subcritical assembly.

    SciTech Connect

    Talamo, A.; Gohar, Y.; Aliberti, G.; Cao, Y.; Smith, D.; Zhong, Z.; Kiyavitskaya, H.; Bournos, V.; Fokov, Y.; Routkovskaya, C.; Serafimovich, I.

    2011-05-01

    This paper compares the numerical results obtained from various nuclear codes and nuclear data libraries with the YALINA Booster subcritical assembly (Minsk, Belarus) experimental results. This subcritical assembly was constructed to study the physics and the operation of accelerator-driven subcritical systems (ADS) for transmuting the light water reactors (LWR) spent nuclear fuel. The YALINA Booster facility has been accurately modeled, with no material homogenization, by the Monte Carlo codes MCNPX (MCNP/MCB) and MONK. The MONK geometrical model matches that of MCNPX. The assembly has also been analyzed by the deterministic code ERANOS. In addition, the differences between the effective neutron multiplication factor and the source multiplication factors have been examined by alternative calculational methodologies. The analyses include the delayed neutron fraction, prompt neutron lifetime, generation time, neutron flux profiles, and spectra in various experimental channels. The accuracy of the numerical models has been enhanced by accounting for all material impurities and the actual density of the polyethylene material used in the assembly (the latter value was obtained by dividing the total weight of the polyethylene by its volume in the numerical model). There is good agreement between the results from MONK, MCNPX, and ERANOS. The ERANOS results show small differences relative to the other results because of material homogenization and the energy and angle discretizations.The MCNPX results match the experimental measurements of the {sup 3}He(n,p) reaction rates obtained with the californium neutron source.

  3. Trunk biomechanical models based on equilibrium at a single-level violate equilibrium at other levels.

    PubMed

    Arjmand, N; Shirazi-Adl, A; Parnianpour, M

    2007-05-01

    Accurate estimation of muscle forces in various occupational tasks is critical for a reliable evaluation of spinal loads and subsequent assessment of risk of injury and management of back disorders. The majority of biomechanical models of multi-segmental spine estimate muscle forces and spinal loads based on the balance of net moments at a single level with no consideration for the equilibrium at remaining levels. This work aimed to quantify the extent of equilibrium violation and alterations in estimations when such models are performed at different levels. Results are compared with those of kinematics-driven model that satisfies equilibrium at all levels and EMG data. Regardless of the method used (optimization or EMG-assisted), single-level free body diagram models yielded estimations that substantially altered depending on the level considered (i.e., level dependency). Equilibrium of net moment was also grossly violated at remaining levels with the error increasing in more demanding tasks. These models may, however, be used to estimate spinal compression forces. PMID:17136359

  4. Learning of Chemical Equilibrium through Modelling-Based Teaching

    ERIC Educational Resources Information Center

    Maia, Poliana Flavia; Justi, Rosaria

    2009-01-01

    This paper presents and discusses students' learning process of chemical equilibrium from a modelling-based approach developed from the use of the "Model of Modelling" diagram. The investigation was conducted in a regular classroom (students 14-15 years old) and aimed at discussing how modelling-based teaching can contribute to students learning…

  5. Equilibrium reconstruction based on core magnetic measurement and its applications on equilibrium transition in Joint-TEXT tokamak

    SciTech Connect

    Chen, J.; Zhuang, G. Jian, X.; Li, Q.; Liu, Y.; Gao, L.; Wang, Z. J.

    2014-10-15

    Evaluation and reconstruction of plasma equilibrium, especially to resolve the safety factor profile, is imperative for advanced tokamak operation and physics study. Based on core magnetic measurement by the high resolution laser polarimeter-interferometer system (POLARIS), the equilibrium of Joint-TEXT (J-TEXT) plasma is reconstructed and profiles of safety factor, current density, and electron density are, therefore, obtained with high accuracy and temporal resolution. The equilibrium reconstruction procedure determines the equilibrium flux surfaces essentially from the data of POLARIS. Refraction of laser probe beam, a major error source of the reconstruction, has been considered and corrected, which leads to improvement of accuracy more than 10%. The error of reconstruction has been systematically assessed with consideration of realistic diagnostic performance and scrape-off layer region of plasma, and its accuracy has been verified. Fast equilibrium transitions both within a single sawtooth cycle and during the penetration of resonant magnetic perturbation have been investigated.

  6. Equilibrium reconstruction based on core magnetic measurement and its applications on equilibrium transition in Joint-TEXT tokamak.

    PubMed

    Chen, J; Zhuang, G; Jian, X; Li, Q; Liu, Y; Gao, L; Wang, Z J

    2014-10-01

    Evaluation and reconstruction of plasma equilibrium, especially to resolve the safety factor profile, is imperative for advanced tokamak operation and physics study. Based on core magnetic measurement by the high resolution laser polarimeter-interferometer system (POLARIS), the equilibrium of Joint-TEXT (J-TEXT) plasma is reconstructed and profiles of safety factor, current density, and electron density are, therefore, obtained with high accuracy and temporal resolution. The equilibrium reconstruction procedure determines the equilibrium flux surfaces essentially from the data of POLARIS. Refraction of laser probe beam, a major error source of the reconstruction, has been considered and corrected, which leads to improvement of accuracy more than 10%. The error of reconstruction has been systematically assessed with consideration of realistic diagnostic performance and scrape-off layer region of plasma, and its accuracy has been verified. Fast equilibrium transitions both within a single sawtooth cycle and during the penetration of resonant magnetic perturbation have been investigated. PMID:25362387

  7. "Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

    PubMed

    Nagarajan, Ramanathan

    2015-07-01

    Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to

  8. Multi-period equilibrium/near-equilibrium in electricity markets based on locational marginal prices

    NASA Astrophysics Data System (ADS)

    Garcia Bertrand, Raquel

    In this dissertation we propose an equilibrium procedure that coordinates the point of view of every market agent resulting in an equilibrium that simultaneously maximizes the independent objective of every market agent and satisfies network constraints. Therefore, the activities of the generating companies, consumers and an independent system operator are modeled: (1) The generating companies seek to maximize profits by specifying hourly step functions of productions and minimum selling prices, and bounds on productions. (2) The goals of the consumers are to maximize their economic utilities by specifying hourly step functions of demands and maximum buying prices, and bounds on demands. (3) The independent system operator then clears the market taking into account consistency conditions as well as capacity and line losses so as to achieve maximum social welfare. Then, we approach this equilibrium problem using complementarity theory in order to have the capability of imposing constraints on dual variables, i.e., on prices, such as minimum profit conditions for the generating units or maximum cost conditions for the consumers. In this way, given the form of the individual optimization problems, the Karush-Kuhn-Tucker conditions for the generating companies, the consumers and the independent system operator are both necessary and sufficient. The simultaneous solution to all these conditions constitutes a mixed linear complementarity problem. We include minimum profit constraints imposed by the units in the market equilibrium model. These constraints are added as additional constraints to the equivalent quadratic programming problem of the mixed linear complementarity problem previously described. For the sake of clarity, the proposed equilibrium or near-equilibrium is first developed for the particular case considering only one time period. Afterwards, we consider an equilibrium or near-equilibrium applied to a multi-period framework. This model embodies binary

  9. NHPP-Based Software Reliability Models Using Equilibrium Distribution

    NASA Astrophysics Data System (ADS)

    Xiao, Xiao; Okamura, Hiroyuki; Dohi, Tadashi

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

  10. Calculation of the Phenix end-of-life test 'Control Rod Withdrawal' with the ERANOS code

    SciTech Connect

    Tiberi, V.

    2012-07-01

    The Inst. of Radiological Protection and Nuclear Safety (IRSN) acts as technical support to French public authorities. As such, IRSN is in charge of safety assessment of operating and under construction reactors, as well as future projects. In this framework, one current objective of IRSN is to evaluate the ability and accuracy of numerical tools to foresee consequences of accidents. Neutronic studies step in the safety assessment from different points of view among which the core design and its protection system. They are necessary to evaluate the core behavior in case of accident in order to assess the integrity of the first barrier and the absence of a prompt criticality risk. To reach this objective one main physical quantity has to be evaluated accurately: the neutronic power distribution in core during whole reactor lifetime. Phenix end of life tests, carried out in 2009, aim at increasing the experience feedback on sodium cooled fast reactors. These experiments have been done in the framework of the development of the 4. generation of nuclear reactors. Ten tests have been carried out: 6 on neutronic and fuel aspects, 2 on thermal hydraulics and 2 for the emergency shutdown. Two of them have been chosen for an international exercise on thermal hydraulics and neutronics in the frame of an IAEA Coordinated Research Project. Concerning neutronics, the Control Rod Withdrawal test is relevant for safety because it allows evaluating the capability of calculation tools to compute the radial power distribution on fast reactors core configurations in which the flux field is very deformed. IRSN participated to this benchmark with the ERANOS code developed by CEA for fast reactors studies. This paper presents the results obtained in the framework of the benchmark activity. A relatively good agreement was found with available measures considering the approximations done in the modeling. The work underlines the importance of burn-up calculations in order to have a fine

  11. Benchmark of Advanced Burner Test Reactor Model Using MCNPX 2.6.0 and ERANOS 2.1

    SciTech Connect

    Kenneth Allen; Travis Knight; Samuel Bays

    2011-08-01

    Significant research is currently being performed whereby fast reactor cores have been designed to burn transuranic materials reducing the volume and long-term radiotoxicity of spent nuclear fuel. These core and depletion models depend on various computer codes. This research used MCNPX 2.6.0 and ERANOS 2.1 to model a standard 250MWt Advanced Burner Test Reactor (ABTR) core. The intent was to benchmark criticality and burnup results from a stochastic Monte Carlo code and a deterministic depletion code using a standard ABTR model created by Argonne National Laboratory. Because each of these codes solve the transport and burnup problem differently, there is a need to benchmark the core models in order to verify results and identify root causes for significant differences in results between codes. Flux calculations in ERANOS were performed using diffusion theory, Legendre polynomial approximations (using the VARIANT module) and discrete ordinates methods. The k-effective for the higher-order transport models remained within 1000 pcm of the MCNPX model. The difference between the total heavy nuclide mass balance in ERANOS using the various flux calculations and the MCNPX depletion model was less than 0.4% out to a burnup of 1095 days (67.45 GWd/MTHM). For individual heavy nuclides, the depletion models closely matched (< 5.0 % difference) throughout the depletion for isotopes of Uranium, Neptunium and Plutonium and most of the higher transuranics. Notable exceptions were 242Am, 242Cm, 243Cm and 246Cm where differences ranged from 0.1 – 0.2% after 26 days and increased to 11 - 136% at 1095 days.

  12. Linear irreversible heat engines based on local equilibrium assumptions

    NASA Astrophysics Data System (ADS)

    Izumida, Yuki; Okuda, Koji

    2015-08-01

    We formulate an endoreversible finite-time Carnot cycle model based on the assumptions of local equilibrium and constant energy flux, where the efficiency and the power are expressed in terms of the thermodynamic variables of the working substance. By analyzing the entropy production rate caused by the heat transfer in each isothermal process during the cycle, and using the endoreversible condition applied to the linear response regime, we identify the thermodynamic flux and force of the present system and obtain a linear relation that connects them. We calculate the efficiency at maximum power in the linear response regime by using the linear relation, which agrees with the Curzon-Ahlborn (CA) efficiency known as the upper bound in this regime. This reason is also elucidated by rewriting our model into the form of the Onsager relations, where our model turns out to satisfy the tight-coupling condition leading to the CA efficiency.

  13. Calculation of dehydration absorbers based on improved phase equilibrium data

    SciTech Connect

    Oi, L.E.

    1999-07-01

    Dehydration using triethylene glycol (TEG) as an absorbent, is a standard process for natural gas treating. New and more accurate TEG/water equilibrium data have been measured between 1980 and 1990. However, this has not influenced much on the design methods of dehydration absorbers. Inaccurate equilibrium data have been extensively used in design calculations. When using data from a common source like Worley, an overall bubble cap tray efficiency between 25--40% has normally been recommended. This has resulted in a quite satisfactory and consistent design method. It is obvious that newer equilibrium data (Herskowitz, Parrish, Bestani) are more accurate. However, to achieve an improved design method, column efficiencies consistent with the new equilibrium data must be recommended. New equilibrium data have been correlated to an activity coefficient model for the liquid phase and combined with an equation of state for the gas phase. Performance data from the North Sea offshore platform Gullfaks C (drying 4--5 MMscmd) have been measured. The bubble cap column has been simulated, and the tray efficiency has been adjusted to fit the performance data. Tray efficiencies calculated with new equilibrium data are higher than 50%. Calculated tray efficiency values are dependent on the equilibrium data used. There are still uncertainties in equilibrium data for the TEC/water/natural gas system. When using accurate equilibrium data, an overall bubble cap tray efficiency of 40--50% and a Murphree efficiency of 55--70% can be expected at normal absorption conditions.

  14. Quadrature-based moment closures for non-equilibrium flows: Hard-sphere collisions and approach to equilibrium

    NASA Astrophysics Data System (ADS)

    Icardi, M.; Asinari, P.; Marchisio, D. L.; Izquierdo, S.; Fox, R. O.

    2012-08-01

    Recently the Quadrature Method of Moments (QMOM) has been extended to solve several kinetic equations, in particular for gas-particle flows and rarefied gases in which the non-equilibrium effects can be important. In this work QMOM is tested as a closure for the dynamics of the Homogeneous Isotropic Boltzmann Equation (HIBE) with a realistic description for particle collisions, namely the hard-sphere model. The behaviour of QMOM far away and approaching the equilibrium is studied. Results are compared to other techniques such as the Grad's moment method (GM) and the off-Lattice Boltzmann Method (oLBM). Comparison with a more accurate and computationally expensive approach, based on the Discrete Velocity Method (DVM), is also carried out. Our results show that QMOM describes very well the evolution when it is far away from equilibrium, without the drawbacks of the GM and oLBM or the computational costs of DVM, but it is not able to accurately reproduce equilibrium and the dynamics close to it. Static and dynamic corrections to cure this behaviour are here proposed and tested.

  15. An Equilibrium-Based Model of Gas Reaction and Detonation

    SciTech Connect

    Trowbridge, L.D.

    2000-04-01

    During gaseous diffusion plant operations, conditions leading to the formation of flammable gas mixtures may occasionally arise. Currently, these could consist of the evaporative coolant CFC-114 and fluorinating agents such as F2 and ClF3. Replacement of CFC-114 with a non-ozone-depleting substitute is planned. Consequently, in the future, the substitute coolant must also be considered as a potential fuel in flammable gas mixtures. Two questions of practical interest arise: (1) can a particular mixture sustain and propagate a flame if ignited, and (2) what is the maximum pressure that can be generated by the burning (and possibly exploding) gas mixture, should it ignite? Experimental data on these systems, particularly for the newer coolant candidates, are limited. To assist in answering these questions, a mathematical model was developed to serve as a tool for predicting the potential detonation pressures and for estimating the composition limits of flammability for these systems based on empirical correlations between gas mixture thermodynamics and flammability for known systems. The present model uses the thermodynamic equilibrium to determine the reaction endpoint of a reactive gas mixture and uses detonation theory to estimate an upper bound to the pressure that could be generated upon ignition. The model described and documented in this report is an extended version of related models developed in 1992 and 1999.

  16. Non-equilibrium Transport in Carbon based Adsorbate Systems

    NASA Astrophysics Data System (ADS)

    Fürst, Joachim; Brandbyge, Mads; Stokbro, Kurt; Jauho, Antti-Pekka

    2007-03-01

    We have used the Atomistix Tool Kit(ATK) and TranSIESTA[1] packages to investigate adsorption of iron atoms on a graphene sheet. The technique of both codes is based on density functional theory using local basis sets[2], and non-equilibrium Green's functions (NEGF) to calculate the charge distribution under external bias. Spin dependent electronic structure calculations are performed for different iron coverages. These reveal adsorption site dependent charge transfer from iron to graphene leading to screening effects. Transport calculations show spin dependent scattering of the transmission which is analysed obtaining the transmission eigenchannels for each spin type. The phenomena of electromigration of iron in these systems at finite bias will be discussed, estimating the so-called wind force from the reflection[3]. [1] M. Brandbyge, J.-L. Mozos, P. Ordejon, J. Taylor, and K. Stokbro. Physical Review B (Condensed Matter and Materials Physics), 65(16):165401/11-7, 2002. [2] Jose M. Soler, Emilio Artacho, Julian D. Gale, Alberto Garcia, Javier Junquera, Pablo Ordejon, and Daniel Sanchez-Portal. Journal of Physics Condensed Matter, 14(11):2745-2779, 2002. [3] Sorbello. Theory of electromigration. Solid State Physics, 1997.

  17. Acid Base Equilibrium in a Lipid/Water Gel

    NASA Astrophysics Data System (ADS)

    Streb, Kristina K.; Ilich, Predrag-Peter

    2003-12-01

    A new and original experiment in which partition of bromophenol blue dye between water and lipid/water gel causes a shift in the acid base equilibrium of the dye is described. The dye-absorbing material is a monoglyceride food additive of plant origin that mixes freely with water to form a stable cubic phase gel; the nascent gel absorbs the dye from aqueous solution and converts it to the acidic form. There are three concurrent processes taking place in the experiment: (a) formation of the lipid/water gel, (b) absorption of the dye by the gel, and (c) protonation of the dye in the lipid/water gel environment. As the aqueous solution of the dye is a deep purple-blue color at neutral pH and yellow at acidic pH the result of these processes is visually striking: the strongly green-yellow particles of lipid/water gel are suspended in purple-blue aqueous solution. The local acidity of the lipid/water gel is estimated by UV vis spectrophotometry. This experiment is an example of host-guest (lipid/water gel dye) interaction and is suitable for project-type biophysics, physical chemistry, or biochemistry labs. The experiment requires three, 3-hour lab sessions, two of which must not be separated by more than two days.

  18. Quadrature--based moment closures for non--equilibrium flows: hard--spheres collisions and approach to equilibrium

    NASA Astrophysics Data System (ADS)

    Icardi, Matteo; Asinari, Pietro; Marchisio, Daniele; Izquierdo, Salvador; Fox, Rodney

    2011-11-01

    Recently the Quadrature Method of Moments (QMOM) has been extended to solve several kinetic equations, in particular for gas-particle flows and rarefied gases. This method is usually coupled with simplified linear models for particle collisions. In this work QMOM is tested as a closure for the dynamics of high-order moments with a more realistic collision model namely the hard-spheres model in the Homogeneous Isotropic Boltzmann Equation. The behavior of QMOM far away and approaching the equilibrium is studied. Results are compared to other techniques such as the Lattice-Boltzmann (LBM) and the Grad's expansion (GM) methods. Comparison with a more accurate and computationally expensive model, based on the Discrete Velocity Method (DVM), is also carried out. Our results show that QMOM describes very well the evolution when it is far away from equilibrium, without the drawbacks of the GM and LBM or the computational costs of DVM but it is not able to accurately reproduce the equilibrium and the dynamics close to it. Corrections to cure this behavior are proposed and tested.

  19. Evidence-Based Approaches to Improving Chemical Equilibrium Instruction

    ERIC Educational Resources Information Center

    Davenport, Jodi L.; Leinhardt, Gaea; Greeno, James; Koedinger, Kenneth; Klahr, David; Karabinos, Michael; Yaron, David J.

    2014-01-01

    Two suggestions for instruction in chemical equilibrium are presented, along with the evidence that supports these suggestions. The first is to use diagrams to connect chemical reactions to the effects of reactions on concentrations. The second is the use of the majority and minority species (M&M) strategy to analyze chemical equilibrium…

  20. Effectiveness of Instruction Based on the Constructivist Approach on Understanding Chemical Equilibrium Concepts

    ERIC Educational Resources Information Center

    Akkus, Huseyin; Kadayifci, Hakki; Atasoy, Basri; Geban, Omer

    2003-01-01

    The purpose of this study was to identify misconceptions concerning chemical equilibrium concepts and to investigate the effectiveness of instruction based on the constructivist approach over traditional instruction on 10th grade students' understanding of chemical equilibrium concepts. The subjects of this study consisted of 71 10th grade…

  1. Equilibrium II: Acids and Bases. Independent Learning Project for Advanced Chemistry (ILPAC). Unit P3.

    ERIC Educational Resources Information Center

    Inner London Education Authority (England).

    This unit on equilibrium is one of 10 first year units produced by the Independent Learning Project for Advanced Chemistry (ILPAC). The unit, which consists of two levels, focuses on the application of equilibrium principles to equilibria involving weak acids and bases, including buffer solutions and indicators. Level one uses Le Chatelier's…

  2. Quasi-Three-Dimensional Mathematical Modeling of Morphological Processes Based on Equilibrium Sediment Transport

    NASA Astrophysics Data System (ADS)

    Charafi, My. M.; Sadok, A.; Kamal, A.; Menai, A.

    A quasi-three-dimensional mathematical model has been developed to study the morphological processes based on equilibrium sediment transport method. The flow velocities are computed by a two-dimensional horizontal depth-averaged flow model (H2D) in combination with logarithmic velocity profiles. The transport of sediment particles by a flow water has been considered in the form of bed load and suspended load. The bed load transport rate is defined as the transport of particles by rolling and saltating along the bed surface and is given by the Van Rijn relationship (1987). The equilibrium suspended load transport is described in terms of an equilibrium sediment concentration profile (ce) and a logarithmic velocity (u). Based on the equilibrium transport, the bed change rate is given by integration of the sediment mass-balance equation. The model results have been compared with a Van Rijn results (equilibrium approach) and good agreement has been found.

  3. An Intuitive and General Approach to Acid-Base Equilibrium Calculations.

    ERIC Educational Resources Information Center

    Felty, Wayne L.

    1978-01-01

    Describes the intuitive approach used in general chemistry and points out its pedagogical advantages. Explains how to extend it to acid-base equilibrium calculations without the need to introduce additional sophisticated concepts. (GA)

  4. Opicinus de Canistris: some notes from Jung's unpublished Eranos Seminar on the medieval Codex Palatinus Latinus 1993.

    PubMed

    Quaglino, Gian Piero; Romano, Augusto; Bernardini, Riccardo

    2010-06-01

    Jung held an informal seminar for a limited number of students after the end of the Eranos Conference in August, 1943. All traces of this seminar were lost until the notes taken on it by one of the students, Alwine von Keller, were found in 2006. Jung's talk consisted of a psychological commentary on a series of images in the medieval Codex Palatinus Latinus 1993, attributed to Opicinus de Canistris (1296-c.1352), a fourteenth-century Italian clergyman, mystic, miniaturist, and cartographer. Jung interpreted Opicinus' images as a series of mandalas in which the Shadow, the dark principle, does not manage to be integrated into a balanced system. Opicinus tried to settle this division into opposites, which constitutes the main problem in modern times, while remaining inside the system of Christian doctrine. However, he did not succeed in his attempt to integrate the principle of the Shadow on the doctrinal level because he was not aware of the very same division in his own unconscious. Our article points out the features in the seminar where Jung seemed to show much more originality in his interpretation than other psychoanalytic studies on Opicinus or other analytical-psychological readings of medieval Christian art.

  5. Effectiveness of instruction based on the constructivist approach on understanding chemical equilibrium concepts

    NASA Astrophysics Data System (ADS)

    Akkuş Hüseyin; Kadayifçi, Hakki; Atasoy, Basri; Geban, Ömer

    2003-02-01

    The purpose of this study was to identify misconceptions concerning chemical equilibrium concepts and to investigate the effectiveness of instruction based on the constructivist approach over traditional instruction on 10th grade students' understanding of chemical equilibrium concepts. The subjects of this study consisted of 71 10th grade students from two chemistry classes of the same teacher. Each teaching strategy was randomly assigned to one class. The data were obtained from 32 students in the experimental group taught with instruction informed by the constructivist approach and 39 students in the control group taught with traditional instruction. The data were analysed using analysis of covariance. The results indicated that the students who used the constructivist principles-oriented instruction earned significantly higher scores than those taught by traditional instruction in terms of achievement related to chemical equilibrium concepts. In addition, students' previous learning and science process skills each made a significant contribution to the achievement related to chemical equilibrium concepts. In light of the findings obtained from the results, an additional misconception of chemical equilibrium concepts was determined in addition to the misconceptions in related literature. This misconception is that when one of the reactants is added to the equilibrium system, the concentration of the substance that was added will decrease below its value at the initial equilibrium.

  6. Influence of substituent on equilibrium of benzoxazine synthesis from Mannich base and formaldehyde.

    PubMed

    Deng, Yuyuan; Zhang, Qin; Zhou, Qianhao; Zhang, Chengxi; Zhu, Rongqi; Gu, Yi

    2014-09-14

    N-Substituted aminomethylphenol (Mannich base) and 3,4-dihydro-2H-3-substituted 1,3-benzoxazine (benzoxazine) were synthesized from substituted phenol (p-cresol, phenol, p-chlorophenol), substituted aniline (p-toluidine, aniline, p-chloroaniline) and formaldehyde to study influence of substituent on equilibrium of benzoxazine synthesis from Mannich base and formaldehyde. (1)H-NMR and charges of nitrogen and oxygen atoms illustrate effect of substituent on reactivity of Mannich base, while oxazine ring stability is characterized by differential scanning calorimetry (DSC) and C-O bond order. Equilibrium constants were tested from 50 °C to 80 °C, and the results show that substituent attached to phenol or aniline has same impact on reactivity of Mannich base; however, it has opposite influence on oxazine ring stability and equilibrium constant. Compared with the phenol-aniline system, electron-donating methyl on phenol or aniline increases the charge of nitrogen and oxygen atoms in Mannich base. When the methyl group is located at para position of phenol, oxazine ring stability increases, and the equilibrium constant climbs, whereas when the methyl group is located at the para position of aniline, oxazine ring stability decreases, the benzoxazine hydrolysis tends to happen and equilibrium constant is significantly low.

  7. [Acid-base equilibrium in sportsmen during physical exercise].

    PubMed

    Brinzak, V P; Kalinskiĭ, M I; Val'tin, A I; Povzhitkova, M S

    1983-01-01

    Acid-base balance in venous blood of basketball players was studied under specific loadings of various intensity by means of the micro-Astrup device. It is established that under acyclic loadings (throwing the ball into the basket) the state of metabolic acidosis is developed in the sportsmen and the more intensive the work, the higher the degree of the state of metabolic acidosis. The efficiency of actions of the persons examined was in inverse dependence on the degree of metabolic disturbances, i.e. the least efficiency was marked under the most profound acidosis.

  8. Using the Logarithmic Concentration Diagram, Log "C", to Teach Acid-Base Equilibrium

    ERIC Educational Resources Information Center

    Kovac, Jeffrey

    2012-01-01

    Acid-base equilibrium is one of the most important and most challenging topics in a typical general chemistry course. This article introduces an alternative to the algebraic approach generally used in textbooks, the graphical log "C" method. Log "C" diagrams provide conceptual insight into the behavior of aqueous acid-base systems and allow…

  9. Development of facile property calculation model for adsorption chillers based on equilibrium adsorption cycle

    NASA Astrophysics Data System (ADS)

    Yano, Masato; Hirose, Kenji; Yoshikawa, Minoru; Thermal management technology Team

    Facile property calculation model for adsorption chillers was developed based on equilibrium adsorption cycles. Adsorption chillers are one of promising systems that can use heat energy efficiently because adsorption chillers can generate cooling energy using relatively low temperature heat energy. Properties of adsorption chillers are determined by heat source temperatures, adsorption/desorption properties of adsorbent, and kinetics such as heat transfer rate and adsorption/desorption rate etc. In our model, dependence of adsorption chiller properties on heat source temperatures was represented using approximated equilibrium adsorption cycles instead of solving conventional time-dependent differential equations for temperature changes. In addition to equilibrium cycle calculations, we calculated time constants for temperature changes as functions of heat source temperatures, which represent differences between equilibrium cycles and real cycles that stemmed from kinetic adsorption processes. We found that the present approximated equilibrium model could calculate properties of adsorption chillers (driving energies, cooling energies, and COP etc.) under various driving conditions quickly and accurately within average errors of 6% compared to experimental data.

  10. A Simple System for Observing Dynamic Phase Equilibrium via an Inquiry-Based Laboratory or Demonstration

    ERIC Educational Resources Information Center

    Cloonan, Carrie A.; Andrew, Julie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    This article describes an activity that can be used as an inquiry-based laboratory or demonstration for either high school or undergraduate chemistry students to provide a basis for understanding both vapor pressure and the concept of dynamic phase equilibrium. The activity includes a simple setup to create a closed system of only water liquid and…

  11. An equilibrium-based model for measuring environmental radon using charcoal canisters.

    PubMed

    Lehnert, A L; Kearfott, K J

    2010-08-01

    Radon in indoor air is often measured using canisters of activated charcoal that function by adsorbing radon gas. The use of a diffusion barrier charcoal canister (DBCC) minimizes the effects of environmental humidity and extends the useful exposure time by several days. Many DBCC protocols model charcoal canisters as simple integrating detectors, which introduces errors due to the fact that radon uptake changes over the exposure period. Errors are compensated for by calculating a calibration factor that is nonlinear with respect to exposure time. This study involves the development and testing of an equilibrium-based model and corresponding measurement protocol that treats the charcoal canisters as a system coming into equilibrium with the surrounding radon environment. This model applies to both constant and temporally varying radon concentration situations, which was essential, as efforts are currently underway using a temporally varying radon chamber. It was found that the DBCCs equilibrate following the relationship E = (1 - e) where E is a measure of how close the DBCC is to equilibrium, t is exposure time, and q is the equilibration constant. This equilibration constant was empirically determined to be 0.019 h. The proposed model was tested in a blind test as well as compared with the currently accepted U.S. Environmental Protection Agency (U.S. EPA) model. Comparisons between the two methods showed a slight decrease in measurement error when using the equilibrium-based method as compared to the U.S. EPA method.

  12. Born energy, acid-base equilibrium, structure and interactions of end-grafted weak polyelectrolyte layers

    SciTech Connect

    Nap, R. J.; Tagliazucchi, M.; Szleifer, I.

    2014-01-14

    This work addresses the effect of the Born self-energy contribution in the modeling of the structural and thermodynamical properties of weak polyelectrolytes confined to planar and curved surfaces. The theoretical framework is based on a theory that explicitly includes the conformations, size, shape, and charge distribution of all molecular species and considers the acid-base equilibrium of the weak polyelectrolyte. Namely, the degree of charge in the polymers is not imposed but it is a local varying property that results from the minimization of the total free energy. Inclusion of the dielectric properties of the polyelectrolyte is important as the environment of a polymer layer is very different from that in the adjacent aqueous solution. The main effect of the Born energy contribution on the molecular organization of an end-grafted weak polyacid layer is uncharging the weak acid (or basic) groups and consequently decreasing the concentration of mobile ions within the layer. The magnitude of the effect increases with polymer density and, in the case of the average degree of charge, it is qualitatively equivalent to a small shift in the equilibrium constant for the acid-base equilibrium of the weak polyelectrolyte monomers. The degree of charge is established by the competition between electrostatic interactions, the polymer conformational entropy, the excluded volume interactions, the translational entropy of the counterions and the acid-base chemical equilibrium. Consideration of the Born energy introduces an additional energetic penalty to the presence of charged groups in the polyelectrolyte layer, whose effect is mitigated by down-regulating the amount of charge, i.e., by shifting the local-acid base equilibrium towards its uncharged state. Shifting of the local acid-base equilibrium and its effect on the properties of the polyelectrolyte layer, without considering the Born energy, have been theoretically predicted previously. Account of the Born energy leads

  13. Born energy, acid-base equilibrium, structure and interactions of end-grafted weak polyelectrolyte layers.

    PubMed

    Nap, R J; Tagliazucchi, M; Szleifer, I

    2014-01-14

    This work addresses the effect of the Born self-energy contribution in the modeling of the structural and thermodynamical properties of weak polyelectrolytes confined to planar and curved surfaces. The theoretical framework is based on a theory that explicitly includes the conformations, size, shape, and charge distribution of all molecular species and considers the acid-base equilibrium of the weak polyelectrolyte. Namely, the degree of charge in the polymers is not imposed but it is a local varying property that results from the minimization of the total free energy. Inclusion of the dielectric properties of the polyelectrolyte is important as the environment of a polymer layer is very different from that in the adjacent aqueous solution. The main effect of the Born energy contribution on the molecular organization of an end-grafted weak polyacid layer is uncharging the weak acid (or basic) groups and consequently decreasing the concentration of mobile ions within the layer. The magnitude of the effect increases with polymer density and, in the case of the average degree of charge, it is qualitatively equivalent to a small shift in the equilibrium constant for the acid-base equilibrium of the weak polyelectrolyte monomers. The degree of charge is established by the competition between electrostatic interactions, the polymer conformational entropy, the excluded volume interactions, the translational entropy of the counterions and the acid-base chemical equilibrium. Consideration of the Born energy introduces an additional energetic penalty to the presence of charged groups in the polyelectrolyte layer, whose effect is mitigated by down-regulating the amount of charge, i.e., by shifting the local-acid base equilibrium towards its uncharged state. Shifting of the local acid-base equilibrium and its effect on the properties of the polyelectrolyte layer, without considering the Born energy, have been theoretically predicted previously. Account of the Born energy leads

  14. A process-based model for non-equilibrium clumped isotope effects in carbonates

    NASA Astrophysics Data System (ADS)

    Watkins, J. M.; Hunt, J. D.

    2015-12-01

    The equilibrium clumped isotope composition of carbonate minerals is independent of the composition of the aqueous solution. However, many carbonate minerals grow at rates that place them in a non-equilibrium regime with respect to carbon and oxygen isotopes with unknown consequences for clumped isotopes. We develop a process-based model that allows one to calculate the oxygen, carbon, and clumped isotope composition of calcite as a function of temperature, crystal growth rate, and solution pH. In the model, carbon and oxygen isotope fractionation occurs through the mass-dependent attachment/detachment kinetics of the isotopologues of HCO-3 and CO2-3 to and from the calcite surface, which in turn, influence the clumped isotope composition of calcite. At experimental and biogenic growth rates, the mineral is expected to inherit a clumped isotopic composition that is similar to that of the DIC pool, which helps to explain (1) why different organisms share the same clumped isotope versus temperature calibration curves, (2) why many inorganic calibration curves are slightly different from one another, and (3) why foraminifera, coccoliths, and deep sea corals can have near-equilibrium clumped isotope compositions but far-from-equilibrium carbon and oxygen isotope compositions. Some aspects of the model can be generalized to other mineral systems and should serve as a useful reference in future efforts to quantify kinetic clumped isotope effects.

  15. Equilibrium partition ratios, densities, and transport phenomena in nickel-base superalloys

    NASA Astrophysics Data System (ADS)

    Sung, Pil Kyung

    To simulate transport phenomena, macrosegregation and segregation defects known as "freckles" during directional solidification of Ni-base superalloys, numerical modeling can be used; hence it is essential to have reasonably accurate values of the thermodynamic and transport properties for the alloys. In this research, therefore, the equilibrium partition ratios of the solutes in the Ni-Al-Ta-Cr quaternary system, as a model alloy, were measured, and the solid- and liquid-densities in Ni-base superalloys. were estimated. Also, the importance of these properties on the sensitivity of the results of numerical simulations was studied. The partition ratios apply to equilibria between melts and gamma-phase in the range of 1615 K to 1694 K, and it was found that the equilibrium partition ratio of Ta varies from approximately 0.6 at dilute Ta to 0.85 at 17 wt.% Ta. For the same range of Ta-contents, the partition ratios of Al and Cr vary much less and range from about 0.92 to 0.96. In addition to the partition ratios, the liquidus temperatures of the liquid in equilibrium with gamma in the Ni-Al-Ta-Cr system were estimated with a multidimensional regression analysis. To calculate the densities of solid Ni-base superalloys as functions of temperature and composition, lattice parameters at 20°C and coefficients of thermal expansion (CTEs) were estimated by combining available data. The CTEs calculated from the regressions result in densities that are within 0.5% error or less for seventeen alloys. To estimate the densities of liquid Ni-base superalloys, the densities and temperature coefficients of density of the liquid transition-metals, which are used as alloy elements in Ni-base superalloys, were applied to a simple correlation. By using this approach, the estimates of the liquid densities of five Ni-base superalloys agree with the measured values to +/-2.5%. Finally, the importance of using reasonably accurate estimates of the transport properties was illustrated by

  16. Reactive solute transport in streams. 1. Development of an equilibrium- based model

    USGS Publications Warehouse

    Runkel, R.L.; Bencala, K.E.; Broshears, R.E.; Chapra, S.C.

    1996-01-01

    An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

  17. Accelerated equilibrium core composition search using a new MCNP-based simulator

    NASA Astrophysics Data System (ADS)

    Seifried, Jeffrey E.; Gorman, Phillip M.; Vujic, Jasmina L.; Greenspan, Ehud

    2014-06-01

    MocDown is a new Monte Carlo depletion and recycling simulator which couples neutron transport with MCNP and transmutation with ORIGEN. This modular approach to depletion allows for flexible operation by incorporating the accelerated progression of a complex fuel processing scheme towards equilibrium and by allowing for the online coupling of thermo-fluids feedback. MocDown also accounts for the variation of decay heat with fuel isotopics evolution. In typical cases, MocDown requires just over a day to find the equilibrium core composition for a multi-recycling fuel cycle, with a self-consistent thermo-fluids solution-a task that required between one and two weeks using previous Monte Carlo-based approaches.

  18. Highly efficient hydrogen storage system based on ammonium bicarbonate/formate redox equilibrium over palladium nanocatalysts.

    PubMed

    Su, Ji; Yang, Lisha; Lu, Mi; Lin, Hongfei

    2015-03-01

    A highly efficient, reversible hydrogen storage-evolution process has been developed based on the ammonium bicarbonate/formate redox equilibrium over the same carbon-supported palladium nanocatalyst. This heterogeneously catalyzed hydrogen storage system is comparable to the counterpart homogeneous systems and has shown fast reaction kinetics of both the hydrogenation of ammonium bicarbonate and the dehydrogenation of ammonium formate under mild operating conditions. By adjusting temperature and pressure, the extent of hydrogen storage and evolution can be well controlled in the same catalytic system. Moreover, the hydrogen storage system based on aqueous-phase ammonium formate is advantageous owing to its high volumetric energy density.

  19. Mechanistic sediment quality guidelines based on contaminant bioavailability: equilibrium partitioning sediment benchmarks.

    PubMed

    Burgess, Robert M; Berry, Walter J; Mount, David R; Di Toro, Dominic M

    2013-01-01

    Globally, estimated costs to manage (i.e., remediate and monitor) contaminated sediments are in the billions of U.S. dollars. Biologically based approaches for assessing the contaminated sediments which pose the greatest ecological risk range from toxicity testing to benthic community analysis. In addition, chemically based sediment quality guidelines (SQGs) provide a relatively inexpensive line of evidence for supporting these assessments. The present study summarizes a mechanistic SQG based on equilibrium partitioning (EqP), which uses the dissolved concentrations of contaminants in sediment interstitial waters as a surrogate for bioavailable contaminant concentrations. The EqP-based mechanistic SQGs are called equilibrium partitioning sediment benchmarks (ESBs). Sediment concentrations less than or equal to the ESB values are not expected to result in adverse effects and benthic organisms should be protected, while sediment concentrations above the ESB values may result in adverse effects to benthic organisms. In the present study, ESB values are reported for 34 polycyclic aromatic hydrocarbon, 32 other organic contaminants, and seven metals (cadmium, chromium, copper, nickel, lead, silver, zinc). Also included is an overview of EqP theory, ESB derivation, examples of applying ESB values, and considerations when using ESBs. The ESBs are intended as a complement to existing sediment-assessment tools, to assist in determining the extent of sediment contamination, to help identify chemicals causing toxicity, and to serve as targets for pollutant loading control measures.

  20. Effects of intravenous solutions on acid-base equilibrium: from crystalloids to colloids and blood components.

    PubMed

    Langer, Thomas; Ferrari, Michele; Zazzeron, Luca; Gattinoni, Luciano; Caironi, Pietro

    2014-01-01

    Intravenous fluid administration is a medical intervention performed worldwide on a daily basis. Nevertheless, only a few physicians are aware of the characteristics of intravenous fluids and their possible effects on plasma acid-base equilibrium. According to Stewart's theory, pH is independently regulated by three variables: partial pressure of carbon dioxide, strong ion difference (SID), and total amount of weak acids (ATOT). When fluids are infused, plasma SID and ATOT tend toward the SID and ATOT of the administered fluid. Depending on their composition, fluids can therefore lower, increase, or leave pH unchanged. As a general rule, crystalloids having a SID greater than plasma bicarbonate concentration (HCO₃-) cause an increase in plasma pH (alkalosis), those having a SID lower than HCO₃- cause a decrease in plasma pH (acidosis), while crystalloids with a SID equal to HCO₃- leave pH unchanged, regardless of the extent of the dilution. Colloids and blood components are composed of a crystalloid solution as solvent, and the abovementioned rules partially hold true also for these fluids. The scenario is however complicated by the possible presence of weak anions (albumin, phosphates and gelatins) and their effect on plasma pH. The present manuscript summarises the characteristics of crystalloids, colloids, buffer solutions and blood components and reviews their effect on acid-base equilibrium. Understanding the composition of intravenous fluids, along with the application of simple physicochemical rules best described by Stewart's approach, are pivotal steps to fully elucidate and predict alterations of plasma acid-base equilibrium induced by fluid therapy.

  1. Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

    PubMed

    Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

    2015-05-01

    Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

  2. Unusual dileptions at RHIC a field theoretic approach based on a non-equilibrium chiral phase transition

    SciTech Connect

    Cooper, F.

    1997-09-22

    This paper contains viewgraphs on unusual dileptons at Brookhaven RHIC. A field theory approach is used based on a non-equilibrium chiral phase transformation utilizing the schroedinger and Heisenberg picture.

  3. Conjugate Acid-Base Pairs, Free Energy, and the Equilibrium Constant

    ERIC Educational Resources Information Center

    Beach, Darrell H.

    1969-01-01

    Describes a method of calculating the equilibrium constant from free energy data. Values of the equilibrium constants of six Bronsted-Lowry reactions calculated by the author's method and by a conventional textbook method are compared. (LC)

  4. General library-based Monte Carlo technique enables equilibrium sampling of semi-atomistic protein models.

    PubMed

    Mamonov, Artem B; Bhatt, Divesh; Cashman, Derek J; Ding, Ying; Zuckerman, Daniel M

    2009-08-01

    We introduce "library-based Monte Carlo" (LBMC) simulation, which performs Boltzmann sampling of molecular systems based on precalculated statistical libraries of molecular-fragment configurations, energies, and interactions. The library for each fragment can be Boltzmann distributed and thus account for all correlations internal to the fragment. LBMC can be applied to both atomistic and coarse-grained models, as we demonstrate in this "proof-of-principle" report. We first verify the approach in a toy model and in implicitly solvated all-atom polyalanine systems. We next study five proteins, up to 309 residues in size. On the basis of atomistic equilibrium libraries of peptide-plane configurations, the proteins are modeled with fully atomistic backbones and simplified Go-like interactions among residues. We show that full equilibrium sampling can be obtained in days to weeks on a single processor, suggesting that more accurate models are well within reach. For the future, LBMC provides a convenient platform for constructing adjustable or mixed-resolution models: the configurations of all atoms can be stored at no run-time cost, while an arbitrary subset of interactions is "turned on". PMID:19594147

  5. Acid-base equilibrium dynamics in methanol and dimethyl sulfoxide probed by two-dimensional infrared spectroscopy.

    PubMed

    Lee, Chiho; Son, Hyewon; Park, Sungnam

    2015-07-21

    Two-dimensional infrared (2DIR) spectroscopy, which has been proven to be an excellent experimental method for studying thermally-driven chemical processes, was successfully used to investigate the acid dissociation equilibrium of HN3 in methanol (CH3OH) and dimethyl sulfoxide (DMSO) for the first time. Our 2DIR experimental results indicate that the acid-base equilibrium occurs on picosecond timescales in CH3OH but that it occurs on much longer timescales in DMSO. Our results imply that the different timescales of the acid-base equilibrium originate from different proton transfer mechanisms between the acidic (HN3) and basic (N3(-)) species in CH3OH and DMSO. In CH3OH, the acid-base equilibrium is assisted by the surrounding CH3OH molecules which can directly donate H(+) to N3(-) and accept H(+) from HN3 and the proton migrates through the hydrogen-bonded chain of CH3OH. On the other hand, the acid-base equilibrium in DMSO occurs through the mutual diffusion of HN3 and N3(-) or direct proton transfer. Our 2DIR experimental results corroborate different proton transfer mechanisms in the acid-base equilibrium in protic (CH3OH) and aprotic (DMSO) solvents.

  6. Fiber Bragg grating dynamic demodulation based on non-equilibrium interferometry

    NASA Astrophysics Data System (ADS)

    Yu, Qi; Jing, Zhenguo; Peng, Wei; Zhang, Xinpu; Liu, Yun; Xing, Chuanqi; Li, Hong; Yao, Wenjuan

    2011-12-01

    Non-equilibrium interferometric Fiber Bragg Grating (FBG) sensor is suitable for the accurate measurements of high-frequency dynamic stress, vibration, etc because of its high sensitivity and high frequency response compared to other types of FBG sensors. In this paper, a Phase Generation Carrier (PGC) demodulation technique of non-equilibrium interferometric FBG sensor that based on ARCTAN algorithm by using an arctangent algorithm with a simple method, has been investigated ,which can avoid the high-frequency noise increases, the error accumulation, the integrator signal jump of the integrator and other inherent weaknesses in the system. ARCTAN has a better response characteristic of the mutant signals, especially for low-frequency large-signal that can be demodulated with a greater range. The experimental result demonstrate that implementing measured resolution can up to 10nɛ/√Hz@500Hz in vibration strain, a signal sampling rate to 100 KHz and a frequency response range up to 1 KHz. This method can improve the performance of the system greatly which has potential significance for practical sensor application.

  7. Weak Acid Ionization Constants and the Determination of Weak Acid-Weak Base Reaction Equilibrium Constants in the General Chemistry Laboratory

    ERIC Educational Resources Information Center

    Nyasulu, Frazier; McMills, Lauren; Barlag, Rebecca

    2013-01-01

    A laboratory to determine the equilibrium constants of weak acid negative weak base reactions is described. The equilibrium constants of component reactions when multiplied together equal the numerical value of the equilibrium constant of the summative reaction. The component reactions are weak acid ionization reactions, weak base hydrolysis…

  8. Equilibrium between a cyclotrisilene and an isolable base adduct of a disilenyl silylene

    NASA Astrophysics Data System (ADS)

    Cowley, Michael J.; Huch, Volker; Rzepa, Henry S.; Scheschkewitz, David

    2013-10-01

    In organic chemistry, compounds with adjacent alkene and carbene functionalities (vinyl carbenes) are studied widely as fleeting intermediates and in the coordination sphere of transition metals. Stable derivatives of vinyl carbenes remain elusive, including the corresponding heavier group 14 homologues. Here we report the isolation and full characterization of a base-stabilized silicon version of a vinyl carbene that features a silicon-silicon double bond as well as a silylene functionality, coordinated by an N-heterocyclic carbene (NHC). In solution, the intensely green disilenyl silylene adduct exists in equilibrium with the corresponding silicon analogue of a cyclopropene and free NHC, which was quantified by nuclear magnetic resonance spectroscopy and ultraviolet-visible spectroscopy. The reversibility of this process raises exciting possibilities for the preparation of extended conjugated π systems of silicon.

  9. NMR structural study of the prototropic equilibrium in solution of Schiff bases as model compounds.

    PubMed

    Ortegón-Reyna, David; Garcías-Morales, Cesar; Padilla-Martínez, Itzia; García-Báez, Efren; Aríza-Castolo, Armando; Peraza-Campos, Ana; Martínez-Martínez, Francisco

    2013-12-31

    An NMR titration method has been used to simultaneously measure the acid dissociation constant (pKa) and the intramolecular NHO prototropic constant ΔKNHO on a set of Schiff bases. The model compounds were synthesized from benzylamine and substituted ortho-hydroxyaldehydes, appropriately substituted with electron-donating and electron-withdrawing groups to modulate the acidity of the intramolecular NHO hydrogen bond. The structure in solution was established by 1H-, 13C- and 15N-NMR spectroscopy. The physicochemical parameters of the intramolecular NHO hydrogen bond (pKa, ΔKNHO and ΔΔG°) were obtained from 1H-NMR titration data and pH measurements. The Henderson-Hasselbalch data analysis indicated that the systems are weakly acidic, and the predominant NHO equilibrium was established using Polster-Lachmann δ-diagram analysis and Perrin model data linearization.

  10. Chemicals loading in acetylated bamboo assisted by supercritical CO2 based on phase equilibrium data

    NASA Astrophysics Data System (ADS)

    Silviana, Petermann, M.

    2015-12-01

    Indonesia has a large tropical forest. However, the deforestation still appears annually and vastly. This reason drives a use of bamboo as wood alternative. Recently, there are many modifications of bamboo in order to prolong the shelf life. Unfortunately, the processes need more chemicals and time. Based on wood modification, esterifying of bamboo was undertaken in present of a dense gas, i.e. supercritical CO2. Calculation of chemicals loading referred to ASTM D1413-99 by using the phase equilibrium data at optimum condition by a statistical design. The results showed that the acetylation of bamboo assisted by supercritical CO2 required 14.73 kg acetic anhydride/m3 of bamboo for a treatment of one hour.

  11. Chromophore Structure of Photochromic Fluorescent Protein Dronpa: Acid-Base Equilibrium of Two Cis Configurations.

    PubMed

    Higashino, Asuka; Mizuno, Misao; Mizutani, Yasuhisa

    2016-04-01

    Dronpa is a novel photochromic fluorescent protein that exhibits fast response to light. The present article is the first report of the resonance and preresonance Raman spectra of Dronpa. We used the intensity and frequency of Raman bands to determine the structure of the Dronpa chromophore in two thermally stable photochromic states. The acid-base equilibrium in one photochromic state was observed by spectroscopic pH titration. The Raman spectra revealed that the chromophore in this state shows a protonation/deprotonation transition with a pKa of 5.2 ± 0.3 and maintains the cis configuration. The observed resonance Raman bands showed that the other photochromic state of the chromophore is in a trans configuration. The results demonstrate that Raman bands selectively enhanced for the chromophore yield valuable information on the molecular structure of the chromophore in photochromic fluorescent proteins after careful elimination of the fluorescence background. PMID:26991398

  12. Chromophore Structure of Photochromic Fluorescent Protein Dronpa: Acid-Base Equilibrium of Two Cis Configurations.

    PubMed

    Higashino, Asuka; Mizuno, Misao; Mizutani, Yasuhisa

    2016-04-01

    Dronpa is a novel photochromic fluorescent protein that exhibits fast response to light. The present article is the first report of the resonance and preresonance Raman spectra of Dronpa. We used the intensity and frequency of Raman bands to determine the structure of the Dronpa chromophore in two thermally stable photochromic states. The acid-base equilibrium in one photochromic state was observed by spectroscopic pH titration. The Raman spectra revealed that the chromophore in this state shows a protonation/deprotonation transition with a pKa of 5.2 ± 0.3 and maintains the cis configuration. The observed resonance Raman bands showed that the other photochromic state of the chromophore is in a trans configuration. The results demonstrate that Raman bands selectively enhanced for the chromophore yield valuable information on the molecular structure of the chromophore in photochromic fluorescent proteins after careful elimination of the fluorescence background.

  13. A rigorous multiple independent binding site model for determining cell-based equilibrium dissociation constants.

    PubMed

    Drake, Andrew W; Klakamp, Scott L

    2007-01-10

    A new 4-parameter nonlinear equation based on the standard multiple independent binding site model (MIBS) is presented for fitting cell-based ligand titration data in order to calculate the ligand/cell receptor equilibrium dissociation constant and the number of receptors/cell. The most commonly used linear (Scatchard Plot) or nonlinear 2-parameter model (a single binding site model found in commercial programs like Prism(R)) used for analysis of ligand/receptor binding data assumes only the K(D) influences the shape of the titration curve. We demonstrate using simulated data sets that, depending upon the cell surface receptor expression level, the number of cells titrated, and the magnitude of the K(D) being measured, this assumption of always being under K(D)-controlled conditions can be erroneous and can lead to unreliable estimates for the binding parameters. We also compare and contrast the fitting of simulated data sets to the commonly used cell-based binding equation versus our more rigorous 4-parameter nonlinear MIBS model. It is shown through these simulations that the new 4-parameter MIBS model, when used for cell-based titrations under optimal conditions, yields highly accurate estimates of all binding parameters and hence should be the preferred model to fit cell-based experimental nonlinear titration data. PMID:17141800

  14. Stability analysis of the Gravito-Electrostatic Sheath-based solar plasma equilibrium

    NASA Astrophysics Data System (ADS)

    Karmakar, P. K.; Goutam, H. P.; Lal, M.; Dwivedi, C. B.

    2016-08-01

    We present approximate solutions of non-local linear perturbational analysis for discussing the stability properties of the Gravito-Electrostatic Sheath (GES)-based solar plasma equilibrium, which is indeed non-uniform on both the bounded and unbounded scales. The relevant physical variables undergoing perturbations are the self-solar gravity, electrostatic potential and plasma flow along with plasma population density. We methodologically derive linear dispersion relation for the GES fluctuations, and solve it numerically to identify and characterize the existent possible natural normal modes. Three distinct natural normal modes are identified and named as the GES-oscillator mode, GES-wave mode and usual (classical) p-mode. In the solar wind plasma, only the p-mode survives. These modes are found to be linearly unstable in wide-range of the Jeans-normalized wavenumber, k. The local plane-wave approximation marginally limits the validity or reliability of the obtained results in certain radial- and k-domains only. The phase and group velocities, time periods of these fluctuation modes are investigated. It is interesting to note that, the oscillation time periods of these modes are 3-10 min, which match exactly with those of the observed helio-seismic waves and solar surface oscillations. The proposed GES model provides a novel physical view of the waves and oscillations of the Sun from a new perspective of plasma-wall interaction physics. Due to simplified nature of the considered GES equilibrium, it is a neonatal stage to highlight its applicability in the real Sun. The proposed GES model and subsequent fluctuation analysis need further improvements to make it more realistic.

  15. Hidden Conformation Events in DNA Base Extrusions: A Generalized Ensemble Path Optimization and Equilibrium Simulation Study.

    PubMed

    Cao, Liaoran; Lv, Chao; Yang, Wei

    2013-08-13

    DNA base extrusion is a crucial component of many biomolecular processes. Elucidating how bases are selectively extruded from the interiors of double-strand DNAs is pivotal to accurately understanding and efficiently sampling this general type of conformational transitions. In this work, the on-the-path random walk (OTPRW) method, which is the first generalized ensemble sampling scheme designed for finite-temperature-string path optimizations, was improved and applied to obtain the minimum free energy path (MFEP) and the free energy profile of a classical B-DNA major-groove base extrusion pathway. Along the MFEP, an intermediate state and the corresponding transition state were located and characterized. The MFEP result suggests that a base-plane-elongation event rather than the commonly focused base-flipping event is dominant in the transition state formation portion of the pathway; and the energetic penalty at the transition state is mainly introduced by the stretching of the Watson-Crick base pair. Moreover to facilitate the essential base-plane-elongation dynamics, the surrounding environment of the flipped base needs to be intimately involved. Further taking the advantage of the extended-dynamics nature of the OTPRW Hamiltonian, an equilibrium generalized ensemble simulation was performed along the optimized path; and based on the collected samples, several base-flipping (opening) angle collective variables were evaluated. In consistence with the MFEP result, the collective variable analysis result reveals that none of these commonly employed flipping (opening) angles alone can adequately represent the base extrusion pathway, especially in the pre-transition-state portion. As further revealed by the collective variable analysis, the base-pairing partner of the extrusion target undergoes a series of in-plane rotations to facilitate the base-plane-elongation dynamics. A base-plane rotation angle is identified to be a possible reaction coordinate to represent

  16. The Effect of Context-Based Chemical Equilibrium on Grade 11 Students' Learning, Motivation and Constructivist Learning Environment

    ERIC Educational Resources Information Center

    ilhan, Nail; Yildirim, Ali; Yilmaz, Sibel Sadi

    2016-01-01

    In recent years, many countries have adopted a context-based approach for designing science curricula for education at all levels. The aim of this study was to determine the effectiveness of a Context-Based Chemistry Course (CBCC) as compared with traditional/existing instruction, on 11th grade students' learning about chemical equilibrium,…

  17. Game Theory Based Security in Wireless Body Area Network with Stackelberg Security Equilibrium.

    PubMed

    Somasundaram, M; Sivakumar, R

    2015-01-01

    Wireless Body Area Network (WBAN) is effectively used in healthcare to increase the value of the patient's life and also the value of healthcare services. The biosensor based approach in medical care system makes it difficult to respond to the patients with minimal response time. The medical care unit does not deploy the accessing of ubiquitous broadband connections full time and hence the level of security will not be high always. The security issue also arises in monitoring the user body function records. Most of the systems on the Wireless Body Area Network are not effective in facing the security deployment issues. To access the patient's information with higher security on WBAN, Game Theory with Stackelberg Security Equilibrium (GTSSE) is proposed in this paper. GTSSE mechanism takes all the players into account. The patients are monitored by placing the power position authority initially. The position authority in GTSSE is the organizer and all the other players react to the organizer decision. Based on our proposed approach, experiment has been conducted on factors such as security ratio based on patient's health information, system flexibility level, energy consumption rate, and information loss rate. Stackelberg Security considerably improves the strength of solution with higher security.

  18. Game Theory Based Security in Wireless Body Area Network with Stackelberg Security Equilibrium

    PubMed Central

    Somasundaram, M.; Sivakumar, R.

