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Sample records for eranos based equilibrium

  1. Sensitivity analysis of Monju using ERANOS with JENDL-4.0

    SciTech Connect

    Tamagno, P.; Van Rooijen, W. F. G.; Takeda, T.; Konomura, M.

    2012-07-01

    This paper deals with sensitivity analysis using JENDL-4.0 nuclear data applied to the Monju reactor. In 2010 the Japan Atomic Energy Agency - JAEA - released a new set of nuclear data: JENDL-4.0. This new evaluation is expected to contain improved data on actinides and covariance matrices. Covariance matrices are a key point in quantification of uncertainties due to basic nuclear data. For sensitivity analysis, the well-established ERANOS [1] code was chosen because of its integrated modules that allow users to perform a sensitivity analysis of complex reactor geometries. A JENDL-4.0 cross-section library is not available for ERANOS. Therefore a cross-section library had to be made from the original nuclear data set, available as ENDF formatted files. This is achieved by using the following codes: NJOY, CALENDF, MERGE and GECCO in order to create a library for the ECCO cell code (part of ERANOS). In order to make sure of the accuracy of the new ECCO library, two benchmark experiments have been analyzed: the MZA and MZB cores of the MOZART program measured at the ZEBRA facility in the UK. These were chosen due to their similarity to the Monju core. Using the JENDL-4.0 ECCO library we have analyzed the criticality of Monju during the restart in 2010. We have obtained good agreement with the measured criticality. Perturbation calculations have been performed between JENDL-3.3 and JENDL-4.0 based models. The isotopes {sup 239}Pu, {sup 238}U, {sup 241}Am and {sup 241}Pu account for a major part of observed differences. (authors)

  2. 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.

  3. Evaluation of AGNI SFR core neutronics parameters with VESTA and ERANOS

    NASA Astrophysics Data System (ADS)

    Ecrabet, Fabrice; Haeck, Wim; Chaitanya Tadepalli, Sai

    2014-06-01

    This paper presents the calculation of core neutronics parameters for so called AGNI Sodium Fast Reactor (SFR) model performed with ERANOS code and Monte Carlo depletion interface software VESTA. The AGNI core has been developed at IRSN for its own R&D needs, i.e. to test performance of calculation codes for safety assessment of a generation IV SFR project. The ERANOS code is used as reference code for SFR core calculations at IRSN. In this work, VESTA calculations have been performed and compared with corresponding ERANOS results. These calculations have a double purpose: mastering the use of tools for the evaluation of SFR core static neutronics parameters and validate the use of VESTA for SFR cores.

  4. 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.

  5. 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…

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

    NASA Astrophysics Data System (ADS)

    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.

  7. 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.

  8. 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.

  9. Punctuated equilibrium based on a locally ambiguous niche.

    PubMed

    Gunji, Yukio-Pegio; Sakiyama, Tomoko; Murakami, Hisashi

    2014-09-01

    Punctuated equilibrium, recently regarded as the power law distribution of lifespan, is estimated with respect to self-organized criticality. Previous explanations were based on a global property, such as the selection of species depending on their fitness, however a particular entity defined through such global property cannot be relevant to the notion of "self". Here, we introduce local ambiguity of a niche with respect to function and define a function network by using two types of maps. Due to the local complex structure of the function network, motif and lateral connections, some species are easily replaced by others, and other species have long lives. Punctuated equilibrium can, therefore, be explained by local ambiguous interaction, which suggests the notion of self and supports the idea of self-organized criticality.

  10. "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

  11. Network capacity with probit-based stochastic user equilibrium problem

    PubMed Central

    Lu, Lili; Wang, Jian; Zheng, Pengjun; Wang, Wei

    2017-01-01

    Among different stochastic user equilibrium (SUE) traffic assignment models, the Logit-based stochastic user equilibrium (SUE) is extensively investigated by researchers. It is constantly formulated as the low-level problem to describe the drivers’ route choice behavior in bi-level problems such as network design, toll optimization et al. The Probit-based SUE model receives far less attention compared with Logit-based model albeit the assignment result is more consistent with drivers’ behavior. It is well-known that due to the identical and irrelevant alternative (IIA) assumption, the Logit-based SUE model is incapable to deal with route overlapping problem and cannot account for perception variance with respect to trips. This paper aims to explore the network capacity with Probit-based traffic assignment model and investigate the differences of it is with Logit-based SUE traffic assignment models. The network capacity is formulated as a bi-level programming where the up-level program is to maximize the network capacity through optimizing input parameters (O-D multiplies and signal splits) while the low-level program is the Logit-based or Probit-based SUE problem formulated to model the drivers’ route choice. A heuristic algorithm based on sensitivity analysis of SUE problem is detailed presented to solve the proposed bi-level program. Three numerical example networks are used to discuss the differences of network capacity between Logit-based SUE constraint and Probit-based SUE constraint. This study finds that while the network capacity show different results between Probit-based SUE and Logit-based SUE constraints, the variation pattern of network capacity with respect to increased level of travelers’ information for general network under the two type of SUE problems is the same, and with certain level of travelers’ information, both of them can achieve the same maximum network capacity. PMID:28178284

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Evaporation from Soils Under Thermal Boundary Conditions: Experimental and Modeling Investigation to Compare Equilibrium and Non-Equilibrium Based Approaches

    NASA Astrophysics Data System (ADS)

    Smits, K. M.; Cihan, A.; Sakaki, T.; Illangasekare, T. H.

    2010-12-01

    In the shallow subsurface immediately below the land-atmosphere interface, it is widely recognized that the movement of water vapor is closely coupled to thermal processes. However, their mutual interactions are rarely considered in most soil water modeling efforts or in practical applications where it becomes necessary to understand and predict the spatial and temporal distribution of soil moisture. The validation of numerical models that are designed to capture these processes is difficult due to the inherent complexities of the problem in field systems and the scarcity of field or laboratory data with accurately known hydraulic and thermal parameters of soils, thus limiting the testing and refinement of heat and water transfer theories. In addition, it is often assumed in traditional soil physics applications that water vapor concentration in the air adjacent to the water phase in soil pores is always in equilibrium with liquid water, i.e., vaporization occurs instantaneously, which can result in over prediction of evaporation from soil. The goal of this work is to perform controlled experiments under transient conditions of soil moisture and temperature using soil with accurately known hydraulic/thermal properties and use this data to test existing theories and develop appropriate numerical models. In this work, water vapor flow under varying temperature gradients was implemented based on a concept that allows non-equilibrium liquid/gas phase change with gas phase vapor diffusion. In order to validate this new approach, we developed a long column apparatus equipped with a network of sensors and generated data under well-controlled thermal boundary conditions at the soil surface. Water saturation, capillary pressure, temperature, relative humidity and column weight to record total mass of water in the column were continuously monitored. Results from numerical simulations based on the conventional equilibrium and non-equilibrium approaches were compared with

  20. 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…

  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. 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…

  3. Fast equilibrium reconstruction for tokamak discharge control based on GPU

    NASA Astrophysics Data System (ADS)

    Yue, X. N.; Xiao, B. J.; Luo, Z. P.; Guo, Y.

    2013-08-01

    A parallel code named P-EFIT which could complete an equilibrium reconstruction iteration in 220 µs is described. It is build with the CUDA™ architecture. Some optimization for middle-scale matrix multiplication on graphics processing unit and an algorithm which could solve block tri-diagonal linear system efficiently in parallel is described. Benchmark test is conducted. Static test proves the correctness of the P-EFIT and simulation-test proves the feasibility of using P-EFIT for real-time reconstruction with a 65 × 65 grid.

  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. Dynamical Systems Based Non Equilibrium Statistical Mechanics for Markov Chains

    NASA Astrophysics Data System (ADS)

    Prevost, Mireille

    We introduce an abstract framework concerning non-equilibrium statistical mechanics in the specific context of Markov chains. This framework encompasses both the Evans-Searles and the Gallavotti-Cohen fluctuation theorems. To support and expand on these concepts, several results are proven, among which a central limit theorem and a large deviation principle. The interest for Markov chains is twofold. First, they model a great variety of physical systems. Secondly, their simplicity allows for an easy introduction to an otherwise complicated field encompassing the statistical mechanics of Anosov and Axiom A diffeomorphisms. We give two examples relating the present framework to physical cases modelled by Markov chains. One of these concerns chemical reactions and links key concepts from the framework to their well known physical counterpart.

  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. 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…

  8. 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…

  9. A new near-equilibrium breakdown parameter based on the Rayleigh-Onsager dissipation function

    NASA Astrophysics Data System (ADS)

    Xiao, H.; Myong, R. S.; Singh, S.

    2014-12-01

    The near-equilibrium breakdown parameter is essential in quantifying the gas flow regions in which the linear Navier-Stokes-Fourier hypothesis is no longer valid. It plays a significant role in the development of a hybrid continuum/DSMC method in which computational domains need to be identified as either rarefied or continuum. There were several breakdown parameters appearing in the literature such as a semi-empirical parameter based on the spatial derivative of flow properties and a parameter based on the maximum gradient-length local Knudsen number. In this study, we present a new near-equilibrium breakdown parameter based on the degree of thermal nonequilibrium and the Rayleigh-Onsager dissipation function related to the calortropy production arising from the irreversible process in the system. The property of the new breakdown parameter is investigated by numerically solving hypersonic rarefied and low Mach microscale gas flows around a cylinder.

  10. 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

  11. 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

  12. 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.

  13. Reactive Solute Transport in Streams: 1. Development of an Equilibrium-Based Model

    NASA Astrophysics Data System (ADS)

    Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

    1996-02-01

    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.

  14. 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.

  15. 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.

  16. 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.

  17. MINFIT: A Spreadsheet-Based Tool for Parameter Estimation in an Equilibrium Speciation Software Program.

    PubMed

    Xie, Xiongfei; Giammar, Daniel E; Wang, Zimeng

    2016-10-07

    Deterpmination of equilibrium constants describing chemical reactions in the aqueous phase and at solid-water interface relies on inverse modeling and parameter estimation. Although there are existing tools available, the steep learning curve prevents the wider community of environmental engineers and chemists to adopt those tools. Stemming from classical chemical equilibrium codes, MINEQL+ has been one of the most widely used chemical equilibrium software programs. We developed a spreadsheet-based tool, which we are calling MINFIT, that interacts with MINEQL+ to perform parameter estimations that optimize model fits to experimental data sets. MINFIT enables automatic and convenient screening of a large number of parameter sets toward the optimal solutions by calling MINEQL+ to perform iterative forward calculations following either exhaustive equidistant grid search or randomized search algorithms. The combined use of the two algorithms can securely guide the searches for the global optima. We developed interactive interfaces so that the optimization processes are transparent. Benchmark examples including both aqueous and surface complexation problems illustrate the parameter estimation and associated sensitivity analysis. MINFIT is accessible at http://minfit.strikingly.com .

  18. 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.

  19. 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

    2015-05-07

    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.

  20. 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.

  1. 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)

  2. 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.

  3. Determination of thermal equilibrium in a sealed cell based on optical depth

    NASA Astrophysics Data System (ADS)

    Zou, Sheng; Zhang, Hong; Chen, Xi-yuan; Shan, Guang-cun; Quan, Wei

    2017-01-01

    An effective method based on optical depth (OD) is presented to measure thermal equilibrium in a cell. First, the principle of determining the temperature distribution in the cell by using the OD is demonstrated. Subsequently, relevant experiments are carried out. Original experimental results showed that some gradients of OD distributions in the cell at different wavelengths and variations of the OD increased slowly along the direction of motion of the beam at a fixed wavelength. At a wavelength of 766.6839 nm, which is about 7 GHz blue shifted with respect to the potassium resonance, the average value of the OD was about 0.764 and the maximal and the minimum inhomogeneity biases among all location points were about 6.07% and 0.56%, respectively. As for the corresponding wavelengths of 766.67785 nm and 766.73004 nm, some deviations from previous results, which were caused by different absorptions of the alkali-metal atoms at different frequencies of the laser beam, were observed. The nonuniform OD values along the direction of motion of the beam reflected an inhomogeneous distribution of the temperature in the cell, which may have been caused by layout of the oven. When the layout of the oven was modified, comparative experiments comparable to these with the previous layout of the oven demonstrated that the uniformity of the temperature distribution in the cell was improved and that thermal equilibrium time was shorter by about 10 minutes. This method played an important role in determining the thermal equilibrium time in the cell.

  4. 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…

  5. Potentiometric determination of equilibrium constants of bases and perchlorates of protonated bases in glacial acetic acid using Superquad.

    PubMed

    Alvarez-Romero, Giaan A; Rojas-Hernández, Alberto; Vázquez, Guillermo A; Ramírez-Silva, Ma Teresa

    2003-03-01

    The traditional method of calculating equilibrium constants in glacial acetic acid medium was developed by Kolthoff and Bruckenstein in 1957; thenceforth, and even presently, few alternatives have been made available to undertake such studies. This paper presents the results obtained with the use of the program Superquad to assess the equilibrium constants of various bases and their protonated perchlorate salts in glacial acetic media. A model of formation equilibria is proposed and fed into the program, considering the species present during an acid-base titration. The calculations of the equilibrium constants using Superquad for pyridine and diethylamine are statistically in agreement with those reported in the literature, (for pyridine: pK(B)=5.98+/-0.02, pK( PyHClO4)=5.47+/-0.02 and for diethylamine pK(B)=5.52+/-0.04, pK( DietHClO4)=4.52+/-0.07). With the use of Superquad, the values found for the aniline were pK(B)=6.95+/-0.06 and pK( AnilHClO4)=4.89+/-0.06.

  6. 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.

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

    PubMed

    Higashino, Asuka; Mizuno, Misao; Mizutani, Yasuhisa

    2016-04-07

    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.

  8. 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.

  9. [The effect of spermine on acid-base equilibrium in DNA molecule].

    PubMed

    Slonitskiĭ, S V; Kuptsov, V Iu

    1990-01-01

    The influence of spermine (Sp) on the acid-induced predenaturational and denaturational transitions in the DNA molecule structure has been studied by means of circular dichroism, spectrophotometric and viscometric titration at supporting electrolyte concentration 10 mM NaCl. The data available indicate that at [N]/[P] less than or equal to 0.60 (here [N] and [P] are molar concentrations of Sp nitrogen and DNA phosphours, respectively) the cooperative structural B----B(+)----S transitions are accompanied by the DNA double-helice winding. No competition for proton acceptor sites in the DNA molecule between H+ and Sp4+ cations has been observed when binding to neutral macromolecule. At 0.60 less than or equal to [N]/[P] less than or equal to 0.75 the displacement of the B----B(+)----S transitions midpoints to acidic pH region has been established. This is accompanied by DNA condensation and the appearance of differential scattering of circularly polarized light. The calculations carried out in the framework of the two-variable Manning theory have shown that the acid-induced reduction of the effective polyion charge density facilitates the Sp-induced DNA condensation. It has been shown that the acid-base equilibrium in the DNA molecule is determined by local [H+] in the 2-3 A hydrated monolayer of the macromolecule. An adequate estimation of [H+] can be obtained on the basis of the Poisson-Boltzman approach. The data obtained are consistent with recently proposed hypothesis of polyelectrolyte invariance of the acid-base equilibrium in the DNA molecule.