    2015-01-01

    Wireless Body Area Network (WBAN) is effectively used in healthcare to increase the value of the patient's life and also the value of healthcare services. The biosensor based approach in medical care system makes it difficult to respond to the patients with minimal response time. The medical care unit does not deploy the accessing of ubiquitous broadband connections full time and hence the level of security will not be high always. The security issue also arises in monitoring the user body function records. Most of the systems on the Wireless Body Area Network are not effective in facing the security deployment issues. To access the patient's information with higher security on WBAN, Game Theory with Stackelberg Security Equilibrium (GTSSE) is proposed in this paper. GTSSE mechanism takes all the players into account. The patients are monitored by placing the power position authority initially. The position authority in GTSSE is the organizer and all the other players react to the organizer decision. Based on our proposed approach, experiment has been conducted on factors such as security ratio based on patient's health information, system flexibility level, energy consumption rate, and information loss rate. Stackelberg Security considerably improves the strength of solution with higher security. PMID:26759829

  19. Statistical enhancement of a dynamic equilibrium-based damage identification strategy: Theory and experimental validation

    NASA Astrophysics Data System (ADS)

    Xu, Hao; Lu, Bo; Su, Zhongqing; Cheng, Li

    2015-09-01

    A previously developed damage identification strategy, named Pseudo-Excitation (PE), was enhanced using a statistical processing approach. In terms of the local dynamic equilibrium of the structural component under inspection, the distribution of its vibration displacements, which are of necessity to construct the damage index in the PE, was re-defined using sole dynamic strains based on the statistical method. On top of those advantages inheriting from the original PE compared with traditional vibration-based damage detection including the independence of baseline signals and pre-developed benchmark structures, the enhanced PE (EPE) possesses improved immunity to the interference of measurement noise. Moreover, the EPE can facilitate practical implementation of online structural health monitoring, benefiting from the use of sole strain information. Proof-of-concept numerical study was conducted to examine the feasibility and accuracy of the EPE, and the effectiveness of the proposed statistical enhancement in re-constructing the vibration displacements was evaluated under noise influence; experimental validation was followed up by characterizing multi-cracks in a beam-like structure, in which the dynamic strains were measured using Lead zirconium titanate (PZT) sensors. For comparison, the original PE, the Gapped Smoothing Method (GSM), and the EPE were respectively used to evaluate the cracks. It was observed from the damage identification results that both the GSM and EPE were able to achieve higher identification accuracy than the original PE, and the robustness of the EPE in damage identification was proven to be superior than that of the GSM.

  20. Pluto's atmosphere - Models based on refraction, inversion, and vapor-pressure equilibrium

    NASA Technical Reports Server (NTRS)

    Eshleman, Von R.

    1989-01-01

    Viking spacecraft radio-occultation measurements indicate that, irrespective of substantial differences, the polar ice cap regions on Mars have inversions similar to those of Pluto, and may also share vapor pressure equilibrium characteristics at the surface. This temperature-inversion phenomenon occurs in a near-surface boundary layer; surface pressure-temperature may correspond to the vapor-pressure equilibrium with CH4 ice, or the temperature may be slightly higher to match the value derived from IRAS data.

  1. A body-force based method to generate supersonic equilibrium turbulent boundary layer profiles

    NASA Astrophysics Data System (ADS)

    Waindim, M.; Gaitonde, D. V.

    2016-01-01

    We further develop a simple counterflow body force-based approach to generate an equilibrium spatially developing turbulent boundary layer suitable for Direct Numerical Simulations (DNS) or Large Eddy Simulations (LES) of viscous-inviscid interactions. The force essentially induces a small separated region in an incoming specified laminar boundary layer. The resulting unstable shear layer then transitions and breaks down to yield the desired unsteady profile. The effects of wall thermal conditions are explored to demonstrate the capability of the method for both fixed wall and adiabatic wall conditions. We then describe an efficient method to select parameters that ensure transition by examining precursor signatures using generalized stability variables. These precursors are shown to be evident in a computational domain spanning only a small region around the trip and can also be detected using 2D simulations. Finally, the method is tested for different Mach numbers ranging from 1.7 to 2.9, with emphasis on flow field surveys, Reynolds stresses, and energy spectra. These results provide guidance on boundary conditions for desired boundary layer thickness at each Mach number. The consequences of using a much lower Reynolds number in computation relative to experiment are evident at the higher Mach number, where a self sustaining turbulent boundary layer is more difficult to obtain.

  2. Stages in Learning Motor Synergies: A View Based on the Equilibrium-Point Hypothesis

    PubMed Central

    Latash, Mark L.

    2009-01-01

    This review describes a novel view on stages in motor learning based on recent developments of the notion of synergies, the uncontrolled manifold hypothesis, and the equilibrium-point hypothesis (referent configuration) that allow to merge these notions into a single scheme of motor control. The principle of abundance and the principle of minimal final action form the foundation for analyses of natural motor actions performed by redundant sets of elements. Two main stages of motor learning are introduced corresponding to (1) discovery and strengthening of motor synergies stabilizing salient performance variable(s), and (2) their weakening when other aspects of motor performance are optimized. The first stage may be viewed as consisting of two steps, the elaboration of an adequate referent configuration trajectory and the elaboration of multi-joint (multi-muscle) synergies stabilizing the referent configuration trajectory. Both steps are expected to lead to more variance in the space of elemental variables that is compatible with a desired time profile of the salient performance variable (“good variability”). Adjusting control to other aspects of performance during the second stage (for example, esthetics, energy expenditure, time, fatigue, etc.) may lead to a drop in the “good variability”. Experimental support for the suggested scheme is reviewed. PMID:20060610

  3. Equilibrium Shaping

    NASA Astrophysics Data System (ADS)

    Izzo, Dario; Petazzi, Lorenzo

    2006-08-01

    We present a satellite path planning technique able to make identical spacecraft aquire a given configuration. The technique exploits a behaviour-based approach to achieve an autonomous and distributed control over the relative geometry making use of limited sensorial information. A desired velocity is defined for each satellite as a sum of different contributions coming from generic high level behaviours: forcing the final desired configuration the behaviours are further defined by an inverse dynamic calculation dubbed Equilibrium Shaping. We show how considering only three different kind of behaviours it is possible to acquire a number of interesting formations and we set down the theoretical framework to find the entire set. We find that allowing a limited amount of communication the technique may be used also to form complex lattice structures. Several control feedbacks able to track the desired velocities are introduced and discussed. Our results suggest that sliding mode control is particularly appropriate in connection with the developed technique.

  4. Efficient Nash Equilibrium Resource Allocation Based on Game Theory Mechanism in Cloud Computing by Using Auction

    PubMed Central

    Nezarat, Amin; Dastghaibifard, GH

    2015-01-01

    One of the most complex issues in the cloud computing environment is the problem of resource allocation so that, on one hand, the cloud provider expects the most profitability and, on the other hand, users also expect to have the best resources at their disposal considering the budget constraints and time. In most previous work conducted, heuristic and evolutionary approaches have been used to solve this problem. Nevertheless, since the nature of this environment is based on economic methods, using such methods can decrease response time and reducing the complexity of the problem. In this paper, an auction-based method is proposed which determines the auction winner by applying game theory mechanism and holding a repetitive game with incomplete information in a non-cooperative environment. In this method, users calculate suitable price bid with their objective function during several round and repetitions and send it to the auctioneer; and the auctioneer chooses the winning player based the suggested utility function. In the proposed method, the end point of the game is the Nash equilibrium point where players are no longer inclined to alter their bid for that resource and the final bid also satisfies the auctioneer’s utility function. To prove the response space convexity, the Lagrange method is used and the proposed model is simulated in the cloudsim and the results are compared with previous work. At the end, it is concluded that this method converges to a response in a shorter time, provides the lowest service level agreement violations and the most utility to the provider. PMID:26431035

  5. Efficient Nash Equilibrium Resource Allocation Based on Game Theory Mechanism in Cloud Computing by Using Auction.

    PubMed

    Nezarat, Amin; Dastghaibifard, G H

    2015-01-01

    One of the most complex issues in the cloud computing environment is the problem of resource allocation so that, on one hand, the cloud provider expects the most profitability and, on the other hand, users also expect to have the best resources at their disposal considering the budget constraints and time. In most previous work conducted, heuristic and evolutionary approaches have been used to solve this problem. Nevertheless, since the nature of this environment is based on economic methods, using such methods can decrease response time and reducing the complexity of the problem. In this paper, an auction-based method is proposed which determines the auction winner by applying game theory mechanism and holding a repetitive game with incomplete information in a non-cooperative environment. In this method, users calculate suitable price bid with their objective function during several round and repetitions and send it to the auctioneer; and the auctioneer chooses the winning player based the suggested utility function. In the proposed method, the end point of the game is the Nash equilibrium point where players are no longer inclined to alter their bid for that resource and the final bid also satisfies the auctioneer's utility function. To prove the response space convexity, the Lagrange method is used and the proposed model is simulated in the cloudsim and the results are compared with previous work. At the end, it is concluded that this method converges to a response in a shorter time, provides the lowest service level agreement violations and the most utility to the provider.

  6. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    PubMed

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  7. Development of 3D full-core ERANOS-2.2/MCNPX-2.7.0 models and neutronic analysis of the BFS-2 zero-power facility

    SciTech Connect

    Girardin, G.; Alonso, M.; Mikityuk, K.

    2012-07-01

    The present paper is addressing the development and validation against experimental data of 3D full-core models of the BFS-2 zero-power fast-reactor using both the deterministic system code ERANOS-2.2 and the stochastic code MCNPX-2.7.0. The model configuration of BFS considered for analysis is the BFS-62-3A benchmark. To extend the - deterministic/stochastic - code-to-code comparison, neutronic parameters, i.e. reactivity, neutron spectrum and reaction rates, were also simulated at the cell level with the Monte Carlo code SERPENT-1.1.7 with two modern data libraries, ENDF-B/VII and JEFF-3.1.1. The BFS-2 critical zero-power facility at the Inst. of Physics and Power Engineering (IPPE) was designed for simulations of the core and shielding of sodium-cooled, fast reactors, for neutron data validation and comparison with experimental results. At the BFS-2 facility, the BFS-62-3A critical benchmark experiment was set-up as a mock-up of the BN-600 reactor, with hybrid MOX fuel and stainless steel reflectors. A UO{sub 2} blanket and a large non-homogeneous stainless-steel reflector surround the core. The lattice is hexagonal of pitch 5.1 cm and metallic dowels are used to keep in central position cylindrical rods made of different types of material (fissile, fertile, blanket, plenum, shielding and absorber). A typical subassembly is formed in piling up various pellets of about 1 cm in height and 4.6 cm in diameter, conferring large heterogeneity in the axial direction. The full-core model development was a complex task due to the large number of subassemblies and the axial subassembly heterogeneity. In ERANOS-2.2, it was necessary to homogenize axially per region the pellets used to form the subassembly. The self-shielded macroscopic cross-sections were calculated using the cell code ECCO in association with JEFF-3.1 and ENDF/B-VI.8 data libraries. The core calculations were performed with broad cross-sections data in 33 neutron energy groups with the solver AVNM in the

  8. The Effect of Cooperative Learning Approach Based on Conceptual Change Condition on Students' Understanding of Chemical Equilibrium Concepts

    ERIC Educational Resources Information Center

    Bilgin, Ibrahim; Geban, Omer

    2006-01-01

    The purpose of this study is to investigate the effects of the cooperative learning approach based on conceptual change conditions over traditional instruction on 10th grade students' conceptual understanding and achievement of computational problems related to chemical equilibrium concepts. The subjects of this study consisted of 87 tenth grade…

  9. Binary mixtures of rod-like colloids under shear: microscopically-based equilibrium theory and order-parameter dynamics.

    PubMed

    Lugo-Frías, Rodrigo; Klapp, Sabine H L

    2016-06-22

    This paper is concerned with the dynamics of a binary mixture of rod-like, repulsive colloidal particles driven out of equilibrium by means of a steady shear flow (Couette geometry). To this end we first derive, starting from a microscopic density functional in Parsons-Lee approximation, a mesoscopic free energy functional whose main variables are the orientational order parameter tensors. Based on this mesoscopic functional we then explore the stability of isotropic and nematic equilibrium phases in terms of composition and rod lengths. Second, by combining the equilibrium theory with the Doi-Hess approach for the order parameter dynamics under shear, we investigate the orientational dynamics of binary mixtures for a range of shear rates and coupling parameters. We find a variety of dynamical states, including synchronized oscillatory states of the two components, but also symmetry breaking behavior where the components display different in-plane oscillatory states.

  10. Binary mixtures of rod-like colloids under shear: microscopically-based equilibrium theory and order-parameter dynamics.

    PubMed

    Lugo-Frías, Rodrigo; Klapp, Sabine H L

    2016-06-22

    This paper is concerned with the dynamics of a binary mixture of rod-like, repulsive colloidal particles driven out of equilibrium by means of a steady shear flow (Couette geometry). To this end we first derive, starting from a microscopic density functional in Parsons-Lee approximation, a mesoscopic free energy functional whose main variables are the orientational order parameter tensors. Based on this mesoscopic functional we then explore the stability of isotropic and nematic equilibrium phases in terms of composition and rod lengths. Second, by combining the equilibrium theory with the Doi-Hess approach for the order parameter dynamics under shear, we investigate the orientational dynamics of binary mixtures for a range of shear rates and coupling parameters. We find a variety of dynamical states, including synchronized oscillatory states of the two components, but also symmetry breaking behavior where the components display different in-plane oscillatory states. PMID:27115342

  11. Binary mixtures of rod-like colloids under shear: microscopically-based equilibrium theory and order-parameter dynamics

    NASA Astrophysics Data System (ADS)

    Lugo-Frías, Rodrigo; Klapp, Sabine H. L.

    2016-06-01

    This paper is concerned with the dynamics of a binary mixture of rod-like, repulsive colloidal particles driven out of equilibrium by means of a steady shear flow (Couette geometry). To this end we first derive, starting from a microscopic density functional in Parsons-Lee approximation, a mesoscopic free energy functional whose main variables are the orientational order parameter tensors. Based on this mesoscopic functional we then explore the stability of isotropic and nematic equilibrium phases in terms of composition and rod lengths. Second, by combining the equilibrium theory with the Doi-Hess approach for the order parameter dynamics under shear, we investigate the orientational dynamics of binary mixtures for a range of shear rates and coupling parameters. We find a variety of dynamical states, including synchronized oscillatory states of the two components, but also symmetry breaking behavior where the components display different in-plane oscillatory states.

  12. Community-Based Global Health Program for Maltreated Children and Adolescents in Brazil: The Equilibrium Program

    PubMed Central

    Marques, Andrea Horvath; Oliveira, Paula Approbato; Scomparini, Luciana Burim; Silva, Uiara Maria Rêgo e; Silva, Angelica Cristine; Doretto, Victoria; de Medeiros Filho, Mauro Victor; Scivoletto, Sandra

    2015-01-01

    The maltreatment of children and adolescents is a global public health problem that affects high- and low-middle income countries (“LMICs”). In the United States, around 1.2 million children suffer from abuse, while in LMICs, such as Brazil, these rates are much higher (an estimated 28 million children). Exposition to early environmental stress has been associated with suboptimal physical and brain development, persistent cognitive impairment, and behavioral problems. Studies have reported that children exposed to maltreatment are at high risk of behavioral problems, learning disabilities, communication and psychiatric disorders, and general clinical conditions, such as obesity and systemic inflammation later in life. The aim of this paper is to describe The Equilibrium Program (“TEP”), a community-based global health program implemented in São Paulo, Brazil to serve traumatized and neglected children and adolescents. We will describe and discuss TEP’s implementation, highlighting its innovation aspects, research projects developed within the program as well as its population profile. Finally, we will discuss TEP’s social impact, challenges, and limitations. The program’s goal is to promote the social and family reintegration of maltreated children and adolescents through an interdisciplinary intervention program that provides multi-dimensional bio-psycho-social treatment integrated with the diverse services needed to meet the unique demands of this population. The program’s cost effectiveness is being evaluated to support the development of more effective treatments and to expand similar programs in other areas of Brazil. Policy makers should encourage early evidence-based interventions for disadvantaged children to promote healthier psychosocial environments and provide them opportunities to become healthy and productive adults. This approach has already shown itself to be a cost-effective strategy to prevent disease and promote health. PMID

  13. Community-Based Global Health Program for Maltreated Children and Adolescents in Brazil: The Equilibrium Program.

    PubMed

    Marques, Andrea Horvath; Oliveira, Paula Approbato; Scomparini, Luciana Burim; Silva, Uiara Maria Rêgo E; Silva, Angelica Cristine; Doretto, Victoria; de Medeiros Filho, Mauro Victor; Scivoletto, Sandra

    2015-01-01

    The maltreatment of children and adolescents is a global public health problem that affects high- and low-middle income countries ("LMICs"). In the United States, around 1.2 million children suffer from abuse, while in LMICs, such as Brazil, these rates are much higher (an estimated 28 million children). Exposition to early environmental stress has been associated with suboptimal physical and brain development, persistent cognitive impairment, and behavioral problems. Studies have reported that children exposed to maltreatment are at high risk of behavioral problems, learning disabilities, communication and psychiatric disorders, and general clinical conditions, such as obesity and systemic inflammation later in life. The aim of this paper is to describe The Equilibrium Program ("TEP"), a community-based global health program implemented in São Paulo, Brazil to serve traumatized and neglected children and adolescents. We will describe and discuss TEP's implementation, highlighting its innovation aspects, research projects developed within the program as well as its population profile. Finally, we will discuss TEP's social impact, challenges, and limitations. The program's goal is to promote the social and family reintegration of maltreated children and adolescents through an interdisciplinary intervention program that provides multi-dimensional bio-psycho-social treatment integrated with the diverse services needed to meet the unique demands of this population. The program's cost effectiveness is being evaluated to support the development of more effective treatments and to expand similar programs in other areas of Brazil. Policy makers should encourage early evidence-based interventions for disadvantaged children to promote healthier psychosocial environments and provide them opportunities to become healthy and productive adults. This approach has already shown itself to be a cost-effective strategy to prevent disease and promote health.

  14. Entropy-based artificial viscosity stabilization for non-equilibrium Grey Radiation-Hydrodynamics

    SciTech Connect

    Delchini, Marc O. Ragusa, Jean C. Morel, Jim

    2015-09-01

    The entropy viscosity method is extended to the non-equilibrium Grey Radiation-Hydrodynamic equations. The method employs a viscous regularization to stabilize the numerical solution. The artificial viscosity coefficient is modulated by the entropy production and peaks at shock locations. The added dissipative terms are consistent with the entropy minimum principle. A new functional form of the entropy residual, suitable for the Radiation-Hydrodynamic equations, is derived. We demonstrate that the viscous regularization preserves the equilibrium diffusion limit. The equations are discretized with a standard Continuous Galerkin Finite Element Method and a fully implicit temporal integrator within the MOOSE multiphysics framework. The method of manufactured solutions is employed to demonstrate second-order accuracy in both the equilibrium diffusion and streaming limits. Several typical 1-D radiation-hydrodynamic test cases with shocks (from Mach 1.05 to Mach 50) are presented to establish the ability of the technique to capture and resolve shocks.

  15. Effect of Non-Equilibrium Surface Thermochemistry in Simulation of Carbon Based Ablators

    NASA Technical Reports Server (NTRS)

    Chen, Yih-Kanq; Gokcen, Tahir

    2012-01-01

    This study demonstrates that coupling of a material thermal response code and a flow solver using non-equilibrium gas/surface interaction model provides time-accurate solutions for the multidimensional ablation of carbon based charring ablators. The material thermal response code used in this study is the Two-dimensional Implicit Thermal-response and AblatioN Program (TITAN), which predicts charring material thermal response and shape change on hypersonic space vehicles. Its governing equations include total energy balance, pyrolysis gas mass conservation, and a three-component decomposition model. The flow code solves the reacting Navier-Stokes equations using Data Parallel Line Relaxation (DPLR) method. Loose coupling between the material response and flow codes is performed by solving the surface mass balance in DPLR and the surface energy balance in TITAN. Thus, the material surface recession is predicted by finite-rate gas/surface interaction boundary conditions implemented in DPLR, and the surface temperature and pyrolysis gas injection rate are computed in TITAN. Two sets of nonequilibrium gas/surface interaction chemistry between air and the carbon surface developed by Park and Zhluktov, respectively, are studied. Coupled fluid-material response analyses of stagnation tests conducted in NASA Ames Research Center arc-jet facilities are considered. The ablating material used in these arc-jet tests was Phenolic Impregnated Carbon Ablator (PICA). Computational predictions of in-depth material thermal response and surface recession are compared with the experimental measurements for stagnation cold wall heat flux ranging from 107 to 1100 Watts per square centimeter.

  16. PC-based package for interactive assessment of MHD equilibrium and poloidal field coil design in axisymmetric toroidal geometry

    SciTech Connect

    Kelleher, W.P.

    1987-01-01

    In the assessment of Magnetohydrodynamic (MHD) equilibrium and Poloidal Field Coil (PFC) arrangement for toroidal axisymmetric geometry, the Grad-Shafranov equation must be solved, either analytically or numerically. Existing numerical tools have been developed primarily for mainframe usage and can prove cumbersome for screening assessments and parametric evaluations. The objective of this thesis was to develop a personal computer (PC)-based calculational tool for assessing MHD/PFC problems in a highly interactive mode, well suited for scoping studies. The approach adopted involves a two-step process: first the MHD equilibrium is calculated and then the PFC arrangement, consistent with the equilibrium, is determined in an interactive design environment. The PC-based system developed consists of two programs: (1) PCEQ, which solve the MHD equilibrium problem and (2) PFDE-SIGN, which is employed to arrive at a PFC arrangement. PCEQ provides an output file including, but not limited to, the following: poloidal beta, total beta, safety factors, q, on axis and on edge. PCEQ plots the following contours and/or profiles: flux, pressure and toroidal current density, safety factor, and ratio of plasma toroidal field to vacuum field.

  17. Heuristic-based energy landscape paving for the circular packing problem with performance constraints of equilibrium

    NASA Astrophysics Data System (ADS)

    Liu, Jingfa; Jiang, Yucong; Li, Gang; Xue, Yu; Liu, Zhaoxia; Zhang, Zhen

    2015-08-01

    The optimal layout problem of circle group in a circular container with performance constraints of equilibrium belongs to a class of NP-hard problem. The key obstacle of solving this problem is the lack of an effective global optimization method. We convert the circular packing problem with performance constraints of equilibrium into the unconstrained optimization problem by using quasi-physical strategy and penalty function method. By putting forward a new updating mechanism of the histogram function in energy landscape paving (ELP) method and incorporating heuristic conformation update strategies into the ELP method, we obtain an improved ELP (IELP) method. Subsequently, by combining the IELP method and the local search (LS) procedure, we put forward a hybrid algorithm, denoted by IELP-LS, for the circular packing problem with performance constraints of equilibrium. We test three sets of benchmarks consisting of 21 representative instances from the current literature. The proposed algorithm breaks the records of all 10 instances in the first set, and achieves the same or even better results than other methods in literature for 10 out of 11 instances in the second and third sets. The computational results show that the proposed algorithm is an effective method for solving the circular packing problem with performance constraints of equilibrium.

  18. Atomistic-level non-equilibrium model for chemically reactive systems based on steepest-entropy-ascent quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Li, Guanchen; Al-Abbasi, Omar; von Spakovsky, Michael R.

    2014-10-01

    This paper outlines an atomistic-level framework for modeling the non-equilibrium behavior of chemically reactive systems. The framework called steepest- entropy-ascent quantum thermodynamics (SEA-QT) is based on the paradigm of intrinsic quantum thermodynamic (IQT), which is a theory that unifies quantum mechanics and thermodynamics into a single discipline with wide applications to the study of non-equilibrium phenomena at the atomistic level. SEA-QT is a novel approach for describing the state of chemically reactive systems as well as the kinetic and dynamic features of the reaction process without any assumptions of near-equilibrium states or weak-interactions with a reservoir or bath. Entropy generation is the basis of the dissipation which takes place internal to the system and is, thus, the driving force of the chemical reaction(s). The SEA-QT non-equilibrium model is able to provide detailed information during the reaction process, providing a picture of the changes occurring in key thermodynamic properties (e.g., the instantaneous species concentrations, entropy and entropy generation, reaction coordinate, chemical affinities, reaction rate, etc). As an illustration, the SEA-QT framework is applied to an atomistic-level chemically reactive system governed by the reaction mechanism F + H2 leftrightarrow FH + H.

  19. Non-equilibrium behaviour in coacervate-based protocells under electric-field-induced excitation

    NASA Astrophysics Data System (ADS)

    Yin, Yudan; Niu, Lin; Zhu, Xiaocui; Zhao, Meiping; Zhang, Zexin; Mann, Stephen; Liang, Dehai

    2016-02-01

    Although numerous strategies are now available to generate rudimentary forms of synthetic cell-like entities, minimal progress has been made in the sustained excitation of artificial protocells under non-equilibrium conditions. Here we demonstrate that the electric field energization of coacervate microdroplets comprising polylysine and short single strands of DNA generates membrane-free protocells with complex, dynamical behaviours. By confining the droplets within a microfluidic channel and applying a range of electric field strengths, we produce protocells that exhibit repetitive cycles of vacuolarization, dynamical fluctuations in size and shape, chaotic growth and fusion, spontaneous ejection and sequestration of matter, directional capture of solute molecules, and pulsed enhancement of enzyme cascade reactions. Our results highlight new opportunities for the study of non-equilibrium phenomena in synthetic protocells, provide a strategy for inducing complex behaviour in electrostatically assembled soft matter microsystems and illustrate how dynamical properties can be activated and sustained in microcompartmentalized media.

  20. Non-equilibrium behaviour in coacervate-based protocells under electric-field-induced excitation

    PubMed Central

    Yin, Yudan; Niu, Lin; Zhu, Xiaocui; Zhao, Meiping; Zhang, Zexin; Mann, Stephen; Liang, Dehai

    2016-01-01

    Although numerous strategies are now available to generate rudimentary forms of synthetic cell-like entities, minimal progress has been made in the sustained excitation of artificial protocells under non-equilibrium conditions. Here we demonstrate that the electric field energization of coacervate microdroplets comprising polylysine and short single strands of DNA generates membrane-free protocells with complex, dynamical behaviours. By confining the droplets within a microfluidic channel and applying a range of electric field strengths, we produce protocells that exhibit repetitive cycles of vacuolarization, dynamical fluctuations in size and shape, chaotic growth and fusion, spontaneous ejection and sequestration of matter, directional capture of solute molecules, and pulsed enhancement of enzyme cascade reactions. Our results highlight new opportunities for the study of non-equilibrium phenomena in synthetic protocells, provide a strategy for inducing complex behaviour in electrostatically assembled soft matter microsystems and illustrate how dynamical properties can be activated and sustained in microcompartmentalized media. PMID:26876162

  1. Non-equilibrium behaviour in coacervate-based protocells under electric-field-induced excitation.

    PubMed

    Yin, Yudan; Niu, Lin; Zhu, Xiaocui; Zhao, Meiping; Zhang, Zexin; Mann, Stephen; Liang, Dehai

    2016-02-15

    Although numerous strategies are now available to generate rudimentary forms of synthetic cell-like entities, minimal progress has been made in the sustained excitation of artificial protocells under non-equilibrium conditions. Here we demonstrate that the electric field energization of coacervate microdroplets comprising polylysine and short single strands of DNA generates membrane-free protocells with complex, dynamical behaviours. By confining the droplets within a microfluidic channel and applying a range of electric field strengths, we produce protocells that exhibit repetitive cycles of vacuolarization, dynamical fluctuations in size and shape, chaotic growth and fusion, spontaneous ejection and sequestration of matter, directional capture of solute molecules, and pulsed enhancement of enzyme cascade reactions. Our results highlight new opportunities for the study of non-equilibrium phenomena in synthetic protocells, provide a strategy for inducing complex behaviour in electrostatically assembled soft matter microsystems and illustrate how dynamical properties can be activated and sustained in microcompartmentalized media.

  2. Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies.

    PubMed

    Hameed, B H; Din, A T M; Ahmad, A L

    2007-03-22

    Bamboo, an abundant and inexpensive natural resource in Malaysia was used to prepare activated carbon by physiochemical activation with potassium hydroxide (KOH) and carbon dioxide (CO(2)) as the activating agents at 850 degrees C for 2h. The adsorption equilibrium and kinetics of methylene blue dye on such carbon were then examined at 30 degrees C. Adsorption isotherm of the methylene blue (MB) on the activated carbon was determined and correlated with common isotherm equations. The equilibrium data for methylene blue adsorption well fitted to the Langmuir equation, with maximum monolayer adsorption capacity of 454.2mg/g. Two simplified kinetic models including pseudo-first-order and pseudo-second-order equation were selected to follow the adsorption processes. The adsorption of methylene blue could be best described by the pseudo-second-order equation. The kinetic parameters of this best-fit model were calculated and discussed.

  3. Equilibrium characteristics of tartrate and EDTA-based electroless copper deposition baths

    SciTech Connect

    Ramasubramanian, M.; Popov, B.N.; White, R.E.; Chen, K.S.

    1997-08-01

    Electroless deposition of copper is being used for a variety of applications, one of them being the development of seed metallic layers on non-metals, which are widely used in electronic circuitry. Solution equilibrium characteristics of two electroless copper baths containing EDTA and tartrate as the complexing agents were studied as functions of pH, chelating agent and metal ion concentrations. Equilibrium diagrams were constructed for both cu-tartrate and Cu-EDTA systems. It was determined that copper is chiefly complexed as Cu(OH){sub 2}L{sub 2}{sup {minus}4} in the tartrate bath, and as CuA{sup {minus}2} in the EDTA bath, where L and A are the complexing tartrate and EDTA ligands, respectively. The operating ranges for electroless copper deposition were identified for both baths. Dependence of Cu(OH){sub 2} precipitation on the pH and species concentrations was also studied for these systems.

  4. Activity Enhancement Based on the Chemical Equilibrium of Multiple-Subunit Nitrile Hydratase from Bordetella petrii.

    PubMed

    Liu, Yi; Liu, Ping; Lin, Lu; Zhao, Yueqin; Zhong, Wenjuan; Wu, Lunjie; Zhou, Zhemin; Sun, Weifeng

    2016-09-01

    The maturation mechanism of nitrile hydratase (NHase) of Pseudomonas putida NRRL-18668 was discovered and named as "self-subunit swapping." Since the NHase of Bordetella petrii DSM 12804 is similar to that of P. putida, the NHase maturation of B. petrii is proposed to be the same as that of P. putida. However, there is no further information on the application of NHase according to these findings. We successfully rapidly purified NHase and its activator through affinity his tag, and found that the cell extracts of NHase possessed multiple types of protein ingredients including α, β, α2β2, and α(P14K)2 who were in a state of chemical equilibrium. Furthermore, the activity was significantly enhanced through adding extra α(P14K)2 to the cell extracts of NHase according to the chemical equilibrium. Our findings are useful for the activity enhancement of multiple-subunit enzyme and for the first time significantly increased the NHase activity according to the chemical equilibrium.

  5. Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Pauly, S.; Tang, M. Q.; Eckert, J.; Zhang, H. F.

    2016-01-01

    The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated.

  6. Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites

    PubMed Central

    Zhang, L.; Pauly, S.; Tang, M. Q.; Eckert, J.; Zhang, H. F.

    2016-01-01

    The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated. PMID:26754315

  7. Reconciling kinetic and equilibrium observations of iron(III) solubility in aqueous solutions with a polymer-based model

    NASA Astrophysics Data System (ADS)

    Rose, Andrew L.; David Waite, T.

    2007-12-01

    Due to hydrolysis reactions, iron(III) forms oxyhydroxide precipitates in natural waters that minimise its availability to living organisms. Thermodynamic studies have established equilibrium concentrations of dissolved iron at various pH values, however these studies offer no insight into the kinetics of iron(III) polymerisation and subsequent precipitation. In recent work, the kinetics of iron(III) precipitation and dissolution of the precipitate have been investigated, but there are apparent discrepancies between the equilibrium solubility of iron(III) calculated from the kinetic parameters and its solubility measured by separation of the solid and dissolved phases at equilibrium. In this work, we reconcile kinetic and thermodynamic measurements using a polymer-based mechanistic model of the processes responsible for iron(III) precipitation in aqueous solutions based on a variety of previously published experimental data. This model is used to explain the existence of a solubility limit, including the effect of precipitate ageing on its solubility. We suggest that the model provides a unified approach for examining aqueous systems containing dissolved, solid-phase and surface species.

  8. Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites.

    PubMed

    Zhang, L; Pauly, S; Tang, M Q; Eckert, J; Zhang, H F

    2016-01-12

    The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated.

  9. Linear two-step gradient counter-current chromatography analysis based on a recursive solution of an equilibrium stage model.

    PubMed

    Beltscheva, Daria; Hugo, Peter; Seidel-Morgenstern, Andreas

    2003-03-01

    The implementation of gradients in continuously operated chromatographic counter-current processes has recently attracted considerable interest as a method to improve the performance of this effective separation method. If liquid mobile phases are applied it is advantageous to set the solvent strength in the desorbent stream higher than that in the feed stream. As a consequence. the components to be separated are more retained in the adsorption zones and more easily eluted in the desorption zones. Due to the additional degrees of freedom the design and the optimization of such a two-step gradient counter-current process is difficult. In this paper a steady state equilibrium stage model is used to simulate the process under linear conditions. A simple solution of the underlying model equations is presented capable to describe efficiently the unit for large stage numbers typically encountered in chromatographic columns. Due to the rapidity of the algorithm developed a broad range of operating conditions can be evaluated systematically for different types of gradients. The impact of (a) the functional dependence of the adsorption equilibrium constants on the solvent composition, (b) the number of equilibrium stages and (c) the specification of purity requirements is illustrated and discussed based on results of parametric calculations. The results achieved emphasize the potential of two-step gradient counter-current chromatography. PMID:12641280

  10. Equilibrium population dynamics when mating is by mutual choice based on age.

    PubMed

    Alpern, Steve; Katrantzi, Ioanna; Ramsey, David

    2014-06-01

    We consider a steady state model of mutual mate choice in which an individual's mate preferences depend on his/her age, and the preferences are over the ages of prospective mates of the opposite sex. We present a discrete time (and age) model corresponding to successive mating seasons. Males are fertile for m periods (corresponding to 'age' i=1 to m) and females for n≤m periods (they have ages j=1 to n), which is all that distinguishes the sexes. Although we can deal with arbitrary preferences, we concentrate on a simple fertility model where the common utility to a male age i and female age j who mate is the number K=min(m-i+1,n-j+1) of future periods of joint fertility. The incoming sex ratio R of age 1 males to age 1 females is given exogenously. In each period individuals are randomly (non assortatively) matched and form a mated couple by mutual consent; otherwise they go into the next period unmated and older. We derive properties of equilibrium threshold acceptance strategies and establish the existence of time-invariant age distributions. Our methods determine the age distribution of couples at marriage (mating) and the population sex ratio (OSR) at equilibrium. Since this can be determined empirically in a population, our model can be used to rule out most systems of age preferences (those not consistent with the observed distribution). This extends earlier models of mutual choice with one dimensional types of Alpern and Reyniers [1999. Strategic mating with homotypic preferences. J. Theor. Biol. 198, 71-88; 2005. Strategic mating with common preferences. J. Theor. Biol. 237, 337-354] where individuals sought, respectively, individuals with similar or high types, but in those models an individual's type was fixed over time. Under the simple fertility model, at equilibrium the maximum age of an acceptable partner is increasing in the age of the searcher. Our results relate to discussions in the literature regarding optimal parental age differences, age

  11. Equilibrium population dynamics when mating is by mutual choice based on age.

    PubMed

    Alpern, Steve; Katrantzi, Ioanna; Ramsey, David

    2014-06-01

    We consider a steady state model of mutual mate choice in which an individual's mate preferences depend on his/her age, and the preferences are over the ages of prospective mates of the opposite sex. We present a discrete time (and age) model corresponding to successive mating seasons. Males are fertile for m periods (corresponding to 'age' i=1 to m) and females for n≤m periods (they have ages j=1 to n), which is all that distinguishes the sexes. Although we can deal with arbitrary preferences, we concentrate on a simple fertility model where the common utility to a male age i and female age j who mate is the number K=min(m-i+1,n-j+1) of future periods of joint fertility. The incoming sex ratio R of age 1 males to age 1 females is given exogenously. In each period individuals are randomly (non assortatively) matched and form a mated couple by mutual consent; otherwise they go into the next period unmated and older. We derive properties of equilibrium threshold acceptance strategies and establish the existence of time-invariant age distributions. Our methods determine the age distribution of couples at marriage (mating) and the population sex ratio (OSR) at equilibrium. Since this can be determined empirically in a population, our model can be used to rule out most systems of age preferences (those not consistent with the observed distribution). This extends earlier models of mutual choice with one dimensional types of Alpern and Reyniers [1999. Strategic mating with homotypic preferences. J. Theor. Biol. 198, 71-88; 2005. Strategic mating with common preferences. J. Theor. Biol. 237, 337-354] where individuals sought, respectively, individuals with similar or high types, but in those models an individual's type was fixed over time. Under the simple fertility model, at equilibrium the maximum age of an acceptable partner is increasing in the age of the searcher. Our results relate to discussions in the literature regarding optimal parental age differences, age

  12. Lignin-based activated carbons for adsorption of sodium dodecylbenzene sulfonate: Equilibrium and kinetic studies.

    PubMed

    Cotoruelo, Luis M; Marqués, María D; Rodríguez-Mirasol, José; Rodríguez, Juan J; Cordero, Tomás

    2009-04-01

    The adsorption of sodium dodecylbenzene sulfonate (SDBS) from its aqueous solution at different temperatures has been studied using three activated carbons prepared in our laboratory. Lignin was used as raw material for the preparation of activated carbons (ACs). The results of the adsorption equilibrium were analyzed and fitted to the Langmuir model. Thermodynamic magnitudes were estimated as well, and their values indicated that the adsorption processes were spontaneous and exothermic. The kinetic study showed that the processes are of second apparent order related to the concentration of the vacant active centers on the surface of the activated carbons. The values of the effective internal diffusion coefficients have been calculated applying the equations developed by Crank and Vermeulen.

  13. Effect of Acid-Base Equilibrium on Absorption Spectra of Humic acid in the Presence of Copper Ions

    NASA Astrophysics Data System (ADS)

    Lavrik, N. L.; Mulloev, N. U.

    2014-03-01

    The reaction between humic acid (HA, sample IHSS) and a metal ion (Cu2+) that was manifested as absorption bands in the range 210-350 nm was recorded using absorption spectroscopy. The reaction was found to be more effective as the pH increased. These data were interpreted in the framework of generally accepted concepts about the influence of acid-base equilibrium on the dissociation of salts, according to which increasing the solution pH increases the concentration of HA anions. It was suggested that [HA-Cu2+] complexes formed.

  14. Speciation and equilibrium relations of soluble aluminum in a headwater stream at base flow and during rain events

    USGS Publications Warehouse

    Burns, Douglas A.

    1989-01-01

    In the Shenandoah National Park, Virginia, the short-term dynamics of soluble aluminum in stream water sampled during rain events differed significantly from stream water sampled during base flow conditions. Three fractions of dissolved aluminum were measured. The inorganic monomeric fraction made up approximately two thirds of the total reactive aluminum at base flow, followed by the acid-soluble and organic monomeric fractions, respectively. Equilibrium modeling showed that hydroxide complexes were the most abundant form of inorganic monomeric aluminum followed by fluoride, free aluminum ion, and sulfate. The activity of inorganic monomeric aluminum at base flow appears to be in equilibrium with an Al(OH)3 phase with solubility intermediate between microcrystalline gibbsite and natural gibbsite. During two rain events, the concentration of all three aluminum fractions increased significantly. The primary cause of the transient increase in the Al(OH)3 saturation index appears to have been the neutralization of excess H+ added by soil water through reaction with stream water HCO3- at a more rapid rate than excess inorganic monomeric aluminum could be removed from solution by hydroxide mineral precipitation. -from Author

  15. Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS

    NASA Astrophysics Data System (ADS)

    Gualda, G. A.; Ghiorso, M. S.; Begue, F.; Pamukcu, A. S.; Gravley, D. M.

    2013-12-01

    Constraining the pressure of crystallization of magmas is an important but elusive task. We propose here a method to derive crystallization pressures for rocks that preserve glass compositions (either glass inclusions or matrix glass) representative of equilibration between melt, quartz, and 1 or 2 feldspars. The method relies on the shift of the quartz-feldspar saturation surface towards higher silica with decreasing pressure. The critical realization is that melt, quartz and feldspars need to be in equilibrium at the liquidus for the melt composition of interest. Thus, this method consists of calculating the saturation surfaces for quartz and feldspars using rhyolite-MELTS over a range of pressures, and searching for the pressure at which the expected assemblage (quartz+1 feldspar or quartz+2 feldspars) is found at the liquidus. We evaluate errors resulting from uncertainties in glass composition using Monte Carlo simulations, which reveal errors of ~20-45 MPa for the quartz+2 feldspars constraint and of ~25-100 MPa for the quartz+1 feldspar constraint; actual errors are likely closer to the lower bounds of these ranges. We demonstrate that the effect of fluid-saturation is more important at higher pressures (~300 MPa) than at lower pressures (~100 MPa), but reasonable pressure estimates can be derived irrespective of fluid saturation for geologically relevant H2O concentrations (>3 wt. %). And, we show that pressures calculated using the rhyolite-MELTS geobarometer compare well with those resulting from H2O-CO2 glass inclusion barometry and Al-in-hornblende barometry for an array of natural systems for which data has been compiled from the literature. We apply the rhyolite-MELTS barometer to three systems we are currently studying in detail: (1) For the Bishop Tuff (CA, USA), we find that quartz-hosted glass inclusion compositions yield indistinguishable crystallization pressures for early-erupted and late-erupted pumice, consistent with the Bishop Tuff having

  16. Development of an identification method of pressure anisotropy based on equilibrium analysis and magnetics

    SciTech Connect

    Asahi, Y.; Suzuki, Y.; Watanabe, K. Y.; Cooper, W. A.

    2013-02-15

    We evaluate the fluxes measured by the magnetic flux loops installed in LHD by using a three dimensional MHD equilibrium analysis code, ANIMEC, which enable us to directly determine the calibration function between the anisotropic pressure and the measured fluxes for the non-axisymmetric plasmas for the first time. The result indicates that the diamagnetic flux represents a nearly single-valued function of the beta perpendicular with respect to the field, and the saddle loop flux represents a nearly single-valued function of an equally weighted average of the beta values parallel and perpendicular to the field, regardless of the pressure anisotropy or the amount of energetic trapped particles. The values of the beta perpendicular to the field and the equal weighting averaged beta estimated by the single-valued functions (calibration functions) are investigated in order to clarify the magnitude of deviation from those original values, and the range of anisotropy where the beta value evaluated by the magnetic flux measurement is calculated within a 10% error.

  17. Effect of water content on the acid-base equilibrium of cyanidin-3-glucoside.

    PubMed

    Coutinho, Isabel B; Freitas, Adilson; Maçanita, António L; Lima, J C

    2015-04-01

    Laser Flash Photolysis was employed to measure the deprotonation and reprotonation rate constants of cyanidin 3-monoglucoside (kuromanin) in water/methanol mixtures. It was found that the deprotonation rate constant kd decreases with decreasing water content, reflecting the lack of free water molecules around kuromanin, which may accommodate and stabilize the outgoing protons. On the other hand, the reprotonation rate constant, kp, increases with the decrease in water concentration from a value of kp = 2 × 10(10) l mol(-1) s(-1) in water up to kp = 6 × 10(10) l mol(-1) s(-1) at 5.6M water concentration in the mixture. The higher value of kp at lower water concentrations reflects the fact that the proton is not freely escaping the solvation shell of the molecule. The deprotonation rate constant decreases with decreasing water content, reflecting the lack of free water molecules around kuromanin that can accommodate the outgoing protons. Overall, the acidity constant of the flavylium cation decreases with the decrease in water concentration from pKa values of 3.8 in water to approximately 4.8 in water-depleted media, thus shifting the equilibrium towards the red-coloured form, AH(+), at low water contents. The presence, or lack, of water, will affect the colour shade (red to blue) of kuromanin. This is relevant for its role as an intrinsic food component and as a food pigment additive (E163). PMID:25442581

  18. Effect of water content on the acid-base equilibrium of cyanidin-3-glucoside.

    PubMed

    Coutinho, Isabel B; Freitas, Adilson; Maçanita, António L; Lima, J C

    2015-04-01

    Laser Flash Photolysis was employed to measure the deprotonation and reprotonation rate constants of cyanidin 3-monoglucoside (kuromanin) in water/methanol mixtures. It was found that the deprotonation rate constant kd decreases with decreasing water content, reflecting the lack of free water molecules around kuromanin, which may accommodate and stabilize the outgoing protons. On the other hand, the reprotonation rate constant, kp, increases with the decrease in water concentration from a value of kp = 2 × 10(10) l mol(-1) s(-1) in water up to kp = 6 × 10(10) l mol(-1) s(-1) at 5.6M water concentration in the mixture. The higher value of kp at lower water concentrations reflects the fact that the proton is not freely escaping the solvation shell of the molecule. The deprotonation rate constant decreases with decreasing water content, reflecting the lack of free water molecules around kuromanin that can accommodate the outgoing protons. Overall, the acidity constant of the flavylium cation decreases with the decrease in water concentration from pKa values of 3.8 in water to approximately 4.8 in water-depleted media, thus shifting the equilibrium towards the red-coloured form, AH(+), at low water contents. The presence, or lack, of water, will affect the colour shade (red to blue) of kuromanin. This is relevant for its role as an intrinsic food component and as a food pigment additive (E163).

  19. Comparative analysis of quantum cascade laser modeling based on density matrices and non-equilibrium Green's functions

    SciTech Connect

    Lindskog, M. Wacker, A.; Wolf, J. M.; Liverini, V.; Faist, J.; Trinite, V.; Maisons, G.; Carras, M.; Aidam, R.; Ostendorf, R.

    2014-09-08

    We study the operation of an 8.5 μm quantum cascade laser based on GaInAs/AlInAs lattice matched to InP using three different simulation models based on density matrix (DM) and non-equilibrium Green's function (NEGF) formulations. The latter advanced scheme serves as a validation for the simpler DM schemes and, at the same time, provides additional insight, such as the temperatures of the sub-band carrier distributions. We find that for the particular quantum cascade laser studied here, the behavior is well described by simple quantum mechanical estimates based on Fermi's golden rule. As a consequence, the DM model, which includes second order currents, agrees well with the NEGF results. Both these simulations are in accordance with previously reported data and a second regrown device.

  20. Nonideal equilibrium dissolution of trichloroethene from a decane-based nonaqueous phase liquid mixture: Experimental and modeling investigation

    NASA Astrophysics Data System (ADS)

    McCray, John E.; Dugan, Pamela J.

    2002-07-01

    Batch equilibrium solubility studies were conducted to examine the solubilization behavior of a chlorinated solvent, trichloroethene (TCE), from a fuel-based nonaqueous phase liquid (NAPL) mixture. An alkane (n-decane) was used as a model compound because it is often a primary compound in jet fuel. The NAPL phase mole fractions of the chlorinated solvent in the mixture (XTCEN) that were investigated are typical of in situ values found at industrial and military waste sites (0.0001 >= XTCEN <= 0.1). The measured aqueous concentrations of TCE were essentially equal to the concentrations predicted with ideal dissolution theory (Raoult's law) at XTCEN values near 0.1. However, the ratio of the measured concentration to the ideal concentration, or the NAPL phase activity coefficient (γNTCE), increased nonlinearly as the XTCEN decreased. The γTCEN approached 6 at XTCEN = 0.0001. The UNIFAC method greatly underpredicts the γTCEN in this surrogate fuel. A NAPL-mixture equilibrium-dissolution model was developed that incorporates the observed nonideal dissolution. This model indicates that nonideal NAPL dissolution is 4 times faster than ideal dissolution for a hypothetical NAPL mixture with an initial XTCEN = 0.001. The magnitude of this effect becomes more important as the initial value of the XTCEN is decreased.

  1. Comparative Analysis of the Flax Immune Receptors L6 and L7 Suggests an Equilibrium-Based Switch Activation Model.

    PubMed

    Bernoux, Maud; Burdett, Hayden; Williams, Simon J; Zhang, Xiaoxiao; Chen, Chunhong; Newell, Kim; Lawrence, Gregory J; Kobe, Bostjan; Ellis, Jeffrey G; Anderson, Peter A; Dodds, Peter N

    2016-01-01

    NOD-like receptors (NLRs) are central components of the plant immune system. L6 is a Toll/interleukin-1 receptor (TIR) domain-containing NLR from flax (Linum usitatissimum) conferring immunity to the flax rust fungus. Comparison of L6 to the weaker allele L7 identified two polymorphic regions in the TIR and the nucleotide binding (NB) domains that regulate both effector ligand-dependent and -independent cell death signaling as well as nucleotide binding to the receptor. This suggests that a negative functional interaction between the TIR and NB domains holds L7 in an inactive/ADP-bound state more tightly than L6, hence decreasing its capacity to adopt the active/ATP-bound state and explaining its weaker activity in planta. L6 and L7 variants with a more stable ADP-bound state failed to bind to AvrL567 in yeast two-hybrid assays, while binding was detected to the signaling active variants. This contrasts with current models predicting that effectors bind to inactive receptors to trigger activation. Based on the correlation between nucleotide binding, effector interaction, and immune signaling properties of L6/L7 variants, we propose that NLRs exist in an equilibrium between ON and OFF states and that effector binding to the ON state stabilizes this conformation, thereby shifting the equilibrium toward the active form of the receptor to trigger defense signaling. PMID:26744216

  2. Acid-base equilibrium during capnoretroperitoneoscopic nephrectomy in patients with end-stage renal failure: a preliminary report.

    PubMed

    Demian, A D; Esmail, O M; Atallah, M M

    2000-04-01

    We have studied the acid-base equilibrium in 12 patients with end-stage renal failure (ESRF) during capnoretroperitoneoscopic nephrectomy. Bupivacaine (12 mL, 0.375%) and morphine (2mg) were given in the lumbar epidural space, and fentanyl (0.5 microg kg(-1)) and midazolam (50 microg kg(-1)) were given intravenously. Anaesthesia was induced by thiopental, maintained with halothane carried by oxygen enriched air (inspired oxygen fraction = 0.35), and ventilation was achieved with a tidal volume of 10 mL kg(-1) at a rate of 12 min(-1). This procedure resulted in a mild degree of respiratory acidosis that was cleared within 60 min. We conclude that capnoretroperitoneoscopic nephrectomy can be performed in patients with end-stage renal failure with minimal transient respiratory acidosis that can be avoided by increased ventilation.

  3. Acid-base equilibrium during capnoretroperitoneoscopic nephrectomy in patients with end-stage renal failure: a preliminary report.

    PubMed

    Demian, A D; Esmail, O M; Atallah, M M

    2000-04-01

    We have studied the acid-base equilibrium in 12 patients with end-stage renal failure (ESRF) during capnoretroperitoneoscopic nephrectomy. Bupivacaine (12 mL, 0.375%) and morphine (2mg) were given in the lumbar epidural space, and fentanyl (0.5 microg kg(-1)) and midazolam (50 microg kg(-1)) were given intravenously. Anaesthesia was induced by thiopental, maintained with halothane carried by oxygen enriched air (inspired oxygen fraction = 0.35), and ventilation was achieved with a tidal volume of 10 mL kg(-1) at a rate of 12 min(-1). This procedure resulted in a mild degree of respiratory acidosis that was cleared within 60 min. We conclude that capnoretroperitoneoscopic nephrectomy can be performed in patients with end-stage renal failure with minimal transient respiratory acidosis that can be avoided by increased ventilation. PMID:10866009

  4. Why and How To Teach Acid-Base Reactions without Equilibrium.

    ERIC Educational Resources Information Center

    Carlton, Terry S.

    1997-01-01

    Recommends an approach to the treatment of acid-base equilibria that involves treating each reaction as either going to completion or not occurring at all. Compares the method with the traditional approach step by step. (DDR)

  5. Mechanistic Sediment Quality Guidelines Based on Contaminant Bioavailability: Equilibrium Partitioning Sediment Benchmarks

    EPA Science Inventory

    Globally, billions of metric tons of contaminated sediments are present in aquatic systems representing a potentially significant ecological risk. Estimated costs to manage (i.e., remediate and monitor) these sediments are in the billions of U.S. dollars. Biologically-based app...

  6. Coordination properties of hydralazine Schiff base. Synthesis and equilibrium studies of some metal ion complexes

    NASA Astrophysics Data System (ADS)

    Shoukry, Azza A.; Shoukry, Mohamed M.

    2008-08-01

    In the present study, a new ligand is prepared by condensation of hydralazine (1-Hydralazinophthalazine) with 2-butanon-3-oxime. The acid-base equilibria of the schiff-base and the complex formation equilibria with the metal ions as Cu(II), Ni(II), Co(II), Cd(II), Mn(II) and Zn(II) are investigated potentiometrically. The stability constants of the complexes are determined and the concentration distribution diagrams of the complexes are evaluated. The effect of metal ion properties as atomic number, ionic radius, electronegativity and ionization potential are investigated. The isolated solid complexes are characterized by conventional chemical and physical methods. The potential coordination sites are assigned using the i.r. and 1H NMR spectra. The structures of the isolated solid complexes are proposed on the basis of the spectral and magnetic studies.

  7. Immunity by equilibrium.

    PubMed

    Eberl, Gérard

    2016-08-01

    The classical model of immunity posits that the immune system reacts to pathogens and injury and restores homeostasis. Indeed, a century of research has uncovered the means and mechanisms by which the immune system recognizes danger and regulates its own activity. However, this classical model does not fully explain complex phenomena, such as tolerance, allergy, the increased prevalence of inflammatory pathologies in industrialized nations and immunity to multiple infections. In this Essay, I propose a model of immunity that is based on equilibrium, in which the healthy immune system is always active and in a state of dynamic equilibrium between antagonistic types of response. This equilibrium is regulated both by the internal milieu and by the microbial environment. As a result, alteration of the internal milieu or microbial environment leads to immune disequilibrium, which determines tolerance, protective immunity and inflammatory pathology.

  8. Adair-based hemoglobin equilibrium with oxygen, carbon dioxide and hydrogen ion activity.

    PubMed

    Mateják, Marek; Kulhánek, Tomáš; Matoušek, Stanislav

    2015-04-01

    As has been known for over a century, oxygen binding onto hemoglobin is influenced by the activity of hydrogen ions (H⁺), as well as the concentration of carbon dioxide (CO₂). As is also known, the binding of both CO₂and H⁺ on terminal valine-1 residues is competitive. One-parametric situations of these hemoglobin equilibria at specific levels of H⁺, O₂or CO₂are also well described. However, we think interpolating or extrapolating this knowledge into an 'empirical' function of three independent variables has not yet been completely satisfactory. We present a model that integrates three orthogonal views of hemoglobin oxygenation, titration, and carbamination at different temperatures. The model is based only on chemical principles, Adair's oxygenation steps and Van't Hoff equation of temperature dependences. Our model fits the measurements of the Haldane coefficient and CO₂hemoglobin saturation. It also fits the oxygen dissociation curve influenced by simultaneous changes in H⁺, CO₂and O₂, which makes it a strong candidate for integration into more complex models of blood acid-base with gas transport, where any combination of mentioned substances can appear. PMID:25594800

  9. Adair-based hemoglobin equilibrium with oxygen, carbon dioxide and hydrogen ion activity.

    PubMed

    Mateják, Marek; Kulhánek, Tomáš; Matoušek, Stanislav

    2015-04-01

    As has been known for over a century, oxygen binding onto hemoglobin is influenced by the activity of hydrogen ions (H⁺), as well as the concentration of carbon dioxide (CO₂). As is also known, the binding of both CO₂and H⁺ on terminal valine-1 residues is competitive. One-parametric situations of these hemoglobin equilibria at specific levels of H⁺, O₂or CO₂are also well described. However, we think interpolating or extrapolating this knowledge into an 'empirical' function of three independent variables has not yet been completely satisfactory. We present a model that integrates three orthogonal views of hemoglobin oxygenation, titration, and carbamination at different temperatures. The model is based only on chemical principles, Adair's oxygenation steps and Van't Hoff equation of temperature dependences. Our model fits the measurements of the Haldane coefficient and CO₂hemoglobin saturation. It also fits the oxygen dissociation curve influenced by simultaneous changes in H⁺, CO₂and O₂, which makes it a strong candidate for integration into more complex models of blood acid-base with gas transport, where any combination of mentioned substances can appear.

  10. Chemical Equilibrium, Unit 4: Equilibria in Acid-Base Systems. A Computer-Enriched Module for Introductory Chemistry. Student's Guide and Teacher's Guide.

    ERIC Educational Resources Information Center

    Settle, Frank A., Jr.

    Presented are the teacher's guide and student materials for one of a series of self-instructional, computer-based learning modules for an introductory, undergraduate chemistry course. The student manual for this acid-base equilibria unit includes objectives, prerequisites, pretest, a discussion of equilibrium constants, and 20 problem sets.…

  11. Estimates of sustainable agricultural water use in northern China based on the equilibrium of groundwater

    NASA Astrophysics Data System (ADS)

    Yali, Y.; Yu, C.