  10. 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.

  11. Development and Assessment of a Computer-Based Equation of State for Equilibrium Air

    DTIC Science & Technology

    2013-09-01

    Pressure .............. 25 10. High-Density Contribution to the Enthalpy Divided by the Equilibrium Enthalpy ............... 26 11. High-Density...Contribution to the Entropy Divided by the Equilibrium Entropy .................. 27 12. Relative Difference in Calculated Enthalpy for Six Temperatures for...13. Relative Difference in Calculated Enthalpy for Six Temperatures for Lowest Densities ... 33 14. Relative Difference in Calculated Enthalpy for

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

    PubMed Central

    Cao, Liaoran; Lv, Chao; Yang, Wei

    2013-01-01

    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

  13. 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,…

  14. 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

  15. 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.

  16. Probing autoinducer-2 based quorum sensing: the biological consequences of molecules unable to traverse equilibrium states.

    PubMed

    Tsuchikama, Kyoji; Lowery, Colin A; Janda, Kim D

    2011-09-02

    Bacteria have developed a cell-to-cell communication system, termed quorum sensing (QS), which allows for the population-dependent coordination of their behavior via the exchange of chemical signals. Autoinducer-2 (AI-2), a class of QS signals derived from 4,5-dihydroxy-2,3-pentandione (DPD), has been revealed as a universal signaling molecule in a variety of bacterial species. In spite of considerable interest, the study of putative AI-2 based QS systems remains a challenging topic in part due to the rapid interconversion between the linear and cyclic forms of DPD. Herein, we report the design and development of efficient syntheses of carbocyclic analogues of DPD, which are locked in the cyclic form. The synthetic analogues were evaluated for the modulation of AI-2-based QS in Vibrio harveyi and Salmonella typhimurium. No agonists were uncovered in either V. harveyi or S. typhimurium assay, whereas weak to moderate antagonists were found against V. harveyi. On the basis of NMR analyses and DFT calculations, the heterocyclic oxygen atom within DPD appears necessary to promote hydration at the C3 position of cyclic DPD to afford the active tetrahydroxy species. These results also shed light on the interaction between the heterocyclic oxygen atom and receptor proteins as well as the importance of the linear form and dynamic equilibrium of DPD as crucial requirements for activation of AI-2 based QS circuits.

  17. Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity

    DOE PAGES

    Cantu, David C.; Lee, Juntaek; Lee, Mal -Soon; ...

    2016-03-28

    The deployment of transformational non-aqueous CO2-capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, this work reveals options tomore » significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. Lastly, the molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.« less

  18. Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity

    SciTech Connect

    Cantu, David C.; Lee, Juntaek; Lee, Mal -Soon; Heldebrant, David J.; Koech, Phillip K.; Freeman, Charles J.; Rousseau, Roger; Glezakou, Vassiliki -Alexandra

    2016-03-28

    The deployment of transformational non-aqueous CO2-capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, this work reveals options to significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. Lastly, the molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.

  19. Chasing equilibrium: measuring the intrinsic solubility of weak acids and bases.

    PubMed

    Stuart, Martin; Box, Karl

    2005-02-15

    A novel procedure is described for rapid (20-80 min) measurement of intrinsic solubility values of organic acids, bases, and ampholytes. In this procedure, a quantity of substance was first dissolved at a pH where it exists predominantly in its ionized form, and then a precipitate of the neutral (un-ionized) species was formed by changing the pH. Subsequently, the rate of change of pH due to precipitation or dissolution was monitored and strong acid and base titrant were added to adjust the pH to discover its equilibrium conditions, and the intrinsic solubility of the neutral form of the compound could then be determined. The procedure was applied to a variety of monoprotic and diprotic pharmaceutical compounds. The results were highly repeatable and had a good correlation to available published values. Data collected during the procedure provided good diagnostic information. Kinetic solubility data were also collected but provided a poor guide to the intrinsic solubility.

  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. Stages in learning motor synergies: a view based on the equilibrium-point hypothesis.

    PubMed

    Latash, Mark L

    2010-10-01

    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.

  2. 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.

  3. 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.

  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. 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…

  6. 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.

  7. Study on two-dimensional equilibrium structure of magnetized complex plasmas based on a Langevin dynamics simulation

    NASA Astrophysics Data System (ADS)

    Kong, Wei; Yang, Fang; Liu, Songfen; Shi, Feng

    2016-10-01

    A Langevin dynamics simulation method is used to study the two-dimensional (2D) equilibrium structure of complex plasmas while considering an external magnetic field. The traditional Yukawa potential and a modified Yukawa potential according to Shukla et al. [Phys. Lett. A 291, 413 (2001); Shukla and Mendonca, Phys. Scr. T113 82 (2004)] and Salimullah et al. [Phys. Plasmas 10, 3047 (2003)] respectively, are employed to account for the interaction of the charged dust particles. It is found that the collisions between neutral gas and charged dust particles have minor effects on the 2D equilibrium structure of the system. Based on the modified Yukawa potential, studies on the 2D equilibrium structure show that the traditional Yukawa potential is still suitable for describing the magnetized complex plasmas, even if the shielding distance of charged dust particles is affected by the strong external magnetic field.

  8. Partition Equilibrium

    NASA Astrophysics Data System (ADS)

    Feldman, Michal; Tennenholtz, Moshe

    We introduce partition equilibrium and study its existence in resource selection games (RSG). In partition equilibrium the agents are partitioned into coalitions, and only deviations by the prescribed coalitions are considered. This is in difference to the classical concept of strong equilibrium according to which any subset of the agents may deviate. In resource selection games, each agent selects a resource from a set of resources, and its payoff is an increasing (or non-decreasing) function of the number of agents selecting its resource. While it has been shown that strong equilibrium exists in resource selection games, these games do not possess super-strong equilibrium, in which a fruitful deviation benefits at least one deviator without hurting any other deviator, even in the case of two identical resources with increasing cost functions. Similarly, strong equilibrium does not exist for that restricted two identical resources setting when the game is played repeatedly. We prove that for any given partition there exists a super-strong equilibrium for resource selection games of identical resources with increasing cost functions; we also show similar existence results for a variety of other classes of resource selection games. For the case of repeated games we identify partitions that guarantee the existence of strong equilibrium. Together, our work introduces a natural concept, which turns out to lead to positive and applicable results in one of the basic domains studied in the literature.

  9. 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

  10. 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.

  11. Stable Equilibrium Based on Lévy Statistics:A Linear Boltzmann Equation Approach

    NASA Astrophysics Data System (ADS)

    Barkai, Eli

    2004-06-01

    To obtain further insight on possible power law generalizations of Boltzmann equilibrium concepts, we consider stochastic collision models. The models are a generalization of the Rayleigh collision model, for a heavy one dimensional particle M interacting with ideal gas particles with a mass m<< M. Similar to previous approaches we assume elastic, uncorrelated, and impulsive collisions. We let the bath particle velocity distribution function to be of general form, namely we do not postulate a specific form of power-law equilibrium. We show, under certain conditions, that the velocity distribution function of the heavy particle is Lévy stable, the Maxwellian distribution being a special case. We demonstrate our results with numerical examples. The relation of the power law equilibrium obtained here to thermodynamics is discussed. In particular we compare between two models: a thermodynamic and an energy scaling approaches. These models yield insight into questions like the meaning of temperature for power law equilibrium, and into the issue of the universality of the equilibrium (i.e., is the width of the generalized Maxwellian distribution functions obtained here, independent of coupling constant to the bath).

  12. 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.

  13. 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.

  14. Upscaling of Compositional Flow Simulation based on a non-Equilibrium Formulation

    NASA Astrophysics Data System (ADS)

    Salehi, A.; Voskov, D.; Tchelepi, H. A.

    2012-12-01

    Modeling multiphase flow of large number of components in natural porous media is a challenging problem of strong interest across many disciplines. Even with the most advanced computational methods and computer platforms, compositional simulation using the fine-scale (so-called geocellular) model is often too expensive; as a result, upscaling methods for compositional flows are essential. We describe a consistent representation of the coarse-scale equations, and we introduce upscaled flow functions to account for the sub-scale variations in both the absolute and relative permeability, as well as, compressibility effects. Upscaling of the thermodynamic phase behavior is the main focus of this work. We assume instantaneous phase equilibrium at the fine scale, and we derive coarse-scale equations, in which the phase behavior is represented in a non-equilibrium form. Viscous fingering, gravity override, and channeling at the sub-grid scale are possible reasons for this non-equilibrium behavior. Coarse-scale thermodynamic functions are introduced to quantify the difference in chemical potential of each component among the different phases and to capture the deviation of coarse blocks from equilibrium. These upscaled functions transform the two-phase region of the fine-scale, formed by equilibrium tie-lines, to a modified region with tilted tie-lines. We quantify the effect of the degree of heterogeneity variance and heterogeneity patterns on the modified non-equilibrium phase space in the upscaled representation. We also analyze the interplay of phase behavior and numerical dispersion at the coarse-scale, and we demonstrate how the averaging of sub-scale heterogeneities and the use of larger grid blocks can alter the solution. The accuracy and efficiency of proposed methodology is tested for various challenging gas injection problems, and we show that the approach accurately reproduces the averaged fine-scale solutions.

  15. Predicting Folding Sequences Based on the Maximum Rock Strength and Mechanical Equilibrium

    NASA Astrophysics Data System (ADS)

    Cubas, N.; Souloumiac, P.; Maillot, B.; Leroy, Y. M.

    2007-12-01

    The objective is to propose and validate simple procedures, compared to the finite-element method, to select and optimize the dominant mode of folding in fold-and-thrust belts and accretionary wedges, and to determine its stress distribution. Mechanical equilibrium as well as the constraints due to the limited rock strength of the bulk material and of major discontinuities, such as décollements, are accounted for. The first part of the proposed procedure, which is at the core of the external approach of classical limit analysis, consists in estimating the least upper bound on the tectonic force by minimisation of the internal dissipation and part of the external work. The new twist to the method is that the optimization is also done with respect to the geometry of the evolving fold. If several folding events are possible, the dominant mode is the one leading to the least upper bound. The second part of the procedure is based on the Equilibrium Element Method, which is an application of the internal approach of limit analysis. The optimum stress field, obtained by spatial discretisation of the fold, provides the best lower bound on the tectonic force. The difference between the two bounds defines an error estimate of the exact unknown tectonic force. To show the merits of the proposed procedure, its first part is applied to predict the life span of a thrust within an accretionary prism, from its onset, its development with a relief build up and its arrest because of the onset of a more favorable new thrust (Cubas et al., 2007). This life span is sensitive to the friction angles over the ramp and the décollement. It is shown how the normal sequence of thrusting in a supercritical wedge is ended with the first out-of sequence event. The second part of the procedure provides the stress state over each thrust showing that the active back thrust is a narrow fan which dip is sensitive to the friction angle over the ramp and the amount of relief build up (Souloumiac et

  16. 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.

  17. 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.

  18. Development of a non-equilibrium quantum transport calculation method based on constrained density functional

    NASA Astrophysics Data System (ADS)

    Kim, Han Seul; Kim, Yong-Hoon

    2015-03-01

    We report on the development of a novel first-principles method for the calculation of non-equilibrium quantum transport process. Within the scheme, non-equilibrium situation and quantum transport within the open-boundary condition are described by the region-dependent Δ self-consistent field method and matrix Green's function theory, respectively. We will discuss our solutions to the technical difficulties in describing bias-dependent electron transport at complicated nanointerfaces and present several application examples. Global Frontier Program (2013M3A6B1078881), Basic Science Research Grant (2012R1A1A2044793), EDISON Program (No. 2012M3C1A6035684), and 2013 Global Ph.D fellowship program of the National Research Foundation. KISTI Supercomputing Center (KSC-2014-C3-021).

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Effect of selection and sequencing of representative wave conditions on process-based predictions of equilibrium embayed beach morphology

    NASA Astrophysics Data System (ADS)

    Daly, Christopher J.; Bryan, Karin R.; Gonzalez, Mauricio R.; Klein, Antonio H. F.; Winter, Christian

    2014-06-01

    In order to decrease the simulation time of morphodynamic models, often-complex wave climates are reduced to a few representative wave conditions (RWC). When applied to embayed beaches, a test of whether a reduced wave climate is representative or not is to see whether it can recreate the observed equilibrium (long-term averaged) bathymetry of the bay. In this study, the wave climate experienced at Milagro Beach, Tarragona, Spain was discretized into `average' and `extreme' RWCs. Process-based morphodynamic simulations were sequenced and merged based on `persistent' and `transient' forcing conditions, the results of which were used to estimate the equilibrium bathymetry of the bay. Results show that the effect of extreme wave events appeared to have less influence on the equilibrium of the bay compared to average conditions of longer overall duration. Additionally, the persistent seasonal variation of the wave climate produces pronounced beach rotation and tends to accumulate sediment at the extremities of the beach, rather than in the central sections. It is, therefore, important to account for directional variability and persistence in the selection and sequencing of representative wave conditions as is it essential for accurately balancing the effects beach rotation events.

  5. 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

  6. Evaporation from soils under diurnal boundary conditions: Experimental and modeling investigation to evaluate Non-equilibrium-based approaches

    NASA Astrophysics Data System (ADS)

    Trautz, Andrew; Smits, Kathleen; Cihan, Abdullah; Illangasekare, Tissa

    2013-04-01

    Evaporation from bare soil is a key component of the hydrologic cycle and the process primarily responsible for governing water and energy exchanges between the land and atmosphere. Despite its importance, there is still a great deal of uncertainty associated with our current understanding of this complex multiphase phenomenon. A common approach when modeling the movement of liquid water, water vapor and heat in the soil immediately below the land-atmosphere interface is to assume that water vapor concentration in air is always in equilibrium with liquid water. However, this equilibrium assumption is called into question by experiments about liquid/gas phase change in porous media suggesting that the equilibrium establishment is not instantaneous; a volatilization or condensation time is observed at the macroscopic scale under certain conditions. Introduction of such a non-equilibrium mass transfer relationship is based on the Hertz-Knudsen equation (HKE) derived from the kinetic theory of gases. Multiple formulations have been presented to represent the rate of phase change between water and vapor, many relying on empirical fitting parameters due to limited experimental data. The purpose of this work is to perform an unbiased comparison between various conceptual and mathematical formulations for non-equilibrium phase change on evaporation and develop appropriate numerical models to be used in simulations. The key to such a comparison is the availability of accurate data. As such data at the scale of interest is not possible to obtain in field settings, a unique two-dimensional cell apparatus was developed. The test cell was equipped with a network of sensors for automated and continuous monitoring of soil moisture, soil and air temperature and relative humidity, and wind velocity to generate precision data. A fully-coupled numerical model to solve the governing equations for heat, liquid water and water vapor transport in soil was developed. The code implements a

  7. Non-equilibrium Green's function calculation for GaN-based terahertz-quantum cascade laser structures

    NASA Astrophysics Data System (ADS)

    Yasuda, H.; Kubis, T.; Hosako, I.; Hirakawa, K.