    2015-12-01

    The northern plain is the important food production region in China. However, due to the lack of surface water resources, it needs overmuch exploitation of groundwater to maintain water use in agriculture, which leads to serious environmental problems. Based on the assumption that the reserves of groundwater matches the statistics and keeps on stable, the author explores the reasonable agricultural water and its spatial distribution based on the principle of sustainable utilization of water resources. According to the priorities of water resources allocation (domestic water and ecological water>industrial water>agricultural water), it is proposed to reduce agricultural water use to balance the groundwater reserves on condition that the total water supply is constant. Method: Firstly, we calculate annual average of northern groundwater reserves changes from 2004 to 2010, which is regarded as the reduction of agricultural water; Then, we estimate the food production changes using variables of typical crop water requirements and unit yields assuming that the efficiency of water use keeps the same during the entire study period; Finally, we evaluate the usage of sustainable agricultural water. The results reveal that there is a significant reduction of groundwater reserves in Haihe river basin and Xinjiang oasis regions; And the annual loss of the corn and wheat production is about 1.86 billion kg and 700 million kg respectively due to the reduction of agricultural water; What's more, in order to ensure China's food security and sustainable agricultural water use, in addition to great efforts to develop water-saving agriculture, an important adjustment in the distribution of food production is in need. This study provided a basis to the availability of agricultural water and a new perspective was put forth for an estimation of agricultural water.

  12. Prediction of the Chapman-Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics.

    PubMed

    Guo, Dezhou; Zybin, Sergey V; An, Qi; Goddard, William A; Huang, Fenglei

    2016-01-21

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman-Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ state parameters, providing the means to predict the performance of new materials prior to synthesis and characterization, allowing the simulation based design to be done in silico. Our Rx2CJ method is based on atomistic reactive molecular dynamics (RMD) using the QM-derived ReaxFF force field. We validate this method here by predicting the CJ point and detonation products for three typical energetic materials. We find good agreement between the predicted and experimental detonation velocities, indicating that this method can reliably predict the CJ state using modest levels of computation.

  13. Uncertainty analysis for an equilibrium partitioning-based estimator of polynuclear aromatic hydrocarbon bioaccumulation potential in sediments

    SciTech Connect

    Clarke, J.U.; McFarland, V.A.

    2000-02-01

    In regulatory evaluations of contaminated sediments, an equilibrium partitioning-based screening test called theoretical bioaccumulation potential (TBP) is often performed to estimate the probable concentrations of neutral organic contaminants that would eventually accumulate in aquatic organisms from continuous exposure to a sediment. The TBP is calculated from contaminant concentration and organic carbon content of the sediment, lipid content of target organisms, and a partition coefficient, usually the biota-sediment accumulation factor (BSAF). However, routine applications of TBP have not included analysis of uncertainty. This paper demonstrates two methods for uncertainty analysis of TBP: a computational method that incorporates random and systematic error and a simulation method using bootstrap resampling of replicated model input parameters to calculate statistical uncertainty measures. For prediction of polynuclear aromatic hydrocarbon (PAH) bioaccumulation in bivalves exposed to contaminated sediments, uncertainty as a factor of TBP ranged from 1.2 to 4.8 using the computational method and 0.5 to 1.9 based on bootstrap 95% confidence intervals. Sensitivity analysis indicated that BSAF parameters, especially tissue contaminant concentration and lipid content, contributed most to TBP uncertainty. In bootstrap tests of significance, TBP significantly over- or underestimated actual PAH bioaccumulation in bivalves in 41% and 10% of comparisons, respectively.

  14. Prediction of the Chapman-Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics.

    PubMed

    Guo, Dezhou; Zybin, Sergey V; An, Qi; Goddard, William A; Huang, Fenglei

    2016-01-21

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman-Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ state parameters, providing the means to predict the performance of new materials prior to synthesis and characterization, allowing the simulation based design to be done in silico. Our Rx2CJ method is based on atomistic reactive molecular dynamics (RMD) using the QM-derived ReaxFF force field. We validate this method here by predicting the CJ point and detonation products for three typical energetic materials. We find good agreement between the predicted and experimental detonation velocities, indicating that this method can reliably predict the CJ state using modest levels of computation. PMID:26688211

  15. Non-equilibrium Green's function calculation of AlGaAs-well-based and GaSb-based terahertz quantum cascade laser structures

    SciTech Connect

    Yasuda, H. Hosako, I.

    2015-03-16

    We investigate the performance of terahertz quantum cascade lasers (THz-QCLs) based on Al{sub x}Ga{sub 1−x}As/Al{sub y}Ga{sub 1−y}As and GaSb/AlGaSb material systems to realize higher-temperature operation. Calculations with the non-equilibrium Green's function method reveal that the AlGaAs-well-based THz-QCLs do not show improved performance, mainly because of alloy scattering in the ternary compound semiconductor. The GaSb-based THz-QCLs offer clear advantages over GaAs-based THz-QCLs. Weaker longitudinal optical phonon–electron interaction in GaSb produces higher peaks in the spectral functions of the lasing levels, which enables more electrons to be accumulated in the upper lasing level.

  16. Equilibrium CO bond lengths

    NASA Astrophysics Data System (ADS)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

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

  17. The Gellyfish: An In-Situ Equilibrium-Based Sampler for Determining Multiple Free Metal Ion Concentrations in Marine Ecosystems

    PubMed Central

    Dong, Zhao; Lewis, Christopher G.; Burgess, Robert M.; Shine, James P.

    2016-01-01

    Free metal ions are usually the most bioavailable and toxic metal species to aquatic organisms, but they are difficult to measure due to their extremely low concentrations in the marine environment. Many of the current methods for determining free metal ions are complicated, time-consuming, and can only measure one metal at a time. We developed a new version of the ‘Gellyfish’, an in-situ equilibrium-based sampler, with significantly reduced equilibration time and the capability of measuring multiple free metal ions simultaneously. By calibrating the Gellyfish to account for its uptake of cationic metal complexes and validating them in multi-metal competition experiments, we were able to determine free metal ion concentrations previously collected over ten months at five locations in Boston Harbor for Cu, Zn, Pb, Ni, and Cd. This work generated one of the largest free metal ion datasets and demonstrated the applicability of the Gellyfish as an easy-to-use and inexpensive tool for monitoring free ion concentrations of metal mixtures in marine ecosystems. PMID:25598362

  18. Kinetics, equilibrium, and thermodynamics investigation on the adsorption of lead(II) by coal-based activated carbon.

    PubMed

    Yi, Zhengji; Yao, Jun; Zhu, Mijia; Chen, Huilun; Wang, Fei; Liu, Xing

    2016-01-01

    The goal of this research is to investigate the feasibility of using activated coal-based activated carbon (CBAC) to adsorb Pb(II) from aqueous solutions through batch tests. Effects of contact time, pH, temperature and initial Pb(II) concentration on the Pb(II) adsorption were examined. The Pb(II) adsorption is strongly dependent on pH, but insensitive to temperature. The best pH for Pb(II) removal is in the range of 5.0-5.5 with more than 90 % of Pb(II) removed. The equilibrium time was found to be 60 min and the adsorption data followed the pseudo-second-order kinetics. Isotherm data followed Langmuir isotherm model with a maximum adsorption capacity of 162.33 mg/g. The adsorption was exothermic and spontaneous in nature. The Fourier transform infrared spectroscopy and scanning electron microscopy analysis suggested that CBAC possessed a porous structure and was rich in carboxyl and hydroxyl groups on its surface, which might play a major role in Pb(II) adsorption. These findings indicated that CBAC has great potential as an alternative adsorbent for Pb(II) removal. PMID:27504258

  19. A study of the scour-fill threshold based on Lane's equilibrium relation: The lower Yellow River

    NASA Astrophysics Data System (ADS)

    Xu, Jiongxin

    2015-12-01

    The scour-fill threshold in river channels is an expression of scour-fill equilibrium, which may be understood as the balance between the river's sediment carrying capability and the sediment load imposed by the drainage basin. In the present study, the above capability-load relation is quantified using Lane's relation, γQJ-QsD50, wherein Q is water discharge, J is channel slope, Qs is sediment transport rate, D50 is median size of bed material, and γ is the specific weight of water. On this basis, we have established scour-fill thresholds for the lower Yellow River based on data from 141 flood events. The results show that the QsD50-γQJ relation may well distinguish between the scour and fill flood events. The following equation has been established: SDRFE = 0.00099(γQJ)0.90(QsD50)- 0.60, wherein SDRFE is channel sediment delivery ratio. From the equation, the scour-fill threshold is established as: QsD50 = 0.00001(γQJ)1.5. Starting from this formula, four possible options are proposed for sediment management of the lower Yellow River.

  20. Nonlinear relative-proportion-based route adjustment process for day-to-day traffic dynamics: modeling, equilibrium and stability analysis

    NASA Astrophysics Data System (ADS)

    Zhu, Wenlong; Ma, Shoufeng; Tian, Junfang; Li, Geng

    2016-11-01

    Travelers' route adjustment behaviors in a congested road traffic network are acknowledged as a dynamic game process between them. Existing Proportional-Switch Adjustment Process (PSAP) models have been extensively investigated to characterize travelers' route choice behaviors; PSAP has concise structure and intuitive behavior rule. Unfortunately most of which have some limitations, i.e., the flow over adjustment problem for the discrete PSAP model, the absolute cost differences route adjustment problem, etc. This paper proposes a relative-Proportion-based Route Adjustment Process (rePRAP) maintains the advantages of PSAP and overcomes these limitations. The rePRAP describes the situation that travelers on higher cost route switch to those with lower cost at the rate that is unilaterally depended on the relative cost differences between higher cost route and its alternatives. It is verified to be consistent with the principle of the rational behavior adjustment process. The equivalence among user equilibrium, stationary path flow pattern and stationary link flow pattern is established, which can be applied to judge whether a given network traffic flow has reached UE or not by detecting the stationary or non-stationary state of link flow pattern. The stability theorem is proved by the Lyapunov function approach. A simple example is tested to demonstrate the effectiveness of the rePRAP model.

  1. The Gellyfish: An in situ equilibrium-based sampler for determining multiple free metal ion concentrations in marine ecosystems.

    PubMed

    Dong, Zhao; Lewis, Christopher G; Burgess, Robert M; Shine, James P

    2015-05-01

    Free metal ions are usually the most bioavailable and toxic metal species to aquatic organisms, but they are difficult to measure because of their extremely low concentrations in the marine environment. Many of the current methods for determining free metal ions are complicated and time-consuming, and they can only measure 1 metal at a time. The authors developed a new version of the "Gellyfish," an in situ equilibrium-based sampler, with significantly reduced equilibration time and the capability of measuring multiple free metal ions simultaneously. By calibrating the Gellyfish to account for its uptake of cationic metal complexes and validating them in multi-metal competition experiments, the authors were able to determine free metal ion concentrations previously collected over 10 mo at 5 locations in Boston Harbor for Cu, Zn, Pb, Ni, and Cd. This generated 1 of the largest free metal ion datasets and demonstrated the applicability of the Gellyfish as an easy-to-use and inexpensive tool for monitoring free ion concentrations of metal mixtures in marine ecosystems.

  2. STUDIES OF THE ACID-BASE EQUILIBRIUM IN DISEASE FROM THE POINT OF VIEW OF BLOOD GASES.

    PubMed

    Means, J H; Bock, A V; Woodwell, M N

    1921-01-31

    Carbon dioxide diagrams (Haggard and Henderson (9)) have been constructed for the blood of a series of hospital patients as a method of studying disturbances in their acid-base equilibrium. A diabetic with a low level of blood alkali, but with a normal blood reaction, a compensated acidosis in other words, showed a rapid return towards normal with no treatment but fasting and increased water and salt intake. A nephritic with a decompensated acidosis and a very low blood alkali was rapidly brought to a condition of decompensated alkalosis with a high blood alkali by the therapeutic administration of sodium bicarbonate. It is suggested that the therapeutic use of alkali in acidosis is probably only indicated in the decompensated variety, and that there it should be controlled carefully and the production of alkalosis avoided. The diagram obtained in three pneumonia patients suggested that they were suffering from a condition of carbonic acidosis, due perhaps to insufficient pulmonary ventilation. In two out of three cases of anemia the dissociation curve was found to lie at a higher level than normal. No explanation for this finding was offered. PMID:19868489

  3. Equilibrium Constants You Can Smell.

    ERIC Educational Resources Information Center

    Anderson, Michael; Buckley, Amy

    1996-01-01

    Presents a simple experiment involving the sense of smell that students can accomplish during a lecture. Illustrates the important concepts of equilibrium along with the acid/base properties of various ions. (JRH)

  4. 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.

  5. A Laser Induced Breakdown Spectroscopy application based on Local Thermodynamic Equilibrium assumption for the elemental analysis of alexandrite gemstone and copper-based alloys

    NASA Astrophysics Data System (ADS)

    De Giacomo, A.; Dell'Aglio, M.; Gaudiuso, R.; Santagata, A.; Senesi, G. S.; Rossi, M.; Ghiara, M. R.; Capitelli, F.; De Pascale, O.

    2012-04-01

    Laser Induced Breakdown Spectroscopy (LIBS) is an appealing technique to study laser-induced plasmas (LIPs), both from the basic diagnostics point of view and for analytical applications. LIPs are complex dynamic systems, expanding at supersonic velocities and undergoing a transition between different plasma regimes. If the Local Thermodynamic Equilibrium (LTE) condition is valid for such plasmas, several analytical methods can be employed and fast quantitative analyses can be performed on a variety of samples. In the present paper, a discussion about LTE is carried out and an innovative application to the analysis of the alexandrite gemstone is presented. In addition, a study about the influence of plasma parameters on the performance of LTE-based methods is reported for bronze and brass targets.

  6. Application of an equilibrium-based model for diffusion barrier charcoal canisters in a small volume non-steady state radon chamber.

    PubMed

    Lehnert, A L; Thompson, K H; Kearfott, K J

    2011-02-01

    Radon in indoor air is often measured using activated charcoal in canisters. These are generally calibrated using large, humidity- and temperature-controlled radon chambers capable of maintaining a constant radon concentration over several days. Reliable and reproducible chambers are expensive and may be difficult to create and maintain. This study characterizes a small radon chamber in which Rn gas is allowed to build up over a period of several days for use in charcoal canister calibration and educational demonstrations, as well as various radon experiments using charcoal canisters. Predictive models have been developed that accurately describe radon gas kinetics in the charcoal canisters. Three models are available for kinetics in the small chamber with and without radon-adsorbing charcoal canisters. Presented here are both theoretical and semi-empirical applications of this equilibrium-based model of radon adsorption as applied to canisters in the small chamber. Several charcoal canister experiments in the small chamber with an equilibrium-based model of radon adsorption applied are reported. Results show that it is necessary to include a continuous radon monitor in the chamber during canister exposures, as the radon removal rate is highly variable. Furthermore, the presence of the canisters significantly decreases the amount of radon in the small chamber, especially when several canisters are present. It was found that canister response in the small chamber is largely consistent with the equilibrium-based model for both applications, with average errors of 1% for the theoretical application and -4% for the semi-empirical approach.

  7. Ionization and thermal equilibrium models for O star winds based on time-independent radiation-driven wind theory

    NASA Technical Reports Server (NTRS)

    Drew, J. E.

    1989-01-01

    Ab initio ionization and thermal equilibrium models are calculated for the winds of O stars using the results of steady state radiation-driven wind theory to determine the input parameters. Self-consistent methods are used for the roles of H, He, and the most abundant heavy elements in both the statistical and the thermal equilibrium. The model grid was chosen to encompass all O spectral subtypes and the full range of luminosity classes. Results of earlier modeling of O star winds by Klein and Castor (1978) are reproduced and used to motivate improvements in the treatment of the hydrogen equilibrium. The wind temperature profile is revealed to be sensitive to gross changes in the heavy element abundances, but insensitive to other factors considered such as the mass-loss rate and velocity law. The reduced wind temperatures obtained in observing the luminosity dependence of the Si IV lambda 1397 wind absorption profile are shown to eliminate any prospect of explaining the observed O VI lambda 1036 line profiles in terms of time-independent radiation-driven wind theory.

  8. Understanding of surface pit formation mechanism of GaN grown in MOCVD based on local thermodynamic equilibrium assumption

    NASA Astrophysics Data System (ADS)

    Zhi-Yuan, Gao; Xiao-Wei, Xue; Jiang-Jiang, Li; Xun, Wang; Yan-Hui, Xing; Bi-Feng, Cui; De-Shu, Zou

    2016-06-01

    Frank’s theory describes that a screw dislocation will produce a pit on the surface, and has been evidenced in many material systems including GaN. However, the size of the pit calculated from the theory deviates significantly from experimental result. Through a careful observation of the variations of surface pits and local surface morphology with growing temperature and V/III ratio for c-plane GaN, we believe that Frank’s model is valid only in a small local surface area where thermodynamic equilibrium state can be assumed to stay the same. If the kinetic process is too vigorous or too slow to reach a balance, the local equilibrium range will be too small for the center and edge of the screw dislocation spiral to be kept in the same equilibrium state. When the curvature at the center of the dislocation core reaches the critical value 1/r 0, at the edge of the spiral, the accelerating rate of the curvature may not fall to zero, so the pit cannot reach a stationary shape and will keep enlarging under the control of minimization of surface energy to result in a large-sized surface pit. Project supported by the National Natural Science Foundation of China (Grant Nos. 11204009 and 61204011) and the Beijing Municipal Natural Science Foundation, China (Grant No. 4142005).

  9. Quantitative Analysis of Caspase-1 Activity in Living Cells Through Dynamic Equilibrium of Chlorophyll-Based Nano-assembly Modulated Photoacoustic Signals.

    PubMed

    Li, Li-Li; Zeng, Qian; Liu, Wei-Jiao; Hu, Xue-Feng; Li, Yongsheng; Pan, Jie; Wan, Dong; Wang, Hao

    2016-07-20

    In situ construction of self-assemblies with unique property in living systems is a promising direction in the biomedical field. The noninvasive methods for significant enzyme activity in living cells or living subjects are imperative and meantime challenge tasks. The dynamic process of self-assembly of chlorophyll-based molecules in complex biological systems can be monitored by photoacoustic signals, which supports a noninvasive way to understand and quantitatively measure the activity of caspase-1. Furthermore, the activity of caspase-1 enables reflection of the bacterial infection in the early stage. Here, we present a biocompatible self-assembly from chlorophyll-peptide derivatives and first correlate the dynamic equilibrium with ratiometric photoacoustic signals. The intracellular equilibrium was managed by a bacterial infection precaution protein, i.e., caspase-1. This system offers a trial of noninvasive method to quantitative detection and real-time monitoring of bacterial infection in the early stage.

  10. Evaporation kinetics of laser heated silica in reactive and inert gases based on near-equilibrium dynamics.

    PubMed

    Elhadj, Selim; Matthews, Manyalibo J; Yang, Steven T; Cooke, Diane J

    2012-01-16

    Evaporation kinetics of fused silica were measured up to ≈3000K using CO(2) laser heating, while solid-gas phase chemistry of silica was assessed with hydrogen, air, and nitrogen. Enhanced evaporation in hydrogen was attributed to an additional reduction pathway, while oxidizing conditions pushed the reaction backwards. The observed mass transport limitations supported use of a near-equilibrium analysis for interpreting kinetic data. A semi-empirical model of the evaporation kinetics is derived that accounts for heating, gas chemistry and transport properties. The approach described should have application to materials laser processing, and in applications requiring knowledge of thermal decomposition chemistry under extreme temperatures.

  11. Estimation of EEC, unattached fraction and equilibrium factor for the assessment of radiological dose using pin-hole cup dosimeters and deposition based progeny sensors.

    PubMed

    Bangotra, Pargin; Mehra, Rohit; Kaur, Kirandeep; Kanse, Sandeep; Mishra, Rosaline; Sahoo, B K

    2015-10-01

    High concentration of radon ((222)Rn), thoron ((220)Rn) and their decay products in environment may increase the risk of radiological exposure to the mankind. The (222)Rn, (220)Rn concentration and their separate attached and unattached progeny concentration in units of EEC have been measured in the dwellings of Muktsar and Mansa districts of Punjab (India), using Pin-hole cup dosimeters and deposition based progeny sensors (DTPS/DRPS). The indoor (222)Rn and (220)Rn concentration was found to vary from 21 Bqm(-3) to 94 Bqm(-3) and 17 Bqm(-3) to 125 Bqm(-3). The average EEC (attached + unattached) of (222)Rn and (220)Rn was 25 Bqm(-3) and 1.8 Bqm(-3). The equilibrium factor for (222)Rn and (220)Rn in studied area was 0.47 ± 0.13 and 0.05 ± 0.03. The equilibrium factor and unattached fraction of (222)Rn and (220)Rn has been calculated separately. Dose conversion factors (DCFs) of different models have been calculated from unattached fraction for the estimation of annual effective dose in the studied area. From the experimental data a correlation relationship has been observed between unattached fraction (f(p)(Rn)) and equilibrium factor (F(Rn)). The present work also aims to evaluate an accurate expression among available expression in literature for the estimation of f(p)(Rn). PMID:26117280

  12. Distinguishing between keto-enol and acid-base forms of firefly oxyluciferin through calculation of excited-state equilibrium constants.

    PubMed

    Falklöf, Olle; Durbeej, Bo

    2014-11-15

    Although recent years have seen much progress in the elucidation of the mechanisms underlying the bioluminescence of fireflies, there is to date no consensus on the precise contributions to the light emission from the different possible forms of the chemiexcited oxyluciferin (OxyLH2) cofactor. Here, this problem is investigated by the calculation of excited-state equilibrium constants in aqueous solution for keto-enol and acid-base reactions connecting six neutral, monoanionic and dianionic forms of OxyLH2. Particularly, rather than relying on the standard Förster equation and the associated assumption that entropic effects are negligible, these equilibrium constants are for the first time calculated in terms of excited-state free energies of a Born-Haber cycle. Performing quantum chemical calculations with density functional theory methods and using a hybrid cluster-continuum approach to describe solvent effects, a suitable protocol for the modeling is first defined from benchmark calculations on phenol. Applying this protocol to the various OxyLH2 species and verifying that available experimental data (absorption shifts and ground-state equilibrium constants) are accurately reproduced, it is then found that the phenolate-keto-OxyLH(-) monoanion is intrinsically the preferred form of OxyLH2 in the excited state, which suggests a potential key role for this species in the bioluminescence of fireflies.

  13. Equilibrium-phase MR angiography: Comparison of unspecific extracellular and protein-binding gadolinium-based contrast media with respect to image quality.

    PubMed

    Erb-Eigner, Katharina; Taupitz, Matthias; Asbach, Patrick

    2016-01-01

    The purpose of this study was to compare contrast and image quality of whole-body equilibrium-phase high-spatial-resolution MR angiography using a non-protein-binding unspecific extracellular gadolinium-based contrast medium with that of two contrast media with different protein-binding properties. 45 patients were examined using either 15 mL of gadobutrol (non-protein-binding, n = 15), 32 mL of gadobenate dimeglumine (weakly protein binding, n = 15) or 11 mL gadofosveset trisodium (protein binding, n = 15) followed by equilibrium-phase high-spatial-resolution MR-angiography of four consecutive anatomic regions. The time elapsed between the contrast injection and the beginning of the equilibrium-phase image acquisition in the respective region was measured and was up to 21 min. Signal intensity was measured in two vessels per region and in muscle tissue. Relative contrast (RC) values were calculated. Vessel contrast, artifacts and image quality were rated by two radiologists in consensus on a five-point scale. Compared with gadobutrol, gadofosveset trisodium revealed significantly higher RC values only when acquired later than 15 min after bolus injection. Otherwise, no significant differences between the three contrast media were found regarding vascular contrast and image quality. Equilibrium-phase high-spatial-resolution MR-angiography using a weakly protein-binding or even non-protein-binding contrast medium is equivalent to using a stronger protein-binding contrast medium when image acquisition is within the first 15 min after contrast injection, and allows depiction of the vasculature with high contrast and image quality. The protein-binding contrast medium was superior for imaging only later than 15 min after contrast medium injection.

  14. A Differential Evolution Algorithm Based on Nikaido-Isoda Function for Solving Nash Equilibrium in Nonlinear Continuous Games

    PubMed Central

    He, Feng; Zhang, Wei; Zhang, Guoqiang

    2016-01-01

    A differential evolution algorithm for solving Nash equilibrium in nonlinear continuous games is presented in this paper, called NIDE (Nikaido-Isoda differential evolution). At each generation, parent and child strategy profiles are compared one by one pairwisely, adapting Nikaido-Isoda function as fitness function. In practice, the NE of nonlinear game model with cubic cost function and quadratic demand function is solved, and this method could also be applied to non-concave payoff functions. Moreover, the NIDE is compared with the existing Nash Domination Evolutionary Multiplayer Optimization (NDEMO), the result showed that NIDE was significantly better than NDEMO with less iterations and shorter running time. These numerical examples suggested that the NIDE method is potentially useful. PMID:27589229

  15. A Differential Evolution Algorithm Based on Nikaido-Isoda Function for Solving Nash Equilibrium in Nonlinear Continuous Games.

    PubMed

    He, Feng; Zhang, Wei; Zhang, Guoqiang

    2016-01-01

    A differential evolution algorithm for solving Nash equilibrium in nonlinear continuous games is presented in this paper, called NIDE (Nikaido-Isoda differential evolution). At each generation, parent and child strategy profiles are compared one by one pairwisely, adapting Nikaido-Isoda function as fitness function. In practice, the NE of nonlinear game model with cubic cost function and quadratic demand function is solved, and this method could also be applied to non-concave payoff functions. Moreover, the NIDE is compared with the existing Nash Domination Evolutionary Multiplayer Optimization (NDEMO), the result showed that NIDE was significantly better than NDEMO with less iterations and shorter running time. These numerical examples suggested that the NIDE method is potentially useful. PMID:27589229

  16. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    PubMed

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  17. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    PubMed

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  18. Shape characteristics of equilibrium and non-equilibrium fractal clusters

    NASA Astrophysics Data System (ADS)

    Mansfield, Marc L.; Douglas, Jack F.

    2013-07-01

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  19. Soft-spring wall based non-periodic boundary conditions for non-equilibrium molecular dynamics of dense fluids

    SciTech Connect

    Ghatage, Dhairyashil; Tomar, Gaurav Shukla, Ratnesh K.

    2015-03-28

    Non-equilibrium molecular dynamics (MD) simulations require imposition of non-periodic boundary conditions (NPBCs) that seamlessly account for the effect of the truncated bulk region on the simulated MD region. Standard implementation of specular boundary conditions in such simulations results in spurious density and force fluctuations near the domain boundary and is therefore inappropriate for coupled atomistic-continuum calculations. In this work, we present a novel NPBC model that relies on boundary atoms attached to a simple cubic lattice with soft springs to account for interactions from particles which would have been present in an untruncated full domain treatment. We show that the proposed model suppresses the unphysical fluctuations in the density to less than 1% of the mean while simultaneously eliminating spurious oscillations in both mean and boundary forces. The model allows for an effective coupling of atomistic and continuum solvers as demonstrated through multiscale simulation of boundary driven singular flow in a cavity. The geometric flexibility of the model enables straightforward extension to nonplanar complex domains without any adverse effects on dynamic properties such as the diffusion coefficient.

  20. Removal of aluminium from aqueous solutions using PAN-based adsorbents: characterisation, kinetics, equilibrium and thermodynamic studies.

    PubMed

    Aly, Zaynab; Graulet, Adrien; Scales, Nicholas; Hanley, Tracey

    2014-03-01

    Economic adsorbents in bead form were fabricated and utilised for the adsorption of Al(3+) from aqueous solutions. Polyacrylonitrile (PAN) beads, PAN powder and the thermally treated PAN beads (250 °C/48 h/Ar and 600 °C/48 h/Ar-H2) were characterised using different techniques including Fourier transform infrared spectroscopy, X-ray diffraction, specific surface analysis (Brunauer-Emmett-Teller), thermogravimetric analysis as well as scanning electron microscopy. Effects of pH, contact time, kinetics and adsorption isotherms at different temperatures were investigated in batch mode experiments. Aluminium kinetic data best fit the Lagergren pseudo-second-order adsorption model indicating a one-step, surface-only, adsorption process with chemisorption being the rate limiting step. Equilibrium adsorption data followed a Langmuir adsorption model with fairly low monolayer adsorption capacities suitable for freshwater clean-up only. Various constants including thermodynamic constants were evaluated from the experimental results obtained at 20, 40 and 60 °C. Positive values of ΔH° indicated that the adsorption of Al(3+) onto all three adsorbents was endothermic with less energy input required for PAN powder compared to PAN beads and low-temperature thermally treated PAN. Negative ΔG° values indicated that the aluminium adsorption process was spontaneous for all adsorbents examined.

  1. Structure-function relationships based on ATP binding and cation occlusion at equilibrium in Na,K-ATPase.

    PubMed

    Jorgensen, P L; Nielsen, J M; Rasmussen, J H; Pedersen, P A

    1998-08-01

    This work evaluates the results of measurements of equilibrium binding of ATP and cations in lethal or partially active mutations of Na,K-ATPase that were expressed at high yield in yeast cells. ATP binding studies allowed estimation of the expense in free energy required to position the gamma-phosphate in proximity of the carboxylate groups of the phosphorylated residue Asp369 and the role of this residue in governing long range E1-E2 transitions. An arginine residue (Arg546) appearing to be involved in ATP binding has been identified. Wild type yeast enzyme was capable of occluding two T1(+)-ions per ouabain binding site or alpha 1 beta 1 unit with high apparent affinity (Kd(T1+) = 7 +/- 2 microM), like the purified Na,K-ATPase from pig kidney. The substitutions to Glu327(Gln,Asp), Asp804(Asn,Glu), Asp808(Asn,Glu) and Glu779(Asp) completely abolished occlusion or severely reduced the affinity for T1+ ions. The substitution of Glu779 for Gln reduced the occlusion capacity to one T1+ ion per alpha 1 beta 1 unit with a 3-fold decrease of the apparent affinity for the ion (Kd(T1+) = 24 +/- 8 mM). These carboxylate groups in transmembrane segments 4, 5, and 6 therefore appear to be essential for high affinity occlusion of K(+)-ions.

  2. The effect of parameters of equilibrium-based 3-D biomechanical models on extracted muscle synergies during isometric lumbar exertion.

    PubMed

    Eskandari, A H; Sedaghat-Nejad, E; Rashedi, E; Sedighi, A; Arjmand, N; Parnianpour, M

    2016-04-11

    A hallmark of more advanced models is their higher details of trunk muscles represented by a larger number of muscles. The question is if in reality we control these muscles individually as independent agents or we control groups of them called "synergy". To address this, we employed a 3-D biomechanical model of the spine with 18 trunk muscles that satisfied equilibrium conditions at L4/5, with different cost functions. The solutions of several 2-D and 3-D tasks were arranged in a data matrix and the synergies were computed by using non-negative matrix factorization (NMF) algorithms. Variance accounted for (VAF) was used to evaluate the number of synergies that emerged by the analysis, which were used to reconstruct the original muscle activations. It was showed that four and six muscle synergies were adequate to reconstruct the input data of 2-D and 3-D torque space analysis. The synergies were different by choosing alternative cost functions as expected. The constraints affected the extracted muscle synergies, particularly muscles that participated in more than one functional tasks were influenced substantially. The compositions of extracted muscle synergies were in agreement with experimental studies on healthy participants. The following computational methods show that the synergies can reduce the complexity of load distributions and allow reduced dimensional space to be used in clinical settings.

  3. An investigation of equilibrium concepts

    NASA Technical Reports Server (NTRS)

    Prozan, R. J.

    1982-01-01

    A different approach to modeling of the thermochemistry of rocket engine combustion phenomena is presented. The methodology described is based on the hypothesis of a new variational principle applicable to compressible fluid mechanics. This hypothesis is extended to treat the thermochemical behavior of a reacting (equilibrium) gas in an open system.

  4. A DFT based equilibrium study on the hydrolysis and the dehydration reactions of MgCl2 hydrates.

    PubMed

    Smeets, B; Iype, E; Nedea, S V; Zondag, H A; Rindt, C C M

    2013-09-28

    Magnesium chloride hydrates are characterized as promising energy storage materials in the built-environment. During the dehydration of these materials, there are chances for the release of harmful HCl gas, which can potentially damage the material as well as the equipment. Hydrolysis reactions in magnesium chloride hydrates are subject of study for industrial applications. However, the information about the possibility of hydrolysis reaction, and its preference over dehydration in energy storage systems is still ambiguous at the operating conditions in a seasonal heat storage system. A density functional theory level study is performed to determine molecular structures, charges, and harmonic frequencies in order to identify the formation of HCl at the operating temperatures in an energy storage system. The preference of hydrolysis over dehydration is quantified by applying thermodynamic equilibrium principles by calculating Gibbs free energies of the hydrated magnesium chloride molecules. The molecular structures of the hydrates (n = 0, 1, 2, 4, and 6) of MgCl2 are investigated to understand the stability and symmetry of these molecules. The structures are found to be noncomplex with almost no meta-stable isomers, which may be related to the faster kinetics observed in the hydration of chlorides compared to sulfates. Also, the frequency spectra of these molecules are calculated, which in turn are used to calculate the changes in Gibbs free energy of dehydration and hydrolysis reactions. From these calculations, it is found that the probability for hydrolysis to occur is larger for lower hydrates. Hydrolysis occurring from the hexa-, tetra-, and di-hydrate is only possible when the temperature is increased too fast to a very high value. In the case of the mono-hydrate, hydrolysis may become favorable at high water vapor pressure and at low HCl pressure.

  5. Ab initio path-integral calculations of kinetic and equilibrium isotope effects on base-catalyzed RNA transphosphorylation models.

    PubMed

    Wong, Kin-Yiu; Xu, Yuqing; York, Darrin M

    2014-06-30

    Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2'-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This article significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and nonenzymatic 2'-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a "gold-standard" coupled-cluster level of theory [CCSD(T)]. In addition to the widely used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently developed ab initio path-integral method, that is, automated integration-free path-integral method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis.

  6. Ab Initio Path-Integral Calculations of Kinetic and Equilibrium Isotope Effects on Base-Catalyzed RNA Transphosphorylation Models

    PubMed Central

    Wong, Kin-Yiu; Yuqing, Xu; York, Darrin M.

    2014-01-01

    Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2′-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This paper significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and non-enzymatic 2′-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a “gold-standard” coupled-cluster level of theory [CCSD(T)]. In addition to the widely-used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently-developed ab initio path-integral method, i.e., automated integration-free path-integral (AIF-PI) method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis. PMID:24841935

  7. A DFT based equilibrium study on the hydrolysis and the dehydration reactions of MgCl2 hydrates

    NASA Astrophysics Data System (ADS)

    Smeets, B.; Iype, E.; Nedea, S. V.; Zondag, H. A.; Rindt, C. C. M.

    2013-09-01

    Magnesium chloride hydrates are characterized as promising energy storage materials in the built-environment. During the dehydration of these materials, there are chances for the release of harmful HCl gas, which can potentially damage the material as well as the equipment. Hydrolysis reactions in magnesium chloride hydrates are subject of study for industrial applications. However, the information about the possibility of hydrolysis reaction, and its preference over dehydration in energy storage systems is still ambiguous at the operating conditions in a seasonal heat storage system. A density functional theory level study is performed to determine molecular structures, charges, and harmonic frequencies in order to identify the formation of HCl at the operating temperatures in an energy storage system. The preference of hydrolysis over dehydration is quantified by applying thermodynamic equilibrium principles by calculating Gibbs free energies of the hydrated magnesium chloride molecules. The molecular structures of the hydrates (n = 0, 1, 2, 4, and 6) of MgCl2 are investigated to understand the stability and symmetry of these molecules. The structures are found to be noncomplex with almost no meta-stable isomers, which may be related to the faster kinetics observed in the hydration of chlorides compared to sulfates. Also, the frequency spectra of these molecules are calculated, which in turn are used to calculate the changes in Gibbs free energy of dehydration and hydrolysis reactions. From these calculations, it is found that the probability for hydrolysis to occur is larger for lower hydrates. Hydrolysis occurring from the hexa-, tetra-, and di-hydrate is only possible when the temperature is increased too fast to a very high value. In the case of the mono-hydrate, hydrolysis may become favorable at high water vapor pressure and at low HCl pressure.

  8. A DFT based equilibrium study on the hydrolysis and the dehydration reactions of MgCl2 hydrates.

    PubMed

    Smeets, B; Iype, E; Nedea, S V; Zondag, H A; Rindt, C C M

    2013-09-28

    Magnesium chloride hydrates are characterized as promising energy storage materials in the built-environment. During the dehydration of these materials, there are chances for the release of harmful HCl gas, which can potentially damage the material as well as the equipment. Hydrolysis reactions in magnesium chloride hydrates are subject of study for industrial applications. However, the information about the possibility of hydrolysis reaction, and its preference over dehydration in energy storage systems is still ambiguous at the operating conditions in a seasonal heat storage system. A density functional theory level study is performed to determine molecular structures, charges, and harmonic frequencies in order to identify the formation of HCl at the operating temperatures in an energy storage system. The preference of hydrolysis over dehydration is quantified by applying thermodynamic equilibrium principles by calculating Gibbs free energies of the hydrated magnesium chloride molecules. The molecular structures of the hydrates (n = 0, 1, 2, 4, and 6) of MgCl2 are investigated to understand the stability and symmetry of these molecules. The structures are found to be noncomplex with almost no meta-stable isomers, which may be related to the faster kinetics observed in the hydration of chlorides compared to sulfates. Also, the frequency spectra of these molecules are calculated, which in turn are used to calculate the changes in Gibbs free energy of dehydration and hydrolysis reactions. From these calculations, it is found that the probability for hydrolysis to occur is larger for lower hydrates. Hydrolysis occurring from the hexa-, tetra-, and di-hydrate is only possible when the temperature is increased too fast to a very high value. In the case of the mono-hydrate, hydrolysis may become favorable at high water vapor pressure and at low HCl pressure. PMID:24089772

  9. Getting Freshman in Equilibrium.

    ERIC Educational Resources Information Center

    Journal of Chemical Education, 1983

    1983-01-01

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

  10. Equilibrium sampling by reweighting nonequilibrium simulation trajectories.

    PubMed

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems. PMID:27078486

  11. Equilibrium sampling by reweighting nonequilibrium simulation trajectories.

    PubMed

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

  12. Equilibrium sampling by reweighting nonequilibrium simulation trajectories

    NASA Astrophysics Data System (ADS)

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

  13. Lysozyme adsorption in pH-responsive hydrogel thin-films: the non-trivial role of acid-base equilibrium.

    PubMed

    Narambuena, Claudio F; Longo, Gabriel S; Szleifer, Igal

    2015-09-01

    We develop and apply a molecular theory to study the adsorption of lysozyme on weak polyacid hydrogel films. The theory explicitly accounts for the conformation of the network, the structure of the proteins, the size and shape of all the molecular species, their interactions as well as the chemical equilibrium of each titratable unit of both the protein and the polymer network. The driving forces for adsorption are the electrostatic attractions between the negatively charged network and the positively charged protein. The adsorption is a non-monotonic function of the solution pH, with a maximum in the region between pH 8 and 9 depending on the salt concentration of the solution. The non-monotonic adsorption is the result of increasing negative charge of the network with pH, while the positive charge of the protein decreases. At low pH the network is roughly electroneutral, while at sufficiently high pH the protein is negatively charged. Upon adsorption, the acid-base equilibrium of the different amino acids of the protein shifts in a nontrivial fashion that depends critically on the particular kind of residue and solution composition. Thus, the proteins regulate their charge and enhance adsorption under a wide range of conditions. In particular, adsorption is predicted above the protein isoelectric point where both the solution lysozyme and the polymer network are negatively charged. This behavior occurs because the pH in the interior of the gel is significantly lower than that in the bulk solution and it is also regulated by the adsorption of the protein in order to optimize protein-gel interactions. Under high pH conditions we predict that the protein changes its charge from negative in the solution to positive within the gel. The change occurs within a few nanometers at the interface of the hydrogel film. Our predictions show the non-trivial interplay between acid-base equilibrium, physical interactions and molecular organization under nanoconfined conditions

  14. Lysozyme adsorption in pH-responsive hydrogel thin-films: the non-trivial role of acid-base equilibrium.

    PubMed

    Narambuena, Claudio F; Longo, Gabriel S; Szleifer, Igal

    2015-09-01

    We develop and apply a molecular theory to study the adsorption of lysozyme on weak polyacid hydrogel films. The theory explicitly accounts for the conformation of the network, the structure of the proteins, the size and shape of all the molecular species, their interactions as well as the chemical equilibrium of each titratable unit of both the protein and the polymer network. The driving forces for adsorption are the electrostatic attractions between the negatively charged network and the positively charged protein. The adsorption is a non-monotonic function of the solution pH, with a maximum in the region between pH 8 and 9 depending on the salt concentration of the solution. The non-monotonic adsorption is the result of increasing negative charge of the network with pH, while the positive charge of the protein decreases. At low pH the network is roughly electroneutral, while at sufficiently high pH the protein is negatively charged. Upon adsorption, the acid-base equilibrium of the different amino acids of the protein shifts in a nontrivial fashion that depends critically on the particular kind of residue and solution composition. Thus, the proteins regulate their charge and enhance adsorption under a wide range of conditions. In particular, adsorption is predicted above the protein isoelectric point where both the solution lysozyme and the polymer network are negatively charged. This behavior occurs because the pH in the interior of the gel is significantly lower than that in the bulk solution and it is also regulated by the adsorption of the protein in order to optimize protein-gel interactions. Under high pH conditions we predict that the protein changes its charge from negative in the solution to positive within the gel. The change occurs within a few nanometers at the interface of the hydrogel film. Our predictions show the non-trivial interplay between acid-base equilibrium, physical interactions and molecular organization under nanoconfined conditions

  15. Application of Molecular Interaction Volume Model for Phase Equilibrium of Sn-Based Binary System in Vacuum Distillation

    NASA Astrophysics Data System (ADS)

    Kong, Lingxin; Yang, Bin; Xu, Baoqiang; Li, Yifu

    2014-09-01

    Based on the molecular interaction volume model (MIVM), the activities of components of Sn-Sb, Sb-Bi, Sn-Zn, Sn-Cu, and Sn-Ag alloys were predicted. The predicted values are in good agreement with the experimental data, which indicate that the MIVM is of better stability and reliability due to its good physical basis. A significant advantage of the MIVM lies in its ability to predict the thermodynamic properties of liquid alloys using only two parameters. The phase equilibria of Sn-Sb and Sn-Bi alloys were calculated based on the properties of pure components and the activity coefficients, which indicates that Sn-Sb and Sn-Bi alloys can be separated thoroughly by vacuum distillation. This study extends previous investigations and provides an effective and convenient model on which to base refining simulations for Sn-based alloys.

  16. Chemical Principles Revisited: Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Mickey, Charles D.

    1980-01-01

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

  17. Response reactions: equilibrium coupling.

    PubMed

    Hoffmann, Eufrozina A; Nagypal, Istvan

    2006-06-01

    It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle. PMID:16722770

  18. Computing Equilibrium Chemical Compositions

    NASA Technical Reports Server (NTRS)

    Mcbride, Bonnie J.; Gordon, Sanford

    1995-01-01

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

  19. Napoleon Is in Equilibrium

    PubMed Central

    Phillips, Rob

    2016-01-01

    It has been said that the cell is the test tube of the twenty-first century. If so, the theoretical tools needed to quantitatively and predictively describe what goes on in such test tubes lag sorely behind the stunning experimental advances in biology seen in the decades since the molecular biology revolution began. Perhaps surprisingly, one of the theoretical tools that has been used with great success on problems ranging from how cells communicate with their environment and each other to the nature of the organization of proteins and lipids within the cell membrane is statistical mechanics. A knee-jerk reaction to the use of statistical mechanics in the description of cellular processes is that living organisms are so far from equilibrium that one has no business even thinking about it. But such reactions are probably too hasty given that there are many regimes in which, because of a separation of timescales, for example, such an approach can be a useful first step. In this article, we explore the power of statistical mechanical thinking in the biological setting, with special emphasis on cell signaling and regulation. We show how such models are used to make predictions and describe some recent experiments designed to test them. We also consider the limits of such models based on the relative timescales of the processes of interest. PMID:27429713

  20. Napoleon Is in Equilibrium

    NASA Astrophysics Data System (ADS)

    Phillips, Rob

    2015-03-01

    It has been said that the cell is the test tube of the twenty-first century. If so, the theoretical tools needed to quantitatively and predictively describe what goes on in such test tubes lag sorely behind the stunning experimental advances in biology seen in the decades since the molecular biology revolution began. Perhaps surprisingly, one of the theoretical tools that has been used with great success on problems ranging from how cells communicate with their environment and each other to the nature of the organization of proteins and lipids within the cell membrane is statistical mechanics. A knee-jerk reaction to the use of statistical mechanics in the description of cellular processes is that living organisms are so far from equilibrium that one has no business even thinking about it. But such reactions are probably too hasty given that there are many regimes in which, because of a separation of timescales, for example, such an approach can be a useful first step. In this article, we explore the power of statistical mechanical thinking in the biological setting, with special emphasis on cell signaling and regulation. We show how such models are used to make predictions and describe some recent experiments designed to test them. We also consider the limits of such models based on the relative timescales of the processes of interest.

  1. Equilibrium games in networks

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  2. Fluorescent sensor for imidazole derivatives based on monomer-dimer equilibrium of a zinc porphyrin complex in a polymeric film.

    PubMed

    Zhang, Ying; Yang, Ronghua; Liu, Feng; Li, Ke'an

    2004-12-15

    A new zinc(II) porphyrin conjugate with an appended pyrene subunit has been synthesized and shown to exhibit significant and analytical usefulness for fluorescence sensing toward imidazole derivatives. The molecular recognition was based on the bridging interaction of the imidazole ring of analyte with the zinc(II) center of the porphyrin, while the transduction signal for the recognition process was the pyrene excimer fluorescence. The sensor was constructed and applied for fluorescence assay of histidine in aqueous solution by immobilizing the sensing material in a plasticized PVC membrane. When the membrane was bathed in an alkaline solution void of histidine, zinc(II) porphyrin was present in the monomer form, and pyrene emitted monomer fluorescence at 378 and 397 nm. With the presence of histidine in the sample solution, histidine was extracted into the membrane phase and bridged with the Zn(II) center of the porphyrin, causing the monomer porphyrin to be converted to its dimeric species. Since the formation of porphyrin dimer was accompanied by the enhancement of pyrene excimer emission at 454 nm, the chemical recognition process could be directly translated into a fluorescent signal. With the optode membrane M1 described, histidine in sample solution from 6.76 x 10(-7) to 5.01 x 10(-3) M can be determined. The limit of detection was 1.34 x 10(-7) M. The optical selectivity coefficient obtained for histidine over biologically relevant amino acids and anions met the selectivity requirements for the determination of histidine in biological samples. Serum histidine values obtained by the optode membrane fell in the normal range of the content reported in the literature and were in good agreement with those obtained by HPLC.

  3. Thermodynamic equilibrium at heterogeneous pressure

    NASA Astrophysics Data System (ADS)

    Vrijmoed, J. C.; Podladchikov, Y. Y.

    2015-07-01

    Recent advances in metamorphic petrology point out the importance of grain-scale pressure variations in high-temperature metamorphic rocks. Pressure derived from chemical zonation using unconventional geobarometry based on equal chemical potentials fits mechanically feasible pressure variations. Here, a thermodynamic equilibrium method is presented that predicts chemical zoning as a result of pressure variations by Gibbs energy minimization. Equilibrium thermodynamic prediction of the chemical zoning in the case of pressure heterogeneity is done by constrained Gibbs minimization using linear programming techniques. In addition to constraining the system composition, a certain proportion of the system is constrained at a specified pressure. Input pressure variations need to be discretized, and each discrete pressure defines an additional constraint for the minimization. The Gibbs minimization method provides identical results to a geobarometry approach based on chemical potentials, thus validating the inferred pressure gradient. The thermodynamic consistency of the calculation is supported by the similar result obtained from two different approaches. In addition, the method can be used for multi-component, multi-phase systems of which several applications are given. A good fit to natural observations in multi-phase, multi-component systems demonstrates the possibility to explain phase assemblages and zoning by spatial pressure variations at equilibrium as an alternative to pressure variation in time due to disequilibrium.

  4. Estimation of polycyclic aromatic hydrocarbon concentrations in the water column based on tissue residues in mussels and salmon: An equilibrium partitioning approach

    SciTech Connect

    Neff, J.M.; Burns, W.A.

    1996-12-01

    Equilibrium partitioning was used to estimate concentrations of dissolved polycyclic aromatic hydrocarbons (PAHs) in the water column from PAH residues in tissues of mussels and juvenile pink salmon collected from coastal marine waters affected by the Exxon Valdez oil spill. Estimated concentrations were within factors of 2 to 5 for fish and 5 to 10 for mussels of average total dissolved and particulate PAHs measured in concurrent water samples. Temporal trends of estimated and measured water-column PAH concentrations were comparable. Water-column PAH concentrations estimated from residues in tissues of mussels (Mytilus trossulus) were higher than estimates based on residues in tissues of juvenile pink salmon (Oncorhynchus gorbuscha). Possible reasons for this difference include seasonal variations in mussel lipid content, differences in PAH uptake and depuration rates between fish and mussels, differences in how fish and mussels interact with particulate oil, and possible short exposure times for juvenile pink salmon. All of these factors may play a role. In any event, estimates of dissolved PAHs in the water column, based on PAH residues in either fish or mussel tissue, confirm that PAH concentrations generally did not exceed water quality standards for protection of marine life.

  5. Determination of equilibrium constant of amino carbamate adduct formation in sisomicin by a high pH based high performance liquid chromatography.

    PubMed

    Wlasichuk, Kenneth B; Tan, Li; Guo, Yushen; Hildebrandt, Darin J; Zhang, Hao; Karr, Dane E; Schmidt, Donald E

    2015-01-01

    Amino carbamate adduct formation from the amino group of an aminoglycoside and carbon dioxide has been postulated as a mechanism for reducing nephrotoxicity in the aminoglycoside class compounds. In this study, sisomicin was used as a model compound for amino carbamate analysis. A high pH based reversed-phase high performance liquid chromatography (RP-HPLC) method is used to separate the amino carbamate from sisomicin. The carbamate is stable as the breakdown is inhibited at high pH and any reactive carbon dioxide is removed as the carbonate. The amino carbamate was quantified and the molar fraction of amine as the carbamate of sisomicin was obtained from the HPLC peak areas. The equilibrium constant of carbamate formation, Kc, was determined to be 3.3 × 10(-6) and it was used to predict the fraction of carbamate over the pH range in a typical biological systems. Based on these results, the fraction of amino carbamate at physiological pH values is less than 13%, and the postulated mechanism for nephrotoxicity protection is not valid. The same methodology is applicable for other aminoglycosides.

  6. Beyond Equilibrium Thermodynamics

    NASA Astrophysics Data System (ADS)

    Öttinger, Hans Christian

    2005-01-01

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

  7. Princeton spectral equilibrium code: PSEC

    SciTech Connect

    Ling, K.M.; Jardin, S.C.

    1985-05-15

    A fast computer code has been developed to calculate free-boundary solutions to the plasma equilibrium equation that are consistent with the currents in external coils and conductors. The free-boundary formulation is based on the minimization of a mean-square error epsilon-c while the fixed-boundary solution is based on a variational principle and spectral representation of the coordinates x(psi, theta) and z(psi, theta). Specific calculations using the Columbia University Torus II, the Poloidal Divertor Experiment (PDX), and the Tokamak Fusion Test Reactor (TFTR) geometries are performed.

  8. Princeton spectral equilibrium code: PSEC

    SciTech Connect

    Ling, K.M.; Jardin, S.C.

    1984-03-01

    A fast computer code has been developed to calculate free-boundary solutions to the plasma equilibrium equation that are consistent with the currents in external coils and conductors. The free-boundary formulation is based on the minimization of a mean-square error epsilon while the fixed-boundary solution is based on a variational principle and spectral representation of the coordinates x(psi,theta) and z(psi,theta). Specific calculations using the Columbia University Torus II, the Poloidal Divertor Experiment (PDX), and the Tokamak Fusion Test Reactor (TFTR) geometries are performed.

  9. Chlorodifluoromethane equilibrium on 13X molecular sieve

    NASA Astrophysics Data System (ADS)

    Carlile, Donna L.; Mahle, John J.; Buettner, Leonard C.; Tevault, David E.; Friday, David K.

    1994-08-01

    Adsorption phase equilibrium data are required for evaluating any adsorption-based gas separation process. The U.S. Army Edgewood Research, Development and Engineering Center is currently measuring adsorption phase equilibrium data for a variety of chemical warfare agents and their surrogates on adsorbent materials to correlate physical properties to filtration/separation efficiencies of each vapor on each adsorbent. This report details the adsorption phase equilibrium data measured for chlorodifluoromethane (R-22) on 13X Molecular Sieve. The 13X Molecular Sieve is a candidate adsorbent for future military air purification systems employing the pressure-swing adsorption separation process.

  10. A Lakatosian Conceptual Change Teaching Strategy Based on Student Ability To Build Models with Varying Degrees of Conceptual Understanding of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Niaz, Mansoor

    1998-01-01

    Reports on a study that constructs a Lakatosian teaching strategy that can facilitate conceptual change in students' understanding of chemical equilibrium. Results indicate that the experimental group performed better on tests. Contains 81 references. (DDR)

  11. An Updated Equilibrium Machine

    ERIC Educational Resources Information Center

    Schultz, Emeric

    2008-01-01

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

  12. Reversible inhibition of proton release activity and the anesthetic-induced acid-base equilibrium between the 480 and 570 nm forms of bacteriorhodopsin.

    PubMed Central

    Boucher, F; Taneva, S G; Elouatik, S; Déry, M; Messaoudi, S; Harvey-Girard, E; Beaudoin, N

    1996-01-01

    In purple membrane added with general anesthetics, there exists an acid-base equilibrium between two spectral forms of the pigment: bR570 and bR480 (apparent pKa = 7.3). As the purple 570 nm bacteriorhodopsin is reversibly transformed into its red 480 nm form, the proton pumping capability of the pigment reversibly decreases, as indicated by transient proton release measurements and proton translocation action spectra of mixture of both spectral forms. It happens in spite of a complete photochemical activity in bR480 that is mostly characterized by fast deprotonation and slow reprotonation steps and which, under continuous illumination, bleaches with a yield comparable to that of bR570. This modified photochemical activity has a correlated specific photoelectrical counterpart: a faster proton extrusion current and a slower reprotonation current. The relative areas of all photocurrent phases are reduced in bR480, most likely because its photochemistry is accompanied by charge movements for shorter distances than in the native pigment, reflecting a reversible inhibition of the pumping activity. PMID:8789112

  13. A New Methodology for Open Pit Slope Design in Karst-Prone Ground Conditions Based on Integrated Stochastic-Limit Equilibrium Analysis

    NASA Astrophysics Data System (ADS)

    Zhang, Ke; Cao, Ping; Ma, Guowei; Fan, Wenchen; Meng, Jingjing; Li, Kaihui

    2016-07-01

    Using the Chengmenshan Copper Mine as a case study, a new methodology for open pit slope design in karst-prone ground conditions is presented based on integrated stochastic-limit equilibrium analysis. The numerical modeling and optimization design procedure contain a collection of drill core data, karst cave stochastic model generation, SLIDE simulation and bisection method optimization. Borehole investigations are performed, and the statistical result shows that the length of the karst cave fits a negative exponential distribution model, but the length of carbonatite does not exactly follow any standard distribution. The inverse transform method and acceptance-rejection method are used to reproduce the length of the karst cave and carbonatite, respectively. A code for karst cave stochastic model generation, named KCSMG, is developed. The stability of the rock slope with the karst cave stochastic model is analyzed by combining the KCSMG code and the SLIDE program. This approach is then applied to study the effect of the karst cave on the stability of the open pit slope, and a procedure to optimize the open pit slope angle is presented.

  14. Stochastic approach to equilibrium and nonequilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Tomé, Tânia; de Oliveira, Mário J.

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

  15. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    PubMed

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions. PMID:25974471

  16. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    PubMed

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

  17. Local Nash Equilibrium in Social Networks

    PubMed Central

    Zhang, Yichao; Aziz-Alaoui, M. A.; Bertelle, Cyrille; Guan, Jihong

    2014-01-01

    Nash equilibrium is widely present in various social disputes. As of now, in structured static populations, such as social networks, regular, and random graphs, the discussions on Nash equilibrium are quite limited. In a relatively stable static gaming network, a rational individual has to comprehensively consider all his/her opponents' strategies before they adopt a unified strategy. In this scenario, a new strategy equilibrium emerges in the system. We define this equilibrium as a local Nash equilibrium. In this paper, we present an explicit definition of the local Nash equilibrium for the two-strategy games in structured populations. Based on the definition, we investigate the condition that a system reaches the evolutionary stable state when the individuals play the Prisoner's dilemma and snow-drift game. The local Nash equilibrium provides a way to judge whether a gaming structured population reaches the evolutionary stable state on one hand. On the other hand, it can be used to predict whether cooperators can survive in a system long before the system reaches its evolutionary stable state for the Prisoner's dilemma game. Our work therefore provides a theoretical framework for understanding the evolutionary stable state in the gaming populations with static structures. PMID:25169150

  18. Theoretical calculations of homoconjugation equilibrium constants in systems modeling acid-base interactions in side chains of biomolecules using the potential of mean force.