    2012-04-01

    We theoretically investigated GaN-based resonant phonon terahertz-quantum cascade laser (QCL) structures for possible high-temperature operation by using the non-equilibrium Green's function method. It was found that the GaN-based THz-QCL structures do not necessarily have a gain sufficient for lasing, even though the thermal backfilling and the thermally activated phonon scattering are effectively suppressed. The main reason for this is the broadening of the subband levels caused by a very strong interaction between electrons and longitudinal optical (LO) phonons in GaN.

  8. Lithium abundances of halo dwarfs based on excitation temperatures. II. Non-local thermodynamic equilibrium

    NASA Astrophysics Data System (ADS)

    Hosford, A.; García Pérez, A. E.; Collet, R.; Ryan, S. G.; Norris, J. E.; Olive, K. A.

    2010-02-01

    Context. The plateau in the abundance of 7Li in metal-poor stars was initially interpreted as an observational indicator of the primordial lithium abundance. However, this observational value is in disagreement with that deduced from calculations of Big Bang nucleosynthesis (BBN), when using the Wilkinson microwave anisotropy probe (WMAP) baryon density measurements. One of the most important factors in determining the stellar lithium abundance is the effective temperature. In a previous study by the authors, new effective temperatures (Teff) for sixteen metal-poor halo dwarfs were derived using a local thermodynamic equilibrium (LTE) description of the formation of Fe lines. This new Teff scale reinforced the discrepancy. Aims: For six of the stars from our previous study we calculate revised temperatures using a non-local thermodynamic equilibrium (NLTE) approach. These are then used to derive a new mean primordial lithium abundance in an attempt to solve the lithium discrepancy. Methods: Using the code MULTI we calculate NLTE corrections to the LTE abundances for the Fe i lines measured in the six stars, and determine new Teff's. We keep other physical parameters, i.e. log g, [Fe/H] and ξ, constant at the values calculated in Paper I. With the revised Teff scale we derive new Li abundances. We compare the NLTE values of Teff with the photometric temperatures of Ryan et al. (1999, ApJ, 523, 654), the infrared flux method (IRFM) temperatures of Meléndez & Ramírez (2004, ApJ, 615, L33), and the Balmer line wing temperatures of Asplund et al. (2006, ApJ, 644, 229). Results: We find that our temperatures are hotter than both the Ryan et al. and Asplund et al. temperatures by typically ~110-160 K, but are still cooler than the temperatures of Meléndez & Ramírez by typically ~190 K. The temperatures imply a primordial Li abundance of 2.19 dex or 2.21 dex, depending on the magnitude of collisions with hydrogen in the calculations, still well below the value of 2

  9. 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

  10. Analysis of the equilibrium droplet shape based on an ellipsoidal droplet model.

    PubMed

    Lubarda, Vlado A; Talke, Kurt A

    2011-09-06

    The extent of a droplet's spreading over a flat, smooth solid substrate and its equilibrium height in the presence of gravity are determined approximately, without a numerical solution of the governing nonlinear differential equation, by assuming that the droplet takes on the shape of an oblate spheroidal cap and by minimizing the corresponding free energy. The comparison with the full numerical evaluations confirms that the introduced approximation and the obtained results are accurate for contact angles below about 120° and for droplet sizes on the order of the capillary length of the liquid. The flattening effect of gravity is to increase the contact radius and decrease the height of the droplet, with these being more pronounced for higher values of the Bond number.

  11. Towards Microeconomic Resource Sharing in End System Multicast Networks Based on Walrasian General Equilibrium

    NASA Astrophysics Data System (ADS)

    Rezvani, Mohammad Hossein; Analoui, Morteza

    2010-11-01

    We have designed a competitive economical mechanism for application level multicast in which a number of independent services are provided to the end-users by a number of origin servers. Each offered service can be thought of as a commodity and the origin servers and the users who relay the service to their downstream nodes can thus be thought of as producers of the economy. Also, the end-users can be viewed as consumers of the economy. The proposed mechanism regulates the price of each service in such a way that general equilibrium holds. So, all allocations will be Pareto optimal in the sense that the social welfare of the users is maximized.

  12. Equilibrium theory-based analysis of nonlinear waves in separation processes.

    PubMed

    Mazzotti, Marco; Rajendran, Arvind

    2013-01-01

    Different areas of engineering, particularly separation process technology, deal with one-dimensional, nonstationary processes that under reasonable assumptions, namely negligible dispersion effects and transport resistances, are described by mathematical models consisting of systems of first-order partial differential equations. Their behavior is characterized by continuous or discontinuous composition (or thermal) fronts that propagate along the separation unit. The equilibrium theory (i.e., the approach discussed here to determine the solution to these model equations) predicts this with remarkable accuracy, despite the simplifications and assumptions. Interesting applications are in adsorption, chromatography and ion-exchange, distillation, gas injection, heat storage, sedimentation, precipitation, and dissolution waves. We show how mathematics can enlighten the engineering aspects, and we guide the researcher not only to reach a synthetic understanding of properties of fundamental and applicative interest but also to discover new, unexpected, and fascinating phenomena. The tools presented here are useful to teachers, researchers, and practitioners alike.

  13. Informational Equilibrium.

    DTIC Science & Technology

    1982-09-01

    that for variouis standard types of equilibria* they hold. In particular, if one uses the teaporary equilibrium framework one can use the standard ...T, the integral converges toward f’ia(da) f fU(b~dc)6(a,b,c)T( asdm ) A B C which is fR (da) f d(lib,c) U0 T (cab) A BxC Me converse Is obvious

  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. A general library-based Monte Carlo technique enables equilibrium sampling of semi-atomistic protein models

    PubMed Central

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

    2009-01-01

    We introduce “library based Monte Carlo” (LBMC) simulation, which performs Boltzmann sampling of molecular systems based on pre-calculated 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 poly-alanine systems. We next study five proteins, up to 309 residues in size. Based on atomistic equilibrium libraries of peptide-plane configurations, the proteins are modeled with fully atomistic backbones and simplified Gō-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

  16. 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

  17. 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.

  18. Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers.

    PubMed

    Maksin, Danijela D; Nastasović, Aleksandra B; Milutinović-Nikolić, Aleksandra D; Suručić, Ljiljana T; Sandić, Zvjezdana P; Hercigonja, Radmila V; Onjia, Antonije E

    2012-03-30

    Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70°C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q(max), at pH 1.8 and 25°C was 143 mg g(-1) for PGME2-deta (sample with the highest amino group concentration) while at 70°C Q(max) reached the high value of 198 mg g(-1). Thermodynamic parameters revealed spontaneous and endothermic nature of Cr(VI) adsorption onto PGME-deta.

  19. 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).

  20. Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity.

    PubMed

    Cantu, David C; Lee, Juntaek; Lee, Mal-Soon; Heldebrant, David J; Koech, Phillip K; Freeman, Charles J; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

    2016-05-05

    The deployment of transformational nonaqueous CO2-capture solvent systems is encumbered by high viscosities even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we present key molecular features that control bulk viscosity. Fast CO2-uptake kinetics arise from close proximity of the alcohol and amine sites involved in CO2 binding in a concerted fashion, resulting in a Zwitterion containing both an alkyl-carbonate and a protonated amine. The population of internal hydrogen bonds between the two functional groups determines the solution viscosity. Unlike the ion pair interactions in ionic liquids, these observations are novel and specific to a hydrogen-bonding network that can be controlled by chemically tuning single molecule CO2 capture solvents. We present a molecular design strategy to reduce viscosity by shifting the proton transfer equilibrium toward a neutral acid/amine species, as opposed to the ubiquitously accepted zwitterionic state. The molecular design concepts proposed here are readily extensible to other CO2 capture technologies.

  1. Predicting the equilibrium protein folding pathway: structure-based analysis of staphylococcal nuclease.

    PubMed

    Hilser, V J; Freire, E

    1997-02-01

    The equilibrium folding pathway of staphylococcal nuclease (SNase) has been approximated using a statistical thermodynamic formalism that utilizes the high-resolution structure of the native state as a template to generate a large ensemble of partially folded states. Close to 400,000 different states ranging from the native to the completely unfolded states were included in the analysis. The probability of each state was estimated using an empirical structural parametrization of the folding energetics. It is shown that this formalism predicts accurately the stability of the protein, the cooperativity of the folding/unfolding transition observed by differential scanning calorimetry (DSC) or urea denaturation and the thermodynamic parameters for unfolding. More importantly, this formalism provides a quantitative account of the experimental hydrogen exchange protection factors measured under native conditions for SNase. These results suggest that the computer-generated distribution of states approximates well the ensemble of conformations existing in solution. Furthermore, this formalism represents the first model capable of quantitatively predicting within a unified framework the probability distribution of states seen under native conditions and its change upon unfolding.

  2. 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.

  3. Tropical forests are non-equilibrium ecosystems governed by interspecific competition based on universal 1/6 niche width.

    PubMed

    Fort, Hugo; Inchausti, Pablo

    2013-01-01

    Tropical forests are mega-diverse ecosystems that display complex and non-equilibrium dynamics. However, theoretical approaches have largely focused on explaining steady-state behaviour and fitting snapshots of data. Here we show that local and niche interspecific competition can realistically and parsimoniously explain the observed non-equilibrium regime of permanent plots of nine tropical forests, in eight different countries. Our spatially-explicit model, besides predicting with accuracy the main biodiversity metrics for these plots, can also reproduce their dynamics. A central finding is that tropical tree species have a universal niche width of approximately 1/6 of the niche axis that echoes the observed widespread convergence in their functional traits enabling them to exploit similar resources and to coexist despite of having large niche overlap. This niche width yields an average ratio of 0.25 between interspecific and intraspecific competition that corresponds to an intermediate value between the extreme claims of the neutral model and the classical niche-based model of community assembly (where interspecific competition is dominant). In addition, our model can explain and yield observed spatial patterns that classical niche-based and neutral theories cannot.

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

    PubMed Central

    Chen, Chunhong; Newell, Kim; Lawrence, Gregory J.; 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

  5. Application of equilibrium chemistry and the Williamsburg equation of state to HMX-based explosives

    NASA Astrophysics Data System (ADS)

    Braithwaite, M.; Swift, D. C.

    1999-06-01

    Thermodynamic equations of state have been demonstrated to give reasonable predictions of the species and states in the reaction products of energetic materials. The Williamsburg is a physically-based algebraic form for an equation of state. The Williamsburg is being used to interpolate and extrapolate a wide-ranging equation of state from a smaller set of chemical calculations of HMX-based explosives. These equations of state will be compared with experiments on explosive performance. Extensions to the Williamsburg form, necessary to treat processes such as carbon condensation in TATB-based explosives, will be discussed.

  6. Design and Quasi-Equilibrium Analysis of a Distributed Frequency-Restoration Controller for Inverter-Based Microgrids

    SciTech Connect

    Ainsworth, Nathan G; Grijalva, Prof. Santiago

    2013-01-01

    This paper discusses a proposed frequency restoration controller which operates as an outer loop to frequency droop for voltage-source inverters. By quasi-equilibrium analysis, we show that the proposed controller is able to provide arbitrarily small steady-state frequency error while maintaing power sharing between inverters without need for communication or centralized control. We derive rate of convergence, discuss design considerations (including a fundamental trade-off that must be made in design), present a design procedure to meet a maximum frequency error requirement, and show simulation results verifying our analysis and design method. The proposed controller will allow flexible plug-and-play inverter-based networks to meet a specified maximum frequency error requirement.

  7. A DFT based equilibrium study of a chemical mixture Tachyhydrite and their lower hydrates for long term heat storage

    NASA Astrophysics Data System (ADS)

    Pathak, A. D.; Nedea, S. V.; Zondag, H. A.; Rindt, C. C. M.; Smeulders, D. M. J.

    2016-09-01

    Chloride based salt hydrates are promising materials for seasonal heat storage. However, hydrolysis, a side reaction, deteriorates, their cycle stability. To improve the kinetics and durability, we have investigated the optimum operating conditions of a chemical mixture of CaCl2 and MgCl2 hydrates. In this study, we apply a GGA-DFT to gain insight into the various hydrates of CaMg2Cl6. We have obtained the structural properties, atomic charges and vibrational frequencies of CaMg2Cl6 hydrates. The entropic contribution and the enthalpy change are quantified from ground state energy and harmonic frequencies. Subsequently, the change in the Gibbs free energy of thermolysis was obtained under a wide range of temperature and pressure. The equilibrium product concentration of thermolysis can be used to design the seasonal heat storage system under different operating conditions.

  8. 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...

  9. Active Learning Session Based on Didactical Engineering Framework for Conceptual Change in Students' Equilibrium and Stability Understanding

    ERIC Educational Resources Information Center

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

    2017-01-01

    Engineering students on control courses lack a deep understanding of equilibrium and stability that are crucial concepts in this discipline. Several studies have shown that students find it difficult to understand simple familiar or academic static equilibrium cases as well as dynamic ones from mechanics even if they know the discipline's criteria…

  10. 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.

  11. [Annual dynamics of acid-base equilibrium indices in dairy cows].

    PubMed

    Bartko, P; Vrzgula, L; Michna, A; Rysul'ová, D

    1980-10-01

    Annual dynamics of the indices of acid-base homeostasis of blood was studied in dairy cows in two production regions, the corn production region and the potato-grain production region; venous blood was examined gasometrically by the Astrup apparatus. The examinations were performed eight times during the year and pH, pCO2, BE, PB, SB, AB and tCO2 were studied. In dairy cows from the corn production region lower values of the studied parameters were obtained than in dairy cows oriented to similar milk production in the potato-grain production region. In the corn production region besides the normal values also the lower values of the indices of acid-base balance were found, indicating the incidence of latent metabolic acidosis. A particularly critical situation occurred in the herd from the corn production region in September when the average value of blood pH was 7.35 logmolc and the following disorders were observed: clinical symptoms of metabolic acidosis, drop of milk yield, drop of milk fat content, hypomagnesemia and hypocalcemia as disorders of the mineral metabolism.

  12. 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.…

  13. 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.

  14. Force-based optimization of pseudopotentials for non-equilibrium configurations

    NASA Astrophysics Data System (ADS)

    Brock, Casey N.; Paikoff, Brandon C.; Md Sallih, Muhammad I.; Tackett, Alan R.; Walker, D. Greg

    2016-04-01

    We have used a multi-objective genetic algorithm to optimize pseudopotentials for force accuracy and computational efficiency. Force accuracy is determined by comparing interatomic forces generated using the pseudopotentials and forces generated using the full-potential linearized augmented-plane wave method. This force-based optimization approach is motivated by applications where interatomic forces are important, including material interfaces, crystal defects, and molecular dynamics. Our method generates Pareto sets of optimized pseudopotentials containing various compromises between accuracy and efficiency. We have tested our method for LiF, Si0.5Ge0.5, and Mo and compared the performance of our pseudopotentials with pseudopotentials available from the ABINIT library. We show that the optimization can generate pseudopotentials with comparable accuracy (in terms of force matching and equation of state) to pseudopotentials in the literature while sometimes significantly improving computational efficiency. For example, we generated pseudopotentials for one system tested that reduced computational work by 71% without loss of accuracy. These results suggest our method can be used to generate pseudopotentials on demand that are tuned for a user's specific application, affording gains in computational efficiency.