    PubMed

    Makowska, Joanna; Makowski, Mariusz; Liwo, Adam; Chmurzyński, Lech

    2005-02-01

    The potentials of mean force (PMFs) were determined for systems forming cationic and anionic homocomplexes composed of acetic acid, phenol, isopropylamine, n-butylamine, imidazole, and 4(5)-methylimidazole, and their conjugated bases or acids, respectively, in three solvents with different polarity and hydrogen-bonding propensity: acetonitrile (AN), dimethyl sulfoxide (DMSO), and water (H(2)O). For each pair and each solvent a series of umbrella-sampling molecular dynamics simulations with the AMBER force field, explicit solvent, and counterions added to maintain a zero net charge of a system were carried out and the PMF was calculated by using the Weighted Histogram Analysis Method (WHAM). Subsequently, homoconjugation-equilibrium constants were calculated by numerical integration of the respective PMF profiles. In all cases but imidazole stable homocomplexes were found to form in solution, which was manifested as the presence of contact minima corresponding to hydrogen-bonded species in the PMF curves. The calculated homoconjugation constants were found to be greater for complexes with the OHO bridge (acetic acid and phenol) than with the NHN bridge and they were found to decrease with increasing polarity and hydrogen-bonding propensity of the solvent (i.e., in the series AN > DMSO > H(2)O), both facts being in agreement with the available experimental data. It was also found that interactions with counterions are manifested as the broadening of the contact minimum or appearance of additional minima in the PMF profiles of the acetic acid-acetate, phenol/phenolate system in acetonitrile, and the 4(5)-methylimidazole/4(5)-methylimidzole cation conjugated base system in dimethyl sulfoxide.

  19. Absolute Equilibrium Entropy

    NASA Technical Reports Server (NTRS)

    Shebalin, John V.

    1997-01-01

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

  20. An Updated Equilibrium Machine

    NASA Astrophysics Data System (ADS)

    Schultz, Emeric

    2008-08-01

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

  1. A DFT-based comparative equilibrium study of thermal dehydration and hydrolysis of CaCl₂ hydrates and MgCl₂ hydrates for seasonal heat storage.

    PubMed

    Pathak, Amar Deep; Nedea, Silvia; Zondag, Herbert; Rindt, Camilo; Smeulders, David

    2016-04-21

    Salt hydrates store solar energy in chemical form via a reversible dehydration-hydration reaction. However, as a side reaction to dehydration, hydrolysis (HCl formation) may occur in chloride based salt hydrates (specially in MgCl2 hydrates), affecting the durability of the storage system. The mixture of CaCl2 and MgCl2 hydrates has been shown experimentally to have exceptional cycle stability and improved kinetics. However, the optimal operating conditions for the mixture are unknown. To understand the appropriate balance between dehydration and hydrolysis kinetics in the mixtures, it is essential to gain in-depth insight into the mixture components. We present a GGA-DFT level study to investigate the various gaseous structures of CaCl2 hydrates and to understand the relative stability of their conformers. The hydration strength and relative stability of conformers are dominated by electrostatic interactions. A wide network of intramolecular homonuclear and heteronuclear hydrogen bonds is observed in CaCl2 hydrates. Equilibrium product concentrations are obtained during dehydration and hydrolysis reactions under various temperature and pressure conditions. The trend of the dehydration curve with temperature in CaCl2 hydrates is similar to the experiments. Comparing these results to those of MgCl2 hydrates, we find that CaCl2 hydrates are more resistant towards hydrolysis in the temperature range of 273-800 K. Specifically, the present study reveals that the onset temperatures of HCl formation, a crucial design parameter for MgCl2 hydrates, are lower than for CaCl2 hydrates except for the mono-hydrate. PMID:27004734

  2. Higher-order compositional modeling of three-phase flow in 3D fractured porous media based on cross-flow equilibrium

    SciTech Connect

    Moortgat, Joachim Firoozabadi, Abbas

    2013-10-01

    Numerical simulation of multiphase compositional flow in fractured porous media, when all the species can transfer between the phases, is a real challenge. Despite the broad applications in hydrocarbon reservoir engineering and hydrology, a compositional numerical simulator for three-phase flow in fractured media has not appeared in the literature, to the best of our knowledge. In this work, we present a three-phase fully compositional simulator for fractured media, based on higher-order finite element methods. To achieve computational efficiency, we invoke the cross-flow equilibrium (CFE) concept between discrete fractures and a small neighborhood in the matrix blocks. We adopt the mixed hybrid finite element (MHFE) method to approximate convective Darcy fluxes and the pressure equation. This approach is the most natural choice for flow in fractured media. The mass balance equations are discretized by the discontinuous Galerkin (DG) method, which is perhaps the most efficient approach to capture physical discontinuities in phase properties at the matrix-fracture interfaces and at phase boundaries. In this work, we account for gravity and Fickian diffusion. The modeling of capillary effects is discussed in a separate paper. We present the mathematical framework, using the implicit-pressure-explicit-composition (IMPEC) scheme, which facilitates rigorous thermodynamic stability analyses and the computation of phase behavior effects to account for transfer of species between the phases. A deceptively simple CFL condition is implemented to improve numerical stability and accuracy. We provide six numerical examples at both small and larger scales and in two and three dimensions, to demonstrate powerful features of the formulation.

  3. Structural design using equilibrium programming

    NASA Technical Reports Server (NTRS)

    Scotti, Stephen J.

    1992-01-01

    Multiple nonlinear programming methods are combined in the method of equilibrium programming. Equilibrium programming theory has been appied to problems in operations research, and in the present study it is investigated as a framework to solve structural design problems. Several existing formal methods for structural optimization are shown to actually be equilibrium programming methods. Additionally, the equilibrium programming framework is utilized to develop a new structural design method. Selected computational results are presented to demonstrate the methods.

  4. A numerical study of EGS heat extraction process based on a thermal non-equilibrium model for heat transfer in subsurface porous heat reservoir

    NASA Astrophysics Data System (ADS)

    Chen, Jiliang; Jiang, Fangming

    2016-02-01

    With a previously developed numerical model, we perform a detailed study of the heat extraction process in enhanced or engineered geothermal system (EGS). This model takes the EGS subsurface heat reservoir as an equivalent porous medium while it considers local thermal non-equilibrium between the rock matrix and the fluid flowing in the fractured rock mass. The application of local thermal non-equilibrium model highlights the temperature-difference heat exchange process occurring in EGS reservoirs, enabling a better understanding of the involved heat extraction process. The simulation results unravel the mechanism of preferential flow or short-circuit flow forming in homogeneously fractured reservoirs of different permeability values. EGS performance, e.g. production temperature and lifetime, is found to be tightly related to the flow pattern in the reservoir. Thermal compensation from rocks surrounding the reservoir contributes little heat to the heat transmission fluid if the operation time of an EGS is shorter than 15 years. We find as well the local thermal equilibrium model generally overestimates EGS performance and for an EGS with better heat exchange conditions in the heat reservoir, the heat extraction process acts more like the local thermal equilibrium process.

  5. Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS—Part 3: Application to the Peach Spring Tuff (Arizona-California-Nevada, USA)

    NASA Astrophysics Data System (ADS)

    Pamukcu, Ayla S.; Gualda, Guilherme A. R.; Ghiorso, Mark S.; Miller, Calvin F.; McCracken, Reba G.

    2015-03-01

    Establishing the depths of magma accumulation is critical to understanding how magmas evolve and erupt, but developing methods to constrain these pressures is challenging. We apply the new rhyolite-MELTS phase-equilibria geobarometer—based on the equilibrium between melt, quartz, and two feldspars—to matrix glass compositions from Peach Spring Tuff (Arizona-California-Nevada, USA) high-silica rhyolite. We compare the results to those from amphibole geothermobarometry, projection of glass compositions onto the haplogranitic ternary, and glass SiO2 geobarometry. Quartz + 2 feldspar rhyolite-MELTS pressures span a relatively small range (185-230 MPa), consistent with nearly homogeneous crystal compositions, and are similar to estimates based on projection onto the haplogranitic ternary (250 ± 50 MPa) and on glass SiO2 (255-275 MPa). Amphibole geothermobarometry gives much wider pressure ranges (temperature-independent: ~65-300 MPa; temperature-dependent: ~75-295 MPa; amphibole-only: ~80-950 MPa); average Anderson and Smith (Am Mineral 80:549-559, 1995) + Blundy and Holland (Contrib Miner Petrol 104:208-224, 1990) or Holland and Blundy (Contrib Miner Petrol 116:433-447, 1994—Thermometer A, B) pressures are most similar to phase-equilibria results (~220, 210, 190 MPa, respectively). Crystallization temperatures determined previously with rhyolite-MELTS (742 °C), Zr-in-sphene (769 ± 20 °C), and zircon saturation (770-780 °C) geothermometry are similar, but temperatures from amphibole geothermometry (~450-955 °C) are notably different; the average Anderson and Smith + Holland and Blundy (1994—Thermometer B; ~710 °C) temperature is most consistent with previous estimates. The rhyolite-MELTS geobarometer effectively culls glass compositions affected by alteration or analytical issues; Peach Spring glass compositions that yield pressure estimates reveal a tight range of plausible Na2O and K2O contents, suggesting that low Na2O and high K2O contents of many

  6. Thermal equilibrium of goats.

    PubMed

    Maia, Alex S C; Nascimento, Sheila T; Nascimento, Carolina C N; Gebremedhin, Kifle G

    2016-05-01

    The effects of air temperature and relative humidity on thermal equilibrium of goats in a tropical region was evaluated. Nine non-pregnant Anglo Nubian nanny goats were used in the study. An indirect calorimeter was designed and developed to measure oxygen consumption, carbon dioxide production, methane production and water vapour pressure of the air exhaled from goats. Physiological parameters: rectal temperature, skin temperature, hair-coat temperature, expired air temperature and respiratory rate and volume as well as environmental parameters: air temperature, relative humidity and mean radiant temperature were measured. The results show that respiratory and volume rates and latent heat loss did not change significantly for air temperature between 22 and 26°C. In this temperature range, metabolic heat was lost mainly by convection and long-wave radiation. For temperature greater than 30°C, the goats maintained thermal equilibrium mainly by evaporative heat loss. At the higher air temperature, the respiratory and ventilation rates as well as body temperatures were significantly elevated. It can be concluded that for Anglo Nubian goats, the upper limit of air temperature for comfort is around 26°C when the goats are protected from direct solar radiation.

  7. Thermal equilibrium of goats.

    PubMed

    Maia, Alex S C; Nascimento, Sheila T; Nascimento, Carolina C N; Gebremedhin, Kifle G

    2016-05-01

    The effects of air temperature and relative humidity on thermal equilibrium of goats in a tropical region was evaluated. Nine non-pregnant Anglo Nubian nanny goats were used in the study. An indirect calorimeter was designed and developed to measure oxygen consumption, carbon dioxide production, methane production and water vapour pressure of the air exhaled from goats. Physiological parameters: rectal temperature, skin temperature, hair-coat temperature, expired air temperature and respiratory rate and volume as well as environmental parameters: air temperature, relative humidity and mean radiant temperature were measured. The results show that respiratory and volume rates and latent heat loss did not change significantly for air temperature between 22 and 26°C. In this temperature range, metabolic heat was lost mainly by convection and long-wave radiation. For temperature greater than 30°C, the goats maintained thermal equilibrium mainly by evaporative heat loss. At the higher air temperature, the respiratory and ventilation rates as well as body temperatures were significantly elevated. It can be concluded that for Anglo Nubian goats, the upper limit of air temperature for comfort is around 26°C when the goats are protected from direct solar radiation. PMID:27157333

  8. Efficiency of muscle contraction. The chemimechanic equilibrium

    NASA Astrophysics Data System (ADS)

    Becker, E. W.

    1991-10-01

    Although muscle contraction is one of the principal themes of biological research, the exact mechanism whereby the chemical free energy of ATP hydrolysis is converted into mechanical work remains elusive. The high thermodynamic efficiency of the process, above all, is difficult to explain on the basis of present theories. A model of the elementary effect in muscle contraction is proposed which aims at high thermodynamic efficiency based on an approximate equilibrium between chemical and mechanical forces throughout the transfer of free energy. The experimental results described in the literature support the assumption that chemimechanic equilibrium is approximated by a free energy transfer system based on the binding of divalent metal ions to the myosin light chains. Muscle contraction demonstrated without light chains is expected to proceed with a considerably lower efficiency. Free energy transfer systems based on the binding of ions to proteins seem to be widespread in the cell. By establishing an approximate chemimechanic equilibrium, they could facilitate biological reactions considerably and save large amounts of free energy. The concept of chemimechanic equilibrium is seen as a supplementation to the concept of chemiosmotic equilibrium introduced for the membrane transport by P. Mitchell.

  9. Dynamic and equilibrium performance of sensors based on short peptide ligands for affinity adsorption of human IgG using surface plasmon resonance.

    PubMed

    Islam, Nafisa; Shen, Fei; Gurgel, Patrick V; Rojas, Orlando J; Carbonell, Ruben G

    2014-08-15

    This paper characterizes the potential of novel hexameric peptide ligands for on-line IgG detection in bioprocesses. Surface Plasmon Resonance (SPR) was used to study the binding of human IgG to the hexameric peptide ligand HWRGWV, which was covalently grafted to alkanethiol self-assembled monolayers (SAM) on gold surfaces. Peptide coupling on SAMs was verified, followed by covalent grafting of peptides with a removable Fmoc or acetylated N-termini via their C-termini to produce active peptide SPR sensors that were tested for IgG binding. The dynamics and extent of peptide-IgG binding were compared with results from a conventional system using protein A attached on a gold surface via disulfide monolayers. IgG binding to protein A on disulfide monolayers yielded equilibrium dissociation constants of 1.4×10(-7)M. The corresponding dissociation constant value for the acetylated version of the peptide (Ac-HWRGWV) supported on alkanethiol SAM was 5.8×10(-7)M and that for HWRGWV on the alkanethiol SAM (after de-protection of Fmoc-HWRGWVA) was 1.2×10(-6)M. Maximum IgG binding capacities, Qm of 6.7, 3.8, and 4.1mgm(-2) were determined for the protein A and the two forms of HWRGWV-based biosensors, respectively. Real-time data for the kinetics of adsorption were used to determine the apparent rate constants for adsorption and desorption. The results were analyzed to understand the mechanism of IgG binding to the protein and peptide ligands. It was found that the peptide-IgG binding was reaction controlled, however the protein A-IgG binding mechanism was partially mass transfer (diffusion) controlled. The adsorption rate constants, ka, for the protein A ligand increased with decreasing concentration of analyte and the peptide ligand ka values was constant at different IgG concentrations and flow rates.

  10. Equilibrium gas flow computations. I - Accurate and efficient calculation of equilibrium gas properties

    NASA Technical Reports Server (NTRS)

    Liu, Yen; Vinokur, Marcel

    1989-01-01

    This paper treats the accurate and efficient calculation of thermodynamic properties of arbitrary gas mixtures for equilibrium flow computations. New improvements in the Stupochenko-Jaffe model for the calculation of thermodynamic properties of diatomic molecules are presented. A unified formulation of equilibrium calculations for gas mixtures in terms of irreversible entropy is given. Using a highly accurate thermo-chemical data base, a new, efficient and vectorizable search algorithm is used to construct piecewise interpolation procedures with generate accurate thermodynamic variable and their derivatives required by modern computational algorithms. Results are presented for equilibrium air, and compared with those given by the Srinivasan program.

  11. Iron isotope fractionation between aqueous Fe(II) and goethite revisited: New insights based on a multi-direction approach to equilibrium and isotopic exchange rate modification

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Beard, Brian L.; Reddy, Thiruchelvi R.; Scherer, Michelle M.; Johnson, Clark M.

    2014-08-01

    The Fe isotope compositions of naturally occurring Fe oxide minerals provide insights into biogeochemical processes that occur in modern and ancient environments. Key to understanding isotopic variations in such minerals is knowledge of the equilibrium Fe isotope fractionation factors between common minerals and aqueous Fe species. Because experimental measurements of isotopic fractionation may reflect a combination of kinetic and equilibrium fractionations during rapid dissolution and precipitation, even in experiments that employ the three-isotope method, assessment of the attainment of equilibrium is often difficult. Here, we re-examine Fe isotope exchange, via a 57Fe tracer, and natural mass-dependent fractionation, through changes in initial 56Fe/54Fe ratios, between aqueous Fe(II) (Fe(II)aq) and goethite. This approach uses the three-isotope method, but is distinct in its evaluation of kinetic isotope fractionation and the attainment of equilibrium by: (i) employing a multi-direction approach to equilibrium at 22 °C via reaction of three Fe(II)aq solutions that had different initial 56Fe/54Fe ratios, (ii) conducting isotopic exchange experiments at elevated temperature (50 °C), and (iii) modifying the rate of isotopic exchange through a combination of trace-element substitutions and particle coarsening to evaluate corresponding temporal changes in fractionation trajectories that may reflect changing instantaneous fractionation factors. We find that rapid isotopic exchange produces kinetic isotope effects between Fe(II)aq and goethite, which shifts the 56Fe/54Fe ratios of Fe(II)aq early in reactions toward that of goethite, indicating that the instantaneous Fe(II)aq-goethite fractionation factor under kinetic conditions is small. Importantly, however, this kinetic fractionation is “erased” with continued reaction, and this is evident by the congruence for multiple-exchange trajectories of distinct initial Fe(II)aq solutions toward the same final value

  12. Phase equilibrium studies

    SciTech Connect

    Mathias, P.M.; Stein, F.P.

    1983-09-01

    A phase equilibrium model has been developed for the SRC-I process, as well as the other coal liquefaction processes. It is applicable to both vapor/liquid and liquid/liquid equilibria; it also provides an approximate but adequate description of aqueous mixtures where the volatile electrolyte components dissociate to form ionic species. This report completes the description of the model presented in an earlier report (Mathias and Stein, 1983a). Comparisons of the model to previously published data on coal-fluid mixtures are presented. Further, a preliminary analysis of new data on SRC-I coal fluids is presented. Finally, the current capabilities and deficiencies of the model are discussed. 25 references, 17 figures, 30 tables.

  13. Statistical physics ""Beyond equilibrium

    SciTech Connect

    Ecke, Robert E

    2009-01-01

    The scientific challenges of the 21st century will increasingly involve competing interactions, geometric frustration, spatial and temporal intrinsic inhomogeneity, nanoscale structures, and interactions spanning many scales. We will focus on a broad class of emerging problems that will require new tools in non-equilibrium statistical physics and that will find application in new material functionality, in predicting complex spatial dynamics, and in understanding novel states of matter. Our work will encompass materials under extreme conditions involving elastic/plastic deformation, competing interactions, intrinsic inhomogeneity, frustration in condensed matter systems, scaling phenomena in disordered materials from glasses to granular matter, quantum chemistry applied to nano-scale materials, soft-matter materials, and spatio-temporal properties of both ordinary and complex fluids.

  14. On applicability of the photochemical-equilibrium approach for retrieval of O and H mesospheric distributions from the satellite-based measurements of the airglow emission and ozone concentration

    NASA Astrophysics Data System (ADS)

    Feigin, Alexander; Belikovich, Mikhail; Kulikov, Mikhail

    2016-04-01

    Atomic oxygen and hydrogen are known to be among key components for the photochemistry and energy balance of the Earth's atmosphere between approximately 80 and 100 km altitude (mesopause region). Therefore, obtaining information about the vertical distributions of O and H concentrations is an important task in studies of this region. Solving of this problem is rather difficult due to the absence of regular methods which allow one to direct measurements of distributions of these components in mesosphere. However, indirect methods used to retrieve O and H distributions from the satellite-based measurements of the OH and O2(1D) airglow emission, as well as the data of IR and microwave O3 measurements have a sufficiently long development history. These methods are rooted in the use of the condition of photochemical equilibrium of ozone density in the range of altitudes from 50 to 100 km. A significant factor is that an insufficient volume of such measurement data forces researchers to use approximate ("truncated") photochemical-equilibrium conditions. In particular, it is assumed that in the daytime the ozone production reaction is perfectly balanced by ozone photodissociation, whereas during the night the only ozone sink is the reaction of ozone with atomic hydrogen, which, in its turn, leads to formation of excited OH and airglow emission of the latter. The presentation analyzes applicability of the photochemical-equilibrium conditions both in the total and truncated forms for description of the spatio-temporal evolution of mesospheric ozone during a year. The analysis is based on year-long time series generated by a 3D chemical transport model, which reproduces correctly various types of atmosphere dynamics in the range of altitudes from 50 to 100 km. These data are used to determine statistics of the ratio between the correct (calculated dynamically) distributions of the O3 density and its uncontracted and truncated equilibrium values for the conditions of the

  15. Exploring Chemical Equilibrium with Poker Chips: A General Chemistry Laboratory Exercise

    ERIC Educational Resources Information Center

    Bindel, Thomas H.

    2012-01-01

    A hands-on laboratory exercise at the general chemistry level introduces students to chemical equilibrium through a simulation that uses poker chips and rate equations. More specifically, the exercise allows students to explore reaction tables, dynamic chemical equilibrium, equilibrium constant expressions, and the equilibrium constant based on…

  16. Neoclassical equilibrium in gyrokinetic simulations

    SciTech Connect

    Garbet, X.; Dif-Pradalier, G.; Nguyen, C.; Sarazin, Y.; Grandgirard, V.; Ghendrih, Ph.

    2009-06-15

    This paper presents a set of model collision operators, which reproduce the neoclassical equilibrium and comply with the constraints of a full-f global gyrokinetic code. The assessment of these operators is based on an entropy variational principle, which allows one to perform a fast calculation of the neoclassical diffusivity and poloidal velocity. It is shown that the force balance equation is recovered at lowest order in the expansion parameter, the normalized gyroradius, hence allowing one to calculate correctly the radial electric field. Also, the conventional neoclassical transport and the poloidal velocity are reproduced in the plateau and banana regimes. The advantages and drawbacks of the various model operators are discussed in view of the requirements for neoclassical and turbulent transport.

  17. Equilibrium Potentials of Membrane Electrodes

    PubMed Central

    Wang, Jui H.; Copeland, Eva

    1973-01-01

    A simple thermodynamic theory of the equilibrium potentials of membrane electrodes is formulated and applied to the glass electrode for measurement of pH. The new formulation assumes the selective adsorption or binding of specific ions on the surface of the membrane which may or may not be permeable to the ion, and includes the conventional derivation based on reversible ion transport across membranes as a special case. To test the theory, a platinum wire was coated with a mixture of stearic acid and methyl-tri-n-octyl-ammonium stearate. When this coated electrode was immersed in aqueous phosphate solution, its potential was found to be a linear function of pH from pH 2 to 12 with a slope equal to the theoretical value of 59.0 mV per pH unit at 24°. PMID:4516194

  18. 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.

  19. Uniqueness of Nash equilibrium in vaccination games.

    PubMed

    Bai, Fan

    2016-12-01

    One crucial condition for the uniqueness of Nash equilibrium set in vaccination games is that the attack ratio monotonically decreases as the vaccine coverage level increasing. We consider several deterministic vaccination models in homogeneous mixing population and in heterogeneous mixing population. Based on the final size relations obtained from the deterministic epidemic models, we prove that the attack ratios can be expressed in terms of the vaccine coverage levels, and also prove that the attack ratios are decreasing functions of vaccine coverage levels. Some thresholds are presented, which depend on the vaccine efficacy. It is proved that for vaccination games in homogeneous mixing population, there is a unique Nash equilibrium for each game.

  20. Equilibrium calculations for helical axis stellarators

    SciTech Connect

    Hender, T.C.; Carreras, B.A.

    1984-04-01

    An average method based on a vacuum flux coordinate system is presented. This average method permits the study of helical axis stellarators with toroidally dominated shifts. An ordering is introduced, and to lowest order the toroidally averaged equilibrium equations are reduced to a Grad-Shafranov equation. Also, to lowest order, a Poisson-type equation is obtained for the toroidally varying corrections to the equilibium. By including these corrections, systems that are toroidally dominated, but with significant helical distortion to the equilibrium, may be studied. Numerical solutions of the average method equations are shown to agree well with three-dimensional calculations.

  1. Chemical Equilibrium Composition of Aqueous Systems

    1996-12-30

    MINEQL is a subroutine package to calculate equilibrium composition of an aqueous system, accounting for mass transfer. MINEQL-EIR contains an additional base on enthalpy and heat capacity data and has the option to do calculations at temperatures different from 25 degrees C.

  2. Non-Poisson processes: regression to equilibrium versus equilibrium correlation functions

    NASA Astrophysics Data System (ADS)

    Allegrini, Paolo; Grigolini, Paolo; Palatella, Luigi; Rosa, Angelo; West, Bruce J.

    2005-03-01

    We study the response to perturbation of non-Poisson dichotomous fluctuations that generate super-diffusion. We adopt the Liouville perspective and with it a quantum-like approach based on splitting the density distribution into a symmetric and an anti-symmetric component. To accomodate the equilibrium condition behind the stationary correlation function, we study the time evolution of the anti-symmetric component, while keeping the symmetric component at equilibrium. For any realistic form of the perturbed distribution density we expect a breakdown of the Onsager principle, namely, of the property that the subsequent regression of the perturbation to equilibrium is identical to the corresponding equilibrium correlation function. We find the directions to follow for the calculation of higher-order correlation functions, an unsettled problem, which has been addressed in the past by means of approximations yielding quite different physical effects.

  3. Analytic prediction of airplane equilibrium spin characteristics

    NASA Technical Reports Server (NTRS)

    Adams, W. M., Jr.

    1972-01-01

    The nonlinear equations of motion are solved algebraically for conditions for which an airplane is in an equilibrium spin. Constrained minimization techniques are employed in obtaining the solution. Linear characteristics of the airplane about the equilibrium points are also presented and their significance in identifying the stability characteristics of the equilibrium points is discussed. Computer time requirements are small making the method appear potentially applicable in airplane design. Results are obtained for several configurations and are compared with other analytic-numerical methods employed in spin prediction. Correlation with experimental results is discussed for one configuration for which a rather extensive data base was available. A need is indicated for higher Reynolds number data taken under conditions which more accurately simulate a spin.

  4. Copolymer Crystallization: Approaching Equilibrium

    NASA Astrophysics Data System (ADS)

    Crist, Buckley; Finerman, Terry

    2002-03-01

    Random ethylene-butene copolymers of uniform chemical composition and degree of polymerization are crystallized by evaporation of thin films (1 μ m - 5 μ m) from solution. Macroscopic films ( 100 μm) formed by sequential layer deposition are characterized by density, calorimetry and X-ray techniques. Most notable is the density, which in some cases implies a crystalline fraction nearly 90% of the equilibrium value calculated from Flory theory. Melting temperature of these solution deposited layers is increased by as much as 8 ^oC over Tm for the same polymer crystallized from the melt. Small-angle X-ray scattering indicates that the amorphous layer thickness is strongly reduced by this layered crystallization process. X-ray diffraction shows a pronounced orientation of chain axes and lamellar normals parallel to the normal of the macroscopic film. It is clear that solvent enhances chain mobility, permitting proper sequences to aggregate and crystallize in a manner that is never achieved in the melt.

  5. Development of a model using the MATLAB System identification toolbox to estimate (222)Rn equilibrium factor from CR-39 based passive measurements.

    PubMed

    Abo-Elmagd, M; Sadek, A M

    2014-12-01

    Can and Bare method is a widely used passive method for measuring the equilibrium factor F through the determination of the track density ratio between bare (D) and filtered (Do) detectors. The dimensions of the used diffusion chamber are altering the deposition ratios of Po-isotopes on the chamber walls as well as the ratios of the existing alpha emitters in air. Then the measured filtered track density and therefore the resultant equilibrium factor is changed according to the diffusion chamber dimensions. For this reason, high uncertainty was expected in the measured F using different diffusion chambers. In the present work, F is derived as a function of both track density ratio (D/Do) and the dimensions of the used diffusion chambers (its volume to the total internal surface area; V/A). The accuracy of the derived formula was verified using the black-box modeling technique via the MATLAB System identification toolbox. The results show that the uncertainty of the calculated F by using the derived formula of F (D/Do, V/A) is only 5%. The obtained uncertainty ensures the quality of the derived function to calculate F using diffusion chambers with wide range of dimensions.

  6. Rapid-Equilibrium Enzyme Kinetics

    ERIC Educational Resources Information Center

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

  7. [Dichotomizing method applied to calculating equilibrium constant of dimerization system].

    PubMed

    Cheng, Guo-zhong; Ye, Zhi-xiang

    2002-06-01

    The arbitrary trivariate algebraic equations are formed based on the combination principle. The univariata algebraic equation of equilibrium constant kappa for dimerization system is obtained through a series of algebraic transformation, and it depends on the properties of monotonic functions whether the equation is solvable or not. If the equation is solvable, equilibrium constant of dimerization system is obtained by dichotomy and its final equilibrium constant of dimerization system is determined according to the principle of error of fitting. The equilibrium constants of trisulfophthalocyanine and biosulfophthalocyanine obtained with this method are 47,973.4 and 30,271.8 respectively. The results are much better than those reported previously.

  8. Equilibrium Shape of Colloidal Crystals.

    PubMed

    Sehgal, Ray M; Maroudas, Dimitrios

    2015-10-27

    Assembling colloidal particles into highly ordered configurations, such as photonic crystals, has significant potential for enabling a broad range of new technologies. Facilitating the nucleation of colloidal crystals and developing successful crystal growth strategies require a fundamental understanding of the equilibrium structure and morphology of small colloidal assemblies. Here, we report the results of a novel computational approach to determine the equilibrium shape of assemblies of colloidal particles that interact via an experimentally validated pair potential. While the well-known Wulff construction can accurately capture the equilibrium shape of large colloidal assemblies, containing O(10(4)) or more particles, determining the equilibrium shape of small colloidal assemblies of O(10) particles requires a generalized Wulff construction technique which we have developed for a proper description of equilibrium structure and morphology of small crystals. We identify and characterize fully several "magic" clusters which are significantly more stable than other similarly sized clusters.

  9. Using Analogies to Prevent Misconceptions about Chemical Equilibrium

    ERIC Educational Resources Information Center

    Sahin Pekmez, Esin

    2010-01-01

    The main purpose of this study was to find the effectiveness of using analogies to prevent misconceptions about chemical equilibrium. Nineteen analogies, which were based on dynamic aspects of chemical equilibrium and application of Le Chatelier's principle, were developed. The participations of this study consisted of 11th grade students (n: 151)…

  10. Caloric and entropic temperatures in non-equilibrium steady states

    NASA Astrophysics Data System (ADS)

    Jou, D.; Restuccia, L.

    2016-10-01

    We examine the non-equilibrium consequences of two different definitions of temperature in systems out of equilibrium: one is based on the internal energy (caloric temperature), and the other one on the entropy (entropic temperature). We discuss the relation between the values obtained from these two definitions in ideal gases and in two-level systems.

  11. Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

    ERIC Educational Resources Information Center

    Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

  12. The need for energy equilibrium.

    PubMed

    Flouris, A D; Klentrou, P

    2005-06-01

    Human bioenergetics has been extensively assessed by means of field proxies (ie, cardiorespiratory fitness field tests) during the last two decades. A systematic review of the germane literature, however, suggests considerable controversy as to whether the present tests lead to valid measurements of energy expenditure/utilisation. The present paper suggests that current modalities of field testing being used as predictive models for bioenergetics may suffer from methodological limitations, stemming primarily from inappropriate design. A major weakness in the theoretical basis of proxies is that, although based on field measurements, it seeks to predict laboratory bioenergetics which, in turn, are used to provide information on field performance. Hence, it seems reasonable that the number of transformations increases the potential for error and may have significant impact on the prediction of bioenergetics. Recent studies asserted the importance of achieving 'energy equilibrium' between the reference standard and each proxy. The suggested approach involves designing proxies that closely simulate each laboratory protocol used as reference standard. The theoretical bases of previous and contemporary approaches are discussed in an attempt to increase the validity of current proxy assessments.

  13. Tuning, ergodicity, equilibrium, and cosmology

    NASA Astrophysics Data System (ADS)

    Albrecht, Andreas

    2015-05-01

    I explore the possibility that the cosmos is fundamentally an equilibrium system and review the attractive features of such theories. Equilibrium cosmologies are commonly thought to fail due to the "Boltzmann brain" problem. I show that it is possible to evade the Boltzmann brain problem if there is a suitable coarse-grained relationship between the fundamental degrees of freedom and the cosmological observables. I make my main points with simple toy models and then review the de Sitter equilibrium model as an illustration.

  14. Understanding thermal equilibrium through activities

    NASA Astrophysics Data System (ADS)

    Pathare, Shirish; Huli, Saurabhee; Nachane, Madhura; Ladage, Savita; Pradhan, Hemachandra

    2015-03-01

    Thermal equilibrium is a basic concept in thermodynamics. In India, this concept is generally introduced at the first year of undergraduate education in physics and chemistry. In our earlier studies (Pathare and Pradhan 2011 Proc. episteme-4 Int. Conf. to Review Research on Science Technology and Mathematics Education pp 169-72) we found that students in India have a rather unsatisfactory understanding of thermal equilibrium. We have designed and developed a module of five activities, which are presented in succession to the students. These activities address the students’ alternative conceptions that underlie their lack of understanding of thermal equilibrium and aim at enhancing their understanding of the concept.

  15. Chemical Equilibrium, Unit 3: Chemical Equilibrium Calculations. A Computer-Enriched Module for Introductory Chemistry. Student's Guide and Teacher's Guide.

    ERIC Educational Resources Information Center

    Jameson, Cynthia J.

    Presented are the teacher's guide and student materials for one of a series of self-instructional, computer-based learning modules for an introductory, undergraduate chemistry course. The student manual for this unit on chemical equilibrium calculations includes objectives, prerequisites, a discussion of the equilibrium constant (K), and ten…

  16. Philicities, Fugalities, and Equilibrium Constants.

    PubMed

    Mayr, Herbert; Ofial, Armin R

    2016-05-17

    The mechanistic model of Organic Chemistry is based on relationships between rate and equilibrium constants. Thus, strong bases are generally considered to be good nucleophiles and poor nucleofuges. Exceptions to this rule have long been known, and the ability of iodide ions to catalyze nucleophilic substitutions, because they are good nucleophiles as well as good nucleofuges, is just a prominent example for exceptions from the general rule. In a reaction series, the Leffler-Hammond parameter α = δΔG(⧧)/δΔG° describes the fraction of the change in the Gibbs energy of reaction, which is reflected in the change of the Gibbs energy of activation. It has long been considered as a measure for the position of the transition state; thus, an α value close to 0 was associated with an early transition state, while an α value close to 1 was considered to be indicative of a late transition state. Bordwell's observation in 1969 that substituent variation in phenylnitromethanes has a larger effect on the rates of deprotonation than on the corresponding equilibrium constants (nitroalkane anomaly) triggered the breakdown of this interpretation. In the past, most systematic investigations of the relationships between rates and equilibria of organic reactions have dealt with proton transfer reactions, because only for few other reaction series complementary kinetic and thermodynamic data have been available. In this Account we report on a more general investigation of the relationships between Lewis basicities, nucleophilicities, and nucleofugalities as well as between Lewis acidities, electrophilicities, and electrofugalities. Definitions of these terms are summarized, and it is suggested to replace the hybrid terms "kinetic basicity" and "kinetic acidity" by "protophilicity" and "protofugality", respectively; in this way, the terms "acidity" and "basicity" are exclusively assigned to thermodynamic properties, while "philicity" and "fugality" refer to kinetics

  17. Equilibrium molecular thermodynamics from Kirkwood sampling.

    PubMed

    Somani, Sandeep; Okamoto, Yuko; Ballard, Andrew J; Wales, David J

    2015-05-21

    We present two methods for barrierless equilibrium sampling of molecular systems based on the recently proposed Kirkwood method (J. Chem. Phys. 2009, 130, 134102). Kirkwood sampling employs low-order correlations among internal coordinates of a molecule for random (or non-Markovian) sampling of the high dimensional conformational space. This is a geometrical sampling method independent of the potential energy surface. The first method is a variant of biased Monte Carlo, where Kirkwood sampling is used for generating trial Monte Carlo moves. Using this method, equilibrium distributions corresponding to different temperatures and potential energy functions can be generated from a given set of low-order correlations. Since Kirkwood samples are generated independently, this method is ideally suited for massively parallel distributed computing. The second approach is a variant of reservoir replica exchange, where Kirkwood sampling is used to construct a reservoir of conformations, which exchanges conformations with the replicas performing equilibrium sampling corresponding to different thermodynamic states. Coupling with the Kirkwood reservoir enhances sampling by facilitating global jumps in the conformational space. The efficiency of both methods depends on the overlap of the Kirkwood distribution with the target equilibrium distribution. We present proof-of-concept results for a model nine-atom linear molecule and alanine dipeptide.

  18. Equilibrium and Orientation in Cephalopods.

    ERIC Educational Resources Information Center

    Budelmann, Bernd-Ulrich

    1980-01-01

    Describes the structure of the equilibrium receptor system in cephalopods, comparing it to the vertebrate counterpart--the vestibular system. Relates the evolution of this complex system to the competition of cephalopods with fishes. (CS)

  19. Transferable Anisotropic United-Atom Force Field Based on the Mie Potential for Phase Equilibrium Calculations: n-Alkanes and n-Olefins.

    PubMed

    Hemmen, Andrea; Gross, Joachim

    2015-09-01

    A new transferable force field parametrization for n-alkanes and n-olefins is proposed in this work. A united-atom approach is taken, where hydrogen atoms are lumped with neighboring atoms to single interaction sites. A comprehensive study is conducted for alkanes, optimizing van der Waals force field parameters in 6 dimensions. A Mie n-6 potential is considered for the van der Waals interaction, where for n-alkanes we simultaneously optimize the energy parameters ϵCH3 and ϵCH2 as well as the size parameters σCH3 and σCH2 of the CH3(sp(3)) and CH2(sp(3)) groups. Further, the repulsive exponent n of the Mie n-6 potential is varied. Moreover, we investigate the bond length toward the terminal CH3 group as a degree of freedom. According to the AUA (anisotropic united-atom) force field, the bond length between the terminal CH3 group and the neighboring interaction site should be increased by Δl compared with the carbon-carbon distance in order to better account for the hydrogen atoms. The parameter Δl is considered as a degree of freedom. The intramolecular force field parametrization is taken from existing force fields. A single objective function for the optimization is defined as squared relative deviations in vapor pressure and in liquid density of propane, n-butane, n-hexane, and n-octane. A similar study is also done for olefins, where the objective function includes 1-butene, 1-hexene, 1-octene, cis-2-pentene, and trans-2-pentene. Molecular simulations are performed in the grand canonical ensemble with transition-matrix sampling where the phase equilibrium properties are obtained with the histogram reweighting technique. The 6-dimensional optimization of strongly correlated parameters is possible, because the analytic PC-SAFT equation of state is used to locally correlate simulation results. The procedure is iterative but leads to very efficient convergence. An implementation is proposed, where the converged result is not affected (disturbed) by the

  20. A search for equilibrium states

    NASA Technical Reports Server (NTRS)

    Zeleznik, F. J.

    1982-01-01

    An efficient search algorithm is described for the location of equilibrium states in a search set of states which differ from one another only by the choice of pure phases. The algorithm has three important characteristics: (1) it ignores states which have little prospect for being an improved approximation to the true equilibrium state; (2) it avoids states which lead to singular iteration equations; (3) it furnishes a search history which can provide clues to alternative search paths.

  1. Edge equilibrium code for tokamaks

    SciTech Connect

    Li, Xujing; Drozdov, Vladimir V.

    2014-01-15

    The edge equilibrium code (EEC) described in this paper is developed for simulations of the near edge plasma using the finite element method. It solves the Grad-Shafranov equation in toroidal coordinate and uses adaptive grids aligned with magnetic field lines. Hermite finite elements are chosen for the numerical scheme. A fast Newton scheme which is the same as implemented in the equilibrium and stability code (ESC) is applied here to adjust the grids.

  2. RINGED ACCRETION DISKS: EQUILIBRIUM CONFIGURATIONS

    SciTech Connect

    Pugliese, D.; Stuchlík, Z. E-mail: zdenek.stuchlik@physics.cz

    2015-12-15

    We investigate a model of a ringed accretion disk, made up by several rings rotating around a supermassive Kerr black hole attractor. Each toroid of the ringed disk is governed by the general relativity hydrodynamic Boyer condition of equilibrium configurations of rotating perfect fluids. Properties of the tori can then be determined by an appropriately defined effective potential reflecting the background Kerr geometry and the centrifugal effects. The ringed disks could be created in various regimes during the evolution of matter configurations around supermassive black holes. Therefore, both corotating and counterrotating rings have to be considered as being a constituent of the ringed disk. We provide constraints on the model parameters for the existence and stability of various ringed configurations and discuss occurrence of accretion onto the Kerr black hole and possible launching of jets from the ringed disk. We demonstrate that various ringed disks can be characterized by a maximum number of rings. We present also a perturbation analysis based on evolution of the oscillating components of the ringed disk. The dynamics of the unstable phases of the ringed disk evolution seems to be promising in relation to high-energy phenomena demonstrated in active galactic nuclei.

  3. Unified theory of quantized electrons, phonons, and photons out of equilibrium: A simplified ab initio approach based on the generalized Baym-Kadanoff ansatz

    NASA Astrophysics Data System (ADS)

    de Melo, Pedro Miguel M. C.; Marini, Andrea

    2016-04-01

    We present a full ab initio description of the coupled out-of-equilibrium dynamics of photons, phonons, and electrons. In the present approach, the quantized nature of the electromagnetic field as well as of the nuclear oscillations is fully taken into account. The result is a set of integrodifferential equations, written on the Keldysh contour, for the Green's functions of electrons, phonons, and photons where the different kinds of interactions are merged together. We then concentrate on the electronic dynamics in order to reduce the problem to a computationally feasible approach. By using the generalized Baym-Kadanoff ansatz and the completed collision approximation, we introduce a series of efficient but controllable approximations. In this way, we reduce all equations to a set of decoupled equations for the density matrix that describe all kinds of static and dynamical correlations. The final result is a coherent, general, and inclusive scheme to calculate several physical quantities: carrier dynamics, transient photoabsorption, and light emission, all of which include, at the same time, electron-electron, electron-phonon, and electron-photon interactions. We further discuss how all these observables can be easily calculated within the present scheme using a fully atomistic ab initio approach.

  4. Spin-polarization and spin-dependent logic gates in a double quantum ring based on Rashba spin-orbit effect: Non-equilibrium Green's function approach

    SciTech Connect

    Eslami, Leila Esmaeilzadeh, Mahdi

    2014-02-28

    Spin-dependent electron transport in an open double quantum ring, when each ring is made up of four quantum dots and threaded by a magnetic flux, is studied. Two independent and tunable gate voltages are applied to induce Rashba spin-orbit effect in the quantum rings. Using non-equilibrium Green's function formalism, we study the effects of electron-electron interaction on spin-dependent electron transport and show that although the electron-electron interaction induces an energy gap, it has no considerable effect when the bias voltage is sufficiently high. We also show that the double quantum ring can operate as a spin-filter for both spin up and spin down electrons. The spin-polarization of transmitted electrons can be tuned from −1 (pure spin-down current) to +1 (pure spin-up current) by changing the magnetic flux and/or the gates voltage. Also, the double quantum ring can act as AND and NOR gates when the system parameters such as Rashba coefficient are properly adjusted.

  5. Study on an effective industrial waste-based adsorbent for the adsorptive removal of phosphorus from wastewater: equilibrium and kinetics studies.

    PubMed

    Xie, Ruzhen; Chen, Yao; Cheng, Ting; Lai, Yuguo; Jiang, Wenju; Yang, Zhishan

    2016-01-01

    In this work, an effective adsorbent for removing phosphate from aqueous solution was developed from modifying industrial waste--lithium silica fume (LSF). The characterization of LSF before and after modification was investigated using an N2 adsorption-desorption technique (Brunauer-Emmett-Teller, BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Studies were conducted to investigate the effect of adsorbent dose, initial solution pH, contact time, phosphate concentration, and temperature on phosphate removal using this novel adsorbent. The specific surface area for modified LSF (LLSF) is 24.4024 m(2)/g, improved 69.8% compared with unmodified LSF. XRD result suggests that the lanthanum phosphate complex was formed on the surface of LLSF. The maximum phosphate adsorption capacity was 24.096 mg P/g for LLSF, and phosphate removal was favored in the pH range of 3-8. The kinetic data fitted pseudo-second-order kinetic equation, intra-particle diffusion was not the only rate controlling step. The adsorption isotherm results illustrated that the Langmuir model provided the best fit for the equilibrium data. The change in free energy (△G(0)), enthalpy (△H(0)) and entropy (△S(0)) revealed that the adsorption of phosphate on LLSF was spontaneous and endothermic. It was concluded that by modifying with lanthanum, LSF can be turned to be a highly efficient adsorbent in phosphate removal.

  6. Study on an effective industrial waste-based adsorbent for the adsorptive removal of phosphorus from wastewater: equilibrium and kinetics studies.

    PubMed

    Xie, Ruzhen; Chen, Yao; Cheng, Ting; Lai, Yuguo; Jiang, Wenju; Yang, Zhishan

    2016-01-01

    In this work, an effective adsorbent for removing phosphate from aqueous solution was developed from modifying industrial waste--lithium silica fume (LSF). The characterization of LSF before and after modification was investigated using an N2 adsorption-desorption technique (Brunauer-Emmett-Teller, BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Studies were conducted to investigate the effect of adsorbent dose, initial solution pH, contact time, phosphate concentration, and temperature on phosphate removal using this novel adsorbent. The specific surface area for modified LSF (LLSF) is 24.4024 m(2)/g, improved 69.8% compared with unmodified LSF. XRD result suggests that the lanthanum phosphate complex was formed on the surface of LLSF. The maximum phosphate adsorption capacity was 24.096 mg P/g for LLSF, and phosphate removal was favored in the pH range of 3-8. The kinetic data fitted pseudo-second-order kinetic equation, intra-particle diffusion was not the only rate controlling step. The adsorption isotherm results illustrated that the Langmuir model provided the best fit for the equilibrium data. The change in free energy (△G(0)), enthalpy (△H(0)) and entropy (△S(0)) revealed that the adsorption of phosphate on LLSF was spontaneous and endothermic. It was concluded that by modifying with lanthanum, LSF can be turned to be a highly efficient adsorbent in phosphate removal. PMID:27120644

  7. Application of novel, low-cost, laterite-based adsorbent for removal of lead from water: Equilibrium, kinetic and thermodynamic studies.

    PubMed

    Chatterjee, Somak; De, Sirshendu

    2016-01-01

    Contamination of groundwater by carcinogenic heavy metal, e.g., lead is an important issue and possibility of using a natural rock, laterite, is explored in this work to mitigate this problem. Treated laterite (TL- prepared using hydrochloric acid and sodium hydroxide) was successfully utilized for this purpose. The adsorbent was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), and Fourier Transform Infrared Spectroscopy (FTIR) to highlight its physical and chemical properties. Optimized equilibrium conditions were 1 g L(-1) adsorbent concentration, 0.26 mm size and a pH of 7 ± 0.2. Monolayer adsorption capacity of lead on treated laterite was 15 mg/g, 14.5 and 13 mg g(-1) at temperatures of 303 K, 313 K and 323 K, respectively. The adsorption was exothermic and physical in nature. At 303 K, value of effective diffusivity of (De) and mass transfer co-efficient (Kf) of lead onto TL were 6.5 × 10(-10) m(2)/s and 3.3 × 10(-4) m/s, respectively (solved from shrinking core model of adsorption kinetics). Magnesium and sulphate show highest interference effect on the adsorption of lead by TL. Efficacy of the adsorbent has been verified using real-life contaminated groundwater. Thus, this work demonstrates performance of a cost-effective media for lead removal. PMID:26646980

  8. Application of novel, low-cost, laterite-based adsorbent for removal of lead from water: Equilibrium, kinetic and thermodynamic studies.

    PubMed

    Chatterjee, Somak; De, Sirshendu

    2016-01-01

    Contamination of groundwater by carcinogenic heavy metal, e.g., lead is an important issue and possibility of using a natural rock, laterite, is explored in this work to mitigate this problem. Treated laterite (TL- prepared using hydrochloric acid and sodium hydroxide) was successfully utilized for this purpose. The adsorbent was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), and Fourier Transform Infrared Spectroscopy (FTIR) to highlight its physical and chemical properties. Optimized equilibrium conditions were 1 g L(-1) adsorbent concentration, 0.26 mm size and a pH of 7 ± 0.2. Monolayer adsorption capacity of lead on treated laterite was 15 mg/g, 14.5 and 13 mg g(-1) at temperatures of 303 K, 313 K and 323 K, respectively. The adsorption was exothermic and physical in nature. At 303 K, value of effective diffusivity of (De) and mass transfer co-efficient (Kf) of lead onto TL were 6.5 × 10(-10) m(2)/s and 3.3 × 10(-4) m/s, respectively (solved from shrinking core model of adsorption kinetics). Magnesium and sulphate show highest interference effect on the adsorption of lead by TL. Efficacy of the adsorbent has been verified using real-life contaminated groundwater. Thus, this work demonstrates performance of a cost-effective media for lead removal.

  9. Study Modules for Calculus-Based General Physics. [Includes Modules 11-14: Collisions; Equilibrium of Rigid Bodies; Rotational Dynamics; and Fluid Mechanics].

    ERIC Educational Resources Information Center

    Fuller, Robert G., Ed.; And Others

    This is part of a series of 42 Calculus Based Physics (CBP) modules totaling about 1,000 pages. The modules include study guides, practice tests, and mastery tests for a full-year individualized course in calculus-based physics based on the Personalized System of Instruction (PSI). The units are not intended to be used without outside materials;…

  10. Uniqueness of Nash equilibrium in vaccination games.

    PubMed

    Bai, Fan

    2016-12-01

    One crucial condition for the uniqueness of Nash equilibrium set in vaccination games is that the attack ratio monotonically decreases as the vaccine coverage level increasing. We consider several deterministic vaccination models in homogeneous mixing population and in heterogeneous mixing population. Based on the final size relations obtained from the deterministic epidemic models, we prove that the attack ratios can be expressed in terms of the vaccine coverage levels, and also prove that the attack ratios are decreasing functions of vaccine coverage levels. Some thresholds are presented, which depend on the vaccine efficacy. It is proved that for vaccination games in homogeneous mixing population, there is a unique Nash equilibrium for each game. PMID:27465224

  11. Tuning universality far from equilibrium

    PubMed Central

    Karl, Markus; Nowak, Boris; Gasenzer, Thomas

    2013-01-01

    Possible universal dynamics of a many-body system far from thermal equilibrium are explored. A focus is set on meta-stable non-thermal states exhibiting critical properties such as self-similarity and independence of the details of how the respective state has been reached. It is proposed that universal dynamics far from equilibrium can be tuned to exhibit a dynamical transition where these critical properties change qualitatively. This is demonstrated for the case of a superfluid two-component Bose gas exhibiting different types of long-lived but non-thermal critical order. Scaling exponents controlled by the ratio of experimentally tuneable coupling parameters offer themselves as natural smoking guns. The results shed light on the wealth of universal phenomena expected to exist in the far-from-equilibrium realm. PMID:23928853

  12. Phase coexistence far from equilibrium

    NASA Astrophysics Data System (ADS)

    Dickman, Ronald

    2016-04-01

    Investigation of simple far-from-equilibrium systems exhibiting phase separation leads to the conclusion that phase coexistence is not well defined in this context. This is because the properties of the coexisting nonequilibrium systems depend on how they are placed in contact, as verified in the driven lattice gas with attractive interactions, and in the two-temperature lattice gas, under (a) weak global exchange between uniform systems, and (b) phase-separated (nonuniform) systems. Thus, far from equilibrium, the notions of universality of phase coexistence (i.e., independence of how systems exchange particles and/or energy), and of phases with intrinsic properties (independent of their environment) are lost.

  13. Toroidal plasma equilibrium with gravity

    SciTech Connect

    Yoshikawa, S.

    1980-09-01

    Toroidal magnetic field configuration in a gravitational field is calculated both from a simple force-balance and from the calculation using magnetic surfaces. The configuration is found which is positionally stable in a star. The vibrational frequency near the equilibrium point is proportional to the hydrostatic frequency of a star multiplied by the ratio (W/sub B//W/sub M/)/sup 1/2/ where W/sub B/ is the magnetic field energy density, and W/sub M/ is the material pressure at the equilibrium point. It is proposed that this frequency may account for the observed solar spot cycles.

  14. Adiabatic evolution of plasma equilibrium

    PubMed Central

    Grad, H.; Hu, P. N.; Stevens, D. C.

    1975-01-01

    A new theory of plasma equilibrium is introduced in which adiabatic constraints are specified. This leads to a mathematically nonstandard structure, as compared to the usual equilibrium theory, in which prescription of pressure and current profiles leads to an elliptic partial differential equation. Topologically complex configurations require further generalization of the concept of adiabaticity to allow irreversible mixing of plasma and magnetic flux among islands. Matching conditions across a boundary layer at the separatrix are obtained from appropriate conservation laws. Applications are made to configurations with planned islands (as in Doublet) and accidental islands (as in Tokamaks). Two-dimensional, axially symmetric, helically symmetric, and closed line equilibria are included. PMID:16578729

  15. Chemical Principles Revisited: Using the Equilibrium Concept.

    ERIC Educational Resources Information Center

    Mickey, Charles D., Ed.

    1981-01-01

    Discusses the concept of equilibrium in chemical systems, particularly in relation to predicting the position of equilibrium, predicting spontaneity of a reaction, quantitative applications of the equilibrium constant, heterogeneous equilibrium, determination of the solubility product constant, common-ion effect, and dissolution of precipitates.…

  16. The Princeton Spectral Equilibrium Code: PSEC

    NASA Astrophysics Data System (ADS)

    Ling, K. M.; Jardin, S. C.

    1985-05-01

    A fast computer code has been developed to calculate free-boundary solutions to the plasma equilibrium equation that are consistent with the currents in external coils and conductors. The free-boundary formulation is based on the minimization of a mean-square error ɛ while the fixed-boundary solution is based on a variational principle and spectral representation of the coordinates x(Ψ, θ) and z(Ψ, θ). Specific calculations using the Columbia University Torus II, the Poloidal Divertor Experiment (PDX), and the Tokamak Fusion Test Reactor (TFTR) geometries are performed.

  17. Magnetospheric equilibrium with anisotropic pressure

    SciTech Connect

    Cheng, C.Z.

    1991-07-01

    Self-consistent magnetospheric equilibrium with anisotropic pressure is obtained by employing an iterative metric method for solving the inverse equilibrium equation in an optimal flux coordinate system. A method of determining plasma parallel and perpendicular pressures from either analytic particle distribution or particle distribution measured along the satellite's path is presented. The numerical results of axisymmetric magnetospheric equilibrium including the effects of finite beta, pressure anisotropy, and boundary conditions are presented for a bi-Maxwellian particle distribution. For the isotropic pressure cases, the finite beta effect produces an outward expansion of the constant magnetic flux surfaces in relation to the dipole field lines, and along the magnetic field the toroidal ring current is maximum at the magnetic equator. The effect of pressure anisotropy is found to further expand the flux surfaces outward. Along the magnetic field lines the westward ring current can be peak away from the equator due to an eastward current contribution resulting from pressure anisotropy. As pressure anisotropy increases, the peak westward current can become more singular. The outer boundary flux surface has significant effect on the magnetospheric equilibrium. For the outer flux boundary resembling dayside compressed flux surface due to solar wind pressure, the deformation of the magnetic field can be quite different from that for the outer flux boundary resembling the tail-like surface. 23 refs., 17 figs.

  18. Understanding Thermal Equilibrium through Activities

    ERIC Educational Resources Information Center

    Pathare, Shirish; Huli, Saurabhee; Nachane, Madhura; Ladage, Savita; Pradhan, Hemachandra

    2015-01-01

    Thermal equilibrium is a basic concept in thermodynamics. In India, this concept is generally introduced at the first year of undergraduate education in physics and chemistry. In our earlier studies (Pathare and Pradhan 2011 "Proc. episteme-4 Int. Conf. to Review Research on Science Technology and Mathematics Education" pp 169-72) we…

  19. TEA: A Code Calculating Thermochemical Equilibrium Abundances

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. We tested the code against the method of Burrows & Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows & Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

  20. TEA: A Code Calculating Thermochemical Equilibrium Abundances

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature–pressure pairs. We tested the code against the method of Burrows & Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows & Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

  1. Biochemical thermodynamics and rapid-equilibrium enzyme kinetics.

    PubMed

    Alberty, Robert A

    2010-12-30

    Biochemical thermodynamics is based on the chemical thermodynamics of aqueous solutions, but it is quite different because pH is used as an independent variable. A transformed Gibbs energy G' is used, and that leads to transformed enthalpies H' and transformed entropies S'. Equilibrium constants for enzyme-catalyzed reactions are referred to as apparent equilibrium constants K' to indicate that they are functions of pH in addition to temperature and ionic strength. Despite this, the most useful way to store basic thermodynamic data on enzyme-catalyzed reactions is to give standard Gibbs energies of formation, standard enthalpies of formation, electric charges, and numbers of hydrogen atoms in species of biochemical reactants like ATP. This makes it possible to calculate standard transformed Gibbs energies of formation, standard transformed enthalpies of formation of reactants (sums of species), and apparent equilibrium constants at desired temperatures, pHs, and ionic strengths. These calculations are complicated, and therefore, a mathematical application in a computer is needed. Rapid-equilibrium enzyme kinetics is based on biochemical thermodynamics because all reactions in the mechanism prior to the rate-determining reaction are at equilibrium. The expression for the equilibrium concentration of the enzyme-substrate complex that yields products can be derived by applying Solve in a computer to the expressions for the equilibrium constants in the mechanism and the conservation equation for enzymatic sites. In 1979, Duggleby pointed out that the minimum number of velocities of enzyme-catalyzed reactions required to estimate the values of the kinetic parameters is equal to the number of kinetic parameters. Solve can be used to do this with steady-state rate equations as well as rapid-equilibrium rate equations, provided that the rate equation is a polynomial. Rapid-equilibrium rate equations can be derived for complicated mechanisms that involve several reactants

  2. Fundamental Research in Engineering Education. Development of Concept Questions and Inquiry-Based Activities in Thermodynamics and Heat Transfer: An Example for Equilibrium vs. Steady-State

    ERIC Educational Resources Information Center

    Vigeant, Margot; Prince, Michael; Nottis, Katharyn

    2011-01-01

    This study examines the use of inquiry-based instruction to promote the understanding of critical concepts in thermodynamics and heat transfer. Significant research shows that students frequently enter our courses with tightly held misconceptions about the physical world that are not effectively addressed through traditional instruction. Students'…

  3. An Experimental Evaluation of Programed Instruction as One of Two Review Techniques for Two-Year College Students Concerned with Solving Acid-Base Chemical Equilibrium Problems.