  15. Removal of Disperse Red dye by bamboo-based activated carbon: optimisation, kinetics and equilibrium.

    PubMed

    Wang, Lianggui

    2013-07-01

    This research involved the use of response surface methodology (RSM) to investigate the adsorption of Disperse Red 167 dye onto the bamboo-based activated carbon activated with H3PO4 (PBAC) in a batch process. F400, a commercially available activated carbon, was used in parallel for comparison. Analysis of variance showed that input variables such as the contact time, temperature, adsorbent dosage and the interaction between the temperature and the contact time had a significant effect on the dye removal for both adsorbents. RSM results show that the optimal contact time, temperature, initial dye concentration and adsorbent dosage for both adsorbents were found to be 15.4 h, 50 °C, 50.0 mg L(-1) and 12.0 g L(-1), respectively. Under these optimal conditions, the removal efficiencies reached 90.23% and 92.13% for PBAC and F400, respectively, with a desirability of 0.937. The validation of the experimental results confirmed the prediction of the models derived from RSM. The adsorption followed a nonlinear pseudo-first-order model and agreed well with the Freundlich and Temkin isotherm as judged by the levels of the AICc and the Akaike weight. Furthermore, the thermodynamics analysis indicated that, for both adsorbents, the adsorption was a physical process that was spontaneous, entropy-increasing and endothermic.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. IgG adsorption on a new protein A adsorbent based on macroporous hydrophilic polymers. I. Adsorption equilibrium and kinetics.

    PubMed

    Perez-Almodovar, Ernie X; Carta, Giorgio

    2009-11-20

    Experimental determination and modeling of IgG binding on a new protein A adsorbent based on a macroporous resin were performed. The new adsorbent consists of polymeric beads based on hydrophilic acrylamido and vinyl monomers with a pore structure optimized to allow favorable interactions of IgG with recombinant protein A coupled to the resin. The particles have average diameter of 57 microm and a narrow particle size distribution. The IgG adsorption equilibrium capacity is 46 mg/cm(3) and the effective pore diffusivity determined from pulse response experiments for non-binding conditions is 8.0 x 10(-8) cm(2)/s. The IgG adsorption kinetics can be described with the same effective diffusivity by taking into account a heterogeneous binding mechanism with fast binding sites, for which adsorption is completely diffusion controlled, and slow binding sites for which adsorption is controlled by the binding kinetics. As a result of this mechanism, the breakthrough curve exhibits a tailing behavior, which appears to be associated with the slow binding sites. A detailed rate model taking into account intraparticle diffusion and binding kinetics is developed and is found capable of predicting both batch adsorption and breakthrough behavior over an ample range of experimental conditions. The corresponding effective diffusivity is independent of protein concentration in solution over the range 0.2-2 mg/cm(3) and of protein binding as a result of the large pore size of the support matrix. Overall, the small particle size and low diffusional hindrance allow capture of IgG with short residence times while attaining substantial dynamic binding capacities.

  2. 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)

  3. 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.

  4. Robustness and management adaptability in tropical rangelands: a viability-based assessment under the non-equilibrium paradigm.

    PubMed

    Accatino, F; Sabatier, R; De Michele, C; Ward, D; Wiegand, K; Meyer, K M

    2014-08-01

    Rangelands provide the main forage resource for livestock in many parts of the world, but maintaining long-term productivity and providing sufficient income for the rancher remains a challenge. One key issue is to maintain the rangeland in conditions where the rancher has the greatest possibility to adapt his/her management choices to a highly fluctuating and uncertain environment. In this study, we address management robustness and adaptability, which increase the resilience of a rangeland. After reviewing how the concept of resilience evolved in parallel to modelling views on rangelands, we present a dynamic model of rangelands to which we applied the mathematical framework of viability theory to quantify the management adaptability of the system in a stochastic environment. This quantification is based on an index that combines the robustness of the system to rainfall variability and the ability of the rancher to adjust his/her management through time. We evaluated the adaptability for four possible scenarios combining two rainfall regimes (high or low) with two herding strategies (grazers only or mixed herd). Results show that pure grazing is viable only for high-rainfall regimes, and that the use of mixed-feeder herds increases the adaptability of the management. The management is the most adaptive with mixed herds and in rangelands composed of an intermediate density of trees and grasses. In such situations, grass provides high quantities of biomass and woody plants ensure robustness to droughts. Beyond the implications for management, our results illustrate the relevance of viability theory for addressing the issue of robustness and adaptability in non-equilibrium environments.

  5. Helical axis stellarator equilibrium model

    SciTech Connect

    Koniges, A.E.; Johnson, J.L.

    1985-02-01

    An asymptotic model is developed to study MHD equilibria in toroidal systems with a helical magnetic axis. Using a characteristic coordinate system based on the vacuum field lines, the equilibrium problem is reduced to a two-dimensional generalized partial differential equation of the Grad-Shafranov type. A stellarator-expansion free-boundary equilibrium code is modified to solve the helical-axis equations. The expansion model is used to predict the equilibrium properties of Asperators NP-3 and NP-4. Numerically determined flux surfaces, magnetic well, transform, and shear are presented. The equilibria show a toroidal Shafranov shift.

  6. 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.

  7. [Hardy-Weinberg equilibrium in genetic epidemiology].

    PubMed

    Liu, Hong; Hu, Yonghua

    2010-01-01

    Hardy-Weinberg equilibrium test is the base of genetic epidemiology. The new methods for Hardy-Weinberg equilibrium test involve: X chromosome-linked single nucleotide polymorphism Hardy-Weinberg test, inbreeding coefficient (F) test, an incomplete enumeration algorithm for an exact test of Hardy-Weinberg proportions with multiple alleles, and graphical tests for Hardy-Weinberg equilibrium based on the ternary plot. It is necessary to conduct Hardy-Weinberg equilibrium test in genetic epidemiology studies and adjust the associations as deviation of Hardy-Weinberg equilibrium occurs.

  8. Determination of equilibrium constants and computational interaction energies for adducts of [Rh2(RCO2)(4-n)(PC)n] (n = 0-2) with Lewis bases.

    PubMed

    Hirva, Pipsa; Esteban, Julio; Lloret, Julio; Lahuerta, Pascual; Pérez-Prieto, Julia

    2007-04-02

    Properties of dirhodium catalysts with cyclometalated aryl phosphine ligands have been studied. We report here the study of the acid-base reaction of Rh2(RCO2)2(PC)2(H2O)2 catalysts (PC = cyclometalated aryl phosphine) with different Lewis bases. The determination of the equilibrium constants of these reactions can be used to study to which extent the properties of the axial coordination site of the catalyst, considered the active site, are affected by modification of the metalated phosphines, the carboxylate ligands, or the incoming axial ligand. The trends in the computational density functional theory interaction energies show good agreement with the major trends in the equilibrium constants, thus enabling a further study of the influence of the modification of the ligand core.

  9. 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).

  10. Evaporation and condensation in soils: Experimental and modeling investigation to compare non-equilibrium-based approaches under different atmospheric boundary conditions

    NASA Astrophysics Data System (ADS)

    Trautz, A.; Smits, K. M.; Cihan, A.; Illangasekare, T. H.

    2013-12-01

    Evaporation and condensation in bare soils govern water and energy fluxes between the land and atmosphere. Despite their importance to the hydrologic cycle, there is great uncertainty associated with our understanding of these complex multiphase phenomena. At the representative elementary volume scale, phase change (i.e. evaporation/condensation) between water vapor and liquid water is commonly evaluated in soil hydrology using the equilibrium assumption. The equilibrium-based approach assumes that within the soil pores, phase change occurs instantaneously. However, finite volatilization/condensation times have been observed experimentally under certain conditions calling into question the validity of using the equilibrium assumption for all possible land-atmospheric interaction scenarios. The use of non-equilibrium mass transfer relationships is based on the Hertz-Knudsen (HK) equation derived from the kinetic theory of gases. Multiple formulations have been posited to numerically represent phase change between water vapor and liquid water, many relying on empirical fitting parameters. The purpose of this investigation was to perform an unbiased comparison between the various non-equilibrium phase change formulations using a fully coupled heat and mass transfer model that simulates the processes of evaporation/condensation from soils using precision generated laboratory data. A non-isothermal solution was implemented in a numerical model to account for five different non-equilibrium phase change formulations reported in literature. A series of five experiments were performed using a unique laboratory system consisting of a soil tank with controlled airflow boundary conditions at the soil surface. The apparatus was equipped with a sensor network for continuous and autonomous collection of soil moisture, soil and air temperature, relative humidity, and wind velocity data. Soil surface conditions (e.g. temperature, diurnal variations and wind speed) and initial

  11. 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.

  12. 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.

  13. 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

  14. Electrospray mass spectrometry of some proteins and the aqueous solution acid/base equilibrium model in the negative ion detection mode

    NASA Astrophysics Data System (ADS)

    Le Blanc, J. C. Y.; Guevremont, R.; Siu, K. W. M.

    1993-06-01

    Basic solutions of myoglobin, [beta]-lactoglobulin, pepsin and ubiquitin have been examined by means of electrospray mass spectrometry in the negative ion detection mode. The distribution of protein ions in the mass spectra was found to correlate well with the distribution of protein species in solution calculated from published titration data. These results lend further credibility to an earlier proposed aqueous solution acid/base equilibrium model, which relates the "bellshape" ion distribution observed in the electrospray mass spectrometry of proteins to the distribution of protein ions in solution.

  15. 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

  16. Multigrain sedimentation/erosion model based on cross-shore equilibrium sediment distribution: Application to nourishment design

    NASA Astrophysics Data System (ADS)

    Li, Fangjun; Dyt, Chris; Griffiths, Cedric

    2006-05-01

    In the light of global warming and sea level rise there are many coastal beaches that suffer from erosion. Beach nourishment has become a common practice to maintain the sediment balance on a shore-face. In this paper, a three-dimensional numerical model for evaluating long-term impact of beach nourishment projects has been developed. The model addresses the longstanding complex issue of coastal morphology and sediment grain size distribution from an unconventional angle, which exploits the strong links between grain size distribution and the prevailing transport direction of each sediment constituent under 'average' wave and storm action. The present model predicts the redistribution of nourished sediment according to the subtle clues implied by equilibrium distribution curves and latest coastal wave transformation theories. After verification against recent field observations in Terschelling, The Netherlands, the model was used to predict long-term effects of different beach nourishment strategies. It was found that: (a) given the source sediment available in Terschelling the tactics of large volume and less frequent implementation are better than otherwise; and (b) from a pure engineering point of view, waterline nourishment outperforms offshore trough nourishment. The model offers an additional tool for coastal engineers to evaluate the feasibility, effectiveness and the optimization of dumping locations for beach nourishment projects. It is also a useful tool for stratigraphic modelling of shallow-marine sedimentation in conjunction with sea level changes.

  17. 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.

  18. 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.

  19. 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.

  20. 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…

  1. Equilibrium of KSTAR Plasma

    NASA Astrophysics Data System (ADS)

    You, K.-I.; Lee, D.-K.; Lee, S. G.; Bak, J. G.; Hahn, S. H.; Lao, L.; Kstar Team

    2011-10-01

    We have installed the EFIT code on our computing system and made some modification to reconstruct the plasma equilibrium of KSTAR (Korea Superconducting Tokamak Advanced Research). KSTAR PF and TF coil systems use a CICC (Cable-In-Conduit Conductor) type superconductor. The CICC jacket material for most PF and all TF coils is Incoloy 908, which is a magnetic material with relative magnetic permeability greater than 10 in low external field. We newly introduced Diamagnetic Loop and variational Motion Stark Effect signals to equilibrium reconstruction. In this paper, we present some results of equilibrium reconstruction with the EFIT code, assess the effects of newly introduced diagnsotics signal on the equilibrium reconstruction and compare the EFIT results with the various diagnostics data in various plasma conditions including H- and L- modes. In addition, we will show the Incoloy908 effects on the plasma equilibrium.

  2. 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.

  3. Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS. Part 2: application to Taupo Volcanic Zone rhyolites

    NASA Astrophysics Data System (ADS)

    Bégué, Florence; Gualda, Guilherme A. R.; Ghiorso, Mark S.; Pamukcu, Ayla S.; Kennedy, Ben M.; Gravley, Darren M.; Deering, Chad D.; Chambefort, Isabelle

    2014-11-01

    Constraining the pressure of crystallisation of large silicic magma bodies gives important insight into the depth and vertical extent of magmatic plumbing systems; however, it is notably difficult to constrain pressure at the level of detail necessary to understand shallow magmatic systems. In this study, we use the recently developed rhyolite-MELTS geobarometer to constrain the crystallisation pressures of rhyolites from the Taupo Volcanic Zone (TVZ). As sanidine is absent from the studied deposits, we calculate the pressures at which quartz and feldspar are found to be in equilibrium with melt now preserved as glass (the quartz +1 feldspar constraint of Gualda and Ghiorso, Contrib Mineral Petrol 168:1033. doi:10.1007/s00410-014-1033-3. 2014). We use glass compositions (matrix glass and melt inclusions) from seven eruptive deposits dated between ~320 and 0.7 ka from four distinct calderas in the central TVZ, and we discuss advantages and limitations of the rhyolite-MELTS geobarometer in comparison with other geobarometers applied to the same eruptive deposits. Overall, there is good agreement with other pressure estimates from the literature (amphibole geobarometry and H2O-CO2 solubility models). One of the main advantages of this new geobarometer is that it can be applied to both matrix glass and melt inclusions—regardless of volatile saturation. The examples presented also emphasise the utility of this method to filter out spurious glass compositions. Pressure estimates obtained with the new rhyolite-MELTS geobarometer range between ~250 to ~50 MPa, with a large majority at ~100 MPa. These results confirm that the TVZ hosts some of the shallowest rhyolitic magma bodies on the planet, resulting from the extensional tectonic regime and thinning of the crust. Distinct populations with different equilibration pressures are also recognised, which is consistent with the idea that multiple batches of eruptible magma can be present in the crust at the same time and

  4. Thermodynamic theory of equilibrium fluctuations

    SciTech Connect

    Mishin, Y.

    2015-12-15

    The postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different from that of statistical mechanics and represents an expanded version of thermodynamics. Based on this theory, we present a regular procedure for calculations of equilibrium fluctuations of extensive parameters, intensive parameters and densities in systems with any number of fluctuating parameters. The proposed fluctuation formalism is demonstrated by four applications: (1) derivation of the complete set of fluctuation relations for a simple fluid in three different ensembles; (2) fluctuations in finite-reservoir systems interpolating between the canonical and micro-canonical ensembles; (3) derivation of fluctuation relations for excess properties of grain boundaries in binary solid solutions, and (4) derivation of the grain boundary width distribution for pre-melted grain boundaries in alloys. The last two applications offer an efficient fluctuation-based approach to calculations of interface excess properties and extraction of the disjoining potential in pre-melted grain boundaries. Possible future extensions of the theory are outlined.

  5. 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.

  6. 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.

  7. 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)

  8. 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.

  9. 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

    2015-09-07

    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

  10. Localization of flunitrazepam in artificial membranes. A spectrophotometric study about the effect the polarity of the medium exerts on flunitrazepam acid-base equilibrium.

    PubMed

    García, D A; Perillo, M A

    1997-02-21

    In the present paper we tried to test the hypothesis that nonspecific flunitrazepam-membrane interactions are consistent with drug molecules accommodated between lipid molecules, becoming an integral part of the bilayer. We developed a spectrophotometric method to determine FNTZH+ equilibrium dissociation constant and applied it to the study of the acid-base equilibria of this drug in homogeneous media of different polarity. In these conditions, pK decreased with the decrement in the dielectric constant (D) of the media. These results, analyzed under the light of the theory developed by Fernandez and Fromherz (1977; J. Phys. Chem. 81, 1755-1761) let us infer that flunitrazepam is localized a region with D = 60. This D value is lower that Dwater = 78 and higher than D of hydrocarbon chains zone (D = 2-5) and would correspond to D of the region of polar groups. This result is compatible with the hypothesis.

  11. 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.

  12. Heterogeneous equilibrium between the condensed phase and vapor of aprotonic solvents and electrolytes based on them II. Solvent mixtures

    NASA Astrophysics Data System (ADS)

    Gaidym, I. L.; Gurevich, I. G.; Shchitnikov, V. K.; Dubasova, V. S.; Tumanov, B. I.

    1982-06-01

    Experimental results for the saturated vapor pressure of mixtures of organic solvents with electrolytes based on them are given, together with thermodynamic characteristics of the vaporization process calculated on this basis.

  13. Toxicokinetics and toxicity of sediment-associated pyrene and phenanthrene in Diporeia spp. : Examination of equilibrium-partitioning theory and residue-based effects for assessing hazard

    SciTech Connect

    Landrum, P.F.; Dupuis, W.S. . Great Lakes Environmental Research Lab.); Kukkonen, J. . Dept. of Biology)

    1994-11-01

    The amphipod Diporeia spp. was exposed to pyrene or phenanthrene-dosed sediments for month-long exposures. Phenanthrene was only slightly toxic with 12 [+-] 3% mortality at the highest sediment dose (0.62 [mu]mol g[sup [minus]1]). Failure to attain and maintain toxic residue body burdens, based on a nonpolar narcosis concentration of approximately 6 [mu]mol g[sup [minus]1], accounts for the low mortality. Phenanthrene toxicokinetic parameters were essentially constant among all doses and consistent with previous measures. Sediment concentration was a poor representation of dose for mortality by pyrene. The relative pyrene distribution among the < 63-[mu]m particles increased in the smallest-sized particles at larger doses. An apparent stimulation of pyrene accumulation was observed as a peak in uptake clearance values between sediment concentrations of 0.16 and 0.26 [mu]mol g[sup [minus]1] dry sediment. The pyrene particle-size distribution and the variation in kinetics with dose provide a partial explanation for the poor representation of dose by the sediment concentration. The pyrene body burdens provided a good dose response yielding LD50 values of 6.3 and 9.4 [mu]mol g[sup [minus]1] for two experiments. These values are consistent with the residue concentrations for 50% mortality by a nonpolar narcosis mechanism. Comparing the experimental and predicted equilibrium partitioning-based sediment concentrations for 50% mortality, the equilibrium prediction overestimates the toxic pyrene sediment concentration by approximately a factor of ten. Diporeia behavior, differential particle-size distribution, and kinetic limitations appear as likely reasons for the variation between calculated and observed concentrations required to produce mortality.

  14. 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.

  15. Napoleon Is in Equilibrium.

    PubMed

    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.

  16. Optical fluoride sensor based on monomer-dimer equilibrium of scandium(III)-octaethylporphyrin in a plasticized polymeric film.

    PubMed

    Kang, Youngjea; Kampf, Jeff W; Meyerhoff, Mark E

    2007-08-29

    A fluoride-selective optical sensor based on scandium(III)-octaethylporphyrin (Sc(III)OEP) as an ionophore within a plasticized PVC film is described. The presence of fluoride ion in the aqueous sample phase increases the formation of a difluoro-bridged Sc(III)OEP dimer species in the polymer film. The ability of the Sc(III) porphyrin to form the dimeric structure in the presence of fluoride is confirmed by UV-vis spectroscopy and X-ray crystallography. For more practical sensing applications, a pH chromoionophore (ETH 7075) is added to the plasticized PVC film along with Sc(III)OEP and the observed optical response is based on coextraction of protons with sample phase fluoride to create the dimeric porphyrin and a protonated chromoionophore species. The selectivity pattern observed is F- > ClO4(-), SCN-, NO3(-) > Br-, Cl-. Only organic salicylate is a significant interferent. Fast and reversible fluoride response is observed over the range of 10(-4) to 10(-2) M fluoride, allowing use of the sensing film in a waveguide configuration for flow-injection measurements.

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

    NASA Astrophysics Data System (ADS)

    Niaz, M.

    The main objective of this study is to construct a Lakatosian teaching strategy that can facilitate conceptual change in students'' understanding of chemical equilibrium. The strategy is based on the premise that cognitive conflicts must have been engendered by the students themselves in trying to cope with different problem solving strategies. Results obtained (based on Venezuelan freshman students) show that the performance of the experimental group of students was generally better (especially on the immediate post tests) than that of the control group. It is concluded that a conceptual change teaching strategy must take into consideration the following aspects: a) core beliefs of the students in the topic (cf. ''hard core'', Lakatos 1970); b) exploration of the relationship between core beliefs and student alternative conceptions (misconceptions); c) cognitive complexity of the core belief can be broken down into a series of related and probing questions; d) students resist changes in their core beliefs by postulating ''auxiliary hypotheses'' in order to resolve their contradictions; e) students'' responses based on their alternative conceptions must be considered not as wrong, but rather as models, perhaps in the same sense as used by scientists to break the complexity of a problem; and f) students'' misconceptions be considered as alternative conceptions (theories) that compete with the present scientific theories and at times recapitulate theories scientists held in the past.

  18. Large-scale screening of metal hydrides for hydrogen storage from first-principles calculations based on equilibrium reaction thermodynamics.

    PubMed

    Kim, Ki Chul; Kulkarni, Anant D; Johnson, J Karl; Sholl, David S

    2011-04-21

    Systematic thermodynamics calculations based on density functional theory-calculated energies for crystalline solids have been a useful complement to experimental studies of hydrogen storage in metal hydrides. We report the most comprehensive set of thermodynamics calculations for mixtures of light metal hydrides to date by performing grand canonical linear programming screening on a database of 359 compounds, including 147 compounds not previously examined by us. This database is used to categorize the reaction thermodynamics of all mixtures containing any four non-H elements among Al, B, C, Ca, K, Li, Mg, N, Na, Sc, Si, Ti, and V. Reactions are categorized according to the amount of H(2) that is released and the reaction's enthalpy. This approach identifies 74 distinct single step reactions having that a storage capacity >6 wt.% and zero temperature heats of reaction 15 ≤ΔU(0)≤ 75 kJ mol(-1) H(2). Many of these reactions, however, are likely to be problematic experimentally because of the role of refractory compounds, B(12)H(12)-containing compounds, or carbon. The single most promising reaction identified in this way involves LiNH(2)/LiH/KBH(4), storing 7.48 wt.% H(2) and having ΔU(0) = 43.6 kJ mol(-1) H(2). We also examined the complete range of reaction mixtures to identify multi-step reactions with useful properties; this yielded 23 multi-step reactions of potential interest.

  19. Determination of nonaxisymmetric equilibrium

    SciTech Connect

    Elkin, D.

    1980-01-01

    The Princeton Equilibrium Code is modified to determine the equilibrium surfaces for a large aspect ratio toroidal system with helical magnetic fields. The code may easily be made to include any variety of modes. Verification of the code is made by comparison with an analytic solution for l = 3. Previously observed shifting of the magnetic axis with increasing pressure or with a changed externally applied vertical field is obtained. The case l = 0, a bumpy torus, gives convergence only for the lenient convergence tolerance of epsilon/sub b/ = 1.0 x 10-/sup 2/.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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…

  6. Local equilibrium in bird flocks

    NASA Astrophysics Data System (ADS)

    Mora, Thierry; Walczak, Aleksandra M.; Del Castello, Lorenzo; Ginelli, Francesco; Melillo, Stefania; Parisi, Leonardo; Viale, Massimiliano; Cavagna, Andrea; Giardina, Irene

    2016-12-01

    The correlated motion of flocks is an example of global order emerging from local interactions. An essential difference with respect to analogous ferromagnetic systems is that flocks are active: animals move relative to each other, dynamically rearranging their interaction network. This non-equilibrium characteristic has been studied theoretically, but its impact on actual animal groups remains to be fully explored experimentally. Here, we introduce a novel dynamical inference technique, based on the principle of maximum entropy, which accommodates network rearrangements and overcomes the problem of slow experimental sampling rates. We use this method to infer the strength and range of alignment forces from data of starling flocks. We find that local bird alignment occurs on a much faster timescale than neighbour rearrangement. Accordingly, equilibrium inference, which assumes a fixed interaction network, gives results consistent with dynamical inference. We conclude that bird orientations are in a state of local quasi-equilibrium over the interaction length scale, providing firm ground for the applicability of statistical physics in certain active systems.

  7. 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.

  8. 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)

  9. Generalized thermodynamic relations for a system experiencing heat and mass diffusion in the far-from-equilibrium realm based on steepest entropy ascent.

    PubMed

    Li, Guanchen; von Spakovsky, Michael R

    2016-09-01

    This paper presents a nonequilibrium thermodynamic model for the relaxation of a local, isolated system in nonequilibrium using the principle of steepest entropy ascent (SEA), which can be expressed as a variational principle in thermodynamic state space. The model is able to arrive at the Onsager relations for such a system. Since no assumption of local equilibrium is made, the conjugate fluxes and forces are intrinsic to the subspaces of the system's state space and are defined using the concepts of hypoequilibrium state and nonequilibrium intensive properties, which describe the nonmutual equilibrium status between subspaces of the thermodynamic state space. The Onsager relations are shown to be a thermodynamic kinematic feature of the system independent of the specific details of the micromechanical dynamics. Two kinds of relaxation processes are studied with different constraints (i.e., conservation laws) corresponding to heat and mass diffusion. Linear behavior in the near-equilibrium region as well as nonlinear behavior in the far-from-equilibrium region are discussed. Thermodynamic relations in the equilibrium and near-equilibrium realm, including the Gibbs relation, the Clausius inequality, and the Onsager relations, are generalized to the far-from-equilibrium realm. The variational principle in the space spanned by the intrinsic conjugate fluxes and forces is expressed via the quadratic dissipation potential. As an application, the model is applied to the heat and mass diffusion of a system represented by a single-particle ensemble, which can also be applied to a simple system of many particles. Phenomenological transport coefficients are also derived in the near-equilibrium realm.

  10. Local Nash equilibrium in social networks.

    PubMed

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

    2014-08-29

    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.

  11. 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.

  12. The Effects of Probenecid and Thiazides and Their Combination on the Urinary Excretion of Electrolytes and on Acid-base Equilibrium

    PubMed Central

    Garcia, D. A.; Yendt, E. R.

    1970-01-01

    The effects of commonly used therapeutic doses of hydrochlorothiazide and probenecid, given singly and in combination, on the urinary excretion of monovalent and divalent ions and on acid-base equilibrium were studied in four patients with idiopathic hypercalciuria. Probenecid had no effect on the urinary excretion of monovalent ions but resulted in a sustained increase in the urinary excretion of calcium, magnesium and citrate and a temporary increase in the urinary excretion of ammonium, in addition to its well-known effects on uric acid metabolism. A temporary fall in serum phosphorus levels was also observed. Probenecid also modified the response to hydrochlorothiazide in that the urinary excretion of calcium, magnesium and citrate was greater during combined therapy than when hydrochlorothiazide was administered alone. Probenecid prevented or abolished the increase in serum uric acid levels associated with the use of thiazide but did not modify the effects of hydrochlorothiazide on the urinary excretion of sodium, chloride, potassiu, phosphorus, ammonium, titratable acid and bicarbonate. PMID:5469617

  13. Equilibrium capillary forces with atomic force microscopy.

    PubMed

    Sprakel, J; Besseling, N A M; Leermakers, F A M; Cohen Stuart, M A

    2007-09-07

    We present measurements of equilibrium forces resulting from capillary condensation. The results give access to the ultralow interfacial tensions between the capillary bridge and the coexisting bulk phase. We demonstrate this with solutions of associative polymers and an aqueous mixture of gelatin and dextran, with interfacial tensions around 10 microN/m. The equilibrium nature of the capillary forces is attributed to the combination of a low interfacial tension and a microscopic confinement geometry, based on nucleation and growth arguments.

  14. Non-Equilibrium Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Ciccotti, Giovanni; Kapral, Raymond; Sergi, Alessandro

    Statistical mechanics provides a well-established link between microscopic equilibrium states and thermodynamics. If one considers systems out of equilibrium, the link between microscopic dynamical properties and non-equilibrium macroscopic states is more difficult to establish [1,2]. For systems lying near equilibrium, linear response theory provides a route to derive linear macroscopic laws and the microscopic expressions for the transport properties that enter the constitutive relations. If the system is displaced far from equilibrium, no fully general theory exists to treat such systems. By restricting consideration to a class of non-equilibrium states which arise from perturbations (linear or non-linear) of an equilibrium state, methods can be developed to treat non-equilibrium states. Furthermore, non-equilibrium molecular dynamics (NEMD) simulation methods can be devised to provide estimates for the transport properties of these systems.

  15. 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.

  16. 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.

  17. Solids Far from Equilibrium

    NASA Astrophysics Data System (ADS)

    Godrèche, C.

    2011-03-01

    Preface; 1. Shape and growth of crystals P. Nozières; 2. Instabilities of planar solidification fronts B. Caroli, C. Caroli and B. Roulet; 3. An introduction to the kinetics of first-order phase transition J. S. Langer; 4. Dendritic growth and related topics Y. Pomeau and M. Ben Amar; 5. Growth and aggregation far from equilibrium L. M. Sander; 6. Kinetic roughening of growing surfaces J. Krug and H. Spohn; Acknowledgements; References; Index.

  18. Molecular equilibrium with condensation

    NASA Astrophysics Data System (ADS)

    Sharp, C. M.; Huebner, W. F.

    1990-02-01

    Minimization of the Gibbs energy of formation for species of chemical elements and compounds in their gas and condensed phases determines their relative abundances in a mixture in chemical equilibrium. The procedure is more general and more powerful than previous abundance determinations in multiphase astrophysical mixtures. Some results for astrophysical equations of state are presented, and the effects of condensation on opacity are briefly indicated.

  19. Equilibrium Electroconvective Instability

    NASA Astrophysics Data System (ADS)

    Rubinstein, I.; Zaltzman, B.