    ERIC Educational Resources Information Center

    Sharon, Jared Bear

    The major purpose of this study was to design and evaluate a programed instructional unit for a first year college chemistry course. The topic of the unit was the categorization and solution of acid-base equilibria problems. The experimental programed instruction text was used by 41 students and the fifth edition of Schaum's Theory and Problems of…

  4. Non-Equilibrium Properties from Equilibrium Free Energy Calculations

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew; Wilson, Michael A.

    2012-01-01

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

  5. A collision history-based approach to Sensitivity/Perturbation calculations in the continuous energy Monte Carlo code SERPENT

    SciTech Connect

    Giuseppe Palmiotti

    2015-05-01

    In this work, the implementation of a collision history-based approach to sensitivity/perturbation calculations in the Monte Carlo code SERPENT is discussed. The proposed methods allow the calculation of the eects of nuclear data perturbation on several response functions: the eective multiplication factor, reaction rate ratios and bilinear ratios (e.g., eective kinetics parameters). SERPENT results are compared to ERANOS and TSUNAMI Generalized Perturbation Theory calculations for two fast metallic systems and for a PWR pin-cell benchmark. New methods for the calculation of sensitivities to angular scattering distributions are also presented, which adopts fully continuous (in energy and angle) Monte Carlo estimators.

  6. Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

    NASA Technical Reports Server (NTRS)

    Levine, J. S.; Summers, M. E.; Ewell, M.

    2010-01-01

    The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

  7. Phonon Mapping in Flowing Equilibrium

    NASA Astrophysics Data System (ADS)

    Ruff, J. P. C.

    2015-03-01

    When a material conducts heat, a modification of the phonon population occurs. The equilibrium Bose-Einstein distribution is perturbed towards flowing-equilibrium, for which the distribution function is not analytically known. Here I argue that the altered phonon population can be efficiently mapped over broad regions of reciprocal space, via diffuse x-ray scattering or time-of-flight neutron scattering, while a thermal gradient is applied across a single crystal sample. When compared to traditional transport measurements, this technique offers a superior, information-rich new perspective on lattice thermal conductivity, wherein the band and momentum dependences of the phonon thermal current are directly resolved. The proposed method is benchmarked using x-ray thermal diffuse scattering measurements of single crystal diamond under transport conditions. CHESS is supported by the NSF & NIH/NIGMS via NSF Award DMR-1332208.

  8. Punctuated equilibrium comes of age

    NASA Astrophysics Data System (ADS)

    Gould, Stephan Jay; Eldredge, Niles

    1993-11-01

    The intense controversies that surrounded the youth of punctuated equilibrium have helped it mature to a useful extension of evolutionary theory. As a complement to phyletic gradualism, its most important implications remain the recognition of stasis as a meaningful and predominant pattern within the history of species, and in the recasting of macroevolution as the differential success of certain species (and their descendants) within clades.

  9. Adaptive Implicit Non-Equilibrium Radiation Diffusion

    SciTech Connect

    Philip, Bobby; Wang, Zhen; Berrill, Mark A; Rodriguez Rodriguez, Manuel; Pernice, Michael

    2013-01-01

    We describe methods for accurate and efficient long term time integra- tion of non-equilibrium radiation diffusion systems: implicit time integration for effi- cient long term time integration of stiff multiphysics systems, local control theory based step size control to minimize the required global number of time steps while control- ling accuracy, dynamic 3D adaptive mesh refinement (AMR) to minimize memory and computational costs, Jacobian Free Newton-Krylov methods on AMR grids for efficient nonlinear solution, and optimal multilevel preconditioner components that provide level independent solver convergence.

  10. Long-term equilibrium tides

    NASA Astrophysics Data System (ADS)

    Shaffer, John A.; Cerveny, Randall S.

    1998-08-01

    Extreme equilibrium tides, or ``hypertides,'' are computed in a new equilibrium tidal model combining algorithms of a version of the Chapront ELP-2000/82 Lunar Theory with the BER78 Milankovitch astronomical expansions. For the recent past, a high correspondence exists between computed semidiurnal tide levels and a record of coastal flooding demonstrating that astronomical alignment is a potential influence on such flooding. For the Holocene and near future, maximum tides demonstrate cyclic variations with peaks at near 5000 B.P. and 4000 A.P. On the late Quaternary timescale, variations in maximum equilibrium tide level display oscillations with periods of approximately 10,000, 100,000 and 400,000 years, because of precessional shifts in tidal maxima between vernal and autumnal equinoxes. While flooding occurs under the combined effects of tides and storms via ``storm surges,'' the most extensive flooding will occur with the coincidence of storms and the rarer hypertides and is thus primarily influenced by hypertides. Therefore we suggest that astronomical alignment's relationship to coastal flooding is probabilistic rather than deterministic. Data derived from this model are applicable to (1) archaeological and paleoclimatic coastal reconstructions, (2) long-term planning, for example, radioactive waste site selection, (3) sealevel change and paleoestuarine studies or (4) ocean-meteorological interactions.

  11. Acid-base titrations of functional groups on the surface of the thermophilic bacterium Anoxybacillus flavithermus: comparing a chemical equilibrium model with ATR-IR spectroscopic data.

    PubMed

    Heinrich, Hannah T M; Bremer, Phil J; Daughney, Christopher J; McQuillan, A James

    2007-02-27

    Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength.

  12. Microhydration of guanine...cytosine base pairs, a theoretical Study on the role of water in stability, structure and tautomeric equilibrium.

    PubMed

    Zelený, Tomás; Hobza, Pavel; Kabelác, Martin

    2009-05-14

    The potential energy surfaces of guanine...cytosine complexes and microhydrated guanine...cytosine (one and two water molecules) were investigated by the molecular dynamics/quenching method (MD/Q), using the empirical potential Parm94 force field, implemented in the Amber program package. The calculations were conducted for all the possible combinations of the four most stable tautomers of guanine and three of cytosine (covering the canonical forms in both cases). The obtained structures were sorted by their structural motifs into three main groups: planar hydrogen-bonded; stacked; and T-shaped structures. The most stable structures found at the empirical potential energy surfaces were fully reoptimised at the second-order Møller-Plesset perturbation theory as well as using the density functional method with an empirical dispersion term (DFT-D). A combination of the canonical form of guanine and cytosine and canonical cytosine with a guanine tautomer where the hydrogen is switched from position N9 to N7 are energetically preferred in microsolvated systems as well as those without the presence of a solvent. The rising number of water molecules leads to smaller differences between the stability of the various combinations of the tautomers of bases in the base pairs. For some of the tautomer combinations (mainly the enol-enol combination), two water molecules are sufficient for the preference of stacked structures over the H-bonded ones. The interaction energies and geometries obtained by the second-order Møller-Plesset perturbation theory method and the much less computationally demanding DFT-D method are comparable, except for stacked complexes, where the interaction energies are overestimated on average by 3 kcal mol(-1) at the MP2 level. PMID:19421545

  13. Equilibrium and non-equilibrium properties of finite-volume crystallites

    NASA Astrophysics Data System (ADS)

    Degawa, Masashi

    Finite volume effects on equilibrium and non-equilibrium properties of nano-crystallites are studied theoretically and compared to both experiment and simulation. When a system is isolated or its size is small compared to the correlation length, all equilibrium and close-to-equilibrium properties will depend on the system boundary condition. Specifically for solid nano-crystallites, their finite size introduces global curvature to the system, which alters its equilibrium properties compared to the thermodynamic limit. Also such global curvature leads to capillary-induced morphology changes of the surface. Interesting dynamics can arise when the crystallite is supported on a substrate, with crossovers of the dominant driving force from the capillary force and crystallite-substrate interactions. To address these questions, we introduce thermodynamic functions for the boundary conditions, which can be derived from microscopic models. For nano-crystallites, the boundary is the surface (including interfaces), the thermodynamic description is based on the steps that define the shape of the surface, and the underlying microscopic model includes kinks. The global curvature of the surface introduces metastable states with different shapes governed by a constant of integration of the extra boundary condition, which we call the shape parameter c. The discrete height of the steps introduces transition states in between the metastable states, and the lowest energy accessible structure (energy barrier less 10k BT) as a function of the volume has been determined. The dynamics of nano-crystallites as they relax from a non-equilibrium structure is described quantitatively in terms of the motion of steps in both capillary-induced and interface-boundary-induced regimes. The step-edge fluctuations of the top facet are also influenced by global curvature and volume conservation and the effect yields different dynamic scaling exponents from a pure 1D system. Theoretical results are

  14. Experimental determination of thermodynamic equilibrium in biocatalytic transamination.

    PubMed

    Tufvesson, Pär; Jensen, Jacob S; Kroutil, Wolfgang; Woodley, John M

    2012-08-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones. Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore, in this communication we suggest a simple experimental methodology which we hope will stimulate more accurate determination of thermodynamic equilibria when reporting the results of transaminase-catalyzed reactions in order to increase understanding of the relationship between substrate and product molecular structure on reaction thermodynamics.

  15. Equilibrium and kinetics in metamorphism

    NASA Astrophysics Data System (ADS)

    Pattison, D. R.

    2012-12-01

    The equilibrium model for metamorphism is founded on the metamorphic facies principle, the repeated association of the same mineral assemblages in rocks of different bulk composition that have been metamorphosed together. Yet, for any metamorphic process to occur, there must be some degree of reaction overstepping (disequilibrium) to initiate reaction. The magnitude and variability of overstepping, and the degree to which it is either a relatively minor wrinkle or a more substantive challenge to the interpretation of metamorphic rocks using the equilibrium model, is an active area of current research. Kinetic barriers to reaction generally diminish with rising temperature due to the Arrhenius relation. In contrast, the rate of build-up of the macroscopic energetic driving force needed to overcome kinetic barriers to reaction, reaction affinity, does not vary uniformly with temperature, instead varying from reaction to reaction. High-entropy reactions that release large quantities of H2O build up reaction affinity more rapidly than low-entropy reactions that release little or no H2O, such that the former are expected to be overstepped less than the latter. Some consequences include: (1) metamorphic reaction intervals may be discrete rather than continuous, initiating at the point that sufficient reaction affinity has built up to overcome kinetic barriers; (2) metamorphic reaction intervals may not correspond in a simple way to reaction boundaries in an equilibrium phase diagram; (3) metamorphic reactions may involve metastable reactions; (4) metamorphic 'cascades' are possible, in which stable and metastable reactions involving the same reactant phases may proceed simultaneously; and (5) fluid generation, and possibly fluid presence in general, may be episodic rather than continuous, corresponding to discrete intervals of reaction. These considerations bear on the interpretation of P-T-t paths from metamorphic mineral assemblages and textures. The success of the

  16. Multicomponent Equilibrium Models for Testing Geothermometry Approaches

    SciTech Connect

    Cooper, D. Craig; Palmer, Carl D.; Smith, Robert W.; McLing, Travis L.

    2013-02-01

    Geothermometry is an important tool for estimating deep reservoir temperature from the geochemical composition of shallower and cooler waters. The underlying assumption of geothermometry is that the waters collected from shallow wells and seeps maintain a chemical signature that reflects equilibrium in the deeper reservoir. Many of the geothermometers used in practice are based on correlation between water temperatures and composition or using thermodynamic calculations based a subset (typically silica, cations or cation ratios) of the dissolved constituents. An alternative approach is to use complete water compositions and equilibrium geochemical modeling to calculate the degree of disequilibrium (saturation index) for large number of potential reservoir minerals as a function of temperature. We have constructed several “forward” geochemical models using The Geochemist’s Workbench to simulate the change in chemical composition of reservoir fluids as they migrate toward the surface. These models explicitly account for the formation (mass and composition) of a steam phase and equilibrium partitioning of volatile components (e.g., CO2, H2S, and H2) into the steam as a result of pressure decreases associated with upward fluid migration from depth. We use the synthetic data generated from these simulations to determine the advantages and limitations of various geothermometry and optimization approaches for estimating the likely conditions (e.g., temperature, pCO2) to which the water was exposed in the deep subsurface. We demonstrate the magnitude of errors that can result from boiling, loss of volatiles, and analytical error from sampling and instrumental analysis. The estimated reservoir temperatures for these scenarios are also compared to conventional geothermometers. These results can help improve estimation of geothermal resource temperature during exploration and early development.

  17. 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

  18. Torque equilibrium attitude control for Skylab reentry

    NASA Technical Reports Server (NTRS)

    Glaese, J. R.; Kennel, H. F.

    1979-01-01

    All the available torque equilibrium attitudes (most were useless from the standpoint of lack of electrical power) and the equilibrium seeking method are presented, as well as the actual successful application during the 3 weeks prior to Skylab reentry.

  19. Temperature of systems out of thermodynamic equilibrium

    NASA Astrophysics Data System (ADS)

    Garden, J.-L.; Richard, J.; Guillou, H.

    2008-07-01

    Two phenomenological approaches are currently used in the study of the vitreous state. One is based on the concept of fictive temperature introduced by Tool [J. Res. Natl. Bur. Stand. 34, 199 (1945)] and recently revisited by Nieuwenhuizen [Phys. Rev. Lett. 80, 5580 (1998)]. The other is based on the thermodynamics of irreversible processes initiated by De Donder at the beginning of the last century [L'Affinité (Gauthier-Villars, Paris, 1927)] and recently used by Möller et al. for a thorough study of the glass transition [J. Chem. Phys. 125, 094505 (2006)]. This latter approach leads to the possibility of describing the glass transition by means of the freezing-in of one or more order parameters connected to the internal structural degrees of freedom involved in the vitrification process. In this paper, the equivalence of the two preceding approaches is demonstrated, not only for glasses but in a very general way for any system undergoing an irreversible transformation. This equivalence allows the definition of an effective temperature for all systems departed from equilibrium generating a positive amount of entropy. In fact, the initial fictive temperature concept of Tool leads to the generalization of the notion of temperature for systems out of thermodynamic equilibrium, for which glasses are just particular cases.

  20. Explicit limit equilibrium solution for slope stability

    NASA Astrophysics Data System (ADS)

    Zhu, D. Y.; Lee, C. F.

    2002-12-01

    Conventional methods of slices used for slope stability analysis satisfying all equilibrium conditions involves generally solving two highly non-linear equations with respect to two unknowns, i.e. the factor of safety and the associated scaling parameter. To solve these two equations, complicated numerical iterations are required with non-convergence occasionally occurring. This paper presents an alternative procedure to derive the three equilibrium equations (horizontal and vertical forces equations and moment equation) based on an assumption regarding the normal stress distribution along the slip surface. Combination of these equations results in a single cubic equation in terms of the factor of safety, which is explicitly solved. Theoretical testing demonstrates that the proposed method yields a factor of safety in reasonable agreement with a closed-form solution based on the theory of plasticity. Example studies show that the difference in values of factor of safety between the proposed method, the Spencer method and the Morgenstern-Price method is within 5%. Application of the proposed method to practical slope engineering problems is rather straightforward, but its solution is of the same precision as those given by the conventional rigorous methods of slices since it is still within the rigorous context.

  1. Open problems in non-equilibrium physics

    SciTech Connect

    Kusnezov, D.

    1997-09-22

    The report contains viewgraphs on the following: approaches to non-equilibrium statistical mechanics; classical and quantum processes in chaotic environments; classical fields in non-equilibrium situations: real time dynamics at finite temperature; and phase transitions in non-equilibrium conditions.

  2. Equilibrium figures of dwarf planets

    NASA Astrophysics Data System (ADS)

    Rambaux, Nicolas; Chambat, Frederic; Castillo-Rogez, Julie; Baguet, Daniel

    2016-10-01

    Dwarf planets including transneptunian objects (TNO) and Ceres are >500 km large and display a spheroidal shape. These protoplanets are left over from the formation of the solar System about 4.6 billion years ago and their study could improve our knowledge of the early solar system. They could be formed in-situ or migrated to their current positions as a consequence of large-scale solar system dynamical evolution. Quantifying their internal composition would bring constraints on their accretion environment and migration history. That information may be inferred from studying their global shapes from stellar occultations or thermal infrared imaging. Here we model the equilibrium shapes of isolated dwarf planets under the assumption of hydrostatic equilibrium that forms the basis for interpreting shape data in terms of interior structure. Deviations from hydrostaticity can shed light on the thermal and geophysical history of the bodies. The dwarf planets are generally fast rotators spinning in few hours, so their shape modeling requires numerically integration with Clairaut's equations of rotational equilibrium expanded up to third order in a small parameter m, the geodetic parameter, to reach an accuracy better than a few kilometers depending on the spin velocity and mean density. We also show that the difference between a 500-km radius homogeneous model described by a MacLaurin ellipsoid and a stratified model assuming silicate and ice layers can reach several kilometers in the long and short axes, which could be measurable. This type of modeling will be instrumental in assessing hydrostaticity and thus detecting large non-hydrostatic contributions in the observed shapes.

  3. Study of equilibrium properties of Cr(III)/polyacrylamide gels by swelling measurement and equilibrium dialysis

    SciTech Connect

    Young, T.S.; Hunt, J.A.; Green, D.W.; Willhite, G.P. )

    1989-08-01

    In observations of the long-term properties of a series of Cr(III)/polyacrylamide (PAAM) gels, the gels either underwent syneresis upon aging or swelled in contact with excess brine. Both syneresis and swelling can substantially change the volume and properties of a gel placed in a formation and therefore influence the effectiveness of a crosslinked-polymer treatment. Efforts were made to develop an understanding of these phenomena and to describe them in terms of the gel's physical and chemical states. A long-term gel's physical and chemical states are characterized by two parameters, effective crosslinking density and chromium density, determined by equilibrium swelling and equilibrium dialysis, respectively. Swelling and syneresis properties were correlated to the effective cross-linking density described in polymer network theory. A model based on Flory and Hermans' swelling equations was developed to calculate the effective crosslinking densities of gels prepared from solution. Attempts were made to relate the swelling and syneresis properties to the compositions of gel systems to allow prediction of long-term stability of a gel based on its composition. An analysis of the amount of chromium that reacted with the PAAM was made by successive equilibrium dialyses of the gel followed by chromium analyses of dialysates by atomic and visible absorptions.

  4. A survey of upwind methods for flows with equilibrium and non-equilibrium chemistry and thermodynamics

    NASA Technical Reports Server (NTRS)

    Grossman, B.; Garrett, J.; Cinnella, P.

    1989-01-01

    Several versions of flux-vector split and flux-difference split algorithms were compared with regard to general applicability and complexity. Test computations were performed using curve-fit equilibrium air chemistry for an M = 5 high-temperature inviscid flow over a wedge, and an M = 24.5 inviscid flow over a blunt cylinder for test computations; for these cases, little difference in accuracy was found among the versions of the same flux-split algorithm. For flows with nonequilibrium chemistry, the effects of the thermodynamic model on the development of flux-vector split and flux-difference split algorithms were investigated using an equilibrium model, a general nonequilibrium model, and a simplified model based on vibrational relaxation. Several numerical examples are presented, including nonequilibrium air chemistry in a high-temperature shock tube and nonequilibrium hydrogen-air chemistry in a supersonic diffuser.

  5. Modulation and Salt-Induced Reverse Modulation of the Excited-State Proton-Transfer Process of Lysozymized Pyranine: The Contrasting Scenario of the Ground-State Acid-Base Equilibrium of the Photoacid.

    PubMed

    Das, Ishita; Panja, Sudipta; Halder, Mintu

    2016-07-28

    Here we report on the excited-state behavior in terms of the excited-state proton-transfer (ESPT) reaction as well as the ground-state acid-base property of pyranine [8-hydroxypyrene-1,3,6-trisulfonate (HPTS)] in the presence of an enzymatic protein, human lysozyme (LYZ). HPTS forms a 1:1 ground-state complex with LYZ having the binding constant KBH = (1.4 ± 0.05) × 10(4) M(-1), and its acid-base equilibrium gets shifted toward the deprotonated conjugate base (RO(-)), resulting in a downward shift in pKa. This suggests that the conjugate base (RO(-)) is thermodynamically more favored over the protonated (ROH) species inside the lysozyme matrix, resulting in an increased population of the deprotonated form. However, for the release of the proton from the excited photoacid, interestingly, the rate of proton transfer gets slowed down due to the "slow" acceptor biological water molecules present in the immediate vicinity of the fluorophore binding region inside the protein. The observed ESPT time constants, ∼140 and ∼750 ps, of protein-bound pyranine are slower than in bulk aqueous media (∼100 ps, single exponential). The molecular docking study predicts that the most probable binding location of the fluorophore is in a region near to the active site of the protein. Here we also report on the effect of external electrolyte (NaCl) on the reverse modulation of ground-state prototropy as well as the ESPT process of the protein-bound pyranine. It is found that there is a dominant role of electrostatic forces in the HPTS-LYZ interaction process, because an increase in ionic strength by the addition of NaCl dislodges the fluorophore from the protein pocket to the bulk again. The study shows a considerably different perspective of the perturbation offered by the model macromolecular host used, unlike the available literature reports on the concerned photoacid. PMID:27355857

  6. Modulation and Salt-Induced Reverse Modulation of the Excited-State Proton-Transfer Process of Lysozymized Pyranine: The Contrasting Scenario of the Ground-State Acid-Base Equilibrium of the Photoacid.

    PubMed

    Das, Ishita; Panja, Sudipta; Halder, Mintu

    2016-07-28

    Here we report on the excited-state behavior in terms of the excited-state proton-transfer (ESPT) reaction as well as the ground-state acid-base property of pyranine [8-hydroxypyrene-1,3,6-trisulfonate (HPTS)] in the presence of an enzymatic protein, human lysozyme (LYZ). HPTS forms a 1:1 ground-state complex with LYZ having the binding constant KBH = (1.4 ± 0.05) × 10(4) M(-1), and its acid-base equilibrium gets shifted toward the deprotonated conjugate base (RO(-)), resulting in a downward shift in pKa. This suggests that the conjugate base (RO(-)) is thermodynamically more favored over the protonated (ROH) species inside the lysozyme matrix, resulting in an increased population of the deprotonated form. However, for the release of the proton from the excited photoacid, interestingly, the rate of proton transfer gets slowed down due to the "slow" acceptor biological water molecules present in the immediate vicinity of the fluorophore binding region inside the protein. The observed ESPT time constants, ∼140 and ∼750 ps, of protein-bound pyranine are slower than in bulk aqueous media (∼100 ps, single exponential). The molecular docking study predicts that the most probable binding location of the fluorophore is in a region near to the active site of the protein. Here we also report on the effect of external electrolyte (NaCl) on the reverse modulation of ground-state prototropy as well as the ESPT process of the protein-bound pyranine. It is found that there is a dominant role of electrostatic forces in the HPTS-LYZ interaction process, because an increase in ionic strength by the addition of NaCl dislodges the fluorophore from the protein pocket to the bulk again. The study shows a considerably different perspective of the perturbation offered by the model macromolecular host used, unlike the available literature reports on the concerned photoacid.

  7. A continuum model for flocking: Obstacle avoidance, equilibrium, and stability

    NASA Astrophysics Data System (ADS)

    Mecholsky, Nicholas Alexander

    The modeling and investigation of the dynamics and configurations of animal groups is a subject of growing attention. In this dissertation, we present a partial-differential-equation based continuum model of flocking and use it to investigate several properties of group dynamics and equilibrium. We analyze the reaction of a flock to an obstacle or an attacking predator. We show that the flock response is in the form of density disturbances that resemble Mach cones whose configuration is determined by the anisotropic propagation of waves through the flock. We investigate the effect of a flock 'pressure' and pairwise repulsion on an equilibrium density distribution. We investigate both linear and nonlinear pressures, look at the convergence to a 'cold' (T → 0) equilibrium solution, and find regions of parameter space where different models produce the same equilibrium. Finally, we analyze the stability of an equilibrium density distribution to long-wavelength perturbations. Analytic results for the stability of a constant density solution as well as stability regimes for constant density solutions to the equilibrium equations are presented.

  8. Equilibrium Studies of Designed Metalloproteins.

    PubMed

    Gibney, B R

    2016-01-01

    Complete thermodynamic descriptions of the interactions of cofactors with proteins via equilibrium studies are challenging, but are essential to the evaluation of designed metalloproteins. While decades of studies on protein-protein interaction thermodynamics provide a strong underpinning to the successful computational design of novel protein folds and de novo proteins with enzymatic activity, the corresponding paucity of data on metal-protein interaction thermodynamics limits the success of computational metalloprotein design efforts. By evaluating the thermodynamics of metal-protein interactions via equilibrium binding studies, protein unfolding free energy determinations, proton competition equilibria, and electrochemistry, a more robust basis for the computational design of metalloproteins may be provided. Our laboratory has shown that such studies provide detailed insight into the assembly and stability of designed metalloproteins, allow for parsing apart the free energy contributions of metal-ligand interactions from those of porphyrin-protein interactions in hemeproteins, and even reveal their mechanisms of proton-coupled electron transfer. Here, we highlight studies that reveal the complex interplay between the various equilibria that underlie metalloprotein assembly and stability and the utility of making these detailed measurements. PMID:27586343

  9. Non-equilibrium phase transitions

    SciTech Connect

    Mottola, E.; Cooper, F.M.; Bishop, A.R.; Habib, S.; Kluger, Y.; Jensen, N.G.

    1998-12-31

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Non-equilibrium phase transitions play a central role in a very broad range of scientific areas, ranging from nuclear, particle, and astrophysics to condensed matter physics and the material and biological sciences. The aim of this project was to explore the path to a deeper and more fundamental understanding of the common physical principles underlying the complex real time dynamics of phase transitions. The main emphasis was on the development of general theoretical tools to deal with non-equilibrium processes, and of numerical methods robust enough to capture the time-evolving structures that occur in actual experimental situations. Specific applications to Laboratory multidivisional efforts in relativistic heavy-ion physics (transition to a new phase of nuclear matter consisting of a quark-gluon plasma) and layered high-temperature superconductors (critical currents and flux flow at the National High Magnetic Field Laboratory) were undertaken.

  10. Are the Concepts of Dynamic Equilibrium and the Thermodynamic Criteria for Spontaneity, Nonspontaneity, and Equilibrium Compatible?

    ERIC Educational Resources Information Center

    Silverberg, Lee J.; Raff, Lionel M.

    2015-01-01

    Thermodynamic spontaneity-equilibrium criteria require that in a single-reaction system, reactions in either the forward or reverse direction at equilibrium be nonspontaneous. Conversely, the concept of dynamic equilibrium holds that forward and reverse reactions both occur at equal rates at equilibrium to the extent allowed by kinetic…

  11. Globally convergent computation of chemical equilibrium composition.

    PubMed

    Patil, Sunil; Aiyer, R C; Sharma, K C

    2008-05-01

    We report the Newton-Raphson based globally convergent computational method for determination of chemical equilibrium composition. In the computation of chemical equilibrium composition, an appearance of nonpositive value of number of moles of any component leads to discrepancy. The process of conditional backtracking and adaptive set of refining factors for Newton-Raphson steps are employed to resolve the problem. The mathematical formulation proposed by Heuze et al. (J Chem Phys 1985, 83, 4734) has been solved using proposed computational method, instead of empirical iterative formulation, as proposed by them. Results for the same numerical example, used by Heuze et al. (J Chem Phys 1985, 83, 4734) and White et al. (J Chem Phys 1958, 28, 751) are presented in addition to decomposition of Cyclotrimethylenetrinitramine for fixed temperature and pressure. It is observed that the proposed method is efficient and globally convergent. An even noteworthy finding is that the set of refining factors can be chosen from the range 0.1 to eta, where eta may be greater than one depending on how smoothly system of nonlinear equations is dependant on corresponding variable. Related analysis and results are discussed.

  12. Structural design using equilibrium programming formulations

    NASA Technical Reports Server (NTRS)

    Scotti, Stephen J.

    1995-01-01

    Solutions to increasingly larger structural optimization problems are desired. However, computational resources are strained to meet this need. New methods will be required to solve increasingly larger problems. The present approaches to solving large-scale problems involve approximations for the constraints of structural optimization problems and/or decomposition of the problem into multiple subproblems that can be solved in parallel. An area of game theory, equilibrium programming (also known as noncooperative game theory), can be used to unify these existing approaches from a theoretical point of view (considering the existence and optimality of solutions), and be used as a framework for the development of new methods for solving large-scale optimization problems. Equilibrium programming theory is described, and existing design techniques such as fully stressed design and constraint approximations are shown to fit within its framework. Two new structural design formulations are also derived. The first new formulation is another approximation technique which is a general updating scheme for the sensitivity derivatives of design constraints. The second new formulation uses a substructure-based decomposition of the structure for analysis and sensitivity calculations. Significant computational benefits of the new formulations compared with a conventional method are demonstrated.

  13. Non-equilibrium many body dynamics

    SciTech Connect

    Creutz, M.; Gyulassy, M.

    1997-09-22

    This Riken BNL Research Center Symposium on Non-Equilibrium Many Body Physics was held on September 23-25, 1997 as part of the official opening ceremony of the Center at Brookhaven National Lab. A major objective of theoretical work at the center is to elaborate on the full spectrum of strong interaction physics based on QCD, including the physics of confinement and chiral symmetry breaking, the parton structure of hadrons and nuclei, and the phenomenology of ultra-relativistic nuclear collisions related to the up-coming experiments at RHIC. The opportunities and challenges of nuclear and particle physics in this area naturally involve aspects of the many body problem common to many other fields. The aim of this symposium was to find common theoretical threads in the area of non-equilibrium physics and modern transport theories. The program consisted of invited talks on a variety topics from the fields of atomic, condensed matter, plasma, astrophysics, cosmology, and chemistry, in addition to nuclear and particle physics. Separate abstracts have been indexed into the database for contributions to this workshop.

  14. The empirical equilibrium structure of diacetylene

    NASA Astrophysics Data System (ADS)

    Thorwirth, Sven; Harding, Michael E.; Muders, Dirk; Gauss, Jürgen

    2008-09-01

    High-level quantum-chemical calculations are reported at the MP2 and CCSD(T) levels of theory for the equilibrium structure and the harmonic and anharmonic force fields of diacetylene, H sbnd C tbnd C sbnd C tbnd C sbnd H. The calculations were performed employing Dunning's hierarchy of correlation-consistent basis sets cc-pV XZ, cc-pCV XZ, and cc-pwCV XZ, as well as the ANO2 basis set of Almlöf and Taylor. An empirical equilibrium structure based on experimental rotational constants for 13 isotopic species of diacetylene and computed zero-point vibrational corrections is determined (reemp:r=1.0615 Å,r=1.2085 Å,r=1.3727 Å) and in good agreement with the best theoretical structure (CCSD(T)/cc-pCV5Z: r=1.0617 Å, r=1.2083 Å, r=1.3737 Å). In addition, the computed fundamental vibrational frequencies are compared with the available experimental data and found in satisfactory agreement.

  15. Gyrokinetic Statistical Absolute Equilibrium and Turbulence

    SciTech Connect

    Jian-Zhou Zhu and Gregory W. Hammett

    2011-01-10

    A paradigm based on the absolute equilibrium of Galerkin-truncated inviscid systems to aid in understanding turbulence [T.-D. Lee, "On some statistical properties of hydrodynamical and magnetohydrodynamical fields," Q. Appl. Math. 10, 69 (1952)] is taken to study gyrokinetic plasma turbulence: A finite set of Fourier modes of the collisionless gyrokinetic equations are kept and the statistical equilibria are calculated; possible implications for plasma turbulence in various situations are discussed. For the case of two spatial and one velocity dimension, in the calculation with discretization also of velocity v with N grid points (where N + 1 quantities are conserved, corresponding to an energy invariant and N entropy-related invariants), the negative temperature states, corresponding to the condensation of the generalized energy into the lowest modes, are found. This indicates a generic feature of inverse energy cascade. Comparisons are made with some classical results, such as those of Charney-Hasegawa-Mima in the cold-ion limit. There is a universal shape for statistical equilibrium of gyrokinetics in three spatial and two velocity dimensions with just one conserved quantity. Possible physical relevance to turbulence, such as ITG zonal flows, and to a critical balance hypothesis are also discussed.

  16. Interactions of Virus Like Particles in Equilibrium and Non-equilibrium Systems

    NASA Astrophysics Data System (ADS)

    Lin, Hsiang-Ku

    This thesis summarizes my Ph.D. research on the interactions of virus like particles in equilibrium and non-equilibrium biological systems. In the equilibrium system, we studied the fluctuation-induced forces between inclusions in a fluid membrane. We developed an exact method to calculate thermal Casimir forces between inclusions of arbitrary shapes and separation, embedded in a fluid membrane whose fluctuations are governed by the combined action of surface tension, bending modulus, and Gaussian rigidity. Each objects shape and mechanical properties enter only through a characteristic matrix, a static analog of the scattering matrix. We calculate the Casimir interaction between two elastic disks embedded in a membrane. In particular, we find that at short separations the interaction is strong and independent of surface tension. In the non-equilibrium system, we studied the transport and deposition dynamics of colloids in saturated porous media under un-favorable filtering conditions. As an alternative to traditional convection-diffusion or more detailed numerical models, we consider a mean-field description in which the attachment and detachment processes are characterized by an entire spectrum of rate constants, ranging from shallow traps which mostly account for hydrodynamic dispersivity, all the way to the permanent traps associated with physical straining. The model has an analytical solution which allows analysis of its properties including the long time asymptotic behavior and the profile of the deposition curves. Furthermore, the model gives rise to a filtering front whose structure, stability and propagation velocity are examined. Based on these results, we propose an experimental protocol to determine the parameters of the model.

  17. 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

    2015-03-01

    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.

  18. Hierarchical condensation near phase equilibrium

    NASA Astrophysics Data System (ADS)

    Olemskoi, A. I.; Yushchenko, O. V.; Borisyuk, V. N.; Zhilenko, T. I.; Kosminska, Yu. O.; Perekrestov, V. I.

    2012-06-01

    A novel mechanism of new phase formation is studied both experimentally and theoretically in the example of quasi-equilibrium stationary condensation in an ion-plasma sputterer. Copper condensates are obtained to demonstrate that a specific network structure is formed as a result of self-assembly in the course of deposition. The fractal pattern related is inherent in the phenomena of diffusion limited aggregation. Condensate nuclei are shown to form statistical ensemble of hierarchically subordinated objects distributed in ultrametric space. The Langevin equation and the Fokker-Planck equation related are found to describe stationary distribution of thermodynamic potential variations at condensation. Time dependence of the formation probability of branching structures is found to clarify the experimental situation.

  19. Equilibrium structure of ferrofluid aggregates

    SciTech Connect

    Yoon, Mina; Tomanek, David

    2010-01-01

    We study the equilibrium structure of large but finite aggregates of magnetic dipoles, representing a colloidal suspension of magnetite particles in a ferrofluid. With increasing system size, the structural motif evolves from chains and rings to multi-chain and multi-ring assemblies. Very large systems form single- and multi-wall coils, tubes and scrolls. These structural changes result from a competition between various energy terms, which can be approximated analytically within a continuum model. We also study the effect of external parameters such as magnetic field on the relative stability of these structures. Our results may give insight into experimental data obtained during solidification of ferrofluid aggregates at temperatures where thermal fluctuations become negligible in comparison to inter-particle interactions. These data may also help to experimentally control the aggregation of magnetic particles.

  20. String fluid in local equilibrium

    NASA Astrophysics Data System (ADS)

    Schubring, Daniel; Vanchurin, Vitaly

    2014-10-01

    We study the solutions of string fluid equations under the assumption of a local equilibrium which was previously obtained in the context of the kinetic theory. We show that the fluid can be foliated into noninteracting submanifolds whose equations of motion are exactly that of the wiggly strings considered previously by Vilenkin and Carter. In a special case of negligible statistical variance in either the left- or the right-moving directions of microscopic strings, the submanifolds are described by the action of a null-current-carrying chiral string. When both variances vanish the submanifolds are described by the Nambu-Goto action and the string fluid reduces to the string dust introduced by Stachel.

  1. Equilibrium calculations of firework mixtures

    SciTech Connect

    Hobbs, M.L.; Tanaka, Katsumi; Iida, Mitsuaki; Matsunaga, Takehiro

    1994-12-31

    Thermochemical equilibrium calculations have been used to calculate detonation conditions for typical firework components including three report charges, two display charges, and black powder which is used as a fuse or launch charge. Calculations were performed with a modified version of the TIGER code which allows calculations with 900 gaseous and 600 condensed product species at high pressure. The detonation calculations presented in this paper are thought to be the first report on the theoretical study of firework detonation. Measured velocities for two report charges are available and compare favorably to predicted detonation velocities. However, the measured velocities may not be true detonation velocities. Fast deflagration rather than an ideal detonation occurs when reactants contain significant amounts of slow reacting constituents such as aluminum or titanium. Despite such uncertainties in reacting pyrotechnics, the detonation calculations do show the complex nature of condensed phase formation at elevated pressures and give an upper bound for measured velocities.

  2. Mean gas opacity for circumstellar environments and equilibrium temperature degeneracy

    NASA Astrophysics Data System (ADS)

    Malygin, M. G.; Kuiper, R.; Klahr, H.; Dullemond, C. P.; Henning, Th.

    2014-08-01

    Context. In a molecular cloud dust opacity typically dominates over gas opacity, yet in the vicinities of forming stars dust is depleted, and gas is the sole provider of opacity. In the optically thin circumstellar environments the radiation temperature cannot be assumed to be equal to the gas temperature, hence the two-temperature Planck means are necessary to calculate the radiative equilibrium. Aims: By using the two-temperature mean opacity one does obtain the proper equilibrium gas temperature in a circumstellar environment, which is in a chemical equilibrium. A careful consideration of a radiative transfer problem reveals that the equilibrium temperature solution can be degenerate in an optically thin gaseous environment. Methods: We compute mean gas opacities based on the publicly available code DFSYNTHE by Kurucz and Castelli. We performed the calculations assuming local thermodynamic equilibrium and an ideal gas equation of state. The values were derived by direct integration of the high-resolution opacity spectrum. Results: We produced two sets of gas opacity tables: Rosseland means and two-temperature Planck means. For three metallicities [Me/H] = 0.0, ± 0.3 we covered the parameter range 3.48 ≤ log Trad [K] ≤ 4.48 in radiation temperature, 2.8 ≤ log Tgas [K] ≤ 6.0 in gas temperature, and -10 ≤ log P [dyn cm-2] ≤ 6 in gas pressure. We show that in the optically thin circumstellar environment for a given stellar radiation field and local gas density there are several equilibrium gas temperatures possible. Conclusions: We conclude that, in general, equilibrium gas temperature cannot be determined without treating the temperature evolution. The opacity tables are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/568/A91 as well as via http://www.mpia.de/~malygin

  3. Punctuated equilibrium dynamics in human communications

    NASA Astrophysics Data System (ADS)

    Peng, Dan; Han, Xiao-Pu; Wei, Zong-Wen; Wang, Bing-Hong

    2015-10-01

    A minimal model based on network incorporating individual interactions is proposed to study the non-Poisson statistical properties of human behavior: individuals in system interact with their neighbors, the probability of an individual acting correlates to its activity, and all the individuals involved in action will change their activities randomly. The model reproduces varieties of spatial-temporal patterns observed in empirical studies of human daily communications, providing insight into various human activities and embracing a range of realistic social interacting systems, particularly, intriguing bimodal phenomenon. This model bridges priority queueing theory and punctuated equilibrium dynamics, and our modeling and analysis is likely to shed light on non-Poisson phenomena in many complex systems.

  4. Dynamic Protonation Equilibrium of Solvated Acetic Acid

    SciTech Connect

    Gu, Wei; Frigato, Tomaso; Straatsma, TP; Helms, Volkhard H.

    2007-04-13

    For the first time, the dynamic protonation equilibrium between an amino acid side chain analogue and bulk water as well as the diffusion properties of the excess proton were successfully reproduced through unbiased computer simulations. During a 50 ns Q-HOP MD simulation, two different regimes of proton transfer were observed. Extended phases of frequent proton swapping between acetic acid and nearby water were separated by phases where the proton freely diffuses in the simulation box until it is captured again by acetic acid. The pKa of acetic acid was calculated around 3.0 based on the relative population of protonated and deprotonated states and the diffusion coefficient of excess proton was computed from the average mean squared displacement in the simulation. Both calculated values agree well with the experimental measurements.

  5. Conformational equilibrium in supramolecular chemistry: Dibutyltriuret case

    PubMed Central

    Mroczyńska, Karina; Kaczorowska, Małgorzata; Kolehmainen, Erkki; Grubecki, Ireneusz; Pietrzak, Marek

    2015-01-01

    Summary The association of substituted benzoates and naphthyridine dianions was used to study the complexation of dibutyltriuret. The title molecule is the simplest molecule able to form two intramolecular hydrogen bonds. The naphthyridine salt was used to break two intramolecular hydrogen bonds at a time while with the use of substituted benzoates the systematic approach to study association was achieved. Both, titrations and variable temperature measurements shed the light on the importance of conformational equilibrium and its influence on association in solution. Moreover, the associates were observed by mass spectrometry. The DFT-based computations for complexes and single bond rotational barriers supports experimental data and helps understanding the properties of multiply hydrogen bonded complexes. PMID:26664631

  6. Nash equilibrium and multi criterion aerodynamic optimization

    NASA Astrophysics Data System (ADS)

    Tang, Zhili; Zhang, Lianhe

    2016-06-01

    Game theory and its particular Nash Equilibrium (NE) are gaining importance in solving Multi Criterion Optimization (MCO) in engineering problems over the past decade. The solution of a MCO problem can be viewed as a NE under the concept of competitive games. This paper surveyed/proposed four efficient algorithms for calculating a NE of a MCO problem. Existence and equivalence of the solution are analyzed and proved in the paper based on fixed point theorem. Specific virtual symmetric Nash game is also presented to set up an optimization strategy for single objective optimization problems. Two numerical examples are presented to verify proposed algorithms. One is mathematical functions' optimization to illustrate detailed numerical procedures of algorithms, the other is aerodynamic drag reduction of civil transport wing fuselage configuration by using virtual game. The successful application validates efficiency of algorithms in solving complex aerodynamic optimization problem.

  7. Strange attractors with various equilibrium types

    NASA Astrophysics Data System (ADS)

    Sprott, J. C.

    2015-07-01

    Of the eight types of hyperbolic equilibrium points in three-dimensional flows, one is overwhelmingly dominant in dissipative chaotic systems. This paper shows examples of chaotic systems for each of the eight types as well as one without any equilibrium and two that are nonhyperbolic. The systems are a generalized form of the Nosé-Hoover oscillator with a single equilibrium point. Six of the eleven cases have hidden attractors, and six of them exhibit multistability for the chosen parameters.

  8. Determining Equilibrium Position For Acoustical Levitation

    NASA Technical Reports Server (NTRS)

    Barmatz, M. B.; Aveni, G.; Putterman, S.; Rudnick, J.

    1989-01-01

    Equilibrium position and orientation of acoustically-levitated weightless object determined by calibration technique on Earth. From calibration data, possible to calculate equilibrium position and orientation in presence of Earth gravitation. Sample not levitated acoustically during calibration. Technique relies on Boltzmann-Ehrenfest adiabatic-invariance principle. One converts resonant-frequency-shift data into data on normalized acoustical potential energy. Minimum of energy occurs at equilibrium point. From gradients of acoustical potential energy, one calculates acoustical restoring force or torque on objects as function of deviation from equilibrium position or orientation.

  9. Equilibrium coexistence of three amphiboles

    USGS Publications Warehouse

    Robinson, P.; Jaffe, H.W.; Klein, C.; Ross, M.

    1969-01-01

    Electron probe and wet chemical analyses of amphibole pairs from the sillimanite zone of central Massachusetts and adjacent New Hampshire indicated that for a particular metamorphic grade there should be a restricted composition range in which three amphiboles can coexist stably. An unequivocal example of such an equilibrium three amphibole rock has been found in the sillimanite-orthoclase zone. It contains a colorless primitive clinoamphibole, space group P21/m, optically and chemically like cummingtonite with blue-green hornblende exsolution lamellae on (100) and (-101) of the host; blue-green hornblende, space group C2/m, with primitive cummingtonite exsolution lamellae on (100) and (-101) of the host; and pale pinkish tan anthophyllite, space group Pnma, that is free of visible exsolution lamellae but is a submicroscopic intergrowth of two orthorhombic amphiboles. Mutual contacts and coarse, oriented intergrowths of two and three host amphiboles indicate the three grew as an equilibrium assemblage prior to exsolution. Electron probe analyses at mutual three-amphibole contacts showed little variation in the composition of each amphibole. Analyses believed to represent most closely the primary amphibole compositions gave atomic proportions on the basis of 23 oxygens per formula unit as follows: for primitive cummingtonite (Na0.02Ca0.21- Mn0.06Fe2+2.28Mg4.12Al0.28) (Al0.17Si7.83), for hornblende (Na0.35Ca1.56Mn0.02Fe1.71Mg2.85Al0.92) (Al1.37Si6.63), and for anthophyllite (Na0.10Ca0.06Mn0.06Fe2.25Mg4.11Al0.47) (Al0.47Si7.53). The reflections violating C-symmetry, on X-ray single crystal photographs of the primitive cummingtonite, are weak and diffuse, and suggest a partial inversion from a C-centered to a primitive clinoamphibole. Single crystal photographs of the anthophyllite show split reflections indicating it is an intergrowth of about 80% anthophyllite and about 20% gedrite which differ in their b crystallographic dimensions. Split reflections are

  10. EASI - EQUILIBRIUM AIR SHOCK INTERFERENCE

    NASA Technical Reports Server (NTRS)

    Glass, C. E.

    1994-01-01

    New research on hypersonic vehicles, such as the National Aero-Space Plane (NASP), has raised concerns about the effects of shock-wave interference on various structural components of the craft. State-of-the-art aerothermal analysis software is inadequate to predict local flow and heat flux in areas of extremely high heat transfer, such as the surface impingement of an Edney-type supersonic jet. EASI revives and updates older computational methods for calculating inviscid flow field and maximum heating from shock wave interference. The program expands these methods to solve problems involving the six shock-wave interference patterns on a two-dimensional cylindrical leading edge with an equilibrium chemically reacting gas mixture (representing, for example, the scramjet cowl of the NASP). The inclusion of gas chemistry allows for a more accurate prediction of the maximum pressure and heating loads by accounting for the effects of high temperature on the air mixture. Caloric imperfections and specie dissociation of high-temperature air cause shock-wave angles, flow deflection angles, and thermodynamic properties to differ from those calculated by a calorically perfect gas model. EASI contains pressure- and temperature-dependent thermodynamic and transport properties to determine heating rates, and uses either a calorically perfect air model or an 11-specie, 7-reaction reacting air model at equilibrium with temperatures up to 15,000 K for the inviscid flowfield calculations. EASI solves the flow field and the associated maximum surface pressure and heat flux for the six common types of shock wave interference. Depending on the type of interference, the program solves for shock-wave/boundary-layer interaction, expansion-fan/boundary-layer interaction, attaching shear layer or supersonic jet impingement. Heat flux predictions require a knowledge (from experimental data or relevant calculations) of a pertinent length scale of the interaction. Output files contain flow

  11. Novel mapping in non-equilibrium stochastic processes

    NASA Astrophysics Data System (ADS)

    Heseltine, James; Kim, Eun-jin

    2016-04-01

    We investigate the time-evolution of a non-equilibrium system in view of the change in information and provide a novel mapping relation which quantifies the change in information far from equilibrium and the proximity of a non-equilibrium state to the attractor. Specifically, we utilize a nonlinear stochastic model where the stochastic noise plays the role of incoherent regulation of the dynamical variable x and analytically compute the rate of change in information (information velocity) from the time-dependent probability distribution function. From this, we quantify the total change in information in terms of information length { L } and the associated action { J }, where { L } represents the distance that the system travels in the fluctuation-based, statistical metric space parameterized by time. As the initial probability density function’s mean position (μ) is decreased from the final equilibrium value {μ }* (the carrying capacity), { L } and { J } increase monotonically with interesting power-law mapping relations. In comparison, as μ is increased from {μ }*,{ L } and { J } increase slowly until they level off to a constant value. This manifests the proximity of the state to the attractor caused by a strong correlation for large μ through large fluctuations. Our proposed mapping relation provides a new way of understanding the progression of the complexity in non-equilibrium system in view of information change and the structure of underlying attractor.

  12. Explicit Integration of Extremely Stiff Reaction Networks: Partial Equilibrium Methods

    SciTech Connect

    Guidry, Mike W; Billings, J. J.; Hix, William Raphael

    2013-01-01

    In two preceding papers [1,2] we have shown that, when reaction networks are well removed from equilibrium, explicit asymptotic and quasi-steady-state approximations can give algebraically stabilized integration schemes that rival standard implicit methods in accuracy and speed for extremely stiff systems. However, we also showed that these explicit methods remain accurate but are no longer competitive in speed as the network approaches equilibrium. In this paper we analyze this failure and show that it is associated with the presence of fast equilibration timescales that neither asymptotic nor quasi-steady-state approximations are able to remove efficiently from the numerical integration. Based on this understanding, we develop a partial equilibrium method to deal effectively with the new partial equilibrium methods, give an integration scheme that plausibly can deal with the stiffest networks, even in the approach to equilibrium, with accuracy and speed competitive with that of implicit methods. Thus we demonstrate that algebraically stabilized explicit methods may offer alternatives to implicit integration of even extremely stiff systems, and that these methods may permit integration of much larger networks than have been feasible previously in a variety of fields.

  13. Two-Fluid Equilibrium for Transonic Poloidal Flows

    NASA Astrophysics Data System (ADS)

    Guazzotto, Luca; Betti, Riccardo

    2012-03-01

    Much analytical and numerical work has been done in the past on ideal MHD equilibrium in the presence of macroscopic flow. In recent years, several authors have worked on equilibrium formulations for a two-fluid system, in which inertial ions and massless electrons are treated as distinct fluids. In this work, we present our approach to the formulation of the two-fluid equilibrium problem. Particular attention is given to the relation between the two-fluid equations and the equilibrium equations for the single-fluid ideal MHD system. Our purpose is to reconsider the results of one-fluid calculation with the more accurate two-fluid model, referring in particular to the so-called transonic discontinuities, which occur when the poloidal velocity spans a range crossing the poloidal sound speed (i.e., the sound speed reduced by a factor Bp/B). It is expected that the one-fluid discontinuity will be resolved into a sharp gradient region by the two-fluid model. Also, contrary to the ideal MHD case, in the two-fluid model the equations governing the equilibrium are elliptic in the whole range of interest for transonic equilibria. The numerical solution of the two-fluid system of equations is going to be based on a code built on the structure of the existing ideal-MHD code FLOW.

  14. DSMC predictions of non-equilibrium reaction rates.

    SciTech Connect

    Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

    2010-04-01

    A set of Direct Simulation Monte Carlo (DSMC) chemical-reaction models recently proposed by Bird and based solely on the collision energy and the vibrational energy levels of the species involved is applied to calculate nonequilibrium chemical-reaction rates for atmospheric reactions in hypersonic flows. The DSMC non-equilibrium model predictions are in good agreement with theoretical models and experimental measurements. The observed agreement provides strong evidence that modeling chemical reactions using only the collision energy and the vibrational energy levels provides an accurate method for predicting non-equilibrium chemical-reaction rates.

  15. Equilibrium-Staged Separations Using Matlab and Mathematica

    ERIC Educational Resources Information Center

    Binous, Housam

    2008-01-01

    We show a new approach, based on the utilization of Matlab and Mathematica, for solving liquid-liquid extraction and binary distillation problems. In addition, the author shares his experience using these two softwares to teach equilibrium staged separations at the National Institute of Applied Sciences and Technology. (Contains 7 figures.)

  16. Composition and Thermodynamic Properties of Air in Chemical Equilibrium

    NASA Technical Reports Server (NTRS)

    Moeckel, W E; Weston, Kenneth C

    1958-01-01

    Charts have been prepared relating the thermodynamic properties of air in chemical equilibrium for temperatures to 15,000 degrees k and for pressures 10(-5) to 10 (plus 4) atmospheres. Also included are charts showing the composition of air, the isentropic exponent, and the speed of sound. These charts are based on thermodynamic data calculated by the National Bureau of Standards.

  17. Microcomputer Calculation of Equilibrium Constants from Molecular Parameters of Gases.

    ERIC Educational Resources Information Center

    Venugopalan, Mundiyath

    1989-01-01

    Lists a BASIC program which computes the equilibrium constant as a function of temperature. Suggests use by undergraduates taking a one-year calculus-based physical chemistry course. Notes the program provides for up to four species, typically two reactants and two products. (MVL)

  18. Equilibrium Distribution of Mutators in the Single Fitness Peak Model

    NASA Astrophysics Data System (ADS)

    Tannenbaum, Emmanuel; Deeds, Eric J.; Shakhnovich, Eugene I.

    2003-09-01

    This Letter develops an analytically tractable model for determining the equilibrium distribution of mismatch repair deficient strains in unicellular populations. The approach is based on the single fitness peak model, which has been used in Eigen’s quasispecies equations in order to understand various aspects of evolutionary dynamics. As with the quasispecies model, our model for mutator-nonmutator equilibrium undergoes a phase transition in the limit of infinite sequence length. This “repair catas­trophe” occurs at a critical repair error probability of ɛr=Lvia/L, where Lvia denotes the length of the genome controlling viability, while L denotes the overall length of the genome. The repair catastrophe therefore occurs when the repair error probability exceeds the fraction of deleterious mutations. Our model also gives a quantitative estimate for the equilibrium fraction of mutators in Escherichia coli.

  19. Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

    PubMed

    Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

    2016-05-26

    The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description.

  20. CO2 and humidity removal system for extended Shuttle missions - CO2, H2O, and trace contaminant equilibrium testing

    NASA Technical Reports Server (NTRS)

    Davis, S. H.; Kissinger, L. D.

    1977-01-01

    The equilibrium relationships for the co-adsorption of CO2 and H2O on an amine coated acrylic ester are presented. The equilibrium data collection and reduction techniques are discussed. Based on the equilibrium relationship, other modes of operation of systems containing HS-C are discussed and specific space applications for HS-C are presented. Equilibrium data for 10 compounds which are found as trace contaminants in closed environments are also presented.

  1. Non-Equilibrium Effects on Hypersonic Turbulent Boundary Layers

    NASA Astrophysics Data System (ADS)

    Kim, Pilbum

    Understanding non-equilibrium effects of hypersonic turbulent boundary layers is essential in order to build cost efficient and reliable hypersonic vehicles. It is well known that non-equilibrium effects on the boundary layers are notable, but our understanding of the effects are limited. The overall goal of this study is to improve the understanding of non-equilibrium effects on hypersonic turbulent boundary layers. A new code has been developed for direct numerical simulations of spatially developing hypersonic turbulent boundary layers over a flat plate with finite-rate reactions. A fifth-order hybrid weighted essentially non-oscillatory scheme with a low dissipation finite-difference scheme is utilized in order to capture stiff gradients while resolving small motions in turbulent boundary layers. The code has been validated by qualitative and quantitative comparisons of two different simulations of a non-equilibrium flow and a spatially developing turbulent boundary layer. With the validated code, direct numerical simulations of four different hypersonic turbulent boundary layers, perfect gas and non-equilibrium flows of pure oxygen and nitrogen, have been performed. In order to rule out uncertainties in comparisons, the same inlet conditions are imposed for each species, and then mean and turbulence statistics as well as near-wall turbulence structures are compared at a downstream location. Based on those comparisons, it is shown that there is no direct energy exchanges between internal and turbulent kinetic energies due to thermal and chemical non-equilibrium processes in the flow field. Instead, these non-equilibria affect turbulent boundary layers by changing the temperature without changing the main characteristics of near-wall turbulence structures. This change in the temperature induces the changes in the density and viscosity and the mean flow fields are then adjusted to satisfy the conservation laws. The perturbation fields are modified according to

  2. 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…

  3. Zeroth Law, Entropy, Equilibrium, and All That

    ERIC Educational Resources Information Center

    Canagaratna, Sebastian G.

    2008-01-01

    The place of the zeroth law in the teaching of thermodynamics is examined in the context of the recent discussion by Gislason and Craig of some problems involving the establishment of thermal equilibrium. The concept of thermal equilibrium is introduced through the zeroth law. The relation between the zeroth law and the second law in the…

  4. Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

    ERIC Educational Resources Information Center

    Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

    2015-01-01

    A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

  5. A general equilibrium analysis of partial-equilibrium welfare measures: The case of climate change

    SciTech Connect

    Kokoski, M.F.; Smith, V.K. )

    1987-06-01

    This paper uses computable general equilibrium models to demonstrate that partial-equilibrium welfare measures can offer reasonable approximations of the true welfare changes for large exogenous changes. With consistency in the size and direction of the indirect price effects associated with large shocks, single sector partial-equilibrium measures will exhibit small errors. Otherwise the errors can be substantial and difficult to sign.