    2015-03-01

    Since its prediction 15 years ago, hydrodynamic instability in concentration polarization at a charge-selective interface has been attributed to nonequilibrium electro-osmosis related to the extended space charge which develops at the limiting current. This attribution had a double basis. On the one hand, it has been recognized that neither equilibrium electro-osmosis nor bulk electroconvection can yield instability for a perfectly charge-selective solid. On the other hand, it has been shown that nonequilibrium electro-osmosis can. The first theoretical studies in which electro-osmotic instability was predicted and analyzed employed the assumption of perfect charge selectivity for the sake of simplicity and so did the subsequent studies of various time-dependent and nonlinear features of electro-osmotic instability. In this Letter, we show that relaxing the assumption of perfect charge selectivity (tantamount to fixing the electrochemical potential of counterions in the solid) allows for the equilibrium electroconvective instability. In addition, we suggest a simple experimental test for determining the true, either equilibrium or nonequilibrium, origin of instability in concentration polarization.

  20. The transformation dynamics towards equilibrium in non-equilibrium w/w/o double emulsions

    NASA Astrophysics Data System (ADS)

    Chao, Youchuang; Mak, Sze Yi; Shum, Ho Cheung

    2016-10-01

    We use a glass-based microfluidic device to generate non-equilibrium water-in-water-in-oil (w/w/o) double emulsions and study how they transform into equilibrium configurations. The method relies on using three immiscible liquids, with two of them from the phase-separated aqueous two-phase systems. We find that the transformation is accompanied by an expansion rim, while the characteristic transformation speed of the rim mainly depends on the interfacial tension between the innermost and middle phases, as well as the viscosity of the innermost phase when the middle phase is non-viscous. Remarkably, the viscosity of the outermost phase has little effect on the transformation speed. Our results account for the dynamics of non-equilibrium double emulsions towards their equilibrium structure and suggest a possibility to utilize the non-equilibrium drops to synthesize functional particles.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. 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.

  3. 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.

  4. 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.

  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. 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.

  7. Equilibrium of nematic vesicles

    NASA Astrophysics Data System (ADS)

    Napoli, Gaetano; Vergori, Luigi

    2010-11-01

    A variational scheme is proposed which allows the derivation of a concise and elegant formulation of the equilibrium equations for closed fluid membranes, endowed with a nematic microstructure. The nematic order is described by an in-plane nematic director and a degree of orientation, as customary in the theory of uniaxial nematics. The only constitutive ingredient in this scheme is a free-energy density which depends on the vesicle geometry and order parameters. The stress and the couple stress tensors related to this free-energy density are provided. As an application of the proposed scheme, a certain number of special theories are deduced: soap bubbles, lipid vesicles, chiral and achiral nematic membranes, and nematics on curved substrates.

  8. 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.

  9. 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

  10. Controlled perturbation of the thermodynamic equilibrium by microfluidic separation of porphyrin-based aggregates in a multi-component self-assembling system.

    PubMed

    Helmich, Floris; Meijer, E W

    2013-03-04

    In a microfluidic H-cell, a multi-component self-assembled system is brought out-of-equilibrium by changing the bimodal composition of porphyrin stacks and pyridine-capped dimers. Driven by their different diffusivities, diffusion-controlled separation in methylcyclohexane reveals different compositions when detected in-line and off-line, which demonstrates the kinetic behaviour of this metastable system. The microfluidic technique also proves to be highly equipped to determine diffusion constants of the different assemblies.

  11. 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…

  12. Equilibrium Policy Proposals with Abstentions.

    DTIC Science & Technology

    1981-05-01

    AB I I I EQUILIBRIUM POLICY PROPOSALS WITH ABSTENTIONS* by Peter Coughlin** 1. Introduction Spatial analyses of economic policy formation in elections...alternative in S at which there is a local equilibrium when the incumbent must defend the status quo. 5. Applications to Related Spatial Voting Models...York: Holt, Rinehart and Winston. Hestenes, M. [19751, Optimization Theoy, New York: Wiley. Hinich, M. [1977], " Equilibrium in Spatial Voting: The Median

  13. 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.

  14. Analytic prediction of airplane equilibrium spin characteristics

    NASA Technical Reports Server (NTRS)

    Adams, W. M., Jr.

    1972-01-01

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

  15. Forebody and base region real gas flow in severe planetary entry by a factored implicit numerical method. II - Equilibrium reactive gas

    NASA Technical Reports Server (NTRS)

    Davy, W. C.; Green, M. J.; Lombard, C. K.

    1981-01-01

    The factored-implicit, gas-dynamic algorithm has been adapted to the numerical simulation of equilibrium reactive flows. Changes required in the perfect gas version of the algorithm are developed, and the method of coupling gas-dynamic and chemistry variables is discussed. A flow-field solution that approximates a Jovian entry case was obtained by this method and compared with the same solution obtained by HYVIS, a computer program much used for the study of planetary entry. Comparison of surface pressure distribution and stagnation line shock-layer profiles indicates that the two solutions agree well.

  16. 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…

  17. Equilibrium states for hyperbolic potentials

    NASA Astrophysics Data System (ADS)

    Ramos, Vanessa; Viana, Marcelo

    2017-02-01

    We prove the existence of finitely many ergodic equilibrium states for local homeomorphisms and hyperbolic potentials. We also deal with partially hyperbolic skew-products over non-uniformly expanding maps with uniform contraction on the fibre. For these systems we prove the existence and finiteness of the equilibrium states associated with a class of Hölder continuous potentials.

  18. Thermodynamic efficiency out of equilibrium

    NASA Astrophysics Data System (ADS)

    Sivak, David; Crooks, Gavin

    2011-03-01

    Molecular-scale machines typically operate far from thermodynamic equilibrium, limiting the applicability of equilibrium statistical mechanics to understand their efficiency. Thermodynamic length analysis relates a non-equilibrium property (dissipation) to equilibrium properties (equilibrium fluctuations and their relaxation time). Herein we demonstrate that the thermodynamic length framework follows directly from the assumptions of linear response theory. Uniting these two frameworks provides thermodynamic length analysis a firmer statistical mechanical grounding, and equips linear response theory with a metric structure to facilitate the prediction and discovery of optimal (minimum dissipation) paths in complicated free energy landscapes. To explore the applicability of this theoretical framework, we examine its accuracy for simple bistable systems, parametrized to model single-molecule force-extension experiments. Through analytic derivation of the equilibrium fluctuations and numerical calculation of the dissipation and relaxation time, we verify that thermodynamic length analysis (though derived in a near-equilibrium limit) provides a strikingly good approximation even far from equilibrium, and thus provides a useful framework for understanding molecular motor efficiency.

  19. [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.

  20. Equilibrium Shape of Colloidal Crystals.

    PubMed

    Sehgal, Ray M; Maroudas, Dimitrios

    2015-10-27

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

  1. 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.

  2. 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…

  3. 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.

  4. 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)…

  5. Equilibrium solutions for microscopic stochastic systems in population dynamics.

    PubMed

    Lachowicz, Mirosław; Ryabukha, Tatiana

    2013-06-01

    The present paper deals with the problem of existence of equilibrium solutions of equations describing the general population dynamics at the microscopic level of modified Liouville equation (individually--based model) corresponding to a Markov jump process. We show the existence of factorized equilibrium solutions and discuss uniqueness. The conditions guaranteeing uniqueness or non-uniqueness are proposed under the assumption of periodic structures.

  6. Non-equilibrium supramolecular polymerization.

    PubMed

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-03-28

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  7. Interregional equilibrium with heterogeneous labor.

    PubMed

    Michel, P; Perrot, A; Thisse J-f

    1996-02-01

    "The impact of labor migration on interregional equilibrium is studied when workers are heterogeneous in productivity and regional mobility. The skilled respond to market disequilibrium by moving into the most attractive region. The unskilled are immobile in the short-run and move with the skilled in the long-run. Both regions have a neoclassical production function affected by an externality depending on the number of skilled. Workers move according to the utility differential when regional amenities vary with population or according to the wage differential. The equilibrium pattern depends on the unskilled's mobility and on migration incentives. Typically, regional imbalance characterizes the equilibrium which is often suboptimal."

  8. 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…

  9. Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state.

    PubMed

    Ustinov, E A; Do, D D

    2002-09-15

    A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption

  10. 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

  11. Generalized convective quasi-equilibrium principle

    NASA Astrophysics Data System (ADS)

    Yano, Jun-Ichi; Plant, Robert S.

    2016-03-01

    A generalization of Arakawa and Schubert's convective quasi-equilibrium principle is presented for a closure formulation of mass-flux convection parameterization. The original principle is based on the budget of the cloud work function. This principle is generalized by considering the budget for a vertical integral of an arbitrary convection-related quantity. The closure formulation includes Arakawa and Schubert's quasi-equilibrium, as well as both CAPE and moisture closures as special cases. The formulation also includes new possibilities for considering vertical integrals that are dependent on convective-scale variables, such as the moisture within convection. The generalized convective quasi-equilibrium is defined by a balance between large-scale forcing and convective response for a given vertically-integrated quantity. The latter takes the form of a convolution of a kernel matrix and a mass-flux spectrum, as in the original convective quasi-equilibrium. The kernel reduces to a scalar when either a bulk formulation is adopted, or only large-scale variables are considered within the vertical integral. Various physical implications of the generalized closure are discussed. These include the possibility that precipitation might be considered as a potentially-significant contribution to the large-scale forcing. Two dicta are proposed as guiding physical principles for the specifying a suitable vertically-integrated quantity.

  12. Equilibrium Molecular Thermodynamics from Kirkwood Sampling

    PubMed Central

    2015-01-01

    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. PMID:25915525

  13. 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.

  14. 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)

  15. Simulations for Teaching Chemical Equilibrium

    NASA Astrophysics Data System (ADS)

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

    2000-07-01

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

  16. Hydraulic non-equilibrium during infiltration induced by structural connectivity

    NASA Astrophysics Data System (ADS)

    Schlüter, Steffen; Vanderborght, Jan; Vogel, Hans-Jörg

    2012-08-01

    Water infiltration into heterogeneous, structured soil leads to hydraulic non-equilibrium across the infiltration front. That is, the water content and pressure head are not in equilibrium according to some static water retention curve. The water content increases more rapidly in more conductive regions followed by a slow relaxation towards an equilibrium state behind the front. An extreme case is preferential infiltration into macropores. Since flow paths adapt to the structural heterogeneity of the porous medium, there is a direct link between structure and non-equilibrium. The aim of our study is to develop an upscaled description of water dynamics which conserves the macroscopic effects of non-equilibrium and which can be directly linked to structural properties of the material. A critical question is how to define averaged state variables at the larger scale. We propose a novel approach based on flux-weighted averaging of pressure head, and compare its performance to alternative methods for averaging. Further, we suggest some meaningful indicators of hydraulic non-equilibrium that can be related to morphological characteristics of infiltration fronts in quantitative terms. These methods provide a sound basis to assess the impact of structural connectivity on hydraulic non-equilibrium. We demonstrate our approach using numerical case studies for infiltration into two-dimensional heterogeneous media using three different structure models with distinct differences in connectivity. Our results indicate that an increased isotropic, short-range connectivity reduces non-equilibrium, whereas anisotropic structures that are elongated in the direction of flow enforce it. We observe a good agreement between front morphology and effective hydraulic non-equilibrium. A detailed comparison of averaged state variables with results from an upscaled model that includes hydraulic non-equilibrium outlines potential improvements in the description of non-equilibrium dynamics

  17. 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.

  18. 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.

  19. 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.

  20. Relevance of equilibrium in multifragmentation

    SciTech Connect

    Furuta, Takuya; Ono, Akira

    2009-01-15

    The relevance of equilibrium in a multifragmentation reaction of very central {sup 40}Ca + {sup 40}Ca collisions at 35 MeV/nucleon is investigated by using simulations of antisymmetrized molecular dynamics (AMD). Two types of ensembles are compared. One is the reaction ensemble of the states at each reaction time t in collision events simulated by AMD, and the other is the equilibrium ensemble prepared by solving the AMD equation of motion for a many-nucleon system confined in a container for a long time. The comparison of the ensembles is performed for the fragment charge distribution and the excitation energies. Our calculations show that there exists an equilibrium ensemble that well reproduces the reaction ensemble at each reaction time t for the investigated period 80{<=}t{<=}300 fm/c. However, there are some other observables that show discrepancies between the reaction and equilibrium ensembles. These may be interpreted as dynamical effects in the reaction. The usual static equilibrium at each instant is not realized since any equilibrium ensemble with the same volume as that of the reaction system cannot reproduce the fragment observables.

  1. 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

    2015-09-03

    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

  2. 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.

  3. 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.

  4. Non-equilibrium dynamics from RPMD and CMD.

    PubMed

    Welsch, Ralph; Song, Kai; Shi, Qiang; Althorpe, Stuart C; Miller, Thomas F

    2016-11-28

    We investigate the calculation of approximate non-equilibrium quantum time correlation functions (TCFs) using two popular path-integral-based molecular dynamics methods, ring-polymer molecular dynamics (RPMD) and centroid molecular dynamics (CMD). It is shown that for the cases of a sudden vertical excitation and an initial momentum impulse, both RPMD and CMD yield non-equilibrium TCFs for linear operators that are exact for high temperatures, in the t = 0 limit, and for harmonic potentials; the subset of these conditions that are preserved for non-equilibrium TCFs of non-linear operators is also discussed. Furthermore, it is shown that for these non-equilibrium initial conditions, both methods retain the connection to Matsubara dynamics that has previously been established for equilibrium initial conditions. Comparison of non-equilibrium TCFs from RPMD and CMD to Matsubara dynamics at short times reveals the orders in time to which the methods agree. Specifically, for the position-autocorrelation function associated with sudden vertical excitation, RPMD and CMD agree with Matsubara dynamics up to O(t(4)) and O(t(1)), respectively; for the position-autocorrelation function associated with an initial momentum impulse, RPMD and CMD agree with Matsubara dynamics up to O(t(5)) and O(t(2)), respectively. Numerical tests using model potentials for a wide range of non-equilibrium initial conditions show that RPMD and CMD yield non-equilibrium TCFs with an accuracy that is comparable to that for equilibrium TCFs. RPMD is also used to investigate excited-state proton transfer in a system-bath model, and it is compared to numerically exact calculations performed using a recently developed version of the Liouville space hierarchical equation of motion approach; again, similar accuracy is observed for non-equilibrium and equilibrium initial conditions.

  5. Hydraulic non-equilibrium during infiltration induced by structural connectivity

    NASA Astrophysics Data System (ADS)

    Schlüter, S.; Vanderborght, J.; Vogel, H.-J.