  6. How Far from Equilibrium Is Active Matter?

    PubMed

    Fodor, Étienne; Nardini, Cesare; Cates, Michael E; Tailleur, Julien; Visco, Paolo; van Wijland, Frédéric

    2016-07-15

    Active matter systems are driven out of thermal equilibrium by a lack of generalized Stokes-Einstein relation between injection and dissipation of energy at the microscopic scale. We consider such a system of interacting particles, propelled by persistent noises, and show that, at small but finite persistence time, their dynamics still satisfy a time-reversal symmetry. To do so, we compute perturbatively their steady-state measure and show that, for short persistent times, the entropy production rate vanishes. This endows such systems with an effective fluctuation-dissipation theorem akin to that of thermal equilibrium systems. Last, we show how interacting particle systems with viscous drags and correlated noises can be seen as in equilibrium with a viscoelastic bath but driven out of equilibrium by nonconservative forces, hence providing energetic insight into the departure of active systems from equilibrium.

  7. Disturbances in equilibrium function after major earthquake

    NASA Astrophysics Data System (ADS)

    Honma, Motoyasu; Endo, Nobutaka; Osada, Yoshihisa; Kim, Yoshiharu; Kuriyama, Kenichi

    2012-10-01

    Major earthquakes were followed by a large number of aftershocks and significant outbreaks of dizziness occurred over a large area. However it is unclear why major earthquake causes dizziness. We conducted an intergroup trial on equilibrium dysfunction and psychological states associated with equilibrium dysfunction in individuals exposed to repetitive aftershocks versus those who were rarely exposed. Greater equilibrium dysfunction was observed in the aftershock-exposed group under conditions without visual compensation. Equilibrium dysfunction in the aftershock-exposed group appears to have arisen from disturbance of the inner ear, as well as individual vulnerability to state anxiety enhanced by repetitive exposure to aftershocks. We indicate potential effects of autonomic stress on equilibrium function after major earthquake. Our findings may contribute to risk management of psychological and physical health after major earthquakes with aftershocks, and allow development of a new empirical approach to disaster care after such events.

  8. Disturbances in equilibrium function after major earthquake.

    PubMed

    Honma, Motoyasu; Endo, Nobutaka; Osada, Yoshihisa; Kim, Yoshiharu; Kuriyama, Kenichi

    2012-01-01

    Major earthquakes were followed by a large number of aftershocks and significant outbreaks of dizziness occurred over a large area. However it is unclear why major earthquake causes dizziness. We conducted an intergroup trial on equilibrium dysfunction and psychological states associated with equilibrium dysfunction in individuals exposed to repetitive aftershocks versus those who were rarely exposed. Greater equilibrium dysfunction was observed in the aftershock-exposed group under conditions without visual compensation. Equilibrium dysfunction in the aftershock-exposed group appears to have arisen from disturbance of the inner ear, as well as individual vulnerability to state anxiety enhanced by repetitive exposure to aftershocks. We indicate potential effects of autonomic stress on equilibrium function after major earthquake. Our findings may contribute to risk management of psychological and physical health after major earthquakes with aftershocks, and allow development of a new empirical approach to disaster care after such events.

  9. Probing local equilibrium in nonequilibrium fluids.

    PubMed

    del Pozo, J J; Garrido, P L; Hurtado, P I

    2015-08-01

    We use extensive computer simulations to probe local thermodynamic equilibrium (LTE) in a quintessential model fluid, the two-dimensional hard-disks system. We show that macroscopic LTE is a property much stronger than previously anticipated, even in the presence of important finite-size effects, revealing a remarkable bulk-boundary decoupling phenomenon in fluids out of equilibrium. This allows us to measure the fluid's equation of state in simulations far from equilibrium, with an excellent accuracy comparable to the best equilibrium simulations. Subtle corrections to LTE are found in the fluctuations of the total energy which strongly point to the nonlocality of the nonequilibrium potential governing the fluid's macroscopic behavior out of equilibrium.

  10. How Far from Equilibrium Is Active Matter?

    NASA Astrophysics Data System (ADS)

    Fodor, Étienne; Nardini, Cesare; Cates, Michael E.; Tailleur, Julien; Visco, Paolo; van Wijland, Frédéric

    2016-07-01

    Active matter systems are driven out of thermal equilibrium by a lack of generalized Stokes-Einstein relation between injection and dissipation of energy at the microscopic scale. We consider such a system of interacting particles, propelled by persistent noises, and show that, at small but finite persistence time, their dynamics still satisfy a time-reversal symmetry. To do so, we compute perturbatively their steady-state measure and show that, for short persistent times, the entropy production rate vanishes. This endows such systems with an effective fluctuation-dissipation theorem akin to that of thermal equilibrium systems. Last, we show how interacting particle systems with viscous drags and correlated noises can be seen as in equilibrium with a viscoelastic bath but driven out of equilibrium by nonconservative forces, hence providing energetic insight into the departure of active systems from equilibrium.

  11. Access point selection game with mobile users using correlated equilibrium.

    PubMed

    Sohn, Insoo

    2015-01-01

    One of the most important issues in wireless local area network (WLAN) systems with multiple access points (APs) is the AP selection problem. Game theory is a mathematical tool used to analyze the interactions in multiplayer systems and has been applied to various problems in wireless networks. Correlated equilibrium (CE) is one of the powerful game theory solution concepts, which is more general than the Nash equilibrium for analyzing the interactions in multiplayer mixed strategy games. A game-theoretic formulation of the AP selection problem with mobile users is presented using a novel scheme based on a regret-based learning procedure. Through convergence analysis, we show that the joint actions based on the proposed algorithm achieve CE. Simulation results illustrate that the proposed algorithm is effective in a realistic WLAN environment with user mobility and achieves maximum system throughput based on the game-theoretic formulation. PMID:25785726

  12. Response to Contradiction: Conflict Resolution Strategies Used by Students in Solving Problems of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Niaz, Mansoor

    2001-01-01

    Illustrates how a novel problem of chemical equilibrium based on a closely related sequence of items can facilitate students' conceptual understanding. Students were presented with a chemical reaction in equilibrium to which a reactant was added as an external effect. Three studies were conducted to assess alternative conceptions. (Author/SAH)

  13. Students' Understanding of Equilibrium and Stability: The Case of Dynamic Systems

    ERIC Educational Resources Information Center

    Canu, Michaël; de Hosson, Cécile; Duque, Mauricio

    2016-01-01

    Engineering students in control courses have been observed to lack an understanding of equilibrium and stability, both of which are crucial concepts in this discipline. The introduction of these concepts is generally based on the study of classical examples from Newtonian mechanics supplemented with a control system. Equilibrium and stability are…

  14. Teaching Chemical Equilibrium with the Jigsaw Technique

    NASA Astrophysics Data System (ADS)

    Doymus, Kemal

    2008-03-01

    This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students’ understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes was randomly assigned as the non-jigsaw group (control) and other as the jigsaw group (cooperative). Students participating in the jigsaw group were divided into four “home groups” since the topic chemical equilibrium is divided into four subtopics (Modules A, B, C and D). Each of these home groups contained four students. The groups were as follows: (1) Home Group A (HGA), representin g the equilibrium state and quantitative aspects of equilibrium (Module A), (2) Home Group B (HGB), representing the equilibrium constant and relationships involving equilibrium constants (Module B), (3) Home Group C (HGC), representing Altering Equilibrium Conditions: Le Chatelier’s principle (Module C), and (4) Home Group D (HGD), representing calculations with equilibrium constants (Module D). The home groups then broke apart, like pieces of a jigsaw puzzle, and the students moved into jigsaw groups consisting of members from the other home groups who were assigned the same portion of the material. The jigsaw groups were then in charge of teaching their specific subtopic to the rest of the students in their learning group. The main data collection tool was a Chemical Equilibrium Achievement Test (CEAT), which was applied to both the jigsaw and non-jigsaw groups The results indicated that the jigsaw group was more successful than the non-jigsaw group (individual learning method).

  15. 3D Equilibrium Reconstructions in DIII-D

    NASA Astrophysics Data System (ADS)

    Lao, L. L.; Ferraro, N. W.; Strait, E. J.; Turnbull, A. D.; King, J. D.; Hirshman, H. P.; Lazarus, E. A.; Sontag, A. C.; Hanson, J.; Trevisan, G.

    2013-10-01

    Accurate and efficient 3D equilibrium reconstruction is needed in tokamaks for study of 3D magnetic field effects on experimentally reconstructed equilibrium and for analysis of MHD stability experiments with externally imposed magnetic perturbations. A large number of new magnetic probes have been recently installed in DIII-D to improve 3D equilibrium measurements and to facilitate 3D reconstructions. The V3FIT code has been in use in DIII-D to support 3D reconstruction and the new magnetic diagnostic design. V3FIT is based on the 3D equilibrium code VMEC that assumes nested magnetic surfaces. V3FIT uses a pseudo-Newton least-square algorithm to search for the solution vector. In parallel, the EFIT equilibrium reconstruction code is being extended to allow for 3D effects using a perturbation approach based on an expansion of the MHD equations. EFIT uses the cylindrical coordinate system and can include the magnetic island and stochastic effects. Algorithms are being developed to allow EFIT to reconstruct 3D perturbed equilibria directly making use of plasma response to 3D perturbations from the GATO, MARS-F, or M3D-C1 MHD codes. DIII-D 3D reconstruction examples using EFIT and V3FIT and the new 3D magnetic data will be presented. Work supported in part by US DOE under DE-FC02-04ER54698, DE-FG02-95ER54309 and DE-AC05-06OR23100.

  16. New Simulator for Non-Equilibrium Modeling of Hydrate Reservoirs

    NASA Astrophysics Data System (ADS)

    Kvamme, B.; Qorbani Nashaqi, K.; Jemai, K.; Vafaei, M.

    2014-12-01

    Due to Gibbs phase rule and combination of first and second law of thermodynamics, hydrate in nature cannot be in equilibrium since they come from different parent phases. In this system hydrate formation and dissociation is affected by local variables such as pressure, temperature and composition with mass and energy transport restrictions. Available simulators have attempted to model hydrate phase transition as an equilibrium reaction. Although those which treated the processes of formation and dissociation as kinetics used model of Kim and Bishnoi based on laboratory PVT experiment, and consequently hard to accept up scaling to real reservoirs condition. Additionally, they merely check equilibrium in terms of pressure and temperature projections and disregard thermodynamic requirements for equilibrium especially along axes of concentrations in phases. Non-equilibrium analysis of hydrate involves putting aside all the phase transitions which are not possible and use kinetic evaluation to measure phase transitions progress in each grid block for each time step. This procedure is Similar to geochemical reservoir simulators logic. As a result RetrasoCodeBright has been chosen as hydrate reservoir simulator and our work involves extension of this code. RetrasoCodeBright (RCB) is able to handle competing processes of formation and dissociation of hydrates as pseudo reactions at each node and each time step according to the temperature, pressure and concentration. Hydrates can therefore be implemented into the structure as pseudo minerals, with appropriate kinetic models. In order to implement competing nature of phase transition kinetics of hydrate formation, we use classical nucleation theory based on Kvamme et al. as a simplified model inside RCB and use advanced theories to fit parameters for the model (PFT). Hydrate formation and dissociation can directly be observed through porosity changes in the specific areas of the porous media. In this work which is in

  17. The Conceptual Change Approach to Teaching Chemical Equilibrium

    ERIC Educational Resources Information Center

    Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

    2006-01-01

    This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

  18. Cavity turnover and equilibrium cavity densities in a cottonwood bottomland

    USGS Publications Warehouse

    Sedgwick, James A.; Knopf, Fritz L.

    1992-01-01

    A fundamental factor regulating the numbers of secondary cavity nesting (SCN) birds is the number of extant cavities available for nesting. The number of available cavities may be thought of as being in an approximate equilibrium maintained by a very rough balance between recruitment and loss of cavities. Based on estimates of cavity recruitment and loss, we ascertained equilibrium cavity densities in a mature plains cottonwood (Populus sargentii) bottomland along the South Platte River in northeastern Colorado. Annual cavity recruitment, derived from density estimates of primary cavity nesting (PCN) birds and cavity excavation rates, was estimated to be 71-86 new cavities excavated/100 ha. Of 180 active cavities of 11 species of cavity-nesting birds found in 1985 and 1986, 83 were no longer usable by 1990, giving an average instantaneous rate of cavity loss of r = -0.230. From these values of cavity recruitment and cavity loss, equilibrium cavity density along the South Platte is 238-289 cavities/100 ha. This range of equilibrium cavity density is only slightly above the minimum of 205 cavities/100 ha required by SCN's and suggests that cavity availability may be limiting SCN densities along the South Platte River. We submit that snag management alone does not adequately address SCN habitat needs, and that cavity management, expressed in terms of cavity turnover and cavity densities, may be more useful.

  19. BE STAR DISK MODELS IN CONSISTENT VERTICAL HYDROSTATIC EQUILIBRIUM

    SciTech Connect

    Sigut, T. A. A.; McGill, M. A.; Jones, C. E. E-mail: mmcgill@astro.uwo.ca

    2009-07-10

    A popular model for the circumstellar disks of Be stars is that of a geometrically thin disk with a density in the equatorial plane that drops as a power law of distance from the star. It is usually assumed that the vertical structure of such a disk (in the direction parallel to the stellar rotation axis) is governed by the hydrostatic equilibrium set by the vertical component of the star's gravitational acceleration. Previous radiative equilibrium models for such disks have usually been computed assuming a fixed density structure. This introduces an inconsistency as the gas density is not allowed to respond to temperature changes and the resultant disk model is not in vertical, hydrostatic equilibrium. In this work, we modify the BEDISK code of Sigut and Jones so that it enforces a hydrostatic equilibrium consistent with the temperature solution. We compare the disk densities, temperatures, H{alpha} line profiles, and near-IR excesses predicted by such models with those computed from models with a fixed density structure. We find that the fixed models can differ substantially from the consistent hydrostatic models when the disk density is high enough that the circumstellar disk develops a cool (T {approx}< 10, 000 K) equatorial region close to the parent star. Based on these new hydrostatic disks, we also predict an approximate relation between the (global) density-averaged disk temperature and the T{sub eff} of the central star, covering the full range of central Be star spectral types.

  20. Equilibrium limit of thermal conduction and boundary scattering in nanostructures.

    PubMed

    Haskins, Justin B; Kınacı, Alper; Sevik, Cem; Çağın, Tahir

    2014-06-28

    Determining the lattice thermal conductivity (κ) of nanostructures is especially challenging in that, aside from the phonon-phonon scattering present in large systems, the scattering of phonons from the system boundary greatly influences heat transport, particularly when system length (L) is less than the average phonon mean free path (MFP). One possible route to modeling κ in these systems is through molecular dynamics (MD) simulations, inherently including both phonon-phonon and phonon-boundary scattering effects in the classical limit. Here, we compare current MD methods for computing κ in nanostructures with both L ⩽ MFP and L ≫ MFP, referred to as mean free path constrained (cMFP) and unconstrained (uMFP), respectively. Using a (10,0) CNT (carbon nanotube) as a benchmark case, we find that while the uMFP limit of κ is well-defined through the use of equilibrium MD and the time-correlation formalism, the standard equilibrium procedure for κ is not appropriate for the treatment of the cMFP limit because of the large influence of boundary scattering. To address this issue, we define an appropriate equilibrium procedure for cMFP systems that, through comparison to high-fidelity non-equilibrium methods, is shown to be the low thermal gradient limit to non-equilibrium results. Further, as a means of predicting κ in systems having L ≫ MFP from cMFP results, we employ an extrapolation procedure based on the phenomenological, boundary scattering inclusive expression of Callaway [Phys. Rev. 113, 1046 (1959)]. Using κ from systems with L ⩽ 3 μm in the extrapolation, we find that the equilibrium uMFP κ of a (10,0) CNT can be predicted within 5%. The equilibrium procedure is then applied to a variety of carbon-based nanostructures, such as graphene flakes (GF), graphene nanoribbons (GNRs), CNTs, and icosahedral fullerenes, to determine the influence of size and environment (suspended versus supported) on κ. Concerning the GF and GNR systems, we find that

  1. Spreadsheet Templates for Chemical Equilibrium Calculations.

    ERIC Educational Resources Information Center

    Joshi, Bhairav D.

    1993-01-01

    Describes two general spreadsheet templates to carry out all types of one-equation chemical equilibrium calculations encountered by students in undergraduate chemistry courses. Algorithms, templates, macros, and representative examples are presented to illustrate the approach. (PR)

  2. Sound speeds in suspensions in thermodynamic equilibrium

    NASA Astrophysics Data System (ADS)

    Temkin, S.

    1992-11-01

    This work considers sound propagation in suspensions of particles of constant mass in fluids, in both relaxed and frozen thermodynamic equilibrium. Treating suspensions as relaxing media, thermodynamic arguments are used to obtain their sound speeds in equilibrium conditions. The results for relaxed equilibrium, which is applicable in the limit of low frequencies, agree with existing theories for aerosols, but disagree with Wood's equation. It is shown that the latter is thermodynamically correct only in the exceptional case when the specific heat ratios of the fluid and of the particles are equal to unity. In all other cases discrepancies occur. These may be significant when one of the two phases in the suspension is a gas, as is the case in aerosols and in bubbly liquids. The paper also includes a brief discussion of the sound speed in frozen equilibrium.

  3. Points of Equilibrium in Electrostatic Fields.

    ERIC Educational Resources Information Center

    Rogers, Peter J.

    1979-01-01

    Discusses the electric field line pattern for four equal charges of the same sign placed at the corners of a square. The electric field intensity and the point of equilibrium are interpreted, taking into account three dimensions. (HM)

  4. An Elementary Discussion of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    David, Carl W.

    1988-01-01

    This discussion uses a more difficult reaction as the prototype to derive the standard equation for chemical equilibrium. It can be used by students who can understand and use partial derivatives. (CW)

  5. Rapid Equilibrium-Ordered Enzyme Mechanisms.

    ERIC Educational Resources Information Center

    Chauncey, Thomas R.; And Others

    1985-01-01

    Discusses: (1) characteristic initial velocity behavior (considering the five-step reaction sequence for rapid equilibrium-order bisubstrate mechanisms); (2) dead-end inhibition; (3) inhibition by single products; and (4) an activator as a leading reactant. (JN)

  6. Thermal equilibrium in Europa's ice shell

    NASA Astrophysics Data System (ADS)

    Moore, William B.

    2006-01-01

    Models of tidal-convective equilibrium for Europa's ice shell are computed using a laboratory-derived composite flow law for ice. Volume diffusion creep is found to dominate the flow law at equilibrium, and thus the thickness of the shell is strongly dependent on the poorly known grain size of the ice. This grain size is, however, constrained to be less than a few millimeters if equilibrium is achieved at the current eccentricity. Europa's ice shell cannot be thinner than about 16 km in equilibrium at present, since tidal dissipation cannot generate enough heat in such a thin shell to balance the heat transport. No conductive equilibria are found; this is likely due to the fact that most of a conductive shell must be cold if temperature gradients are to be large enough to carry the heat. A minimum eccentricity of about 0.0025 (about 1/4 the present value) below which there are no equilibria is also found.

  7. Radiative-dynamical equilibrium states for Jupiter

    NASA Technical Reports Server (NTRS)

    Trafton, L. M.; Stone, P. H.

    1974-01-01

    In order to obtain accurate estimates of the radiative heating that drives motions in Jupiter's atmosphere, previous radiative equilibrium calculations are improved by including the NH3 opacities and updated results for the pressure-induced opacities. These additions increase the radiative lapse rate near the top of the statically unstable region and lead to a fairly constant radiative lapse rate below the tropopause. The radiative-convective equilibrium temperature structure consistent with these changes is calculated, but it differs only slightly from earlier calculations. The radiative equilibrium calculations are used to calculate whether equilibrium states can occur on Jupiter which are similar to the baroclinic instability regimes on the earth and Mars. The results show that Jupiter's dynamical regime cannot be of this kind, except possibly at very high latitudes, and that its regime must be a basically less stable one than this kind.

  8. Equilibrium fluctuation energy of gyrokinetic plasma

    SciTech Connect

    Krommes, J.A.; Lee, W.W.; Oberman, C.

    1985-11-01

    The thermal equilibrium electric field fluctuation energy of the gyrokinetic model of magnetized plasma is computed, and found to be smaller than the well-known result (k)/8..pi.. = 1/2T/(1 + (klambda/sub D/)/sup 2/) valid for arbitrarily magnetized plasmas. It is shown that, in a certain sense, the equilibrium electric field energy is minimum in the gyrokinetic regime. 13 refs., 2 figs.

  9. Edge Equilibrium Code (EEC) For Tokamaks

    SciTech Connect

    Li, Xujling

    2014-02-24

    The edge equilibrium code (EEC) described in this paper is developed for simulations of the near edge plasma using the finite element method. It solves the Grad-Shafranov equation in toroidal coordinate and uses adaptive grids aligned with magnetic field lines. Hermite finite elements are chosen for the numerical scheme. A fast Newton scheme which is the same as implemented in the equilibrium and stability code (ESC) is applied here to adjust the grids

  10. Non-equilibrium Kinematics in Merging Galaxies

    NASA Astrophysics Data System (ADS)

    Mihos, J. C.

    Measurements of the kinematics of merging galaxies are often used to derive dynamical masses, study evolution onto the fundamental plane, or probe relaxation processes. These measurements are often compromised to some degree by strong non-equilibrium motions in the merging galaxies. This talk focuses on the evolution of the kinematics of merging galaxies, and highlights some pitfalls which occur when studying non-equilibrium systems.

  11. A theoretical analysis of vertical flow equilibrium

    SciTech Connect

    Yortsos, Y.C.

    1992-01-01

    The assumption of Vertical Flow Equilibrium (VFE) and of parallel flow conditions, in general, is often applied to the modeling of flow and displacement in natural porous media. However, the methodology for the development of the various models is rather intuitive, and no rigorous method is currently available. In this paper, we develop an asymptotic theory using as parameter the variable R{sub L} = (L/H){radical}(k{sub V})/(k{sub H}). It is rigorously shown that present models represent the leading order term of an asymptotic expansion with respect to 1/R{sub L}{sup 2}. Although this was numerically suspected, it is the first time that is is theoretically proved. Based on the general formulation, a series of models are subsequently obtained. In the absence of strong gravity effects, they generalize previous works by Zapata and Lake (1981), Yokoyama and Lake (1981) and Lake and Hirasaki (1981), on immiscible and miscible displacements. In the limit of gravity-segregated flow, we prove conditions for the fluids to be segregated and derive the Dupuit and Dietz (1953) approximations. Finally, we also discuss effects of capillarity and transverse dispersion.

  12. Pre-equilibrium studies in monoisotopic praseodymium

    SciTech Connect

    Singh, B.P.; Mustafa, M.M.; Sankarcharyulu, M.G.V.

    1994-12-31

    Measurement and analysis of excitation functions in {alpha}-induced reactions has become an important tool for studying the pre-equilibrium (PE) phenomenon. As part of the programme of precise measurement and analysis of excitation functions in reactions for a large number of nuclei, the authors report the measurement of excitation functions for the reactions {sup 141}Pr({alpha},n){sup 144}Pm and {sup 141}Pr({alpha},2n){sup 143}Pm in the energy range from threshold to {approx}40 MeV. To the best of their knowledge, these excitation functions have been measured for the first time. Measurements have been performed using stacked foil activation technique. The irradiation has been carried out at the Variable Energy Cyclotron Centre (VECC), Calcutta, India using the {alpha}-beam of {approx} 40 MeV. The post irradiation analysis has been done using the HPGe detector coupled to the ORTEC`s PC based multichannel analyser. The analysis of the excitation functions has been carried out using the semi-classical computer codes ACT and ALICE-82. These codes use Hauser-Feshbach/ Welsskopf-Ewing formalism for compound nucleus calculations and exciton/hybrid model for simulating PE contributions. The quantum mechanical statistical multistep code EXIFON has also been used for the analysis of these excitation functions. The comparison of results with different codes will be presented.

  13. Inferring unstable equilibrium configurations from experimental data

    NASA Astrophysics Data System (ADS)

    Virgin, L. N.; Wiebe, R.; Spottswood, S. M.; Beberniss, T.

    2016-09-01

    This research considers the structural behavior of slender, mechanically buckled beams and panels of the type commonly found in aerospace structures. The specimens were deflected and then clamped in a rigid frame in order to exhibit snap-through. That is, the initial equilibrium and the buckled (snapped-through) equilibrium configurations both co-existed for the given clamped conditions. In order to transit between these two stable equilibrium configurations (for example, under the action of an externally applied load), it is necessary for the structural component to pass through an intermediate unstable equilibrium configuration. A sequence of sudden impacts was imparted to the system, of various strengths and at various locations. The goal of this impact force was to induce relatively intermediate-sized transients that effectively slowed-down in the vicinity of the unstable equilibrium configuration. Thus, monitoring the velocity of the motion, and specifically its slowing down, should give an indication of the presence of an equilibrium configuration, even though it is unstable and not amenable to direct experimental observation. A digital image correlation (DIC) system was used in conjunction with an instrumented impact hammer to track trajectories and statistical methods used to infer the presence of unstable equilibria in both a beam and a panel.

  14. Approaches to the Treatment of Equilibrium Perturbations

    NASA Astrophysics Data System (ADS)

    Canagaratna, Sebastian G.

    2003-10-01

    Perturbations from equilibrium are treated in the textbooks by a combination of Le Châtelier's principle, the comparison of the equilibrium constant K with the reaction quotient Q,and the kinetic approach. Each of these methods is briefly reviewed. This is followed by derivations of the variation of the equilibrium value of the extent of reaction, ξeq, with various parameters on which it depends. Near equilibrium this relationship can be represented by a straight line. The equilibrium system can be regarded as moving on this line as the parameter is varied. The slope of the line depends on quantities like enthalpy of reaction, volume of reaction and so forth. The derivation shows that these quantities pertain to the equilibrium system, not the standard state. Also, the derivation makes clear what kind of assumptions underlie our conclusions. The derivation of these relations involves knowledge of thermodynamics that is well within the grasp of junior level physical chemistry students. The conclusions that follow from the derived relations are given as subsidiary rules in the form of the slope of ξeq, with T, p, et cetera. The rules are used to develop a visual way of predicting the direction of shift of a perturbed system. This method can be used to supplement one of the other methods even at the introductory level.

  15. Knowledge Management through the Equilibrium Pattern Model for Learning

    NASA Astrophysics Data System (ADS)

    Sarirete, Akila; Noble, Elizabeth; Chikh, Azeddine

    Contemporary students are characterized by having very applied learning styles and methods of acquiring knowledge. This behavior is consistent with the constructivist models where students are co-partners in the learning process. In the present work the authors developed a new model of learning based on the constructivist theory coupled with the cognitive development theory of Piaget. The model considers the level of learning based on several stages and the move from one stage to another requires learners' challenge. At each time a new concept is introduced creates a disequilibrium that needs to be worked out to return back to its equilibrium stage. This process of "disequilibrium/equilibrium" has been analyzed and validated using a course in computer networking as part of Cisco Networking Academy Program at Effat College, a women college in Saudi Arabia. The model provides a theoretical foundation for teaching especially in a complex knowledge domain such as engineering and can be used in a knowledge economy.

  16. Complementary relations in non-equilibrium stochastic processes

    NASA Astrophysics Data System (ADS)

    Kim, Eun-jin; Nicholson, S. B.

    2015-08-01

    We present novel complementary relations in non-equilibrium stochastic processes. Specifically, by utilising path integral formulation, we derive statistical measures (entropy, information, and work) and investigate their dependence on variables (x, v), reference frames, and time. In particular, we show that the equilibrium state maximises the simultaneous information quantified by the product of the Fisher information based on x and v while minimising the simultaneous disorder/uncertainty quantified by the sum of the entropy based on x and v as well as by the product of the variances of the PDFs of x and v. We also elucidate the difference between Eulerian and Lagrangian entropy. Our theory naturally leads to Hamilton-Jacobi relation for forced-dissipative systems.

  17. Modified equilibrium temperature models for cold-water streams

    NASA Astrophysics Data System (ADS)

    Herb, William R.; Stefan, Heinz G.

    2011-06-01

    Water temperature determines the spatial distribution of fish species, including cold-water fish such as trout, and is driven by the balance of the heat flux across the water surface and the heat flux across the sediment surface. In this study, a modified equilibrium temperature model was developed for cold-water streams that includes the effect of groundwater inflow. The modified equilibrium temperature model gives estimates of daily average stream temperature based on climate conditions, riparian shading, stream width, and groundwater input rate and temperature. For a small tributary stream with relatively uniform riparian shading, the modified equilibrium temperature was found to be a good predictor of daily average stream temperature, with a root-mean-square errors (RMSE) of 1.2°C. The modified equilibrium temperature model also gave good estimates (1.4°C RMSE) of daily average stream temperature for a larger stream when riparian shading was averaged over sufficiently long distances. A sensitivity analysis using the modified equilibrium temperature model confirmed that water temperature in cold-water streams varies strongly with riparian shading, stream width, and both groundwater inflow rate and temperature. These groundwater parameters therefore need to be taken into account when climate change impacts on stream temperature are projected. The stream temperature model developed in this study is a useful tool to characterize temperature conditions in cold-water streams with different levels of riparian shading and groundwater inputs and to assess the impact of future land use and climate change on temperature in these streams.

  18. CET89 - CHEMICAL EQUILIBRIUM WITH TRANSPORT PROPERTIES, 1989

    NASA Technical Reports Server (NTRS)

    Mcbride, B.

    1994-01-01

    Scientists and engineers need chemical equilibrium composition data to calculate the theoretical thermodynamic properties of a chemical system. This information is essential in the design and analysis of equipment such as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical processing equipment. The substantial amount of numerical computation required to obtain equilibrium compositions and transport properties for complex chemical systems led scientists at NASA's Lewis Research Center to develop CET89, a program designed to calculate the thermodynamic and transport properties of these systems. CET89 is a general program which will calculate chemical equilibrium compositions and mixture properties for any chemical system with available thermodynamic data. Generally, mixtures may include condensed and gaseous products. CET89 performs the following operations: it 1) obtains chemical equilibrium compositions for assigned thermodynamic states, 2) calculates dilute-gas transport properties of complex chemical mixtures, 3) obtains Chapman-Jouguet detonation properties for gaseous species, 4) calculates incident and reflected shock properties in terms of assigned velocities, and 5) calculates theoretical rocket performance for both equilibrium and frozen compositions during expansion. The rocket performance function allows the option of assuming either a finite area or an infinite area combustor. CET89 accommodates problems involving up to 24 reactants, 20 elements, and 600 products (400 of which may be condensed). The program includes a library of thermodynamic and transport properties in the form of least squares coefficients for possible reaction products. It includes thermodynamic data for over 1300 gaseous and condensed species and transport data for 151 gases. The subroutines UTHERM and UTRAN convert thermodynamic and transport data to unformatted form for faster processing. The program conforms to the FORTRAN 77 standard, except for

  19. Phenomenon of Life: Between Equilibrium and Non-Linearity

    NASA Astrophysics Data System (ADS)

    Galimov, E. M.

    2004-12-01

    A model of ordering applicable to biological evolution is presented. It is shown that a steady state (more precisely approaching to a steady state) system of irreversible processes, under conditions of disproportionation of entropy, produces a lower-entropy product, that is, ordering. The ordering is defined as restricting of degrees of freedom: freedom of motion, interactions etc. The model differs from previous ones in that it relates the ordering to processes running not far from equilibrium, described in the linear field of non-equilibrium thermodynamics. It is shown that a system, which includes adenosine triphosphate (ATP) to adenosine diphosphate (ADP) conversion meets the demands of the physical model: it provides energy maintaining steady state conditions, and hydrolysis of ATP proceeding with consumption of water can be tightly conjugated with the most important reactions of synthesis of organic polymers (peptides, nucleotide chains etc.), which proceed with release of water. For these and other reasons ATP seems to be a key molecule of prebiotic evolution. It is argued that the elementary chemical reaction proceeding under control of an enzyme is not necessarily far from equilibrium. The experimental evidence supporting this idea, is presented. It is based on isotope data. Carbon isotope distribution in biochemical systems reveals regularity, which is inherent to steady state systems of chemical reactions, proceeding not far from equilibrium. In living organisms this feature appears at the statistical level, as many completely irreversible and non-linear processes occur in organisms. However not-far-from-equilibrium reactions are inherent to biochemical systems as a matter of principle. They are reconcilable with biochemical behavior. Extant organisms are highly evolved entities which, however, show in their basis the same features, as the simplest chemical systems must have had been involved in the origin of life. Some consequences following from the

  20. BOOK REVIEW: Relativistic Figures of Equilibrium

    NASA Astrophysics Data System (ADS)

    Mars, M.

    2009-08-01

    Compact fluid bodies in equilibrium under its own gravitational field are abundant in the Universe and a proper treatment of them can only be carried out using the full theory of General Relativity. The problem is of enormous complexity as it involves two very different regimes, namely the interior and the exterior of the fluid, coupled through the surface of the body. This problem is very challenging both from a purely theoretical point of view, as well as regarding the obtaining of realistic models and the description of their physical properties. It is therefore an excellent piece of news that the book 'Relativistic Figures of Equilibrium' by R Meinel, M Ansorg, A Kleinwächter, G Neugebauer and D Petroff has been recently published. This book approaches the topic in depth and its contents will be of interest to a wide range of scientists working on gravitation, including theoreticians in general relativity, mathematical physicists, astrophysicists and numerical relativists. This is an advanced book that intends to present some of the present-day results on this topic. The most basic results are presented rather succinctly, and without going into the details, of their derivations. Although primarily not intended to serve as a textbook, the presentation is nevertheless self-contained and can therefore be of interest both for experts on the field as well as for anybody wishing to learn more about rotating self-gravitating compact bodies in equilibrium. It should be remarked, however, that this book makes a rather strong selection of topics and concentrates fundamentally on presenting the main results obtained by the authors during their research in this field. The book starts with a chapter where the fundamental aspects of rotating fluids in equilibrium, including its thermodynamic properties, are summarized. Of particular interest are the so-called mass-shedding limit, which is the limit where the body is rotating so fast that it is on the verge of starting

  1. Numerical study of ion orbits in EAST plasmas with a current-reversal equilibrium configuration

    NASA Astrophysics Data System (ADS)

    Zhong, Yi-jun; Gong, Xue-yu; Hu, Ye-ming; Li, Xin-xia

    2015-06-01

    By solving the Grad-Shafranov equation in the cylindrical coordinate system, we numerically obtain the tokamak plasma equilibrium configurations of the conventional mode and the high-to-lowfield-side current-reversal equilibrium mode (HL-CREC) by using the discharge parameters for the Experimental Advanced Superconductor Tokamak (EAST). By coupling with the particle's motion equation, we obtain the orbits of trapped particles and passing particles under both equilibrium configurations. We find that the orbit of the passing particle in the HL-CREC is wholly confined on the low-field side and that the half width of the banana orbit of trapped particles increases greatly compared with those in the conventional equilibrium configuration. In addition, the ion loss is studied based on the Monte Carlo method. The results show that for ions near the plasma edge, a much high ion loss rate can be obtained in HL-CREC than that in the conventional equilibrium configuration.

  2. Near-equilibrium dumb-bell-shaped figures for cohesionless small bodies

    NASA Astrophysics Data System (ADS)

    Descamps, Pascal

    2016-02-01

    In a previous paper (Descamps, P. [2015]. Icarus 245, 64-79), we developed a specific method aimed to retrieve the main physical characteristics (shape, density, surface scattering properties) of highly elongated bodies from their rotational lightcurves through the use of dumb-bell-shaped equilibrium figures. The present work is a test of this method. For that purpose we introduce near-equilibrium dumb-bell-shaped figures which are base dumb-bell equilibrium shapes modulated by lognormal statistics. Such synthetic irregular models are used to generate lightcurves from which our method is successfully applied. Shape statistical parameters of such near-equilibrium dumb-bell-shaped objects are in good agreement with those calculated for example for the Asteroid (216) Kleopatra from its dog-bone radar model. It may suggest that such bilobed and elongated asteroids can be approached by equilibrium figures perturbed be the interplay with a substantial internal friction modeled by a Gaussian random sphere.

  3. Non-Equilibrium Transitions of Heliospheric plasma

    NASA Astrophysics Data System (ADS)

    Livadiotis, G.; McComas, D. J.

    2011-12-01

    Recent advances in Space Physics theory have established the connection between non-extensive Statistical Mechanics and space plasmas by providing a theoretical basis for the empirically derived kappa distributions commonly used to describe the phase space distribution functions of these systems [1]. The non-equilibrium temperature and the kappa index that govern these distributions are the two independent controlling parameters of non-equilibrium systems [1-3]. The significance of the kappa index is primarily given by its role in identifying the non-equilibrium stationary states, and measuring their "thermodynamic distance" from thermal equilibrium [4], while its physical meaning is connected to the correlation between the system's particles [5]. For example, analysis of the IBEX high Energetic Neutral Atom spectra [6] showed that the vast majority of measured kappa indices are between ~1.5 and ~2.5, consistent with the far-equilibrium "cavity" of minimum entropy discovered by Livadiotis & McComas [2]. Spontaneous procedures that can increase the entropy, move the system gradually toward equilibrium, that is the state with the maximum (infinite) kappa index. Other external factors that may decrease the entropy, move the system back to states further from equilibrium where the kappa indices are smaller. Newly formed pick-up ions can play this critical role in the solar wind and other space plasmas. We have analytically shown that their highly ordered motion can reduce the average entropy in the plasma beyond the termination shock, inside the inner heliosheath [7]. Non-equilibrium transitions have a key role in understanding the governing thermodynamical processes of space plasmas. References 1. Livadiotis, G., & McComas, D. J. 2009, JGR, 114, 11105. 2. Livadiotis, G., & McComas, D. J. 2010a, ApJ, 714, 971. 3. Livadiotis, G., & McComas, D. J. 2010c, in AIP Conf. Proc. 9, Pickup Ions Throughout the Heliosphere and Beyond, ed. J. LeRoux, V. Florinski, G. P. Zank, & A

  4. A Computationally Efficient Multicomponent Equilibrium Solver for Aerosols (MESA)

    SciTech Connect

    Zaveri, Rahul A.; Easter, Richard C.; Peters, Len K.

    2005-12-23

    This paper describes the development and application of a new multicomponent equilibrium solver for aerosol-phase (MESA) to predict the complex solid-liquid partitioning in atmospheric particles containing H+, NH4+, Na+, Ca2+, SO4=, HSO4-, NO3-, and Cl- ions. The algorithm of MESA involves integrating the set of ordinary differential equations describing the transient precipitation and dissolution reactions for each salt until the system satisfies the equilibrium or mass convergence criteria. Arbitrary values are chosen for the dissolution and precipitation rate constants such that their ratio is equal to the equilibrium constant. Numerically, this approach is equivalent to iterating all the equilibrium reactions simultaneously with a single iteration loop. Because CaSO4 is sparingly soluble, it is assumed to exist as a solid over the entire RH range to simplify the algorithm for calcium containing particles. Temperature-dependent mutual deliquescence relative humidity polynomials (valid from 240 to 310 K) for all the possible salt mixtures were constructed using the comprehensive Pitzer-Simonson-Clegg (PSC) activity coefficient model at 298.15 K and temperature-dependent equilibrium constants in MESA. Performance of MESA is evaluated for 16 representative mixed-electrolyte systems commonly found in tropospheric aerosols using PSC and two other multicomponent activity coefficient methods – Multicomponent Taylor Expansion Method (MTEM) of Zaveri et al. [2004], and the widely-used Kusik and Meissner method (KM), and the results are compared against the predictions of the Web-based AIM Model III or available experimental data. Excellent agreement was found between AIM, MESA-PSC, and MESA-MTEM predictions of the multistage deliquescence growth as a function of RH. On the other hand, MESA-KM displayed up to 20% deviations in the mass growth factors for common salt mixtures in the sulfate-poor cases while significant discrepancies were found in the predicted multistage

  5. Sorption: Equilibrium partitioning and QSAR development using molecular predictors

    SciTech Connect

    Means, J.C.

    1994-12-31

    Sorption of chemical contaminants to sediments and soils has long been a subject of intensive investigation and QSAR development. Progressing the development of organic carbon-normalized, equilibrium partition constants (Koc) have greatly advanced the prediction of environmental fate. Integration of observed experimental results with thermodynamic modeling of compound behavior, based upon concepts of phase activities and fugacity have placed these QSARs on a firm theoretical base. An increasing spectrum of compound properties such as solubility, chemical activity, molecular surface area and other molecular topological indices have been evaluated for their utility as predictors of sorption properties. Questions concerning the effects of nonequilibrium states, hysteresis or irreversibility in desorption kinetics and equilibria, and particle-concentrations effects upon equilibrium constants as they affect fate predictions remain areas of contemporary investigation. These phenomena are considered and reviewed. The effects of modifying factors such as the effects of salinity or the presence of co-solvents may alter predicted fate of a compound. Competitive sorption with mobile microparticulate or colloidal phases may also impact OSAR predictions. Research on the role of both inorganic and organic-rich colloidal phases as a modifying influence on soil/sediment equilibrium partitioning theory is summarized.

  6. Punctuated equilibrium and power law in economic dynamics

    NASA Astrophysics Data System (ADS)

    Gupta, Abhijit Kar

    2012-02-01

    This work is primarily based on a recently proposed toy model by Thurner et al. (2010) [3] on Schumpeterian economic dynamics (inspired by the idea of economist Joseph Schumpeter [9]). Interestingly, punctuated equilibrium has been shown to emerge from the dynamics. The punctuated equilibrium and Power law are known to be associated with similar kinds of biologically relevant evolutionary models proposed in the past. The occurrence of the Power law is a signature of Self-Organised Criticality (SOC). In our view, power laws can be obtained by controlling the dynamics through incorporating the idea of feedback into the algorithm in some way. The so-called 'feedback' was achieved by introducing the idea of fitness and selection processes in the biological evolutionary models. Therefore, we examine the possible emergence of a power law by invoking the concepts of 'fitness' and 'selection' in the present model of economic evolution.

  7. Non-equilibrium Flows of Reacting Air Components in Nozzles

    NASA Astrophysics Data System (ADS)

    Bazilevich, S. S.; Sinitsyn, K. A.; Nagnibeda, E. A.

    2008-12-01

    The paper presents the results of the investigation of non-equilibrium flows of reacting air mixtures in nozzles. State-to-state approach based on the solution of the equations for vibrational level populations of molecules and atomic concentrations coupled to the gas dynamics equations is used. For the 5-component air mixture (N2, O2, NO, N, O) non-equilibrium distributions and gasdynamical parameters are calculated for different conditions in a nozzle throat. The influence of various kinetic processes on distributions and gas dynamics parameters is studied. The paper presents the comparison of the results with ones obtained for binary mixtures of molecules and atoms and various models of elementary processes.

  8. Non-equilibrium quantum heat machines

    NASA Astrophysics Data System (ADS)

    Alicki, Robert; Gelbwaser-Klimovsky, David

    2015-11-01

    Standard heat machines (engine, heat pump, refrigerator) are composed of a system (working fluid) coupled to at least two equilibrium baths at different temperatures and periodically driven by an external device (piston or rotor) sometimes called the work reservoir. The aim of this paper is to go beyond this scheme by considering environments which are stationary but cannot be decomposed into a few baths at thermal equilibrium. Such situations are important, for example in solar cells, chemical machines in biology, various realizations of laser cooling or nanoscopic machines driven by laser radiation. We classify non-equilibrium baths depending on their thermodynamic behavior and show that the efficiency of heat machines powered by them is limited by the generalized Carnot bound.

  9. Principles of Equilibrium Statistical Mechanics

    NASA Astrophysics Data System (ADS)

    Chowdhury, Debashish; Stauffer, Dietrich

    2000-09-01

    This modern textbook provides a complete survey of the broad field of statistical mechanics. Based on a series of lectures, it adopts a special pedagogical approach. The authors, both excellent lecturers, clearly distinguish between general principles and their applications in solving problems. Analogies between phase transitions in fluids and magnets using continuum and spin models are emphasized, leading to a better understanding. Such special features as historical notes, summaries, problems, mathematical appendix, computer programs and order of magnitude estimations distinguish this volume from competing works. Due to its ambitious level and an extensive list of references for technical details on advanced topics, this is equally a must for researchers in condensed matter physics, materials science, polymer science, solid state physics, and astrophysics. From the contents Thermostatics: phase stability, phase equilibria, phase transitions; Statistical Mechanics: calculation, correlation functions, ideal classical gases, ideal quantum gases; Interacting Systems: models, computer simulation, mean-field approximation; Interacting Systems beyond Mean-field Theory: scaling and renormalization group, foundations of statistical mechanics "The present book, however, is unique that it both is written in a very pedagogic, easily comprehensible style, and, nevertheless, goes from the basic principles all the way to these modern topics, containing several chapters on the various approaches of mean field theory, and a chapter on computer simulation. A characteristic feature of this book is that often first some qualitative arguments are given, or a "pedestrians's approach", and then a more general and/or more rigorous derivation is presented as well. Particularly useful are also "supplementary notes", pointing out interesting applications and further developments of the subject, a detailed bibliography, problems and historical notes, and many pedagogic figures."

  10. Equilibrium and kinetic selectivity profiling on the human adenosine receptors.

    PubMed

    Guo, Dong; Dijksteel, Gabrielle S; van Duijl, Tirsa; Heezen, Maxime; Heitman, Laura H; IJzerman, Adriaan P

    2016-04-01

    Classical evaluation of target selectivity is usually undertaken by measuring the binding affinity of lead compounds against a number of potential targets under equilibrium conditions, without considering the kinetics of the ligand-receptor interaction. In the present study we propose a combined strategy including both equilibrium- and kinetics-based selectivity profiling. The adenosine receptor (AR) was chosen as a prototypical drug target. Six in-house AR antagonists were evaluated in a radioligand displacement assay for their affinity and in a competition association assay for their binding kinetics on three AR subtypes. One of the compounds with a promising kinetic selectivity profile was also examined in a [(35)S]-GTPγS binding assay for functional activity. We found that XAC and LUF5964 were kinetically more selective for the A1R and A3R, respectively, although they are non-selective in terms of their affinity. In comparison, LUF5967 displayed a strong equilibrium-based selectivity for the A1R over the A2AR, yet its kinetic selectivity thereon was less pronounced. In a GTPγS assay, LUF5964 exhibited insurmountable antagonism on the A3R while having a surmountable effect on the A1R, consistent with its kinetic selectivity profile. This study provides evidence that equilibrium and kinetic selectivity profiling can both be important in the early phases of the drug discovery process. Our proposed combinational strategy could be considered for future medicinal chemistry efforts and aid the design and discovery of different or even better leads for clinical applications.

  11. Equilibrium and kinetic selectivity profiling on the human adenosine receptors.

    PubMed

    Guo, Dong; Dijksteel, Gabrielle S; van Duijl, Tirsa; Heezen, Maxime; Heitman, Laura H; IJzerman, Adriaan P

    2016-04-01

    Classical evaluation of target selectivity is usually undertaken by measuring the binding affinity of lead compounds against a number of potential targets under equilibrium conditions, without considering the kinetics of the ligand-receptor interaction. In the present study we propose a combined strategy including both equilibrium- and kinetics-based selectivity profiling. The adenosine receptor (AR) was chosen as a prototypical drug target. Six in-house AR antagonists were evaluated in a radioligand displacement assay for their affinity and in a competition association assay for their binding kinetics on three AR subtypes. One of the compounds with a promising kinetic selectivity profile was also examined in a [(35)S]-GTPγS binding assay for functional activity. We found that XAC and LUF5964 were kinetically more selective for the A1R and A3R, respectively, although they are non-selective in terms of their affinity. In comparison, LUF5967 displayed a strong equilibrium-based selectivity for the A1R over the A2AR, yet its kinetic selectivity thereon was less pronounced. In a GTPγS assay, LUF5964 exhibited insurmountable antagonism on the A3R while having a surmountable effect on the A1R, consistent with its kinetic selectivity profile. This study provides evidence that equilibrium and kinetic selectivity profiling can both be important in the early phases of the drug discovery process. Our proposed combinational strategy could be considered for future medicinal chemistry efforts and aid the design and discovery of different or even better leads for clinical applications. PMID:26930564

  12. Algorithm For Hypersonic Flow In Chemical Equilibrium

    NASA Technical Reports Server (NTRS)

    Palmer, Grant

    1989-01-01

    Implicit, finite-difference, shock-capturing algorithm calculates inviscid, hypersonic flows in chemical equilibrium. Implicit formulation chosen because overcomes limitation on mathematical stability encountered in explicit formulations. For dynamical portion of problem, Euler equations written in conservation-law form in Cartesian coordinate system for two-dimensional or axisymmetric flow. For chemical portion of problem, equilibrium state of gas at each point in computational grid determined by minimizing local Gibbs free energy, subject to local conservation of molecules, atoms, ions, and total enthalpy. Major advantage: resulting algorithm naturally stable and captures strong shocks without help of artificial-dissipation terms to damp out spurious numerical oscillations.

  13. Putting A Human Face on Equilibrium

    NASA Astrophysics Data System (ADS)

    Glickstein, Neil

    2005-03-01

    A short biography of chemist Fritz Haber is used to personalize the abstract concepts of equilibrium chemistry for high school students in an introductory course. In addition to giving the Haber Bosch process an historic, an economic, and a scientific background the reading and subsequent discussion allows students for whom the human perspective is of paramount importance a chance to investigate the irony of balance or equilibrium in Haber's life story. Since the inclusion of the Haber biography, performance in the laboratory and on examinations for those students who are usually only partially engaged has dramatically improved.

  14. Equilibrium stability of single-species metapopulations.

    PubMed

    Jang, S R; Mitra, A K

    2000-01-01

    We investigate the effect of migration between local populations of a single discrete-generation species living in a ring or an array of habitats. The commonly used symmetric dispersal assumption is relaxed to include the biologically more reasonable asymmetric dispersion. It is demonstrated analytically that density independent migration has no effect on the equilibrium stability of individual populations. However, the positive equilibrium may be destabilizing if the migration is density dependent in such a way that it increases with increasing population density at the source patch.

  15. Far-from-equilibrium kinetic processes

    NASA Astrophysics Data System (ADS)

    Rubí, J. Miguel; Pérez-Madrid, Agustin

    2015-12-01

    We analyze the kinetics of activated processes that take place under far-from-equilibrium conditions, when the system is subjected to external driving forces or gradients or at high values of affinities. We use mesoscopic non-equilibrium thermodynamics to show that when a force is applied, the reaction rate depends on the force. In the case of a chemical reaction at high affinity values, the reaction rate is no longer constant but depends on affinity, which implies that the law of mass action is no longer valid. This result is in good agreement with the kinetic theory of reacting gases, which uses a Chapman-Enskog expansion of the probability distribution.

  16. Computing Properties Of Chemical Mixtures At Equilibrium

    NASA Technical Reports Server (NTRS)

    Mcbride, B. J.; Gordon, S.

    1995-01-01

    Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

  17. Isodynamic axisymmetric equilibrium near the magnetic axis

    SciTech Connect

    Arsenin, V. V.

    2013-08-15

    Plasma equilibrium near the magnetic axis of an axisymmetric toroidal magnetic confinement system is described in orthogonal flux coordinates. For the case of a constant current density in the vicinity of the axis and magnetic surfaces with nearly circular cross sections, expressions for the poloidal and toroidal magnetic field components are obtained in these coordinates by using expansion in the reciprocal of the aspect ratio. These expressions allow one to easily derive relationships between quantities in an isodynamic equilibrium, in which the absolute value of the magnetic field is constant along the magnetic surface (Palumbo’s configuration)

  18. Non-equilibrium calcium ionisation in the solar atmosphere

    NASA Astrophysics Data System (ADS)

    Wedemeyer-Böhm, S.; Carlsson, M.

    2011-04-01

    Context. The chromosphere of the Sun is a temporally and spatially very varying medium for which the assumption of ionisation equilibrium is questionable. Aims: Our aim is to determine the dominant processes and timescales for the ionisation equilibrium of calcium under solar chromospheric conditions. Methods: The study is based on numerical simulations with the RADYN code, which combines hydrodynamics with a detailed solution of the radiative transfer equation. The calculations include a detailed non-equilibrium treatment of hydrogen, calcium, and helium. Next to an hour long simulation sequence, additional simulations are produced, for which the stratification is slightly perturbed so that a ionisation relaxation timescale can be determined. The simulations are characterised by upwards propagating shock waves, which cause strong temperature fluctuations and variations of the (non-equilibrium) ionisation degree of calcium. Results: The passage of a hot shock front leads to a strong net ionisation of Ca II, rapidly followed by net recombination. The relaxation timescale of the calcium ionisation state is found to be of the order of a few seconds at the top of the photosphere and 10 to 30 s in the upper chromosphere. At heights around 1 Mm, we find typical values around 60 s and in extreme cases up to ~150 s. Generally, the timescales are significantly reduced in the wakes of ubiquitous hot shock fronts. The timescales can be reliably determined from a simple analysis of the eigenvalues of the transition rate matrix. The timescales are dominated by the radiative recombination from Ca III into the metastable Ca II energy levels of the 4d 2D term. These transitions depend strongly on the density of free electrons and therefore on the (non-equilibrium) ionisation degree of hydrogen, which is the main electron donor. Conclusions: The ionisation/recombination timescales derived here are too long for the assumption of an instantaneous ionisation equilibrium to be valid

  19. 46 CFR 42.20-12 - Conditions of equilibrium.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 2 2010-10-01 2010-10-01 false Conditions of equilibrium. 42.20-12 Section 42.20-12... BY SEA Freeboards § 42.20-12 Conditions of equilibrium. The following conditions of equilibrium are... stability. Through an angle of 20 degrees beyond its position of equilibrium, the vessel must meet...

  20. 46 CFR 42.20-12 - Conditions of equilibrium.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 2 2012-10-01 2012-10-01 false Conditions of equilibrium. 42.20-12 Section 42.20-12... BY SEA Freeboards § 42.20-12 Conditions of equilibrium. The following conditions of equilibrium are... stability. Through an angle of 20 degrees beyond its position of equilibrium, the vessel must meet...

  1. 46 CFR 42.20-12 - Conditions of equilibrium.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 2 2013-10-01 2013-10-01 false Conditions of equilibrium. 42.20-12 Section 42.20-12... BY SEA Freeboards § 42.20-12 Conditions of equilibrium. The following conditions of equilibrium are... stability. Through an angle of 20 degrees beyond its position of equilibrium, the vessel must meet...

  2. 46 CFR 42.20-12 - Conditions of equilibrium.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 2 2014-10-01 2014-10-01 false Conditions of equilibrium. 42.20-12 Section 42.20-12... BY SEA Freeboards § 42.20-12 Conditions of equilibrium. The following conditions of equilibrium are... stability. Through an angle of 20 degrees beyond its position of equilibrium, the vessel must meet...

  3. 46 CFR 42.20-12 - Conditions of equilibrium.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 2 2011-10-01 2011-10-01 false Conditions of equilibrium. 42.20-12 Section 42.20-12... BY SEA Freeboards § 42.20-12 Conditions of equilibrium. The following conditions of equilibrium are... stability. Through an angle of 20 degrees beyond its position of equilibrium, the vessel must meet...

  4. 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.

  5. Chlorodifluoromethane equilibrium on 13X molecular sieve. Final report, September 1992-March 1993

    SciTech Connect

    Carlile, D.L.; Mahle, J.J.; Buettner, L.C.; Tevault, D.E.; Friday, D.K.

    1994-08-01

    Adsorption phase equilibrium data are required for evaluating any adsorption-based gas separation process. The U.S. Army Edgewood Research, Development and Engineering Center is currently measuring adsorption phase equilibrium data for a variety of chemical warfare agents and their surrogates on adsorbent materials to correlate physical properties to filtration/separation efficiencies of each vapor on each adsorbent. This report details the adsorption phase equilibrium data measured for chlorodifluoromethane (R-22) on 13X Molecular Sieve. The 13X Molecular Sieve is a candidate adsorbent for future military air purification systems employing the pressure-swing adsorption separation process.

  6. Group Contribution Methods for Phase Equilibrium Calculations.

    PubMed

    Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

    2015-01-01

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

  7. Ergodicity: a historical perspective. Equilibrium and Nonequilibrium

    NASA Astrophysics Data System (ADS)

    Gallavotti, Giovanni

    2016-10-01

    A view on the physical meaning of the so called ergodic hypothesis: its role on the foundations of equilibrium statistical mechanics in mid '1800, its interpretations and hints at its relevance for modern nonequilibrium statistical mechanics. Followed by appendices with detailed comments on the original papers.

  8. Conditions for the Existence of Market Equilibrium.

    ERIC Educational Resources Information Center

    Bryant, William D. A.

    1997-01-01

    Maintains that most graduate-level economics textbooks rarely mention the need for consumers to be above their minimum wealth position as a condition for market equilibrium. Argues that this omission leaves students with a mistaken sense about the range of circumstances under which market equilibria can exist. (MJP)

  9. Spontaneity and Equilibrium II: Multireaction Systems

    ERIC Educational Resources Information Center

    Raff, Lionel M.

    2014-01-01

    The thermodynamic criteria for spontaneity and equilibrium in multireaction systems are developed and discussed. When N reactions are occurring simultaneously, it is shown that G and A will depend upon N independent reaction coordinates, ?a (a = 1,2, ..., N), in addition to T and p for G or T and V for A. The general criteria for spontaneity and…

  10. Equilibrium thermodynamics in modified gravitational theories

    NASA Astrophysics Data System (ADS)

    Bamba, Kazuharu; Geng, Chao-Qiang; Tsujikawa, Shinji

    2010-04-01

    We show that it is possible to obtain a picture of equilibrium thermodynamics on the apparent horizon in the expanding cosmological background for a wide class of modified gravity theories with the Lagrangian density f(R,ϕ,X), where R is the Ricci scalar and X is the kinetic energy of a scalar field ϕ. This comes from a suitable definition of an energy-momentum tensor of the “dark” component that respects to a local energy conservation in the Jordan frame. In this framework the horizon entropy S corresponding to equilibrium thermodynamics is equal to a quarter of the horizon area A in units of gravitational constant G, as in Einstein gravity. For a flat cosmological background with a decreasing Hubble parameter, S globally increases with time, as it happens for viable f(R) inflation and dark energy models. We also show that the equilibrium description in terms of the horizon entropy S is convenient because it takes into account the contribution of both the horizon entropy S' in non-equilibrium thermodynamics and an entropy production term.

  11. Assessing Students' Conceptual Understanding of Solubility Equilibrium.

    ERIC Educational Resources Information Center

    Raviolo, Andres

    2001-01-01

    Presents a problem on solubility equilibrium which involves macroscopic, microscopic, and symbolic levels of representation as a resource for the evaluation of students, and allows for assessment as to whether students have acquired an adequate conceptual understanding of the phenomenon. Also diagnoses difficulties with regard to previous…

  12. The ``Schwarzschild-Kerr'' Equilibrium Configurations

    NASA Astrophysics Data System (ADS)

    Manko, V. S.; Ruiz, E.

    2010-12-01

    We discuss the possibility of equilibrium between a Schwarzschild black hole possessing zero intrinsic angular momentum and a hyperextreme Kerr source. The balance occurs due to frame-dragging exerted by the latter source on the black-hole constituent, thus giving rise to a non-zero horizon's angular velocity parallel to the angular momentum of the Kerr object.

  13. The 'Schwarzschild-Kerr' Equilibrium Configurations

    SciTech Connect

    Manko, V. S.; Ruiz, E.

    2010-12-07

    We discuss the possibility of equilibrium between a Schwarzschild black hole possessing zero intrinsic angular momentum and a hyperextreme Kerr source. The balance occurs due to frame-dragging exerted by the latter source on the black-hole constituent, thus giving rise to a non-zero horizon's angular velocity parallel to the angular momentum of the Kerr object.

  14. Ergodicity: a historical perspective. Equilibrium and Nonequilibrium

    NASA Astrophysics Data System (ADS)

    Gallavotti, Giovanni

    2016-09-01

    A view on the physical meaning of the so called ergodic hypothesis: its role on the foundations of equilibrium statistical mechanics in mid '1800, its interpretations and hints at its relevance for modern nonequilibrium statistical mechanics. Followed by appendices with detailed comments on the original papers.

  15. Calculating Shocks In Flows At Chemical Equilibrium

    NASA Technical Reports Server (NTRS)

    Eberhardt, Scott; Palmer, Grant

    1988-01-01

    Boundary conditions prove critical. Conference paper describes algorithm for calculation of shocks in hypersonic flows of gases at chemical equilibrium. Although algorithm represents intermediate stage in development of reliable, accurate computer code for two-dimensional flow, research leading up to it contributes to understanding of what is needed to complete task.

  16. A Progression of Static Equilibrium Laboratory Exercises

    ERIC Educational Resources Information Center

    Kutzner, Mickey; Kutzner, Andrew

    2013-01-01

    Although simple architectural structures like bridges, catwalks, cantilevers, and Stonehenge have been integral in human societies for millennia, as have levers and other simple tools, modern students of introductory physics continue to grapple with Newton's conditions for static equilibrium. As formulated in typical introductory physics…

  17. General Equilibrium Models: Improving the Microeconomics Classroom

    ERIC Educational Resources Information Center

    Nicholson, Walter; Westhoff, Frank

    2009-01-01

    General equilibrium models now play important roles in many fields of economics including tax policy, environmental regulation, international trade, and economic development. The intermediate microeconomics classroom has not kept pace with these trends, however. Microeconomics textbooks primarily focus on the insights that can be drawn from the…

  18. Exploring Equilibrium Chemistry for Hot Exoplanets

    NASA Astrophysics Data System (ADS)

    Blumenthal, Sarah; Harrington, Joseph; Mandell, Avi; Hébrard, Eric; Venot, Olivia; Cubillos, Patricio; Challener, Ryan

    2015-11-01

    It has been established that equilibrium chemistry is usually achieved deep in the atmosphere of hot Jovians where timescales are short (Line and Young 2013). Thus, equilibrium chemistry has been used as a starting point (setting initial conditions) for evaluating disequilibrium processes. We explore parameters of setting these initial conditions including departures from solar metallicity, the number of species allowed in a system, the types of species allowed in a system, and different thermodynamic libraries in an attempt to create a standard for evaluating equilibrium chemistry. NASA's open source code Chemical Equilibrium and Applications (CEA) is used to calculate model planet abundances by varying the metallicity, in the pressure regime of 0.1 to 1 bar. These results are compared to a variety of exoplanets (Teq between 600 and 2100K) qualitatively by color maps of the dayside with different temperature redistributions. Additionally, CEA (with an updated thermodynamic library) is validated with the thermochemical model presented in Venot et al. (2012) for HD 209458b and HD 189733b. This same analysis has then been extended to the cooler planet HD 97658b. Spectra are generated from both models’ abundances using the open source code transit (https://github.com/exosports/transit) using the opacities of 15 molecules. We make the updated CEA thermodyanamic library and supporting Python scripts to do the CEA analyses available open source. This work was supported by NASA Planetary Atmospheres grant NNX12AI69G.

  19. Exploring Chemical Equilibrium in Hot Jovians

    NASA Astrophysics Data System (ADS)

    Blumenthal, Sarah; Harrington, Joseph; Mandell, Avi; Hébrard, Eric; Venot, Olivia; Cubillos, Patricio; Blecic, Jasmina; Challener, Ryan

    2016-01-01

    It has been established that equilibrium chemistry is usually achieved deep in the atmosphere of hot Jovians where timescales are short (Line and Yung 2013). Thus, equilibrium chemistry has been used as a starting point (setting initial conditions) for evaluating disequilibrium processes. We explore parameters of setting these initial conditions including departures from solar metallicity, the number of species allowed in a system, the types of species allowed in a system, and different thermodynamic libraries in an attempt to create a standard for evaluating equilibrium chemistry. NASA's open source code Chemical Equilibrium and Applications (CEA) is used to calculate model planet abundances by varying the metallicity, in the pressure regime 0.1 to 1 bar. These results are compared to a variety of exoplanets(Teq between 600 and 2100K) qualitatively by color maps of the dayside with different temperature redistributions. Additionally, CEA (with an up-dated thermodynamic library) is compared with the thermochemical model presented in Venotet al. (2012) for HD 209458b and HD 189733b. This same analysis is then applied to the cooler planet HD 97658b. Spectra are generated and we compare both models' outputs using the open source codetransit (https://github.com/exosports/transit) using the opacities of 15 molecules. We make the updated CEA thermodyanamic library and supporting Python scripts to do the CEA analyses available open source. Thiswork was supported by NASA Planetary Atmospheres grant NNX12AI69G.

  20. Teaching Chemical Equilibrium with the Jigsaw Technique

    ERIC Educational Resources Information Center

    Doymus, Kemal

    2008-01-01

    This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students' understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes…

  1. Slope Stability Analysis Using Limit Equilibrium Method in Nonlinear Criterion

    PubMed Central

    Lin, Hang; Zhong, Wenwen; Xiong, Wei; Tang, Wenyu

    2014-01-01

    In slope stability analysis, the limit equilibrium method is usually used to calculate the safety factor of slope based on Mohr-Coulomb criterion. However, Mohr-Coulomb criterion is restricted to the description of rock mass. To overcome its shortcomings, this paper combined Hoek-Brown criterion and limit equilibrium method and proposed an equation for calculating the safety factor of slope with limit equilibrium method in Hoek-Brown criterion through equivalent cohesive strength and the friction angle. Moreover, this paper investigates the impact of Hoek-Brown parameters on the safety factor of slope, which reveals that there is linear relation between equivalent cohesive strength and weakening factor D. However, there are nonlinear relations between equivalent cohesive strength and Geological Strength Index (GSI), the uniaxial compressive strength of intact rock σci, and the parameter of intact rock mi. There is nonlinear relation between the friction angle and all Hoek-Brown parameters. With the increase of D, the safety factor of slope F decreases linearly; with the increase of GSI, F increases nonlinearly; when σci is relatively small, the relation between F and σci is nonlinear, but when σci is relatively large, the relation is linear; with the increase of mi, F decreases first and then increases. PMID:25147838

  2. Local-equilibrium formalism applied to mechanics of solids

    SciTech Connect

    Kestin, J.

    1992-08-01

    The lecture starts with an expression of good wishes to George Herrmann on the occasion of his seventieth birthday and continues with a lament that the majority of research workers in the field of solid mechanics have failed to appreciate the power and relevance of ``conventional`` thermodynamics which is based on the acceptance of the hypothesis of local equilibrium (principle of local state). The lecture then proceeds to motivate the essential concepts of conventional thermodynamics and emphasizes the differences between the description of nonequilibrium states in physical space and equilibrium states in the Gibbsian phase space. It is asserted that the subject acquires its simplest form by the recognition of the relevance of Bridgman`s internal variables. With their aid it is possible to define the accompanying equilibrium state and the accompanying reversible process. An elimination of internal energy between the field equation of energy (First Law) and the Gibbs equation in rate form results in an explicit expression for the local rate of entropy production, {theta}. It is asserted that the preceding elements supplemented with appropriate rate equations result in a closed system of partial differential equations whose solution, subject to appropriate initial and boundary conditions, constitutes the process (``history``) under consideration. 11 refs.

  3. Local-equilibrium formalism applied to mechanics of solids

    SciTech Connect

    Kestin, J.

    1992-01-01

    The lecture starts with an expression of good wishes to George Herrmann on the occasion of his seventieth birthday and continues with a lament that the majority of research workers in the field of solid mechanics have failed to appreciate the power and relevance of conventional'' thermodynamics which is based on the acceptance of the hypothesis of local equilibrium (principle of local state). The lecture then proceeds to motivate the essential concepts of conventional thermodynamics and emphasizes the differences between the description of nonequilibrium states in physical space and equilibrium states in the Gibbsian phase space. It is asserted that the subject acquires its simplest form by the recognition of the relevance of Bridgman's internal variables. With their aid it is possible to define the accompanying equilibrium state and the accompanying reversible process. An elimination of internal energy between the field equation of energy (First Law) and the Gibbs equation in rate form results in an explicit expression for the local rate of entropy production, {theta}. It is asserted that the preceding elements supplemented with appropriate rate equations result in a closed system of partial differential equations whose solution, subject to appropriate initial and boundary conditions, constitutes the process ( history'') under consideration. 11 refs.

  4. Equilibrium shape and dislocation nucleation in strained epitaxial nanoislands

    NASA Astrophysics Data System (ADS)

    Jalkanen, J.; Trushin, O.; Elder, K.; Granato, E.; Ala-Nissilä, T.; Ying, S.-C.

    2006-03-01

    We study numerically the equilibrium shapes, shape transitions and dislocation nucleation of small strained epitaxial islands with a two-dimensional atomistic model, using simple pair potentials [1]. We first map out the phase diagram for equilibrium island shapes as a function of island size and lattice misfit with the substrate. When the interactomic potential minimum depth ɛ is the same for substrate and adsorbate, the latter either wets the surface or has one of three generic equilibrium island shapes. As ɛ favours substrate-adsorbate interface, Stranski-Krastanow growth mode emerges between complete wetting and island formation zones while in the opposite case the islanding zone is extended. A simulation based extrapolation scheme predicts an optimal island shape for attractive ɛ. The energy barriers and transition paths between different island shapes and dislocation nucleation in initially coherent islands are investigated with Nudged Elastic Band method. We also discuss the elastic behaviour of these systems in terms of the Phase Field Crystal model [2]. [1] J. Jalkanen, O. Trushin, E. Granato, S. C. Ying, and T. Ala-Nissila, Phys. Rev. B 72, 081403 (2005) [2] K. Elder and M. Grant, Phys. Rev. E 70, 051605 (2004)

  5. Equilibrium water and solute uptake in silicone hydrogels.

    PubMed

    Liu, D E; Dursch, T J; Oh, Y; Bregante, D T; Chan, S Y; Radke, C J

    2015-05-01

    Equilibrium water content of and solute partitioning in silicone hydrogels (SiHys) are investigated using gravimetric analysis, fluorescence confocal laser-scanning microscopy (FCLSM), and back extraction with UV/Vis-absorption spectrophotometry. Synthesized silicone hydrogels consist of silicone monomer, hydrophilic monomer, cross-linking agent, and triblock-copolymer macromer used as an amphiphilic compatibilizer to prevent macrophase separation. In all cases, immiscibility of the silicone and hydrophilic polymers results in microphase-separated morphologies. To investigate solute uptake in each of the SiHy microphases, equilibrium partition coefficients are obtained for two hydrophilic solutes (i.e., theophylline and caffeine dissolved in aqueous phosphate-buffered saline) and two oleophilic solutes (i.e., Nile Red and Bodipy Green dissolved in silicone oil), respectively. Measured water contents and aqueous-solute partition coefficients increase linearly with increasing solvent-free hydrophilic-polymer volume fraction. Conversely, oleophilic-solute partition coefficients decrease linearly with rising solvent-free hydrophilic-polymer volume fraction (i.e., decreasing hydrophobic silicone-polymer fraction). We quantitatively predict equilibrium SiHy water and solute uptake assuming that water and aqueous solutes reside only in hydrophilic microdomains, whereas oleophilic solutes partition predominately into silicone microdomains. Predicted water contents and solute partition coefficients are in excellent agreement with experiment. Our new procedure permits a priori estimation of SiHy water contents and solute partition coefficients based solely on properties of silicone and hydrophilic homopolymer hydrogels, eliminating the need for further mixed-polymer-hydrogel experiments.

  6. Primordial Magnetic Fields from Out of Equilibrium Cosmological Phase Transitions

    SciTech Connect

    Boyanovsky, D.; Vega, H.J. de

    2005-09-28

    The universe cools down monotonically following its expansion. This generates a sequence of phase transitions. If a second order phase transition happens during the radiation dominated era with a charged order parameter, spinodal unstabilities generate large numbers of charged particles. These particles hence produce magnetic fields. We use out of equilibrium field theory methods to study the dynamics in a mean field or large N setup. The dynamics after the transition features two distinct stages: a spinodal regime dominated by linear long-wavelength instabilities, and a scaling stage in which the non-linearities and backreaction of the scalar fields are dominant. This second stage describes the growth of horizon sized domains. We implement a formulation based on the non-equilibrium Schwinger-Dyson equations to obtain the spectrum of magnetic fields that includes the dissipative effects of the plasma. We find that large scale magnetogenesis is efficient during the scaling regime. Charged scalar field fluctuations with wavelengths of the order of the Hubble radius induce large scale magnetogenesis via loop effects. The leading processes are: pair production, pair annihilation and low energy bremsstrahlung, these processes while forbidden in equilibrium are allowed strongly out of equilibrium. The ratio between the energy density on scales larger than L and that in the background radiation r(L,T) {rho}B(L,T)/{rho}cmb(T) is r(L,T) {approx} 10-34 at the Electroweak scale and r(L,T) {approx} 10-14 at the QCD scale for L {approx} 1 Mpc. The resulting spectrum is insensitive to the magnetic diffusion length and equipartition between electric and magnetic fields does not hold. We conjecture that a similar mechanism could be operative after the QCD chiral phase transition.

  7. Effective equilibrium theory of nonequilibrium quantum transport

    SciTech Connect

    Dutt, Prasenjit; Koch, Jens; Han, Jong; Le Hur, Karyn

    2011-12-15

    The theoretical description of strongly correlated quantum systems out of equilibrium presents several challenges and a number of open questions persist. Here, we focus on nonlinear electronic transport through an interacting quantum dot maintained at finite bias using a concept introduced by Hershfield [S. Hershfield, Phys. Rev. Lett. 70 2134 (1993)] whereby one can express such nonequilibrium quantum impurity models in terms of the system's Lippmann-Schwinger operators. These scattering operators allow one to reformulate the nonequilibrium problem as an effective equilibrium problem associated with a modified Hamiltonian. In this paper, we provide a pedagogical analysis of the core concepts of the effective equilibrium theory. First, we demonstrate the equivalence between observables computed using the Schwinger-Keldysh framework and the effective equilibrium approach, and relate Green's functions in the two theoretical frameworks. Second, we expound some applications of this method in the context of interacting quantum impurity models. We introduce a novel framework to treat effects of interactions perturbatively while capturing the entire dependence on the bias voltage. For the sake of concreteness, we employ the Anderson model as a prototype for this scheme. Working at the particle-hole symmetric point, we investigate the fate of the Abrikosov-Suhl resonance as a function of bias voltage and magnetic field. - Highlights: > Reformulation of steady-state nonequilibrium quantum transport, following Hershfield. > Derivation of effective equilibrium density operator using the 'open-system' approach. > Equivalence with the Keldysh description and formulas relating the two approaches. > Novel framework to treat interactions perturbatively. > Application to nonequilibrium Anderson model and fate of Abrikosov-Suhl resonance.

  8. Equilibrium and non-equilibrium dynamics simultaneously operate in the Galápagos islands.

    PubMed

    Valente, Luis M; Phillimore, Albert B; Etienne, Rampal S

    2015-08-01

    Island biotas emerge from the interplay between colonisation, speciation and extinction and are often the scene of spectacular adaptive radiations. A common assumption is that insular diversity is at a dynamic equilibrium, but for remote islands, such as Hawaii or Galápagos, this idea remains untested. Here, we reconstruct the temporal accumulation of terrestrial bird species of the Galápagos using a novel phylogenetic method that estimates rates of biota assembly for an entire community. We show that species richness on the archipelago is in an ascending phase and does not tend towards equilibrium. The majority of the avifauna diversifies at a slow rate, without detectable ecological limits. However, Darwin's finches form an exception: they rapidly reach a carrying capacity and subsequently follow a coalescent-like diversification process. Together, these results suggest that avian diversity of remote islands is rising, and challenge the mutual exclusivity of the non-equilibrium and equilibrium ecological paradigms.

  9. Equilibrium and non-equilibrium dynamics simultaneously operate in the Galápagos islands.

    PubMed

    Valente, Luis M; Phillimore, Albert B; Etienne, Rampal S

    2015-08-01

    Island biotas emerge from the interplay between colonisation, speciation and extinction and are often the scene of spectacular adaptive radiations. A common assumption is that insular diversity is at a dynamic equilibrium, but for remote islands, such as Hawaii or Galápagos, this idea remains untested. Here, we reconstruct the temporal accumulation of terrestrial bird species of the Galápagos using a novel phylogenetic method that estimates rates of biota assembly for an entire community. We show that species richness on the archipelago is in an ascending phase and does not tend towards equilibrium. The majority of the avifauna diversifies at a slow rate, without detectable ecological limits. However, Darwin's finches form an exception: they rapidly reach a carrying capacity and subsequently follow a coalescent-like diversification process. Together, these results suggest that avian diversity of remote islands is rising, and challenge the mutual exclusivity of the non-equilibrium and equilibrium ecological paradigms. PMID:26105791

  10. Experimental Determination of Equilibrium and Non-equilibrium Thermodynamic Propertiesof Natural Porous Media.

    NASA Astrophysics Data System (ADS)

    Peluso, F.; Arienzo, I.

    Experimental investigation of the behavior of porous media is a field of interest of modern non-equilibrium thermodynamics. In the frame of a multi-disciplinary re- search project we are performing in our laboratory experimental tests to measure equilibrium and nonequilibrium thermodynamic properties of natural porous media. Aim of our study is to characterize some stone samples and to verify whether a mass transport due to coupled pressure and temperature gradients (thermo-mechanic) is ap- preciable in this kind of porous medium. We have designed an apparatus that allows to measure the volume flux across a porous sample at various, predefined pressures and temperatures, both in isothermal and non isothermal conditions. A mechanical piston compels a liquid to flow through the sample, previously saturated under vacuum with the same fluid. Knowing the geometrical dimensions of the stone, the volume flux is estimated by measuring the time needed to a known amount of liquid to flow across the sample. Measurements have been performed in isothermal conditions at various temperatures and in non-isothermal conditions. Non-isothermal measurements have been performed both in unsteady and steady-state thermal conditions. Before to be undergone to a measurement cycle, samples are dried and weighted. Then they are sat- urated under vacuum with pure distilled water and weighted once again. By difference between the two measurements, porosity is determined. In all examined samples the volume flux has been found linear with respect to the applied pressure at the various temperatures. The values of volume flux in unsteady thermal conditions are consid- erably higher than the one obtained at the same pressure in isothermal conditions at the higher temperature (T=+45rC). This could be the evidence of a thermo-mechanic effect, pushing the water from hot to cold. Once the steady thermal state is reached, however, this effect disappears. Only measurements performed in unsteady thermal

  11. Cosmic curvature from de Sitter equilibrium cosmology.

    PubMed

    Albrecht, Andreas

    2011-10-01

    I show that the de Sitter equilibrium cosmology generically predicts observable levels of curvature in the Universe today. The predicted value of the curvature, Ω(k), depends only on the ratio of the density of nonrelativistic matter to cosmological constant density ρ(m)(0)/ρ(Λ) and the value of the curvature from the initial bubble that starts the inflation, Ω(k)(B). The result is independent of the scale of inflation, the shape of the potential during inflation, and many other details of the cosmology. Future cosmological measurements of ρ(m)(0)/ρ(Λ) and Ω(k) will open up a window on the very beginning of our Universe and offer an opportunity to support or falsify the de Sitter equilibrium cosmology.

  12. 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.

  13. Instability of quantum equilibrium in Bohm's dynamics

    PubMed Central

    Colin, Samuel; Valentini, Antony

    2014-01-01

    We consider Bohm's second-order dynamics for arbitrary initial conditions in phase space. In principle, Bohm's dynamics allows for ‘extended’ non-equilibrium, with initial momenta not equal to the gradient of phase of the wave function (as well as initial positions whose distribution departs from the Born rule). We show that extended non-equilibrium does not relax in general and is in fact unstable. This is in sharp contrast with de Broglie's first-order dynamics, for which non-standard momenta are not allowed and which shows an efficient relaxation to the Born rule for positions. On this basis, we argue that, while de Broglie's dynamics is a tenable physical theory, Bohm's dynamics is not. In a world governed by Bohm's dynamics, there would be no reason to expect to see an effective quantum theory today (even approximately), in contradiction with observation. PMID:25383020

  14. Absence of equilibrium chiral magnetic effect

    NASA Astrophysics Data System (ADS)

    Zubkov, M. A.

    2016-05-01

    We analyze the (3 +1 )D equilibrium chiral magnetic effect (CME). We apply derivative expansion to the Wigner transform of the two-point Green function. This technique allows us to express the response of electric current to the external electromagnetic field strength through the momentum space topological invariant. We consider the wide class of the lattice regularizations of quantum field theory (that includes, in particular, the regularization with Wilson fermions) and also certain lattice models of solid state physics (including those of Dirac semimetals). It appears that in these models the mentioned topological invariant vanishes identically at nonzero chiral chemical potential. That means that the bulk equilibrium CME is absent in those systems.

  15. Equilibrium fluctuation relations for voltage coupling in membrane proteins.

    PubMed

    Kim, Ilsoo; Warshel, Arieh

    2015-11-01

    A general theoretical framework is developed to account for the effects of an external potential on the energetics of membrane proteins. The framework is based on the free energy relation between two (forward/backward) probability densities, which was recently generalized to non-equilibrium processes, culminating in the work-fluctuation theorem. Starting from the probability densities of the conformational states along the "voltage coupling" reaction coordinate, we investigate several interconnected free energy relations between these two conformational states, considering voltage activation of ion channels. The free energy difference between the two conformational states at zero (depolarization) membrane potential (i.e., known as the chemical component of free energy change in ion channels) is shown to be equivalent to the free energy difference between the two "equilibrium" (resting and activated) conformational states along the one-dimensional voltage couplin reaction coordinate. Furthermore, the requirement that the application of linear response approximation to the free energy functionals of voltage coupling should satisfy the general free energy relations, yields a novel closed-form expression for the gating charge in terms of other basic properties of ion channels. This connection is familiar in statistical mechanics, known as the equilibrium fluctuation-response relation. The theory is illustrated by considering the coupling of a unit charge to the external voltage in the two sites near the surface of membrane, representing the activated and resting states. This is done using a coarse-graining (CG) model of membrane proteins, which includes the membrane, the electrolytes and the electrodes. The CG model yields Marcus-type voltage dependent free energy parabolas for the response of the electrostatic environment (electrolytes etc.) to the transition from the initial to the final configuratinal states, leading to equilibrium free energy difference and free

  16. Radioactive equilibrium in ancient marine sediments

    USGS Publications Warehouse

    Breger, I.A.

    1955-01-01

    Radioactive equilibrium in eight marine sedimentary formations has been studied by means of direct determinations of uranium, radium and thorium. Alpha-particle counting has also been carried out in order to cross-calibrate thick-source counting techniques. The maximum deviation from radioactive equilibrium that has been noted is 11 per cent-indicating that there is probably equilibrium in all the formations analyzed. Thick-source alpha-particle counting by means of a proportional counter or an ionization chamber leads to high results when the samples contain less than about 10 p.p.m. of uranium. For samples having a higher content of uranium the results are in excellent agreement with each other and with those obtained by direct analytical techniques. The thorium contents that have been obtained correspond well to the average values reported in the literature. The uranium content of marine sediments may be appreciably higher than the average values that have been reported for sedimentary rocks. Data show that there is up to fourteen times the percentage of uranium as of thorium in the formations studied and that the percentage of thorium never exceeds that of uranium. While the proximity of a depositional environment to a land mass may influence the concentration of uranium in a marine sediment, this is not true with thorium. ?? 1955.

  17. Equilibrium behavior of coarse-grained chaos

    NASA Astrophysics Data System (ADS)

    Egolf, David A.; Ballard, Christopher C.; Esty, C. Clark

    2015-03-01

    A wide variety of systems exhibiting spatiotemporal chaos have been shown to be extensive, in that their fractal dimensions grow linearly with volume. Ruelle argued that this extensivity is evidence that these systems can be viewed as a gas of weakly-interacting regions. We have tested this idea by performing large-scale computational studies of spatiotemporal chaos in the 1D complex Ginzburg-Landau equation, and we have found that aspects of the coarse-grained system are well-described not only as a gas, but as an equilibrium gas -- in particular, a Tonks gas (and variants) in the grand canonical ensemble. Furthermore, for small system sizes, the average number of particles in the corresponding Tonks gas exhibits oscillatory, decaying deviations from extensivity in agreement with deviations in the fractal dimension found by Fishman and Egolf. This result not only supports Ruelle's picture but also suggests that the coarse-grained behavior of this far-from-equilibrium system might be understood using equilibrium statistical mechanics.

  18. The Dynamical Equilibrium of Galaxy Clusters

    NASA Astrophysics Data System (ADS)

    Carlberg, R. G.; Yee, H. K. C.; Ellingson, E.; Morris, S. L.; Abraham, R.; Gravel, P.; Pritchet, C. J.; Smecker-Hane, T.; Hartwick, F. D. A.; Hesser, J. E.; Hutchings, J. B.; Oke, J. B.

    1997-02-01

    If a galaxy cluster is effectively in dynamical equilibrium, then all galaxy populations within the cluster must have distributions in velocity and position that individually reflect the same underlying mass distribution, although the derived virial masses can be quite different. Specifically, within the Canadian Network for Observational Cosmology cluster sample, the virial radius of the red galaxy population is, on the average, a factor of 2.05 +/- 0.34 smaller than that of the blue population. The red galaxies also have a smaller rms velocity dispersion, a factor of 1.31 +/- 0.13 within our sample. Consequently, the virial mass calculated from the blue galaxies is 3.5 +/- 1.3 times larger than from the red galaxies. However, applying the Jeans equation of stellar hydrodynamic equilibrium to the red and blue subsamples separately gives statistically identical cluster mass profiles. This is strong evidence that these clusters are effectively equilibrium systems and therefore demonstrates empirically that the masses in the virialized region are reliably estimated using dynamical techniques.

  19. Statistical approach to partial equilibrium analysis

    NASA Astrophysics Data System (ADS)

    Wang, Yougui; Stanley, H. E.

    2009-04-01

    A statistical approach to market equilibrium and efficiency analysis is proposed in this paper. One factor that governs the exchange decisions of traders in a market, named willingness price, is highlighted and constitutes the whole theory. The supply and demand functions are formulated as the distributions of corresponding willing exchange over the willingness price. The laws of supply and demand can be derived directly from these distributions. The characteristics of excess demand function are analyzed and the necessary conditions for the existence and uniqueness of equilibrium point of the market are specified. The rationing rates of buyers and sellers are introduced to describe the ratio of realized exchange to willing exchange, and their dependence on the market price is studied in the cases of shortage and surplus. The realized market surplus, which is the criterion of market efficiency, can be written as a function of the distributions of willing exchange and the rationing rates. With this approach we can strictly prove that a market is efficient in the state of equilibrium.

  20. Recovery of postural equilibrium control following spaceflight

    NASA Technical Reports Server (NTRS)

    Paloski, W. H.; Reschke, M. F.; Black, F. O.; Doxey, D. D.; Harm, D. L.

    1992-01-01

    Decreased postural stability is observed in most astronauts immediately following spaceflight. Because ataxia may present postflight operational hazards, it is important to determine the incidence of postural instability immediately following landing and the dynamics of recovery of normal postural equilibrium control. It is postulated that postflight postural instability results from in-flight adaptive changes in central nervous system (CNS) processing of sensory information from the visual, vestibular, and proprioceptive systems. The purpose of the present investigation was to determine the magnitude and time course of postflight recovery of postural equilibrium control and, hence, readaptation of CNS processing of sensory information. Thirteen crew members from six spaceflight missions were studied pre- and postflight using a modified commercial posturography system. Postural equilibrium control was found to be seriously disrupted immediately following spaceflight in all subjects. Readaptation to the terrestrial environment began immediately upon landing, proceeded rapidly for the first 10-12 hours, and then proceeded much more slowly for the subsequent 2-4 days until preflight stability levels were reachieved. It is concluded that the overall postflight recovery of postural stability follows a predictable time course.

  1. Hamiltonian approach to the magnetostatic equilibrium problem

    SciTech Connect

    Tessarotto, M.; Zheng, Lin Jin; Johnson, J.L.

    1995-02-01

    The purpose of this paper is to investigate the classical scalar-pressure magnetostatic equilibrium problem for non-symmetric configurations in the framework of a Hamiltonian approach. Requiring that the equilibrium admits locally, in a suitable subdomain, a family of nested toroidal magnetic surfaces, the Hamiltonian equations describing the magnetic flux lines in such a subdomain are obtained for general curvilinear coordinate systems. The properties of such Hamiltonian system are investigated. A representation of the magnetic field in terms of arbitrary general curvilinear coordinates is thus obtained. Its basic feature is that the magnetic field must fulfill suitable periodicity constraints to be imposed on arbitrary rational magnetic surfaces for general non-symmetric toroidal equilibria, i.e., it is quasi-symmetric. Implications for the existence of magnetostatic equilibria are pointed out. In particular, it is proven that a generalized equilibrium equation exists for such quasi-symmetric equilibria, which extends the Grad-Shafranov equation to fully three-dimensional configurations. As an application, the case is considered of quasi-helical equilibria, i.e., displaying a magnetic field magnitude depending on the poloidal ({chi}) and toroidal ({var_theta}) angles only in terms of {alpha}={chi}-N{theta} with N an arbitrary integer.

  2. Bifurcated helical core equilibrium states in tokamaks

    NASA Astrophysics Data System (ADS)

    Cooper, W. A.; Chapman, I. T.; Schmitz, O.; Turnbull, A. D.; Tobias, B. J.; Lazarus, E. A.; Turco, F.; Lanctot, M. J.; Evans, T. E.; Graves, J. P.; Brunetti, D.; Pfefferlé, D.; Reimerdes, H.; Sauter, O.; Halpern, F. D.; Tran, T. M.; Coda, S.; Duval, B. P.; Labit, B.; Pochelon, A.; Turnyanskiy, M. R.; Lao, L.; Luce, T. C.; Buttery, R.; Ferron, J. R.; Hollmann, E. M.; Petty, C. C.; van Zeeland, M.; Fenstermacher, M. E.; Hanson, J. M.; Lütjens, H.

    2013-07-01

    Tokamaks with weak to moderate reversed central shear in which the minimum inverse rotational transform (safety factor) qmin is in the neighbourhood of unity can trigger bifurcated magnetohydrodynamic equilibrium states, one of which is similar to a saturated ideal internal kink mode. Peaked prescribed pressure profiles reproduce the ‘snake’ structures observed in many tokamaks which has led to a novel explanation of the snake as a bifurcated equilibrium state. Snake equilibrium structures are computed in simulations of the tokamak à configuration variable (TCV), DIII-D and mega amp spherical torus (MAST) tokamaks. The internal helical deformations only weakly modulate the plasma-vacuum interface which is more sensitive to ripple and resonant magnetic perturbations. On the other hand, the external perturbations do not alter the helical core deformation in a significant manner. The confinement of fast particles in MAST simulations deteriorate with the amplitude of the helical core distortion. These three-dimensional bifurcated solutions constitute a paradigm shift that motivates the applications of tools developed for stellarator research in tokamak physics investigations.

  3. On Non-Equilibrium Thermodynamics of Space-Time and Quantum Gravity

    NASA Astrophysics Data System (ADS)

    Munkhammar, Joakim

    Based on recent results from general relativistic statistical mechanics and black hole information transfer limits, a space-time entropy-action equivalence is proposed as a generalization of the holographic principle. With this conjecture, the action principle can be replaced by the second law of thermodynamics, and for the Einstein-Hilbert action the Einstein field equations are conceptually the result of thermodynamic equilibrium. For non-equilibrium situations, Jaynes' information-theoretic approach to maximum entropy production is adopted instead of the second law of thermodynamics. As it turns out for appropriate choices of constants, quantum gravity is obtained. For the special case of a free particle the Bekenstein-Verlinde entropy-to-displacement relation of holographic gravity and thus the traditional holographic principle emerges. Although Jacobson's original thermodynamic equilibrium approach proposed that gravity might not necessarily be quantized, this particular non-equilibrium treatment might require it.

  4. On the Vertical Equilibrium of the Local Galactic Disk and the Search for Disk Dark Matter

    NASA Astrophysics Data System (ADS)

    Sánchez-Salcedo, F. J.; Flynn, Chris; Hidalgo-Gámez, A. M.

    2011-04-01

    Estimates of the dynamical surface mass density at the solar Galactocentric distance are commonly derived assuming that the disk is in vertical equilibrium with the Galactic potential. This assumption has recently been called into question, based on the claim that the ratio between the kinetic and the gravitational energy in such solutions is a factor of three larger than required if virial equilibrium is to hold. Here we show that this ratio between energies was overestimated and that the disk solutions are likely to be in virial equilibrium after all. We additionally demonstrate, using one-dimensional numerical simulations, that the disks are indeed in equilibrium. Hence, given the uncertainties, we find no reason to cast doubt on the steady-state solutions which are traditionally used to measure the matter density of the disk.

  5. ON THE VERTICAL EQUILIBRIUM OF THE LOCAL GALACTIC DISK AND THE SEARCH FOR DISK DARK MATTER

    SciTech Connect

    Sanchez-Salcedo, F. J.; Flynn, Chris; Hidalgo-Gamez, A. M.

    2011-04-20

    Estimates of the dynamical surface mass density at the solar Galactocentric distance are commonly derived assuming that the disk is in vertical equilibrium with the Galactic potential. This assumption has recently been called into question, based on the claim that the ratio between the kinetic and the gravitational energy in such solutions is a factor of three larger than required if virial equilibrium is to hold. Here we show that this ratio between energies was overestimated and that the disk solutions are likely to be in virial equilibrium after all. We additionally demonstrate, using one-dimensional numerical simulations, that the disks are indeed in equilibrium. Hence, given the uncertainties, we find no reason to cast doubt on the steady-state solutions which are traditionally used to measure the matter density of the disk.

  6. Modeling Inflation Using a Non-Equilibrium Equation of Exchange

    NASA Technical Reports Server (NTRS)

    Chamberlain, Robert G.

    2013-01-01

    Inflation is a change in the prices of goods that takes place without changes in the actual values of those goods. The Equation of Exchange, formulated clearly in a seminal paper by Irving Fisher in 1911, establishes an equilibrium relationship between the price index P (also known as "inflation"), the economy's aggregate output Q (also known as "the real gross domestic product"), the amount of money available for spending M (also known as "the money supply"), and the rate at which money is reused V (also known as "the velocity of circulation of money"). This paper offers first a qualitative discussion of what can cause these factors to change and how those causes might be controlled, then develops a quantitative model of inflation based on a non-equilibrium version of the Equation of Exchange. Causal relationships are different from equations in that the effects of changes in the causal variables take time to play out-often significant amounts of time. In the model described here, wages track prices, but only after a distributed lag. Prices change whenever the money supply, aggregate output, or the velocity of circulation of money change, but only after a distributed lag. Similarly, the money supply depends on the supplies of domestic and foreign money, which depend on the monetary base and a variety of foreign transactions, respectively. The spreading of delays mitigates the shocks of sudden changes to important inputs, but the most important aspect of this model is that delays, which often have dramatic consequences in dynamic systems, are explicitly incorporated.macroeconomics, inflation, equation of exchange, non-equilibrium, Athena Project

  7. Dynamic processes of conceptual change: Analysis of constructing mental models of chemical equilibrium

    NASA Astrophysics Data System (ADS)

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

    2002-10-01

    The purpose of this study was to investigate students' mental models of chemical equilibrium using dynamic science assessments. Research in chemical education has shown that students at various levels have misconceptions about chemical equilibrium. According to Chi's theory of conceptual change, the concept of chemical equilibrium has constraint-based features (e.g., random, simultaneous, uniform activities) that might prevent students from deeply understanding the nature of the concept of chemical equilibrium. In this study, we examined how students learned and constructed their mental models of chemical equilibrium in a cognitive apprenticeship context. Thirty 10th-grade students participated in the study: 10 in a control group and 20 in a treatment group. Both groups were presented with a series of hands-on chemical experiments. The students in the treatment group were instructed based on the main features of cognitive apprenticeship (CA), such as coaching, modeling, scaffolding, articulation, reflection, and exploration. However, the students in the control group (non-CA group) learned from the tutor without explicit CA support. The results revealed that the CA group significantly outperformed the non-CA group. The students in the CA group were capable of constructing the mental models of chemical equilibrium - including dynamic, random activities of molecules and interactions between molecules in the microworld - whereas the students in the non-CA group failed to construct similar correct mental models of chemical equilibrium. The study focuses on the process of constructing mental models, on dynamic changes, and on the actions of students (such as self-monitoring/self-correction) who are learning the concept of chemical equilibrium. Also, we discuss the implications for science education.

  8. Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

    NASA Astrophysics Data System (ADS)

    Domagal-Goldman, S.; Kubicki, J. D.

    2006-05-01

    Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the

  9. On the Concept "Chemical Equilibrium": The Associative Framework.

    ERIC Educational Resources Information Center

    Gussarsky, Esther; Gorodetsky, Malka

    1990-01-01

    Word associations were used to map high school students' concepts of "chemical equilibrium" and "equilibrium." It was found that the preconception of the two concepts was differentiated on noncritical dimensions. (Author/CW)

  10. Existence of best proximity pairs and equilibrium pairs

    NASA Astrophysics Data System (ADS)

    Kim, Won Kyu; Lee, Kyoung Hee

    2006-04-01

    In this paper, using the fixed point theorem for Kakutani factorizable multifunctions, we shall prove new existence theorems of best proximity pairs and equilibrium pairs for free abstract economies, which include the previous fixed point theorems and equilibrium existence theorems.

  11. Thermodynamics and Kinetics of Chemical Equilibrium in Solution.

    ERIC Educational Resources Information Center

    Leenson, I. A.

    1986-01-01

    Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)

  12. On the Equilibrium States of Interconnected Bubbles or Balloons.

    ERIC Educational Resources Information Center

    Weinhaus, F.; Barker, W.

    1978-01-01

    Describes the equilibrium states of a system composed of two interconnected, air-filled spherical membranes of different sizes. The equilibrium configurations are determined by the method of minimization of the availability of the system at constant temperature. (GA)

  13. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system.

    PubMed

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-20

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

  14. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

    PubMed Central

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-01

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion–fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies. PMID:26786848

  15. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

    NASA Astrophysics Data System (ADS)

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-01

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

  16. Towards breaking temperature equilibrium in multi-component Eulerian schemes

    SciTech Connect

    Grove, John W; Masser, Thomas

    2009-01-01

    We investigate the effects ofthermal equilibrium on hydrodynamic flows and describe models for breaking the assumption ofa single temperature for a mixture of components in a cell. A computational study comparing pressure-temperature equilibrium simulations of two dimensional implosions with explicit front tracking is described as well as implementation and J-D calculations for non-equilibrium temperature methods.

  17. Investigating High School Students' Understanding of Chemical Equilibrium Concepts

    ERIC Educational Resources Information Center

    Karpudewan, Mageswary; Treagust, David F.; Mocerino, Mauro; Won, Mihye; Chandrasegaran, A. L.

    2015-01-01

    This study investigated the year 12 students' (N = 56) understanding of chemical equilibrium concepts after instruction using two conceptual tests, the "Chemical Equilibrium Conceptual Test 1" ("CECT-1") consisting of nine two-tier multiple-choice items and the "Chemical Equilibrium Conceptual Test 2"…

  18. Misconceptions of Students and Teachers in Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Banerjee, Anil C.

    1991-01-01

    Written test was developed and administered to diagnose misconceptions in different areas of chemical equilibrium among 162 undergraduate chemistry students and 69 teachers of chemistry. Responses reveal widespread misconceptions among students and teachers in areas related to the prediction of equilibrium conditions, rate and equilibrium,…

  19. Hanging an Airplane: A Case Study in Static Equilibrium

    ERIC Educational Resources Information Center

    Katz, Debora M.

    2009-01-01

    Our classrooms are filled with engineering majors who take a semester-long course in static equilibrium. Many students find this class too challenging and drop their engineering major. In our introductory physics class, we often breeze through static equilibrium; to physicists equilibrium is just a special case of Newton's second law. While it is…

  20. 14 CFR 67.205 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 2 2013-01-01 2013-01-01 false Ear, nose, throat, and equilibrium. 67.205... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Second-Class Airman Medical Certificate § 67.205 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class...

  1. 14 CFR 67.105 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 2 2012-01-01 2012-01-01 false Ear, nose, throat, and equilibrium. 67.105... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION First-Class Airman Medical Certificate § 67.105 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class...

  2. 14 CFR 67.105 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 2 2013-01-01 2013-01-01 false Ear, nose, throat, and equilibrium. 67.105... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION First-Class Airman Medical Certificate § 67.105 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class...

  3. 14 CFR 67.105 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 2 2014-01-01 2014-01-01 false Ear, nose, throat, and equilibrium. 67.105... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION First-Class Airman Medical Certificate § 67.105 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class...

  4. 14 CFR 67.305 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 2 2014-01-01 2014-01-01 false Ear, nose, throat, and equilibrium. 67.305... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Third-Class Airman Medical Certificate § 67.305 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class...

  5. 14 CFR 67.305 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 2 2012-01-01 2012-01-01 false Ear, nose, throat, and equilibrium. 67.305... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Third-Class Airman Medical Certificate § 67.305 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class...

  6. 14 CFR 67.205 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 2 2014-01-01 2014-01-01 false Ear, nose, throat, and equilibrium. 67.205... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Second-Class Airman Medical Certificate § 67.205 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class...

  7. 14 CFR 67.205 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 2 2012-01-01 2012-01-01 false Ear, nose, throat, and equilibrium. 67.205... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Second-Class Airman Medical Certificate § 67.205 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class...

  8. 14 CFR 67.305 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 2 2013-01-01 2013-01-01 false Ear, nose, throat, and equilibrium. 67.305... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Third-Class Airman Medical Certificate § 67.305 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class...

  9. 14 CFR 67.205 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Ear, nose, throat, and equilibrium. 67.205... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Second-Class Airman Medical Certificate § 67.205 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class...

  10. 14 CFR 67.105 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 2 2011-01-01 2011-01-01 false Ear, nose, throat, and equilibrium. 67.105... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION First-Class Airman Medical Certificate § 67.105 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class...

  11. 14 CFR 67.205 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 2 2011-01-01 2011-01-01 false Ear, nose, throat, and equilibrium. 67.205... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Second-Class Airman Medical Certificate § 67.205 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class...

  12. 14 CFR 67.105 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Ear, nose, throat, and equilibrium. 67.105... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION First-Class Airman Medical Certificate § 67.105 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class...

  13. 14 CFR 67.305 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 2 2011-01-01 2011-01-01 false Ear, nose, throat, and equilibrium. 67.305... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Third-Class Airman Medical Certificate § 67.305 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class...

  14. 14 CFR 67.305 - Ear, nose, throat, and equilibrium.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Ear, nose, throat, and equilibrium. 67.305... (CONTINUED) AIRMEN MEDICAL STANDARDS AND CERTIFICATION Third-Class Airman Medical Certificate § 67.305 Ear, nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class...

  15. Stochastic linearization of turbulent dynamics of dispersive waves in equilibrium and non-equilibrium state

    NASA Astrophysics Data System (ADS)

    Jiang, Shixiao W.; Lu, Haihao; Zhou, Douglas; Cai, David

    2016-08-01

    Characterizing dispersive wave turbulence in the long time dynamics is central to understanding of many natural phenomena, e.g., in atmosphere ocean dynamics, nonlinear optics, and plasma physics. Using the β-Fermi-Pasta-Ulam nonlinear system as a prototypical example, we show that in thermal equilibrium and non-equilibrium steady state the turbulent state even in the strongly nonlinear regime possesses an effective linear stochastic structure in renormalized normal variables. In this framework, we can well characterize the spatiotemporal dynamics, which are dominated by long-wavelength renormalized waves. We further demonstrate that the energy flux is nearly saturated by the long-wavelength renormalized waves in non-equilibrium steady state. The scenario of such effective linear stochastic dynamics can be extended to study turbulent states in other nonlinear wave systems.

  16. Thermo-chemical dynamics and chemical quasi-equilibrium of plasmas in thermal non-equilibrium

    SciTech Connect

    Massot, Marc; Graille, Benjamin; Magin, Thierry E.

    2011-05-20

    We examine both processes of ionization by electron and heavy-particle impact in spatially uniform plasmas at rest in the absence of external forces. A singular perturbation analysis is used to study the following physical scenario, in which thermal relaxation becomes much slower than chemical reactions. First, electron-impact ionization is investigated. The dynamics of the system rapidly becomes close to a slow dynamics manifold that allows for defining a unique chemical quasi-equilibrium for two-temperature plasmas and proving that the second law of thermodynamics is satisfied. Then, all ionization reactions are taken into account simultaneously, leading to a surprising conclusion: the inner layer for short time scale (or time boundary layer) directly leads to thermal equilibrium. Global thermo-chemical equilibrium is reached within a short time scale, involving only chemical reactions, even if thermal relaxation through elastic collisions is assumed to be slow.

  17. Non-equilibrium Dynamics of DNA Nanotubes

    NASA Astrophysics Data System (ADS)

    Hariadi, Rizal Fajar

    Can the fundamental processes that underlie molecular biology be understood and simulated by DNA nanotechnology? The early development of DNA nanotechnology by Ned Seeman was driven by the desire to find a solution to the protein crystallization problem. Much of the later development of the field was also driven by envisioned applications in computing and nanofabrication. While the DNA nanotechnology community has assembled a versatile tool kit with which DNA nanostructures of considerable complexity can be assembled, the application of this tool kit to other areas of science and technology is still in its infancy. This dissertation reports on the construction of non-equilibrium DNA nanotube dynamic to probe molecular processes in the areas of hydrodynamics and cytoskeletal behavior. As the first example, we used DNA nanotubes as a molecular probe for elongational flow measurement in different micro-scale flow settings. The hydrodynamic flow in the vicinity of simple geometrical objects, such as a rigid DNA nanotube, is amenable to rigorous theoretical investigation. We measured the distribution of elongational flows produced in progressively more complex settings, ranging from the vicinity of an orifice in a microfluidic chamber to within a bursting bubble of Pacific ocean water. This information can be used to constrain theories on the origin of life in which replication involves a hydrodynamically driven fission process, such as the coacervate fission proposed by Oparin. A second theme of this dissertation is the bottom-up construction of a de novo artificial cytoskeleton with DNA nanotubes. The work reported here encompasses structural, locomotion, and control aspects of non-equilibrium cytoskeletal behavior. We first measured the kinetic parameters of DNA nanotube assembly and tested the accuracy of the existing polymerization models in the literature. Toward recapitulation of non-equilibrium cytoskeletal dynamics, we coupled the polymerization of DNA

  18. Migration cost externality and interregional equilibrium.

    PubMed

    Shin, C

    1994-01-01

    "This paper will investigate the characteristics of population allocation between two regions in the presence of migration cost. It will also examine both populations and the non-migration range of the initial population in which migration does not occur, in social optimum and market equilibrium with central government intervention, to reveal migration cost externality, and to propose a remedy for it." The author finds that "migration cost gives the social planner an additional burden of population reallocation, and it has an important effect upon an individual's decisions on migration in a decentralized market mechanism."

  19. Process for operating equilibrium controlled reactions

    DOEpatents

    Nataraj, Shankar; Carvill, Brian Thomas; Hufton, Jeffrey Raymond; Mayorga, Steven Gerard; Gaffney, Thomas Richard; Brzozowski, Jeffrey Richard

    2001-01-01

    A cyclic process for operating an equilibrium controlled reaction in a plurality of reactors containing an admixture of an adsorbent and a reaction catalyst suitable for performing the desired reaction which is operated in a predetermined timed sequence wherein the heating and cooling requirements in a moving reaction mass transfer zone within each reactor are provided by indirect heat exchange with a fluid capable of phase change at temperatures maintained in each reactor during sorpreaction, depressurization, purging and pressurization steps during each process cycle.

  20. Equilibrium of an elastically confined liquid drop

    NASA Astrophysics Data System (ADS)

    Kwon, Hyuk-Min; Kim, Ho-Young; Puëll, Jérôme; Mahadevan, L.

    2008-05-01

    When a liquid drop is confined between an elastic plate and a rigid substrate, it spreads spontaneously due to the effects of interfacial forces, eventually reaching an equilibrium shape determined by the balance between elastic and capillary effects. We provide an analytical theory for the static shape of the sheet and the extent of liquid spreading and show that our experiments are quantitatively consistent with the theory. The theory is relevant for the first step of painting when a brush is brought down on to canvas. More mundanely, it allows us to understand the stiction of microcantilevers to wafer substrates occurring in microelectromechanical fabrication processes.

  1. Equilibrium water and solute uptake in silicone hydrogels.

    PubMed

    Liu, D E; Dursch, T J; Oh, Y; Bregante, D T; Chan, S Y; Radke, C J

    2015-05-01

    Equilibrium water content of and solute partitioning in silicone hydrogels (SiHys) are investigated using gravimetric analysis, fluorescence confocal laser-scanning microscopy (FCLSM), and back extraction with UV/Vis-absorption spectrophotometry. Synthesized silicone hydrogels consist of silicone monomer, hydrophilic monomer, cross-linking agent, and triblock-copolymer macromer used as an amphiphilic compatibilizer to prevent macrophase separation. In all cases, immiscibility of the silicone and hydrophilic polymers results in microphase-separated morphologies. To investigate solute uptake in each of the SiHy microphases, equilibrium partition coefficients are obtained for two hydrophilic solutes (i.e., theophylline and caffeine dissolved in aqueous phosphate-buffered saline) and two oleophilic solutes (i.e., Nile Red and Bodipy Green dissolved in silicone oil), respectively. Measured water contents and aqueous-solute partition coefficients increase linearly with increasing solvent-free hydrophilic-polymer volume fraction. Conversely, oleophilic-solute partition coefficients decrease linearly with rising solvent-free hydrophilic-polymer volume fraction (i.e., decreasing hydrophobic silicone-polymer fraction). We quantitatively predict equilibrium SiHy water and solute uptake assuming that water and aqueous solutes reside only in hydrophilic microdomains, whereas oleophilic solutes partition predominately into silicone microdomains. Predicted water contents and solute partition coefficients are in excellent agreement with experiment. Our new procedure permits a priori estimation of SiHy water contents and solute partition coefficients based solely on properties of silicone and hydrophilic homopolymer hydrogels, eliminating the need for further mixed-polymer-hydrogel experiments. PMID:25725471

  2. Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

    2016-02-01

    We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

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

    PubMed

    Niu, Yuanling; Wang, Yue; Zhou, Da

    2015-12-01

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

  4. Variability of radon and thoron equilibrium factors in indoor environment of Garhwal Himalaya.

    PubMed

    Prasad, Mukesh; Rawat, Mukesh; Dangwal, Anoop; Kandari, Tushar; Gusain, G S; Mishra, Rosaline; Ramola, R C

    2016-01-01

    The measurements of radon, thoron and their progeny concentrations have been carried out in the dwellings of Uttarkashi and Tehri districts of Garhwal Himalaya, India using LR-115 detector based pin-hole dosimeter and DRPS/DTPS techniques. The equilibrium factors for radon, thoron and their progeny were calculated by using the values measured with these techniques. The average values of equilibrium factor between radon and its progeny have been found to be 0.44, 0.39, 0.39 and 0.28 for rainy, autumn, winter and summer seasons, respectively. For thoron and its progeny, the average values of equilibrium factor have been found to be 0.04, 0.04, 0.04 and 0.03 for rainy, autumn, winter and summer seasons, respectively. The equilibrium factor between radon and its progeny has been found to be dependent on the seasonal changes. However, the equilibrium factor for thoron and progeny has been found to be same for rainy, autumn and winter seasons but slightly different for summer season. The annual average equilibrium factors for radon and thoron have been found to vary from 0.23 to 0.80 with an average of 0.42 and from 0.01 to 0.29 with an average of 0.07, respectively. The detailed discussion of the measurement techniques and the explanation for the results obtained is given in the paper. PMID:26520684

  5. Equilibrium and kinetic analysis of CO2-N2 adsorption separation by concentration pulse chromatography.

    PubMed

    Li, Peiyuan; Tezel, F Handan

    2007-09-01

    CO2 and N(2) adsorption kinetics and equilibrium behaviours have been studied with silicalite, NaY and 13X by using concentration pulse chromatography for the separation of these gases in the present study. Adsorption Henry's Law constants, the heat of adsorption values, micropore diffusion coefficients and corresponding activation energies are determined experimentally and the three different mass transfer mechanisms are discussed. From the equilibrium data, the corresponding separation factors are obtained for the adsorption separation processes. The heat of adsorption values as well as the Henry's Law adsorption equilibrium constants of CO(2) are much higher than those of N(2) for all the adsorbents studied. 13X, NaY and silicalite all have good separation factors for CO(2)/N(2) system based on equilibrium processes. The order of the equilibrium separation factors is 13X (Ceca)>13X (Zeochem)>NaY (UOP)>silicalite (UOP). Equilibrium selectivity favours CO(2) over N(2). Micropore diffusion resistance is the definite dominant mass transfer mechanism for CO(2) with silicalite and NaY.

  6. Students' and teachers' misapplication of le chatelier's principle: Implications for the teaching of chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Quílez-Pardo, Juan; Solaz-Portolés, Joan Josep

    The aim of this article was to study the reasons, strategies, and procedures that both students and teachers use to solve some chemical equilibrium questions and problems. Inappropriate conceptions on teaching and a lack of knowledge regarding the limited usefulness of Le Chatelier's principle, with its vague and ambiguous formulation and textbook presentation, may be some of the sources of misconceptions about the prediction of the effect of changing conditions on chemical equilibrium. To diagnose misconceptions and their possible sources, a written test was developed and administered to 170 1st-year university chemistry students. A chemical equilibrium problem, relating to the students' test, was solved by 40 chemistry teachers. First, we ascertained that teacher's conceptions might influence the problem-solving strategies of the learner. Based on this first aspect, our discussion also concerns students' and teachers' misconceptions related to the Le Chatelier's principle. Misconceptions emerged through: (a) misapplication and misunderstanding of Le Chatelier's principle; (b) use of rote-learning recall and algorithmic procedures; (c) incorrect control of the variables involved; (d) limited use of the chemical equilibrium law; (e) a lack of mastery of chemical equilibrium principles and difficulty in transferring such principles to new situations. To avoid chemical equilibrium misconceptions, a specific pattern of conceptual and methodological change may be considered.Received: 16 November 1993; Revised: 21 September 1994;

  7. Revised lattice Boltzmann model for traffic flow with equilibrium traffic pressure

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Lu, Wei-Zhen; Xue, Yu; He, Hong-Di

    2016-02-01

    A revised lattice Boltzmann model concerning the equilibrium traffic pressure is proposed in this study to tackle the phase transition phenomena of traffic flow system. The traditional lattice Boltzmann model has limitation to investigate the complex traffic phase transitions due to its difficulty for modeling the equilibrium velocity distribution. Concerning this drawback, the equilibrium traffic pressure is taken into account to derive the equilibrium velocity distribution in the revised lattice Boltzmann model. In the proposed model, a three-dimensional velocity-space is assumed to determine the equilibrium velocity distribution functions and an alternative, new derivative approach is introduced to deduct the macroscopic equations with the first-order accuracy level from the lattice Boltzmann model. Based on the linear stability theory, the stability conditions of the corresponding macroscopic equations can be obtained. The outputs indicate that the stability curve is divided into three regions, i.e., the stable region, the neutral stability region, and the unstable region. In the stable region, small disturbance appears in the initial uniform flow and will vanish after long term evolution, while in the unstable region, the disturbance will be enlarged and finally leads to the traffic system entering the congested state. In the neutral stability region, small disturbance does not vanish with time and maintains its amplitude in the traffic system. Conclusively, the stability of traffic system is found to be enhanced as the equilibrium traffic pressure increases. Finally, the numerical outputs of the proposed model are found to be consistent with the recognized, theoretical results.