    2012-04-01

    Water infiltration into heterogeneous, structured soil leads to hydraulic non-equilibrium across the infiltration front. That is the water content and water potential is not in equilibrium according to some static water retention curve. The water content increases more rapidly in more conductive regions followed by a slow relaxation towards an equilibrium state. An extreme case is preferential infiltration into macro-pores. As flow paths adapt to the structural heterogeneity of the subsurface, there is a direct link between structure and non-equilibrium. The aim of our study is to develop an upscaled description of water dynamics which conserves the macroscopic effects of non-equilibrium and which can be linked to structural properties of the material. However, this relationship cannot be rigorously examined without an upscaling approach that conserves non-equilibrium during averaging of state variables. We achieve this with a novel approach, that is based on flux-weighted averaging of hydraulic potential, and compare its performance to existing averaging approaches by means of infiltration simulations. Further, we set up some meaningful indicators of hydraulic non-equilibrium that can be easily compared to morphological characteristics of the infiltration front. These methods provide a sound basis to assess the impact of structural connectivity on hydraulic non-equilibrium. We generate several realizations of two-dimensional random fields originating from three heterogeneity models with distinct differences in connectivity of high-K areas and conduct infiltration simulations with them. Our results indicate, that an increased isotropic, short-range connectivity reduces non-equilibrium, whereas anisotropic, macropore-like structures enforce it. We observed a good agreement between front morphology and upscaled non-equilibrium. Our findings encourage to use flux-weighted potentials for upscaling of state variables during transient conditions. We demonstrate, that

  6. Hydraulic non-equilibrium during infiltration induced by structural connectivity

    NASA Astrophysics Data System (ADS)

    Schlüter, S.; Vogel, H.

    2011-12-01

    Water infiltration into heterogeneous, structured soil leads to hydraulic non-equilibrium across the infiltration front. That is the water content and water potential is not in equilibrium according to some static water retention curve. The water content increases more rapidly in more conductive regions followed by a slow relaxation towards an equilibrium state. An extreme case is preferential infiltration into macro-pores. As flowpaths adapt to the structural heterogeneity of the subsurface, there is a direct link between structure and non-equilibrium. The aim of our study is to develop an upscaled description of water dynamics which conserves the macroscopic effects of non-equilibrium and which can be linked to structural properties of the material. However, this relationship cannot be rigorously examined without an upscaling approach that conserves non-equilibrium during averaging of state variables. We achieve this with a novel approach, that is based on flux-weighted averaging of hydraulic potential, and compare its performance to existing averaging approaches by means of infiltration simulations. Further, we set up some meaningful indicators of hydraulic non-equilibrium that can be easily compared to morphological characteristics of the infiltration front. These methods provide a sound basis to assess the impact of structural connectivity on hydraulic non-equilibrium. We generate several realizations of two-dimensional random fields originating from three heterogeneity models with distinct differences in connectivity of high-K areas and conduct infiltration simulations with them. Our results indicate, that an increased isotropic, short-range connectivity reduces non-equilibrium, whereas anisotropic, macropore-like structures enforce it. We observed a good agreement between front morphology and upscaled non-equilibrium. Our findings encourage to use flux-weighted potentials for upscaling of state variables during transient conditions. We demonstrate, that this

  7. Non-equilibrium dynamics from RPMD and CMD

    NASA Astrophysics Data System (ADS)

    Welsch, Ralph; Song, Kai; Shi, Qiang; Althorpe, Stuart C.; Miller, Thomas F.

    2016-11-01

    We investigate the calculation of approximate non-equilibrium quantum time correlation functions (TCFs) using two popular path-integral-based molecular dynamics methods, ring-polymer molecular dynamics (RPMD) and centroid molecular dynamics (CMD). It is shown that for the cases of a sudden vertical excitation and an initial momentum impulse, both RPMD and CMD yield non-equilibrium TCFs for linear operators that are exact for high temperatures, in the t = 0 limit, and for harmonic potentials; the subset of these conditions that are preserved for non-equilibrium TCFs of non-linear operators is also discussed. Furthermore, it is shown that for these non-equilibrium initial conditions, both methods retain the connection to Matsubara dynamics that has previously been established for equilibrium initial conditions. Comparison of non-equilibrium TCFs from RPMD and CMD to Matsubara dynamics at short times reveals the orders in time to which the methods agree. Specifically, for the position-autocorrelation function associated with sudden vertical excitation, RPMD and CMD agree with Matsubara dynamics up to O (t4) and O (t1) , respectively; for the position-autocorrelation function associated with an initial momentum impulse, RPMD and CMD agree with Matsubara dynamics up to O (t5) and O (t2) , respectively. Numerical tests using model potentials for a wide range of non-equilibrium initial conditions show that RPMD and CMD yield non-equilibrium TCFs with an accuracy that is comparable to that for equilibrium TCFs. RPMD is also used to investigate excited-state proton transfer in a system-bath model, and it is compared to numerically exact calculations performed using a recently developed version of the Liouville space hierarchical equation of motion approach; again, similar accuracy is observed for non-equilibrium and equilibrium initial conditions.

  8. Neural network differential equation and plasma equilibrium solver

    NASA Astrophysics Data System (ADS)

    van Milligen, B. Ph.; Tribaldos, V.; Jiménez, J. A.

    1995-11-01

    A new generally applicable method to solve differential equations, based on neural networks, is proposed. Straightforward to implement, finite differences and coordinate transformations are not used. The neural network provides a flexible and compact base for representing the solution, found through the global minimization of an error functional. As a proof of principle, a two-dimensional ideal magnetohydrodynamic plasma equilibrium is solved. Since no particular topology is assumed, the technique is especially promising for the three-dimensional plasma equilibrium problem.

  9. Equilibrium Partitioning Sediment Benchmarks (ESBs) for the ...

    EPA Pesticide Factsheets

    This document describes procedures to determine the concentrations of nonionic organic chemicals in sediment interstitial waters. In previous ESB documents, the general equilibrium partitioning (EqP) approach was chosen for the derivation of sediment benchmarks because it accounts for the varying bioavailability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms.  This equilibrium partitioning sediment benchmark (ESB) document was prepared by scientists from the Atlantic Ecology Division, Mid-Continent Ecology Division, and Western Ecology Division, the Office of Water, and private consultants. The document describes procedures to determine the interstitial water concentrations of nonionic organic chemicals in contaminated sediments. Based on these concentrations, guidance is provided on the derivation of toxic units to assess whether the sediments are likely to cause adverse effects to benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it is based on the concentrations of chemical(s) that are known to be harmful and bioavailable in the environment.  This document, and five others published over the last nine years, will be useful for the Program Offices, including Superfund, a

  10. Equilibrium properties on the EAST superconducting tokamak

    NASA Astrophysics Data System (ADS)

    Qian, J. P.; Wan, B. N.; Lao, L. L.; Shen, B.; Sabbagh, S. A.; Menard, J.; Sun, Y. W.; Duan, Y. M.; Li, J. H.; Xiao, B. J.; Gong, X. Z.; Gong

    2009-06-01

    The Experimental Advanced Superconducting Tokamak (EAST) has a major radius of R0 = 1.75 m and a midplane halfwidth of 0.5 m. It has been operated with a toroidal magnetic field B0 = 2 T and Ip ≤ 500 kA. The evolution of the plasma equilibrium is analysed between discharges by Equilibrium Fitting Code (EFIT). Limiter, single-null and double-null diverted configurations have been produced. A plasma elongation in the range 1.3 ≤ κ ≤ 1.9 and a triangularity in the range 0.1 ≤ δ ≤ 0.55 have been sustained. The operation space of elongated discharges is also presented based on the EAST database.

  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. 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;…

  13. 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

  14. Equilibrium in a Production Economy

    SciTech Connect

    Chiarolla, Maria B.; Haussmann, Ulrich G.

    2011-06-15

    Consider a closed production-consumption economy with multiple agents and multiple resources. The resources are used to produce the consumption good. The agents derive utility from holding resources as well as consuming the good produced. They aim to maximize their utility while the manager of the production facility aims to maximize profits. With the aid of a representative agent (who has a multivariable utility function) it is shown that an Arrow-Debreu equilibrium exists. In so doing we establish technical results that will be used to solve the stochastic dynamic problem (a case with infinite dimensional commodity space so the General Equilibrium Theory does not apply) elsewhere.

  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. Equilibrium Principles: A Game for Students

    NASA Astrophysics Data System (ADS)

    Edmonson, Lionel J., Jr.; Lewis, Don L.

    1999-04-01

    The laboratory exercise is a game using marked sugar cubes as dice. The game emphasizes the dynamic character of equilibrium. Forward and reverse rate-constant values are used to calculate an equilibrium constant and to predict equilibrium populations. Predicted equilibrium populations are compared with experimental results.

  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. Generalized Convective Quasi-Equilibrium Closure

    NASA Astrophysics Data System (ADS)

    Yano, Jun-Ichi; Plant, Robert

    2016-04-01

    Arakawa and Schubert proposed convective quasi-equilibrium as a basic principle for closing their spectrum mass-flux convection parameterization. In deriving this principle, they show that the cloud work function is a key variable that controls the growth of convection. Thus, this closure hypothesis imposes a steadiness of the cloud work function tendency. This presentation shows how this principle can be generalized so that it can also encompasses both the CAPE and the moisture-convergence closures. Note that the majority of the current mass-flux convection parameterization invokes a CAPE closure, whereas the moisture-convergence closure was extremely popular historically. This generalization, in turn, includes both closures as special cases of convective quasi-equilibrium. This generalization further suggests wide range of alternative possibilities for convective closure. In general, a vertical integral of any function depending on both large-scale and convective-scale variables can be adopted as an alternative closure variables, leading to an analogous formulation as Arakawa and Schubert's convective quasi-equilibrium formulation. Among those, probably the most fascinating possibility is to take a vertical integral of the convective-scale moisture for the closure. Use of a convective-scale variable for closure has a particular appeal by not suffering from a loss of predictability of any large-scale variables. That is a main problem with any of the current convective closures, not only for the moisture-convergence based closure as often asserted.

  1. 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.

  2. 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

  3. 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.

  4. Contributions of equilibrium and non-equilibrium clusters to viscosity in concentrated protein solutions

    NASA Astrophysics Data System (ADS)

    Sarangapani, Prasad; Hudson, Steven; Pathak, Jai; Migler, Kalman

    2013-03-01

    Equilibrium and non-equilibrium clustering are ubiquitous phenomena in soft matter physics and are typically observed in systems ranging from colloidal suspensions to monoclonal antibodies (mAbs). Such phenomena are central to understanding and preventing irreversible aggregation in addition to controlling viscosity challenges related to formulation and drug delivery of protein therapeutics. Curiously, little work has been done in exploring the cluster size dependence of low-shear viscosity and intrinsic viscosity in protein solutions in a controlled manner. In this work, we carefully control cluster size of reversible and irreversible clusters formed by globular proteins or monoclonal antibodies over a concentration range of 2 mg/mL-500 mg/mL and pH from 3-9. We find a marked dependence of low-shear viscosity on cluster size using custom-designed silicon-based microfluidic viscometers. Measurements of cluster sizes using static light scattering reveal a correlation of low shear viscosity as well as intrinsic viscosity with the average cluster size. We model the composition dependence of viscosity for the case of equilibrium and non-equilibrium clusters using an adaptation of a model recently presented by Minton for protein mixtures.

  5. 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.

  6. 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'…

  7. 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…

  8. Korshunov instantons out of equilibrium

    NASA Astrophysics Data System (ADS)

    Titov, M.; Gutman, D. B.

    2016-04-01

    Zero-dimensional dissipative action possesses nontrivial minima known as Korshunov instantons. They have been known so far only for imaginary time representation that is limited to equilibrium systems. In this work we reconstruct and generalise Korshunov instantons using real-time Keldysh approach. This allows us to formulate the dissipative action theory for generic nonequilibrium conditions. Possible applications of the theory to transport in strongly biased quantum dots are discussed.

  9. 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.

  10. 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.

  11. Label-free solution-based kinetic study of aptamer-small molecule interactions by kinetic capillary electrophoresis with UV detection revealing how kinetics control equilibrium.

    PubMed

    Bao, Jiayin; Krylova, Svetlana M; Reinstein, Oren; Johnson, Philip E; Krylov, Sergey N

    2011-11-15

    Here we demonstrate a label-free solution-based approach for studying the kinetics of biopolymer-small molecule interactions. The approach utilizes kinetic capillary electrophoresis (KCE) separation and UV light absorption detection of the unlabeled small molecule. In this proof-of-concept work, we applied KCE-UV to study kinetics of interaction between a small molecule and a DNA aptamer. From the kinetic analysis of a series of aptamers, we found that dissociation rather than binding controls the stability of the complex. Because of its label-free features and generic nature, KCE-UV promises to become a practical tool for challenging kinetic studies of biopolymer-small molecule interactions.

  12. Synthesis, characterization, equilibrium study and biological activity of Cu(II), Ni(II) and Co(II) complexes of polydentate Schiff base ligand.

    PubMed

    El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

    2012-10-01

    Schiff base ligand, 1,4-bis[(2-hydroxybenzaldehyde)propyl]piperazine (BHPP), and its Cu(II), Ni(II) and Co(II) metal complexes were synthesized and characterized by elemental analysis, magnetic susceptibility, molar conductance and spectral (IR and UV-vis) studies. The ground state of BHPP ligand was investigated using the BUILDER module of MOE. Metal complexes are formed in the 1:1 (M:L) ratio as found from the elemental analysis and found to have the general formula [ML]·nH(2)O, where M=Co(II), Ni(II) and Cu(II), L=BHPP. In all the studied complexes, the (BHPP) ligand behaves as a hexadentate divalent anion with coordination involving the two azomethine nitrogen's, the two nitrogen atoms of piperazine ring and the two deprotonated phenolic OH-groups. The magnetic and spectral data indicates octahedral geometry of metal(II) complexes. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria and fungi. They were found to be more active against Gram-positive than Gram-negative bacteria. Protonation constants of (BHPP) ligand and stability constants of its Cu(2+), Co(2+) and Ni(2+) complexes were determined by potentiometric titration method in 50% DMSO-water solution at ionic strength of 0.1 M sodium nitrate. It has been observed that the protonated Schiff base ligand (BHPP) have four protonation constants. The divalent metal ions Cu(2+), Ni(2+) and Co(2+) form 1:1 complexes.

  13. 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.

  14. Equilibrium and non-equilibrium metal-ceramic interfaces

    SciTech Connect

    Gao, Y.; Merkle, K.L.

    1991-12-31

    Metal-ceramic interfaces in thermodynamic equilibrium (Au/ZrO{sub 2}) and non-equilibrium (Au/MgO) have been studied by TEM and HREM. In the Au/ZrO{sub 2} system, ZrO{sub 2} precipitates formed by internal oxidation of a 7%Zr-Au alloy show a cubic ZrO{sub 2} phase. It appears that formation of the cubic ZrO{sub 2} is facilitated by alignment with the Au matrix. Most of the ZrO{sub 2} precipitates have a perfect cube-on-cube orientation relationship with the Au matrix. The large number of interfacial steps observed in a short-time annealing experiment indicate that the precipitates are formed by the ledge growth mechanism. The lowest interfacial energy is indicated by the dominance of closed-packed [111] Au/ZrO{sub 2} interfaces. In the Au/MgO system, composite films with small MgO smoke particles embedded in a Au matrix were prepared by a thin film technique. HREM observations show that most of the Au/MgO interfaces have a strong tendency to maintain a dense lattice structure across the interfaces irrespective of whether the interfaces are incoherent of semi-coherent. This indicates that there may be relatively strong bond between MgO and Au.

  15. Equilibrium and non-equilibrium metal-ceramic interfaces

    SciTech Connect

    Gao, Y.; Merkle, K.L.