  8. Variability of radon and thoron equilibrium factors in indoor environment of Garhwal Himalaya.

    PubMed

    Prasad, Mukesh; Rawat, Mukesh; Dangwal, Anoop; Kandari, Tushar; Gusain, G S; Mishra, Rosaline; Ramola, R C

    2016-01-01

    The measurements of radon, thoron and their progeny concentrations have been carried out in the dwellings of Uttarkashi and Tehri districts of Garhwal Himalaya, India using LR-115 detector based pin-hole dosimeter and DRPS/DTPS techniques. The equilibrium factors for radon, thoron and their progeny were calculated by using the values measured with these techniques. The average values of equilibrium factor between radon and its progeny have been found to be 0.44, 0.39, 0.39 and 0.28 for rainy, autumn, winter and summer seasons, respectively. For thoron and its progeny, the average values of equilibrium factor have been found to be 0.04, 0.04, 0.04 and 0.03 for rainy, autumn, winter and summer seasons, respectively. The equilibrium factor between radon and its progeny has been found to be dependent on the seasonal changes. However, the equilibrium factor for thoron and progeny has been found to be same for rainy, autumn and winter seasons but slightly different for summer season. The annual average equilibrium factors for radon and thoron have been found to vary from 0.23 to 0.80 with an average of 0.42 and from 0.01 to 0.29 with an average of 0.07, respectively. The detailed discussion of the measurement techniques and the explanation for the results obtained is given in the paper.

  9. Under What Conditions Can Equilibrium Gas-Particle Partitioning Be Expected to Hold in the Atmosphere?

    PubMed

    Mai, Huajun; Shiraiwa, Manabu; Flagan, Richard C; Seinfeld, John H

    2015-10-01

    The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas-particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas-particle equilibrium may be achieved slowly. The approach to gas-particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas-particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50-500 nm), the time scale to establish gas-particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.

  10. Mineral equilibrium in fractionated nebular systems

    NASA Technical Reports Server (NTRS)

    Wood, John A.; Hashimoto, Akihiko

    1993-01-01

    We investigated the equilibrium mineral assemblages in chemically fractionated nebular systems, using a computer routine that finds the set of minerals and gases which minimizes the Gibbs free energy of a system with stipulated elemental abundances. Diagrams are presented showing the equilibrium mineralogy, as a function of temperature (400-2300 K), for unfractionated solar material and five fractionated systems. The fractionated systems were defined by mixing, in various proportions, the following four volatility components that solar material can be divided into: refractory dust, carbonaceous matter, ices, and H2 gas. Dust enrichment is seen to increase temperatures of condensation/evaporation and the Fe(2+) content of mafic minerals and to permit existence of stable melt phases. Enrichment of dust and organic matter produces mineral assemblages that are similar in many ways to those of enstatite chondrites, but with mafic minerals that are far more reduced than those in primitive enstatite chondrites. Enrichment of dust, organics, and ices leads to highly ferrous mineralogies even at the highest temperatures but does not predict the stability of hydrous phases above about 450 K.

  11. Equilibrium crystal phases of triblock Janus colloids

    NASA Astrophysics Data System (ADS)

    Reinhart, Wesley F.; Panagiotopoulos, Athanassios Z.

    2016-09-01

    Triblock Janus colloids, which are colloidal spheres decorated with attractive patches at each pole, have recently generated significant interest as potential building blocks for functional materials. Their inherent anisotropy is known to induce self-assembly into open structures at moderate temperatures and pressures, where they are stabilized over close-packed crystals by entropic effects. We present a numerical investigation of the equilibrium phases of triblock Janus particles with many different patch geometries in three dimensions, using Monte Carlo simulations combined with free energy calculations. In all cases, we find that the free energy difference between crystal polymorphs is less than 0.2 kBT per particle. By varying the patch fraction and interaction range, we show that large patches stabilize the formation of structures with four bonds per patch over those with three. This transition occurs abruptly above a patch fraction of 0.30 and has a strong dependence on the interaction range. Furthermore, we find that a short interaction range favors four bonds per patch, with longer range increasingly stabilizing structures with only three bonds per patch. By quantifying the effect of patch geometry on the stability of the equilibrium crystal structures, we provide insights into the fundamental design rules for constructing complex colloidal crystals.

  12. Turbulence modeling for non-equilibrium flow

    NASA Technical Reports Server (NTRS)

    Durbin, P. A.

    1995-01-01

    The work performed during this year has involved further assessment and extension of the k-epsilon-v(exp 2) model, and initiation of work on scalar transport. The latter is introduced by the contribution of Y. Shabany to this volume. Flexible, computationally tractable models are needed for engineering CFD. As computational technology has progressed, the ability and need to use elaborate turbulence closure models has increased. The objective of our work is to explore and develop new analytical frameworks that might extend the applicability of the modeling techniques. In past years the development of a method for near-wall modeling was described. The method has been implemented into a CFD code and its viability has been demonstrated by various test cases. Further tests are reported herein. Non-equilibrium near-wall models are needed for some heat transfer applications. Scalar transport seems generally to be more sensitive to non-equilibrium effects than is momentum transport. For some applications turbulence anisotropy plays a role and an estimate of the full Reynolds stress tensor is needed. We have begun work on scalar transport per se, but in this brief I will only report on an extension of the k-epsilon-v(exp 2) model to predict the Reynolds stress tensor.

  13. Symmetries in fluctuations far from equilibrium.

    PubMed

    Hurtado, Pablo I; Pérez-Espigares, Carlos; del Pozo, Jesús J; Garrido, Pedro L

    2011-05-10

    Fluctuations arise universally in nature as a reflection of the discrete microscopic world at the macroscopic level. Despite their apparent noisy origin, fluctuations encode fundamental aspects of the physics of the system at hand, crucial to understand irreversibility and nonequilibrium behavior. To sustain a given fluctuation, a system traverses a precise optimal path in phase space. Here we show that by demanding invariance of optimal paths under symmetry transformations, new and general fluctuation relations valid arbitrarily far from equilibrium are unveiled. This opens an unexplored route toward a deeper understanding of nonequilibrium physics by bringing symmetry principles to the realm of fluctuations. We illustrate this concept studying symmetries of the current distribution out of equilibrium. In particular we derive an isometric fluctuation relation that links in a strikingly simple manner the probabilities of any pair of isometric current fluctuations. This relation, which results from the time-reversibility of the dynamics, includes as a particular instance the Gallavotti-Cohen fluctuation theorem in this context but adds a completely new perspective on the high level of symmetry imposed by time-reversibility on the statistics of nonequilibrium fluctuations. The new symmetry implies remarkable hierarchies of equations for the current cumulants and the nonlinear response coefficients, going far beyond Onsager's reciprocity relations and Green-Kubo formulas. We confirm the validity of the new symmetry relation in extensive numerical simulations, and suggest that the idea of symmetry in fluctuations as invariance of optimal paths has far-reaching consequences in diverse fields.

  14. Symmetries in fluctuations far from equilibrium

    PubMed Central

    Hurtado, Pablo I.; Pérez-Espigares, Carlos; del Pozo, Jesús J.; Garrido, Pedro L.

    2011-01-01

    Fluctuations arise universally in nature as a reflection of the discrete microscopic world at the macroscopic level. Despite their apparent noisy origin, fluctuations encode fundamental aspects of the physics of the system at hand, crucial to understand irreversibility and nonequilibrium behavior. To sustain a given fluctuation, a system traverses a precise optimal path in phase space. Here we show that by demanding invariance of optimal paths under symmetry transformations, new and general fluctuation relations valid arbitrarily far from equilibrium are unveiled. This opens an unexplored route toward a deeper understanding of nonequilibrium physics by bringing symmetry principles to the realm of fluctuations. We illustrate this concept studying symmetries of the current distribution out of equilibrium. In particular we derive an isometric fluctuation relation that links in a strikingly simple manner the probabilities of any pair of isometric current fluctuations. This relation, which results from the time-reversibility of the dynamics, includes as a particular instance the Gallavotti–Cohen fluctuation theorem in this context but adds a completely new perspective on the high level of symmetry imposed by time-reversibility on the statistics of nonequilibrium fluctuations. The new symmetry implies remarkable hierarchies of equations for the current cumulants and the nonlinear response coefficients, going far beyond Onsager’s reciprocity relations and Green–Kubo formulas. We confirm the validity of the new symmetry relation in extensive numerical simulations, and suggest that the idea of symmetry in fluctuations as invariance of optimal paths has far-reaching consequences in diverse fields. PMID:21493865

  15. Equilibrium states of homogeneous sheared compressible turbulence

    NASA Astrophysics Data System (ADS)

    Riahi, M.; Lili, T.

    2011-06-01

    Equilibrium states of homogeneous compressible turbulence subjected to rapid shear is studied using rapid distortion theory (RDT). The purpose of this study is to determine the numerical solutions of unsteady linearized equations governing double correlations spectra evolution. In this work, RDT code developed by authors solves these equations for compressible homogeneous shear flows. Numerical integration of these equations is carried out using a second-order simple and accurate scheme. The two Mach numbers relevant to homogeneous shear flow are the turbulent Mach number Mt, given by the root mean square turbulent velocity fluctuations divided by the speed of sound, and the gradient Mach number Mg which is the mean shear rate times the transverse integral scale of the turbulence divided by the speed of sound. Validation of this code is performed by comparing RDT results with direct numerical simulation (DNS) of [A. Simone, G.N. Coleman, and C. Cambon, Fluid Mech. 330, 307 (1997)] and [S. Sarkar, J. Fluid Mech. 282, 163 (1995)] for various values of initial gradient Mach number Mg0. It was found that RDT is valid for small values of the non-dimensional times St (St < 3.5). It is important to note that RDT is also valid for large values of St (St > 10) in particular for large values of Mg0. This essential feature justifies the resort to RDT in order to determine equilibrium states in the compressible regime.

  16. In command of non-equilibrium.

    PubMed

    Roduner, Emil; Radhakrishnan, Shankara Gayathri

    2016-05-21

    The second law of thermodynamics is well known for determining the direction of spontaneous processes in the laboratory, life and the universe. It is therefore often called the arrow of time. Less often discussed but just as important is the effect of kinetic barriers which intercept equilibration and preserve highly ordered, high energy non-equilibrium states. Examples of such states are many modern materials produced intentionally for technological applications. Furthermore, all living organisms fuelled directly by photosynthesis and those fuelled indirectly by living on high energy nutrition represent preserved non-equilibrium states. The formation of these states represents the local reversal of the arrow of time which only seemingly violates the second law. It has been known since the seminal work of Prigogine that the stabilisation of these states inevitably requires the dissipation of energy in the form of waste heat. It is this feature of waste heat dissipation following the input of energy that drives all processes occurring at a non-zero rate. Photosynthesis, replication of living organisms, self-assembly, crystal shape engineering and distillation have this principle in common with the well-known Carnot cycle in the heat engine. Drawing on this analogy, we subsume these essential and often sophisticated driven processes under the term machinery of life. PMID:27146424

  17. Equilibrium crystal phases of triblock Janus colloids.

    PubMed

    Reinhart, Wesley F; Panagiotopoulos, Athanassios Z

    2016-09-01

    Triblock Janus colloids, which are colloidal spheres decorated with attractive patches at each pole, have recently generated significant interest as potential building blocks for functional materials. Their inherent anisotropy is known to induce self-assembly into open structures at moderate temperatures and pressures, where they are stabilized over close-packed crystals by entropic effects. We present a numerical investigation of the equilibrium phases of triblock Janus particles with many different patch geometries in three dimensions, using Monte Carlo simulations combined with free energy calculations. In all cases, we find that the free energy difference between crystal polymorphs is less than 0.2 kBT per particle. By varying the patch fraction and interaction range, we show that large patches stabilize the formation of structures with four bonds per patch over those with three. This transition occurs abruptly above a patch fraction of 0.30 and has a strong dependence on the interaction range. Furthermore, we find that a short interaction range favors four bonds per patch, with longer range increasingly stabilizing structures with only three bonds per patch. By quantifying the effect of patch geometry on the stability of the equilibrium crystal structures, we provide insights into the fundamental design rules for constructing complex colloidal crystals. PMID:27609002

  18. Equilibrium & Nonequilibrium Fluctuation Effects in Biopolymer Networks

    NASA Astrophysics Data System (ADS)

    Kachan, Devin Michael

    Fluctuation-induced interactions are an important organizing principle in a variety of soft matter systems. In this dissertation, I explore the role of both thermal and active fluctuations within cross-linked polymer networks. The systems I study are in large part inspired by the amazing physics found within the cytoskeleton of eukaryotic cells. I first predict and verify the existence of a thermal Casimir force between cross-linkers bound to a semi-flexible polymer. The calculation is complicated by the appearance of second order derivatives in the bending Hamiltonian for such polymers, which requires a careful evaluation of the the path integral formulation of the partition function in order to arrive at the physically correct continuum limit and properly address ultraviolet divergences. I find that cross linkers interact along a filament with an attractive logarithmic potential proportional to thermal energy. The proportionality constant depends on whether and how the cross linkers constrain the relative angle between the two filaments to which they are bound. The interaction has important implications for the synthesis of biopolymer bundles within cells. I model the cross-linkers as existing in two phases: bound to the bundle and free in solution. When the cross-linkers are bound, they behave as a one-dimensional gas of particles interacting with the Casimir force, while the free phase is a simple ideal gas. Demanding equilibrium between the two phases, I find a discontinuous transition between a sparsely and a densely bound bundle. This discontinuous condensation transition induced by the long-ranged nature of the Casimir interaction allows for a similarly abrupt structural transition in semiflexible filament networks between a low cross linker density isotropic phase and a higher cross link density bundle network. This work is supported by the results of finite element Brownian dynamics simulations of semiflexible filaments and transient cross-linkers. I

  19. Solving chemical equilibrium problems using nonlinear optimization. [NEWT

    SciTech Connect

    Parkinson, W.J.; Sanderson, J.G.

    1984-06-01

    This report describes a program that will solve general chemical equilibrium problems of the type found in synthetic fossil-fuel plants. The program described here will also solve chemical equilibrium problems that are associated with unit operations that are found in refineries and ammonia plants. The most common problem encountered involves finding the equilibrium composition of a mixture, given feed composition, and the desired equilibrium temperature and pressure. Another less common problem requires the computation of the equilibrium temperature as well as the equilibrium composition for an adiabatic or other nonisothermal reaction. A constrained multidimensional Newton's method is used to solve the common isothermal equilibrium problem. The nonisothermal problem is solved by nesting the same multidimensional Newton's method inside a one-dimensional Newton's method that iterates on temperature. The program allows a gas phase with up to 20 reacting gases and the possibility of one solid phase (graphitic carbon).

  20. Equilibrium properties of a one-dimensional kinetic system.

    NASA Technical Reports Server (NTRS)

    Williams, J. H.; Joyce, G.

    1973-01-01

    One-dimensional systems of N = 500 and 250 particles in equilibrium are numerically simulated utilizing the method of molecular dynamics. Periodic boundary conditions are imposed. The classical two-body interaction potential is short range, repulsive and has a corresponding finite force. The equations of state are determined for densities both less and greater than one. Corresponding theoretical isochores are determined from models based on nearest-neighbor interactions and on a truncated virial expansion, and a comparison is made with the experimental isochores. Time independent radial distributions are constructed numerically and discussed. A change of state from a solidlike state to a fluid-gas state based on the penetrability of the particles is predicted. The transition temperatures are estimated from the radial distribution functions and the nearest-neighbor model. Self-diffusion is observed and the corresponding constants are determined from the velocity autocorrelation functions.

  1. Altering the equilibrium condition in Sr-doped lanthanum manganite.

    SciTech Connect

    Carter, J. D.; Krumpelt, M.; Vaughey, J.; Wang, X.

    1999-05-28

    The material of choice for a solid oxide fuel cell cathode based on a yttria-stabilized zirconia (YSZ) electrolyte is doped lanthanum manganite, (La, Sr)MnO{sub 3}. It excels at many of the attributes necessary for a system to work at the required operating temperature and is flexible enough to allow for materials optimization. Although strontium-doping increases the electronic conductivity of the material, the ionic conductivity of the material remains negligible under operating conditions. Studies have shown that the internal equilibrium of the material heavily favors oxidation of the manganese and rather than the loss of lattice oxygen as a charge compensation mechanism. This lack of oxygen vacancies in the structure retards the ability of the material to conduct oxygen ions; thus the optimized system requires a large number of engineered triple point boundary locations to work efficiently. We have successfully doped the host LSM lattice to alter the interred equilibrium of the material to increase its ionic conductivity and thus lower the cathodic overpotential of the system. Our presentation will discuss these new materials, the results of cell tests, and a number of characterization experiments performed.

  2. Distinguishing two Population Processes with Identical Equilibrium Densities

    NASA Astrophysics Data System (ADS)

    Jakeman, E.; Hopcraft, K. I.; Matthews, J. O.

    2003-04-01

    We analyze the relationship between the evolution of simple population processes and the rate of emigration of individuals. An external monitoring scheme is defined by counting the number leaving the population in fixed time intervals. This is the analogue of photon counting in quantum optics. It is a reasonable measurement in many situations of interest and also has the merit of being analytically tractable. The formalism we develop is used to investigate the statistical and correlation properties of two stochastic population models that give rise to identical first order probability densities. The first is the birth-death- immigration process for which many well-known results can be found in the literature. The second is based on a population sustained by multiple immigration. This model is a generalization of the pair process investigated previously [1]. It can be used to generate populations with a range of equilibrium densities including those with power law tails to be described in a companion paper. Here we show that, in the case of a geometric distribution of multiples, the equilibrium density is negative binomial and higher order joint statistical properties must be used to distinguish the model from the conventional birth-death-immigration process. Formulae characterizing the integrated counting statistics of the two models are derived and it is shown how they may be exploited to achieve this objective.

  3. Electrostatic interaction of two charged macroparticles in an equilibrium plasma

    SciTech Connect

    Filippov, A. V. Pal’, A. F.; Starostin, A. N.

    2015-11-15

    This article is a critical review of publications devoted to studying the electrostatic interaction of two charged macroparticles in an equilibrium plasma. It is shown from an analysis of the force of interaction based on the Maxwell stress tensor that two macroparticles with identical charges in the Poisson–Boltzmann model always repel each other both in isothermal and nonisothermal plasmas. At distances between macroparticles for which the Boltzmann exponents can be linearized, the interaction between macroparticles is completely described by the Debye–Hückel model. The correction to free energy due to the electrostatic interaction in the system of two macroparticles is determined by integrating the correction to the internal energy and by direct calculation of the correction for entropy. It is shown that the free energy coincides with the Yukawa potential. The coincidence of the interaction energy obtained by integrating the force of interaction with the free energy leads to the conclusion about the potential nature of the force of interaction between two macroparticles in an equilibrium plasma. The effect of the outer boundary on the electrostatic interaction force is analyzed; it is shown that the type of interaction depends on the choice of the boundary conditions at the outer boundary. It is also shown that the accumulation of space charge near the outer boundary can lead to the attraction of similarly charged particles at distances comparable with the radius of the outer boundary.

  4. Network representations of knowledge about chemical equilibrium: Variations with achievement

    NASA Astrophysics Data System (ADS)

    Wilson, Janice M.

    This study examined variation in the organization of domain-specific knowledge by 50 Year-12 chemistry students and 4 chemistry teachers. The study used nonmetric multidimensional scaling (MDS) and the Pathfinder network-generating algorithm to investigate individual and group differences in student concepts maps about chemical equilibrium. MDS was used to represent the individual maps in two-dimensional space, based on the presence or absence of paired propositional links. The resulting separation between maps reflected degree of hierarchical structure, but also reflected independent measures of student achievement. Pathfinder was then used to produce semantic networks from pooled data from high and low achievement groups using proximity matrices derived from the frequencies of paired concepts. The network constructed from maps of higher achievers (coherence measure = 0.18, linked pairs = 294, and number of subjects = 32) showed greater coherence, more concordance in specific paired links, more important specific conceptual relationships, and greater hierarchical organization than did the network constructed from maps of lower achievers (coherence measure = 0.12, linked pairs = 552, and number of subjects = 22). These differences are interpreted in terms of qualitative variation in knowledge organization by two groups of individuals with different levels of relative expertise (as reflected in achievement scores) concerning the topic of chemical equilibrium. The results suggest that the technique of transforming paired links in concept maps into proximity matrices for input to multivariate analyses provides a suitable methodology for comparing and documenting changes in the organization and structure of conceptual knowledge within and between individual students.

  5. Static and dynamic properties of large polymer melts in equilibrium

    NASA Astrophysics Data System (ADS)

    Hsu, Hsiao-Ping; Kremer, Kurt

    2016-04-01

    We present a detailed study of the static and dynamic behaviors of long semiflexible polymer chains in a melt. Starting from previously obtained fully equilibrated high molecular weight polymer melts [G. Zhang et al., ACS Macro Lett. 3, 198 (2014)], we investigate their static and dynamic scaling behaviors as predicted by theory. We find that for semiflexible chains in a melt, results of the mean square internal distance, the probability distributions of the end-to-end distance, and the chain structure factor are well described by theoretical predictions for ideal chains. We examine the motion of monomers and chains by molecular dynamics simulations using the ESPResSo++ package. The scaling predictions of the mean squared displacement of inner monomers, center of mass, and relations between them based on the Rouse and the reptation theory are verified, and related characteristic relaxation times are determined. Finally, we give evidence that the entanglement length Ne,PPA as determined by a primitive path analysis (PPA) predicts a plateau modulus, GN 0 = /4 5 ( ρ k B T / N e ) , consistent with stresses obtained from the Green-Kubo relation. These comprehensively characterized equilibrium structures, which offer a good compromise between flexibility, small Ne, computational efficiency, and small deviations from ideality, provide ideal starting states for future non-equilibrium studies.

  6. Comparison of equilibrium and non-equilibrium distribution coefficients for the human drug carbamazepine

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The distribution coefficient (KD) for the human drug carbamazepine was measured using a non-equilibrium technique. Repacked soil columns were prepared using an Airport silt loam (Typic Natrustalf) with an average organic matter content of 2.45%. Carbamazepine solutions were then leached through th...

  7. Equilibrium and non-equilibrium cluster phases in colloids with competing interactions.

    PubMed

    Mani, Ethayaraja; Lechner, Wolfgang; Kegel, Willem K; Bolhuis, Peter G

    2014-07-01

    The phase behavior of colloids that interact via competing interactions - short-range attraction and long-range repulsion - is studied by computer simulation. In particular, for a fixed strength and range of repulsion, the effect of the strength of an attractive interaction (ε) on the phase behavior is investigated at various colloid densities (ρ). A thermodynamically stable equilibrium colloidal cluster phase, consisting of compact crystalline clusters, is found below the fluid-solid coexistence line in the ε-ρ parameter space. The mean cluster size is found to linearly increase with the colloid density. At large ε and low densities, and at small ε and high densities, a non-equilibrium cluster phase, consisting of elongated Bernal spiral-like clusters, is observed. Although gelation can be induced either by increasing ε at constant density or vice versa, the gelation mechanism is different in either route. While in the ρ route gelation occurs via a glass transition of compact clusters, gelation in the ε route is characterized by percolation of elongated clusters. This study both provides the location of equilibrium and non-equilibrium cluster phases with respect to the fluid-solid coexistence, and reveals the dependencies of the gelation mechanism on the preparation route.

  8. An approximate method for calculating composition of the non-equilibrium explosion products of hydrocarbons and oxygen

    NASA Astrophysics Data System (ADS)

    Shargatov, V. A.; Gubin, S. A.; Okunev, D. Yu

    2016-09-01

    We develop a method for calculating the changes in composition of the explosion products in the case where the complete chemical equilibrium is absent but the bimolecular reactions are in quasi-equilibrium with the exception bimolecular reactions with one of the components of the mixture. We investigate the possibility of using the method of "quasiequilibrium" for mixtures of hydrocarbons and oxygen. The method is based on the assumption of the existence of the partial chemical equilibrium in the explosion products. Without significant loss of accuracy to the solution of stiff differential equations detailed kinetic mechanism can be replaced by one or two differential equation and a system of algebraic equations. This method is always consistent with the detailed mechanism and can be used separately or in conjunction with the solution of a stiff system for chemically non-equilibrium mixtures replacing it when bimolecular reactions are near to equilibrium.

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

    SciTech Connect

    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 DNA duplex unbinding and show that the reconstruction accurately predicts duplex melting enthalpy.

  10. Selection maintaining protein stability at equilibrium.

    PubMed

    Miyazawa, Sanzo

    2016-02-21

    The common understanding of protein evolution has been that neutral mutations are fixed by random drift, and a proportion of neutral mutations depending on the strength of structural and functional constraints primarily determines evolutionary rate. Recently it was indicated that fitness costs due to misfolded proteins are a determinant of evolutionary rate and selection originating in protein stability is a driving force of protein evolution. Here we examine protein evolution under the selection maintaining protein stability. Protein fitness is a generic form of fitness costs due to misfolded proteins; s=κexp(ΔG/kT)(1-exp(ΔΔG/kT)), where s and ΔΔG are selective advantage and stability change of a mutant protein, ΔG is the folding free energy of the wildtype protein, and κ is a parameter representing protein abundance and indispensability. The distribution of ΔΔG is approximated to be a bi-Gaussian distribution, which represents structurally slightly- or highly-constrained sites. Also, the mean of the distribution is negatively proportional to ΔG. The evolution of this gene has an equilibrium point (ΔGe) of protein stability, the range of which is consistent with observed values in the ProTherm database. The probability distribution of Ka/Ks, the ratio of nonsynonymous to synonymous substitution rate per site, over fixed mutants in the vicinity of the equilibrium shows that nearly neutral selection is predominant only in low-abundant, non-essential proteins of ΔGe>-2.5 kcal/mol. In the other proteins, positive selection on stabilizing mutations is significant to maintain protein stability at equilibrium as well as random drift on slightly negative mutations, although the average 〈Ka/Ks〉 is less than 1. Slow evolutionary rates can be caused by both high protein abundance/indispensability and large effective population size, which produces positive shifts of ΔΔG through decreasing ΔGe, and strong structural constraints, which directly make

  11. Using Performance Reference Compounds (PRCs) to measure dissolved water concentrations (Cfree) in the water column: Assessing equilibrium models

    EPA Science Inventory

    Equilibrium-based passive sampling methods are often used in aquatic environmental monitoring to measure hydrophobic organic contaminants (HOCs) and in the subsequent evaluation of their effects on ecological and human health. HOCs freely dissolved in water (Cfree) will partition...

  12. Equilibrium pricing in an order book environment: Case study for a spin model

    NASA Astrophysics Data System (ADS)

    Meudt, Frederik; Schmitt, Thilo A.; Schäfer, Rudi; Guhr, Thomas

    2016-07-01

    When modeling stock market dynamics, the price formation is often based on an equilibrium mechanism. In real stock exchanges, however, the price formation is governed by the order book. It is thus interesting to check if the resulting stylized facts of a model with equilibrium pricing change, remain the same or, more generally, are compatible with the order book environment. We tackle this issue in the framework of a case study by embedding the Bornholdt-Kaizoji-Fujiwara spin model into the order book dynamics. To this end, we use a recently developed agent based model that realistically incorporates the order book. We find realistic stylized facts. We conclude for the studied case that equilibrium pricing is not needed and that the corresponding assumption of a "fundamental" price may be abandoned.

  13. Equilibrium and Kinetics of Block Copolymers Micelles

    NASA Astrophysics Data System (ADS)

    Mysona, Joshua; Morse, David

    Both equilibrium properties of micelles, such as the critical micelle concentration (CMC), and dynamical properties such as the micelle lifetime are difficult to study in simulations because of the slow dynamics of the processes by which micelles are created and destroyed. We first discuss a method of precisely identifying the CMC in a simple model of block copolymer micelles in a homopolymer matrix, which makes use of thermodynamic integration to compute the free energy of formation. We then examine the free energy barriers to competing mechanisms for creating and destroying micelles, which could occur predominantly either by a step-wise process involving insertion and extraction of single molecules or by fission and fusion of entire micelles.

  14. Anisotropic pressure tokamak equilibrium and stability considerations

    SciTech Connect

    Salberta, E.R.; Grimm, R.C.; Johnson, J.L.; Manickam, J.; Tang, W.M.

    1987-02-01

    Investigation of the effect of pressure anisotropy on tokamak equilibrium and stability is made with an MHD model. Realistic perpendicular and parallel pressure distributions, P/sub perpendicular/(psi,B) and P/sub parallel/(psi,B), are obtained by solving a one-dimensional Fokker-Planck equation for neutral beam injection to find a distribution function f(E, v/sub parallel//v) at the position of minimum field on each magnetic surface and then using invariance of the magnetic moment to determine its value at each point on the surface. The shift of the surfaces of constant perpendicular and parallel pressure from the flux surfaces depends strongly on the angle of injection. This shift explains the observed increase or decrease in the stability conditions. Estimates of the stabilizing effect of hot trapped ions indicates that a large fraction must be nonresonant and thus decoupled from the bad curvature before it becomes important.

  15. Thermal equilibrium of two quantum Brownian particles

    SciTech Connect

    Valente, D. M.; Caldeira, A. O.

    2010-01-15

    The influence of the environment in the thermal equilibrium properties of a bipartite continuous variable quantum system is studied. The problem is treated within a system-plus-reservoir approach. The considered model reproduces the Brownian motion when the two particles are isolated and induces an effective interaction between them, depending on the choice of the spectral function of the bath. The coupling between the system and the environment guarantees the translational invariance of the system in the absence of an external potential. The entanglement between the particles is measured by the logarithmic negativity, which is shown to monotonically decrease with the increase of the temperature. A range of finite temperatures is found in which entanglement is still induced by the reservoir.

  16. Equilibrium properties of chemically reacting gases

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The equilibrium energy, enthalpy, entropy, specific heat at constant volume and constant pressure, and the equation of state of the gas are all derived for chemically reacting gas mixtures in terms of the compressibility, the mol fractions, the thermodynamic properties of the pure gas components, and the change in zero point energy due to reaction. Results are illustrated for a simple diatomic dissociation reaction and nitrogen is used as an example. Next, a gas mixture resulting from combined diatomic dissociation and atomic ionization reactions is treated and, again, nitrogen is used as an example. A short discussion is given of the additional complexities involved when precise solutions for high-temperature air are desired, including effects caused by NO produced in shuffle reactions and by other trace species formed from CO2, H2O and Ar found in normal air.

  17. Radiative equilibrium model of Titan's atmosphere

    NASA Technical Reports Server (NTRS)

    Samuelson, R. E.

    1983-01-01

    The present global radiative equilibrium model for the Saturn satellite Titan is restricted to the two-stream approximation, is vertically homogeneous in its scattering properties, and is spectrally divided into one thermal and two solar channels. Between 13 and 33% of the total incident solar radiation is absorbed at the planetary surface, and the 30-60 ratio of violet to thermal IR absorption cross sections in the stratosphere leads to the large temperature inversion observed there. The spectrally integrated mass absorption coefficient at thermal wavelengths is approximately constant throughout the stratosphere, and approximately linear with pressure in the troposphere, implying the presence of a uniformly mixed aerosol in the stratosphere. There also appear to be two regions of enhanced opacity near 30 and 500 mbar.

  18. Hall MHD Equilibrium of Accelerated Compact Toroids

    NASA Astrophysics Data System (ADS)

    Howard, S. J.; Hwang, D. Q.; Horton, R. D.; Evans, R. W.; Brockington, S. J.

    2007-11-01

    We examine the structure and dynamics of the compact toroid's magnetic field. The compact toroid is dramatically accelerated by a large rail-gun Lorentz force density equal to j xB. We use magnetic data from the Compact Toroid Injection Experiment to answer the question of exactly where in the system j xB has nonzero values, and to what extent we can apply the standard model of force-free equilibrium. In particular we present a method of analysis of the magnetic field probe signals that allows direct comparison to the predictions of the Woltjer-Taylor force-free model and Turner's generalization of magnetic relaxation in the presence of a non-zero Hall term and fluid vorticity.

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  20. Chemical bonding and the equilibrium composition of Grignard reagents in ethereal solutions.

    PubMed

    Henriques, André M; Barbosa, André G H

    2011-11-10

    A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et(2)O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R(•), R(-), (•)MgX, and RMgX(2)(-) must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a "radical-based" pathway, and fluoride must follow a "carbanionic-based" pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.

  1. A Progression of Static Equilibrium Laboratory Exercises

    NASA Astrophysics Data System (ADS)

    Kutzner, Mickey; Kutzner, Andrew

    2013-10-01

    Although simple architectural structures like bridges, catwalks, cantilevers, and Stonehenge have been integral in human societies for millennia, as have levers and other simple tools, modern students of introductory physics continue to grapple with Newton's conditions for static equilibrium. As formulated in typical introductory physics textbooks, these two conditions appear as ΣF=0(1) and Στ=0,(2) where each torque τ is defined as the cross product between the lever arm vector r and the corresponding applied force F, τ =r×F,(3) having magnitude, τ =Frsinθ.(4) The angle θ here is between the two vectors F and r. In Eq. (1), upward (downward) forces are considered positive (negative). In Eq. (2), counterclockwise (clockwise) torques are considered positive (negative). Equation (1) holds that the vector sum of the external forces acting on an object must be zero to prevent linear accelerations; Eq. (2) states that the vector sum of torques due to external forces about any axis must be zero to prevent angular accelerations. In our view these conditions can be problematic for students because a) the equations contain the unfamiliar summation notation Σ, b) students are uncertain of the role of torques in causing rotations, and c) it is not clear why the sum of torques is zero regardless of the choice of axis. Gianino5 describes an experiment using MBL and a force sensor to convey the meaning of torque as applied to a rigid-body lever system without exploring quantitative aspects of the conditions for static equilibrium.

  2. Radiation temperature of non-equilibrium plasmas

    SciTech Connect

    Arunasalam, V.

    1991-07-01

    In fusion devices measurements of the radiation temperature T{sub r} ({omega}, k) near the electron cyclotron frequency {omega}{sub C} and the second harmonic 2{omega}{sub C} in directions nearly perpendicular to the confining magnetic field B (i.e., k {approx} k {perpendicular}) serve to map out the electron temperature profiles T{sub e}(r,t). For optically thick plasma at thermodynamic equilibrium T{sub r} = T{sub e}. However, there is increasing experimental evidence for the presence of non-equilibrium electron distributions (such as a drifting Maxwellian with appreciable values of the streaming parameter {omicron} = v{sub d}/v{sub t}, a bi- Maxwellian, and anisotropic Maxwellian with T {perpendicular} {ne} T {parallel}, etc.,) in tokamak plasmas, especially in the presence of radio-frequency heating. Here, we examine (both non-relativistically and relativistically) the dependence of T{sub r} on {omicron}, T{perpendicular}/T{parallel}, T{sub h}/T{sub b}, n{sub h}/n{sub b}etc., where n{sub b}, n{sub h}, T{sub b}, T{sub h} are the densities and temperatures, respectively, of the bulk and the hot components of the bi-Maxwellian plasma. Our bi-Maxwellian results predict that the ratio T{sub r}/T{sub e} is a very sensitive function of the ratios n{sub h}/n{sub b} and T{sub h}/T{sub b}. Further, these relativistic and non-relativistic results satisfy the well-known limit c {yields} {infinity} correspondence principle'', showing that the intensity of the emission and absorption line is independent of the line broadening mechanism. 44 refs., 2 figs.

  3. Shear viscosity and out of equilibrium dynamics

    SciTech Connect

    El, Andrej; Xu Zhe; Greiner, Carsten; Muronga, Azwinndini

    2009-04-15

    Using Grad's method, we calculate the entropy production and derive a formula for the second-order shear viscosity coefficient in a one-dimensionally expanding particle system, which can also be considered out of chemical equilibrium. For a one-dimensional expansion of gluon matter with Bjorken boost invariance, the shear tensor and the shear viscosity to entropy density ratio {eta}/s are numerically calculated by an iterative and self-consistent prescription within the second-order Israel-Stewart hydrodynamics and by a microscopic parton cascade transport theory. Compared with {eta}/s obtained using the Navier-Stokes approximation, the present result is about 20% larger at a QCD coupling {alpha}{sub s}{approx}0.3 (with {eta}/s{approx_equal}0.18) and is a factor of 2-3 larger at a small coupling {alpha}{sub s}{approx}0.01. We demonstrate an agreement between the viscous hydrodynamic calculations and the microscopic transport results on {eta}/s, except when employing a small {alpha}{sub s}. On the other hand, we demonstrate that for such small {alpha}{sub s}, the gluon system is far from kinetic and chemical equilibrium, which indicates the break down of second-order hydrodynamics because of the strong nonequilibrium evolution. In addition, for large {alpha}{sub s} (0.3-0.6), the Israel-Stewart hydrodynamics formally breaks down at large momentum p{sub T} > or approx. 3 GeV but is still a reasonably good approximation.

  4. Uncertainty Quantification of Equilibrium Climate Sensitivity

    NASA Astrophysics Data System (ADS)

    Lucas, D. D.; Brandon, S. T.; Covey, C. C.; Domyancic, D. M.; Johannesson, G.; Klein, R.; Tannahill, J.; Zhang, Y.

    2011-12-01

    Significant uncertainties exist in the temperature response of the climate system to changes in the levels of atmospheric carbon dioxide. We report progress to quantify the uncertainties of equilibrium climate sensitivity using perturbed parameter ensembles of the Community Earth System Model (CESM). Through a strategic initiative at the Lawrence Livermore National Laboratory, we have been developing uncertainty quantification (UQ) methods and incorporating them into a software framework called the UQ Pipeline. We have applied this framework to generate a large number of ensemble simulations using Latin Hypercube and other schemes to sample up to three dozen uncertain parameters in the atmospheric (CAM) and sea ice (CICE) model components of CESM. The parameters sampled are related to many highly uncertain processes, including deep and shallow convection, boundary layer turbulence, cloud optical and microphysical properties, and sea ice albedo. An extensive ensemble database comprised of more than 46,000 simulated climate-model-years of recent climate conditions has been assembled. This database is being used to train surrogate models of CESM responses and to perform statistical calibrations of the CAM and CICE models given observational data constraints. The calibrated models serve as a basis for propagating uncertainties forward through climate change simulations using a slab ocean model configuration of CESM. This procedure is being used to quantify the probability density function of equilibrium climate sensitivity accounting for uncertainties in climate model processes. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and was funded by the Uncertainty Quantification Strategic Initiative Laboratory Directed Research and Development Project at LLNL under project tracking code 10-SI-013. (LLNL-ABS-491765)

  5. Lower Bound on Earth's Transient and Equilibrium Climate Sensitivities

    NASA Astrophysics Data System (ADS)

    Schwartz, S. E.; Bengtsson, L.

    2012-12-01

    Earth's equilibrium climate sensitivity, the change in global mean near-surface air temperature Ts that would ultimately be attained in response to a sustained change of the radiative budget (forcing F) ratioed to the forcing, is a key geophysical property of Earth's climate system and an important index of the susceptibility of the climate to perturbations in the radiation budget. Here we distinguish between the transient sensitivity Str, which is reached on the time scale of a decade and which likely represents the majority of the climate system response, and the equilibrium sensitivity Seq, which would be reached only on a time scale of 1000 years or so. Climate sensitivity has been resistant to confident determination either by models or by empirical inference, with best estimate of the central value of the equilibrium sensitivity, expressed as a CO2 doubling temperature ΔT2×,eq = F2×Seq, where F2× is the forcing for doubled CO2, 3.7 W m-2, and 1-σ uncertainty range 3 (2 - 4.5) K. Here we use measurements of change in Ts and current estimates of change in forcing by long-lived greenhouse gases, LLGHGs, over the period 1970 - 2010, Figure 1, to determine what we consider a lower bound on Str, 0.39 ± 0.05 K (W m-2)-1, equivalent to ΔT2×,tr = 1.5 ± 0.2 K (1-σ), arguing that changes in other forcings over this period would be negative and therefore result in an actual sensitivity greater than this value. Equilibrium sensitivity is related to transient sensitivity through the planetary heating rate N. Here we use current (Levitus et al., GRL, 2012) assessment of the heating rate of the world ocean together with estimates of other heat sinks to determine N = 0.37 ± 0.03 W m-2 over the same period, from which we obtain a lower bound to Earth's equilibrium sensitivity Seq, 0.55 ± 0.11 K (W m-2)-1, equivalent to ΔT2×,eq = 2.0 ± 0.40 K (1-σ). Actual climate sensitivity, determined similarly but accounting for change in tropospheric aerosol forcing over

  6. Path integral Liouville dynamics for thermal equilibrium systems

    SciTech Connect

    Liu, Jian

    2014-06-14

    We show a new imaginary time path integral based method—path integral Liouville dynamics (PILD), which can be derived from the equilibrium Liouville dynamics [J. Liu and W. H. Miller, J. Chem. Phys. 134, 104101 (2011)] in the Wigner phase space. Numerical tests of PILD with the simple (white noise) Langevin thermostat have been made for two strongly anharmonic model problems. Since implementation of PILD does not request any specific form of the potential energy surface, the results suggest that PILD offers a potentially useful approach for general condensed phase molecular systems to have the two important properties: conserves the quantum canonical distribution and recovers exact thermal correlation functions (of even nonlinear operators, i.e., nonlinear functions of position or momentum operators) in the classical, high temperature, and harmonic limits.

  7. Biological Implications of Dynamical Phases in Non-equilibrium Networks

    NASA Astrophysics Data System (ADS)

    Murugan, Arvind; Vaikuntanathan, Suriyanarayanan

    2016-03-01

    Biology achieves novel functions like error correction, ultra-sensitivity and accurate concentration measurement at the expense of free energy through Maxwell Demon-like mechanisms. The design principles and free energy trade-offs have been studied for a variety of such mechanisms. In this review, we emphasize a perspective based on dynamical phases that can explain commonalities shared by these mechanisms. Dynamical phases are defined by typical trajectories executed by non-equilibrium systems in the space of internal states. We find that coexistence of dynamical phases can have dramatic consequences for function vs free energy cost trade-offs. Dynamical phases can also provide an intuitive picture of the design principles behind such biological Maxwell Demons.

  8. Honeybee combs: construction through a liquid equilibrium process?

    NASA Astrophysics Data System (ADS)

    Pirk, C. W. W.; Hepburn, H. R.; Radloff, S. E.; Tautz, J.

    Geometrical investigations of honeycombs and speculations on how honeybees measure and construct the hexagons and rhombi of their cells are centuries old. Here we show that honeybees neither have to measure nor construct the highly regular structures of a honeycomb, and that the observed pattern of combs can be parsimoniously explained by wax flowing in liquid equilibrium. The structure of the combs of honeybees results from wax as a thermoplastic building medium, which softens and hardens as a result of increasing and decreasing temperatures. It flows among an array of transient, close-packed cylinders which are actually the self-heated honeybees themselves. The three apparent rhomboids forming the base of each cell do not exist but arise as optical artefacts from looking through semi-transparent combs.

  9. A Variational Method in Out-of-Equilibrium Physical Systems

    PubMed Central

    Pinheiro, Mario J.

    2013-01-01

    We propose a new variational principle for out-of-equilibrium dynamic systems that are fundamentally based on the method of Lagrange multipliers applied to the total entropy of an ensemble of particles. However, we use the fundamental equation of thermodynamics on differential forms, considering U and S as 0-forms. We obtain a set of two first order differential equations that reveal the same formal symplectic structure shared by classical mechanics, fluid mechanics and thermodynamics. From this approach, a topological torsion current emerges of the form , where Aj and ωk denote the components of the vector potential (gravitational and/or electromagnetic) and where ω denotes the angular velocity of the accelerated frame. We derive a special form of the Umov-Poynting theorem for rotating gravito-electromagnetic systems. The variational method is then applied to clarify the working mechanism of particular devices. PMID:24316718

  10. Development of unified Reynolds stress models for non-equilibrium turbulent flows

    NASA Astrophysics Data System (ADS)

    Xu, Xiang-Hua

    Turbulence modeling has played a major role in the calculation of turbulent flows of engineering importance. To solve the flow problems that arise in both nature and engineering, a variety of Reynolds stress models--including simple eddy viscosity models based on the Prandtl mixing length hypothesis, one-equation and two-equation models, nonlinear two-equation and explicit algebraic stress models, as well as full second-order closures--have been proposed during the past few decades. These models, which are typically based on benchmark near-equilibrium turbulence experimental data, perform fairly well in a variety of turbulent flows that are not far from equilibrium. However, it is now well recognized that these models cannot correctly predict turbulent flows that are far from equilibrium. In this dissertation, it is shown that they cannot even properly predict homogeneous turbulent flows that are in strongly strained non-equilibrium states. Two benchmark flows--homogeneous turbulent shear flow and homogeneous plane strain turbulence--are chosen to evaluate the performance of existing turbulence models since these two benchmark flows constitute idealizations of real engineering turbulent flows. It is found that none of the existing Reynolds stress models (including a recent version of a non-equilibrium, near-wall model) can predict results that compare favorably with Rapid Distortion Theory (RDT) in strongly distorted turbulent flows that are far from equilibrium. Moreover, it is demonstrated that the standard linear and nonlinear two-equation models can predict enormous negative values of the normal Reynolds stresses in non-equilibrium homogeneous turbulence that strongly violate basic realizability constraints. In light of the poor performance of existing Reynolds stress models in non-equilibrium homogeneous turbulence, two new Reynolds stress models are developed herein--an explicit algebraic stress model and a full second-order closure--that can correctly

  11. Statistical physics of shear flow: a non-equilibrium problem

    NASA Astrophysics Data System (ADS)

    Evans, R. M. L.

    2010-09-01

    Complex fluids are easily and reproducibly driven into non-equilibrium steady states by the action of shear flow. The statistics of the microstructure of non-equilibrium fluids is important to the material properties of every complex fluid that flows, e.g. axle grease on a rotating bearing; blood circulating in capillaries; molten plastic flowing into a mould; the non-equilibrium onion phase of amphiphiles used for drug delivery; the list is endless. Such states are as diverse and interesting as equilibrium states, but are not governed by the same statistics as equilibrium materials. I review some recently discovered principles governing the probabilities of various types of molecular re-arrangements taking place within a sheared fluid. As well as providing new foundations for the study of non-equilibrium matter, the principles are applied to some simple models of particles interacting under flow, showing that the theory exhibits physically convincing behaviour.

  12. Equilibrium & Nonequilibrium Fluctuation Effects in Biopolymer Networks

    NASA Astrophysics Data System (ADS)

    Kachan, Devin Michael

    Fluctuation-induced interactions are an important organizing principle in a variety of soft matter systems. In this dissertation, I explore the role of both thermal and active fluctuations within cross-linked polymer networks. The systems I study are in large part inspired by the amazing physics found within the cytoskeleton of eukaryotic cells. I first predict and verify the existence of a thermal Casimir force between cross-linkers bound to a semi-flexible polymer. The calculation is complicated by the appearance of second order derivatives in the bending Hamiltonian for such polymers, which requires a careful evaluation of the the path integral formulation of the partition function in order to arrive at the physically correct continuum limit and properly address ultraviolet divergences. I find that cross linkers interact along a filament with an attractive logarithmic potential proportional to thermal energy. The proportionality constant depends on whether and how the cross linkers constrain the relative angle between the two filaments to which they are bound. The interaction has important implications for the synthesis of biopolymer bundles within cells. I model the cross-linkers as existing in two phases: bound to the bundle and free in solution. When the cross-linkers are bound, they behave as a one-dimensional gas of particles interacting with the Casimir force, while the free phase is a simple ideal gas. Demanding equilibrium between the two phases, I find a discontinuous transition between a sparsely and a densely bound bundle. This discontinuous condensation transition induced by the long-ranged nature of the Casimir interaction allows for a similarly abrupt structural transition in semiflexible filament networks between a low cross linker density isotropic phase and a higher cross link density bundle network. This work is supported by the results of finite element Brownian dynamics simulations of semiflexible filaments and transient cross-linkers. I

  13. Charge states of energetic tellurium ions: Equilibrium and non-equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Kartavykh, Y.; Droege, W.; Klecker, B.; Kocharov, L.; Moebius, E.

    2007-12-01

    Recently, very high abundances of ultraheavy ions were observed in impulsive SEP events, compared to coronal abundances with enrichment factors of >100 for atomic mass > 100 amu. Because wave/particle interaction processes, as discussed for heavy ion enrichment and acceleration, depend critically on the mass per charge (M/Q) of the ions, an estimate of the ionic charge is very important for model calculations. In any realistic acceleration model one would have to use the ionization and recombination rates of these ions as a function of energy, because charge changing processes in the solar corona are inevitable and energy dependent. As an example of high mass ions, we calculate the equilibrium and non-equilibrium charge states for tellurium ions (Te, nuclear charge 52), and present a method to estimate the cross sections and rates for ionization and recombination of ions with arbitrary nuclear charge Z and atomic mass number A.

  14. Equilibrium and nonequilibrium dynamics of soft sphere fluids.

    PubMed

    Ding, Yajun; Mittal, Jeetain

    2015-07-14

    We use computer simulations to test the freezing-point scaling relationship between equilibrium transport coefficients (self-diffusivity, viscosity) and thermodynamic parameters for soft sphere fluids. The fluid particles interact via the inverse-power potential (IPP), and the particle softness is changed by modifying the exponent of the distance-dependent potential term. In the case of IPP fluids, density and temperature are not independent variables and can be combined to obtain a coupling parameter to define the thermodynamic state of the system. We find that the rescaled coupling parameter, based on its value at the freezing point, can approximately collapse the diffusivity and viscosity data for IPP fluids over a wide range of particle softness. Even though the collapse is far from perfect, the freezing-point scaling relationship provides a convenient and effective way to compare the structure and dynamics of fluid systems with different particle softness. We further show that an alternate scaling relationship based on two-body excess entropy can provide an almost perfect collapse of the diffusivity and viscosity data below the freezing transition. Next, we perform nonequilibrium molecular dynamics simulations to calculate the shear-dependent viscosity and to identify the distinct role of particle softness in underlying structural changes associated with rheological properties. Qualitatively, we find a similar shear-thinning behavior for IPP fluids with different particle softness, though softer particles exhibit stronger shear-thinning tendency. By investigating the distance and angle-dependent pair correlation functions in these systems, we find different structural features in the case of IPP fluids with hard-sphere like and softer particle interactions. Interestingly, shear-thinning in hard-sphere like fluids is accompanied by enhanced translational order, whereas softer fluids exhibit loss of order with shear. Our results provide a systematic evaluation

  15. Equilibrium Initialization and Stability of Three-Dimensional Gas Disks

    SciTech Connect

    Wang, Hsiang-Hsu; Klessen, Ralf S.; Dullemond, Cornelis P.; Bosch, Frank C.van den; Fuchs, Burkhard; /KIPAC, Menlo Park

    2010-08-25

    We present a new systematic way of setting up galactic gas disks based on the assumption of detailed hydrodynamic equilibrium. To do this, we need to specify the density distribution and the velocity field which supports the disk. We first show that the required circular velocity has no dependence on the height above or below the midplane so long as the gas pressure is a function of density only. The assumption of disks being very thin enables us to decouple the vertical structure from the radial direction. Based on that, the equation of hydrostatic equilibrium together with the reduced Poisson equation leads to two sets of second-order non-linear differential equation, which are easily integrated to set-up a stable disk. We call one approach 'density method' and the other one 'potential method'. Gas disks in detailed balance are especially suitable for investigating the onset of the gravitational instability. We revisit the question of global, axisymmetric instability using fully three-dimensional disk simulations. The impact of disk thickness on the disk instability and the formation of spontaneously induced spirals is studied systematically with or without the presence of the stellar potential. In our models, the numerical results show that the threshold value for disk instability is shifted from unity to 0.69 for self-gravitating thick disks and to 0.75 for combined stellar and gas thick disks. The simulations also show that self-induced spirals occur in the correct regions and with the right numbers as predicted by the analytic theory.

  16. The Lewis Chemical Equilibrium Program with parametric study capability

    NASA Technical Reports Server (NTRS)

    Sevigny, R.

    1981-01-01

    The program was developed to determine chemical equilibrium in complex systems. Using a free energy minimization technique, the program permits calculations such as: chemical equilibrium for assigned thermodynamic states; theoretical rocket performance for both equilibrium and frozen compositions during expansion; incident and reflected shock properties; and Chapman-Jouget detonation properties. It is shown that the same program can handle solid coal in an entrained flow coal gasification problem.

  17. Abrupt PN junctions: Analytical solutions under equilibrium and non-equilibrium

    NASA Astrophysics Data System (ADS)

    Khorasani, Sina

    2016-08-01

    We present an explicit solution of carrier and field distributions in abrupt PN junctions under equilibrium. An accurate logarithmic numerical method is implemented and results are compared to the analytical solutions. Analysis of results shows reasonable agreement with numerical solution as well as the depletion layer approximation. We discuss extensions to the asymmetric junctions. Approximate relations for differential capacitance C-V and current-voltage I-V characteristics are also found under non-zero external bias.

  18. Modeling rocky coastline evolution and equilibrium

    NASA Astrophysics Data System (ADS)

    Limber, P. W.; Murray, A. B.

    2010-12-01

    Many of the world’s rocky coastlines exhibit planform roughness in the form of alternating headlands and embayments. Along cliffed coasts, it is often assumed that headlands consist of rock that is more resistant to wave attack than in neighboring bays, because of either structural or lithologic variations. Bays would then retreat landward faster than headlands, creating the undulating planform profiles characteristic of a rocky coastal landscape. While the interplay between alongshore rock strength and nearshore wave energy is, in some circumstances, a fundamental control on coastline shape, beach sediment is also important. Laboratory experiments and field observations have shown that beach sediment, in small volumes, can act as an abrasive tool to encourage sea cliff retreat. In large volumes, though, sediment discourages wave attack on the cliff face, acting as a protective barrier. This nonlinearity suggests a means for headland persistence, even without alongshore variations in rock strength: bare-rock headlands could retreat more slowly than, or at the same rate as, neighboring sediment-filled embayments because of alongshore variations in the availability of beach sediment. Accordingly, nearshore sediment dynamics (i.e. sediment production from sea cliff retreat and alongshore sediment transport) could promote the development of autogenic planform geometry. To explore these ideas, we present numerical and analytical modeling of large-scale (> one kilometer) and long-term (millennial-scale) planform rocky coastline evolution, in which sediment is supplied by both sea cliff erosion and coastal rivers and is distributed by alongshore sediment transport. We also compare model predictions with real landscapes. Previously, our modeling exercises focused on a basic rocky coastline configuration where lithologically-homogeneous sea cliffs supplied all beach sediment and maintained a constant alongshore height. Results showed that 1) an equilibrium alongshore

  19. Equilibrium and non-equilibrium thermodynamics of templating reactions for the formation of nanowires

    NASA Astrophysics Data System (ADS)

    Watson, Scott M. D.; Houlton, Andrew; Horrocks, Benjamin R.

    2012-12-01

    The thermodynamics of the templating of materials on one-dimensional templates, such as DNA, is modeled by considering two terms: the surface tension of the material (γ) and a line energy (σ = 2πrTγT) that represents the adhesion of the material to the template (radius rT). We show that as long as the reaction stoichiometry does not exceed a certain limit (\\sqrt{\\frac{3 v}{2 \\pi }}\\lt {r}_{T}\\frac{\\vert {\\gamma }_{T}\\vert }{\\gamma }; v = volume of material per unit length of template) then a sample of smooth, uniform wires is the equilibrium state. If the amount of material exceeds this limit, then the material will comprise a single macroscopic particle at equilibrium. The behavior of the system is similar to a morphological wetting transition and the model can rationalize the available experimental data on the reaction conditions required to form smooth DNA-templated nanowires. Using the framework of linear non-equilibrium thermodynamics, we also show that the model can describe qualitatively the observed evolution of these nanostructures from beads-on-a-string morphologies to smooth nanowires and construct a stochastic differential equation for the process. Numerical simulations and scaling arguments suggest that the same scaling behavior as the Edwards-Wilkinson equation is observed.

  20. Equilibrium econophysics: A unified formalism for neoclassical economics and equilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Sousa, Tânia; Domingos, Tiago

    2006-11-01

    We develop a unified conceptual and mathematical structure for equilibrium econophysics, i.e., the use of concepts and tools of equilibrium thermodynamics in neoclassical microeconomics and vice versa. Within this conceptual structure the results obtained in microeconomic theory are: (1) the definition of irreversibility in economic behavior; (2) the clarification that the Engel curve and the offer curve are not descriptions of real processes dictated by the maximization of utility at constant endowment; (3) the derivation of a relation between elasticities proving that economic elasticities are not all independent; (4) the proof that Giffen goods do not exist in a stable equilibrium; (5) the derivation that ‘economic integrability’ is equivalent to the generalized Le Chatelier principle and (6) the definition of a first order phase transition, i.e., a transition between separate points in the utility function. In thermodynamics the results obtained are: (1) a relation between the non-dimensional isothermal and adiabatic compressibilities and the increase or decrease in the thermodynamic potentials; (2) the distinction between mathematical integrability and optimization behavior and (3) the generalization of the Clapeyron equation.