    1991-01-01

    Metal-ceramic interfaces in thermodynamic equilibrium (Au/ZrO{sub 2}) and non-equilibrium (Au/MgO) have been studied by TEM and HREM. In the Au/ZrO{sub 2} system, ZrO{sub 2} precipitates formed by internal oxidation of a 7%Zr-Au alloy show a cubic ZrO{sub 2} phase. It appears that formation of the cubic ZrO{sub 2} is facilitated by alignment with the Au matrix. Most of the ZrO{sub 2} precipitates have a perfect cube-on-cube orientation relationship with the Au matrix. The large number of interfacial steps observed in a short-time annealing experiment indicate that the precipitates are formed by the ledge growth mechanism. The lowest interfacial energy is indicated by the dominance of closed-packed (111) Au/ZrO{sub 2} interfaces. In the Au/MgO system, composite films with small MgO smoke particles embedded in a Au matrix were prepared by a thin film technique. HREM observations show that most of the Au/MgO interfaces have a strong tendency to maintain a dense lattice structure across the interfaces irrespective of whether the interfaces are incoherent of semi-coherent. This indicates that there may be relatively strong bond between MgO and Au.

  16. 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.

  17. Conformations of Proteins in Equilibrium

    NASA Astrophysics Data System (ADS)

    Micheletti, Cristian; Banavar, Jayanth R.; Maritan, Amos

    2001-08-01

    We introduce a simple theoretical approach for an equilibrium study of proteins with known native-state structures. We test our approach with results on well-studied globular proteins, chymotrypsin inhibitor (2ci2), barnase, and the alpha spectrin SH3 domain, and present evidence for a hierarchical onset of order on lowering the temperature with significant organization at the local level even at high temperatures. A further application to the folding process of HIV-1 protease shows that the model can be reliably used to identify key folding sites that are responsible for the development of drug resistance.

  18. Equilibrium of nucleotides in the dogfish brain.

    PubMed

    Andjus, Radoslav K; Dzakula, Zeljko; Marjanović, Marina

    2005-06-01

    In the past, the results of experiments on the time course of concentration changes of adenylates, phosphocreatine, and free creatine in muscle appeared compatible with an equilibrium hypothesis involving only the Lohmann and the myokinase reactions. Other reports, however, denied the applicability of the equilibrium hypothesis to the same tissue. The controversy may have been due to the high probability of experimental errors since time sampling was performed at second intervals. We presently test the hypothesis in the living brain of the small-spotted dogfish shark (Scyliorhinus canicula), an animal-model allowing for timing of sampling at hourly intervals. According to our earlier work, the dogfish shark can easily be resuscitated 8.2 h on average after being brought into the state of "suspended animation" at 0 degree C body temperature and exposed, out of water, to an atmosphere of nitrogen gas. To obtain a complete mathematical description of the time course of concentration changes of brain adenylates and phosphocreatine, we devised a kinetic model based on principles of classical multicompartmental analysis and biochemical kinetics. Model testing of the equilibrium hypothesis resulted in very good agreement between the hypothesis and our experimental data. Time-course modeling, achieved by simultaneously fitting the time series of our data by the set of four equations constituting our model resulted in an excellent agreement between data points and the computed curves. Finally, modeling of the depletion profiles of brain energy status concerning three of its descriptors (energy charge, total adenylate, and primary energy stores expressed in high-energy phosphate equivalents) allowed for a correlation to be established between energy status and the "revival time," a valuable physiological descriptor of tolerance.

  19. Diffusion and thermodynamic equilibrium under pressure variations

    NASA Astrophysics Data System (ADS)

    Moulas, Evangelos; Tajčmanová, Lucie; Vrijmoed, Johannes; Podladchikov, Yuri

    2015-04-01

    Pressure is one of the most fundamental variables in mineral thermodynamics. In that respect, pressure-sensitive mineral reactions provide an important constraint on pressure under which the rock was developed. One implicit assumption when interpreting such pressure estimates is that the state-of-stress is close to hydrostatic, homogeneous and that the differential stress is negligible. Recent spectroscopic data from the mineral scale documenting pressure variations do not support this assumption. In addition to observations, mechanical models (numerical and analytical) suggest that rocks can develop and maintain heterogeneous pressure distributions at geological time scales. The recently developed unconventional barometry explains chemical zoning in minerals as a result of a pressure variation. We focus to apply the unconventional barometry in cases where chemical zoning in minerals cannot be explained by sluggish kinetics. In that respect, the unconventional barometry offers an alternative view of the chemical zoning which is consistent with thermodynamic equilibrium. However, to distinguish between a pressure-controlled chemical zoning and a zoning reflecting an incomplete chemical reaction is still challenging, especially for multicomponent systems. In this contribution, different types of chemical zoning are discussed. We investigate plagioclase rims around kyanite from an amphibolitized eclogite from Rhodope Metamorphic Complex (Greece-Bulgaria) as a case study and compare them with similar published textures from the Bohemian Massif. Mineral microstructures and phase equilibrium suggest that both rocks experienced near-isothermal decompression at high (>700C) temperatures. However, several distinct microstructural features suggest the development and/or the decay of mechanically maintained heterogeneous pressure distributions. We discuss our results and interpretations based on phase-equilibrium modeling, unconventional barometry and diffusion modeling under

  20. 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.

  1. The geometry of structural equilibrium

    PubMed Central

    2017-01-01

    Building on a long tradition from Maxwell, Rankine, Klein and others, this paper puts forward a geometrical description of structural equilibrium which contains a procedure for the graphic analysis of stress resultants within general three-dimensional frames. The method is a natural generalization of Rankine’s reciprocal diagrams for three-dimensional trusses. The vertices and edges of dual abstract 4-polytopes are embedded within dual four-dimensional vector spaces, wherein the oriented area of generalized polygons give all six components (axial and shear forces with torsion and bending moments) of the stress resultants. The relevant quantities may be readily calculated using four-dimensional Clifford algebra. As well as giving access to frame analysis and design, the description resolves a number of long-standing problems with the incompleteness of Rankine’s description of three-dimensional trusses. Examples are given of how the procedure may be applied to structures of engineering interest, including an outline of a two-stage procedure for addressing the equilibrium of loaded gridshell rooves.

  2. 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.

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

    ERIC Educational Resources Information Center

    Silverberg, Lee J.; Raff, Lionel M.

    2015-01-01

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

  4. Dynamic Stability of Equilibrium Capillary Drops

    NASA Astrophysics Data System (ADS)

    Feldman, William M.; Kim, Inwon C.

    2014-03-01

    We investigate a model for contact angle motion of quasi-static capillary drops resting on a horizontal plane. We prove global in time existence and long time behavior (convergence to equilibrium) in a class of star-shaped initial data for which we show that topological changes of drops can be ruled out for all times. Our result applies to any drop which is initially star-shaped with respect to a small ball inside the drop, given that the volume of the drop is sufficiently large. For the analysis, we combine geometric arguments based on the moving-plane type method with energy dissipation methods based on the formal gradient flow structure of the problem.

  5. 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.

  6. 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.

  7. On statistical equilibrium in helical fluid flows

    NASA Astrophysics Data System (ADS)

    Kurgansky, M. V.

    2006-06-01

    The statistical mechanics of 3-D helical flows is re-examined for a continuum truncated at a top wavenumber. Based on the principle of equipartition of the flow enstrophy between helical modes, the emerging (i) energy spectrum law "-2" and (ii) formal mathematical analogy between the helicity and the thermodynamic entropy are discussed. It is noted that the "-2" scaling law is consistent with both spectral equilibrium and spectral cascade paradigms. In an attempt to apply the obtained results to a turbulent flow regime within the Earth's outer liquid core, where the net helicity of a turbulent flow component is presumably explained by Earth's rotation, it has been noticed that it is the energy spectral law "-1", but not "-2", which is likely realized there and within the logarithmic accuracy corresponds to the case of the velocity structure function [u(l)]2 independency on the spatial scale l, the latter is consistent with observations. It is argued that the "-1" scaling law can also be interpreted in terms of the spectral equilibrium and it is emphasized that the causes of the likely dominance of the spectral law "-1" over the spectral law "-2" in this geophysical application deserve further investigation and clarification.

  8. 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.

  9. Revealing patterns of cultural transmission from frequency data: equilibrium and non-equilibrium assumptions

    NASA Astrophysics Data System (ADS)

    Crema, Enrico R.; Kandler, Anne; Shennan, Stephen

    2016-12-01

    A long tradition of cultural evolutionary studies has developed a rich repertoire of mathematical models of social learning. Early studies have laid the foundation of more recent endeavours to infer patterns of cultural transmission from observed frequencies of a variety of cultural data, from decorative motifs on potsherds to baby names and musical preferences. While this wide range of applications provides an opportunity for the development of generalisable analytical workflows, archaeological data present new questions and challenges that require further methodological and theoretical discussion. Here we examine the decorative motifs of Neolithic pottery from an archaeological assemblage in Western Germany, and argue that the widely used (and relatively undiscussed) assumption that observed frequencies are the result of a system in equilibrium conditions is unwarranted, and can lead to incorrect conclusions. We analyse our data with a simulation-based inferential framework that can overcome some of the intrinsic limitations in archaeological data, as well as handle both equilibrium conditions and instances where the mode of cultural transmission is time-variant. Results suggest that none of the models examined can produce the observed pattern under equilibrium conditions, and suggest. instead temporal shifts in the patterns of cultural transmission.

  10. Revealing patterns of cultural transmission from frequency data: equilibrium and non-equilibrium assumptions

    PubMed Central

    Crema, Enrico R.; Kandler, Anne; Shennan, Stephen

    2016-01-01

    A long tradition of cultural evolutionary studies has developed a rich repertoire of mathematical models of social learning. Early studies have laid the foundation of more recent endeavours to infer patterns of cultural transmission from observed frequencies of a variety of cultural data, from decorative motifs on potsherds to baby names and musical preferences. While this wide range of applications provides an opportunity for the development of generalisable analytical workflows, archaeological data present new questions and challenges that require further methodological and theoretical discussion. Here we examine the decorative motifs of Neolithic pottery from an archaeological assemblage in Western Germany, and argue that the widely used (and relatively undiscussed) assumption that observed frequencies are the result of a system in equilibrium conditions is unwarranted, and can lead to incorrect conclusions. We analyse our data with a simulation-based inferential framework that can overcome some of the intrinsic limitations in archaeological data, as well as handle both equilibrium conditions and instances where the mode of cultural transmission is time-variant. Results suggest that none of the models examined can produce the observed pattern under equilibrium conditions, and suggest. instead temporal shifts in the patterns of cultural transmission. PMID:27974814

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

    PubMed

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

    2015-03-03

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

  12. Nanomechanics Model for Static Equilibrium

    NASA Astrophysics Data System (ADS)

    Jung, Sunghoon

    2002-09-01

    This study presented a computational technique to model and simulate atomistic behavior of materials under static loads, Interatomic potential energy was used to maintain equilibrium among atoms under static loads and constraints, In addition, the atomistic model was coupled with the finite element analysis model so that more flexible loads and constraints could be applied to the atomistic model A multi-scale technique was also presented for some single wall nanotubes of both zigzag and armchair and then their effective stiffness were estimated Those designed nanotubes are woven into fabric composites, which can be used in various military applications including body armored, vehicles, and infantry transportation vehicles because advanced nano- composites could be much lighter and stronger than current ones, Some example problems were presented to illustrate the developed technique for the nano-composites and SWNTs, The proposed technique for nanomechanics can be used for design and analysis of materials at the atomic or molecular level,

  13. Equilibrium structure of ferrofluid aggregates.

    PubMed

    Yoon, Mina; Tománek, David

    2010-11-17

    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.

  14. 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.

  15. Local non-equilibrium thermodynamics

    PubMed Central

    Jinwoo, Lee; Tanaka, Hajime

    2015-01-01

    Local Shannon entropy lies at the heart of modern thermodynamics, with much discussion of trajectory-dependent entropy production. When taken at both boundaries of a process in phase space, it reproduces the second law of thermodynamics over a finite time interval for small scale systems. However, given that entropy is an ensemble property, it has never been clear how one can assign such a quantity locally. Given such a fundamental omission in our knowledge, we construct a new ensemble composed of trajectories reaching an individual microstate, and show that locally defined entropy, information, and free energy are properties of the ensemble, or trajectory-independent true thermodynamic potentials. We find that the Boltzmann-Gibbs distribution and Landauer's principle can be generalized naturally as properties of the ensemble, and that trajectory-free state functions of the ensemble govern the exact mechanism of non-equilibrium relaxation. PMID:25592077

  16. Equilibrium avalanches in spin glasses

    NASA Astrophysics Data System (ADS)

    Le Doussal, Pierre; Müller, Markus; Wiese, Kay Jörg

    2012-06-01

    We study the distribution of equilibrium avalanches (shocks) in Ising spin glasses which occur at zero temperature upon small changes in the magnetic field. For the infinite-range Sherrington-Kirkpatrick (SK) model, we present a detailed derivation of the density ρ(ΔM) of the magnetization jumps ΔM. It is obtained by introducing a multicomponent generalization of the Parisi-Duplantier equation, which allows us to compute all cumulants of the magnetization. We find that ρ(ΔM)˜ΔM-τ with an avalanche exponent τ=1 for the SK model, originating from the marginal stability (criticality) of the model. It holds for jumps of size 1≪ΔMequilibrium dynamics of the SK model. For finite-range models, using droplet arguments, we obtain the prediction τ=(df+θ)/dm where df,dm, and θ are the fractal dimension, magnetization exponent, and energy exponent of a droplet, respectively. This formula is expected to apply to other glassy disordered systems, such as the random-field model and pinned interfaces. We make suggestions for further numerical investigations, as well as experimental studies of the Barkhausen noise in spin glasses.

  17. Approximate Equilibrium Shapes for Spinning, Gravitating Rubble Asteroids

    NASA Astrophysics Data System (ADS)

    Burns, Joseph A.; Sharma, I.; Jenkins, J. T.

    2007-10-01

    Approximate Equilibrium Shapes for Spinning, Gravitating Rubble Asteroids Joseph A. Burns, Ishan Sharma and James T. Jenkins Many asteroids are thought to be particle aggregates held together principally by self-gravity. Here we study those equilibrium shapes of spinning asteroids that are permitted for rubble piles. As in the case of spinning fluid masses, not all shapes may be compatible with a granular rheology. We take the asteroid to always be an ellipsoid with an interior modeled as a rigid-plastic, cohesion-less material. Using an approximate volume-averaged procedure, based on the classical method of moments, we investigate the dynamical process by which such objects may achieve equilibrium. First, to instill confidence in our approach, we have collapsed our dynamical approach to its statical limit to re-derive regions in spin-shape parameter space that allow equilibrium solutions to exist. Not surprisingly, our results duplicate static results reported by Holsapple (Icarus 154 [2001], 432; 172 [2004], 272) since the two sets of final equations match, although the formalisms to reach these expressions differ. We note that the approach applied here was obtained independently by I.S. in his Ph.D. dissertation (Cornell University, 2004); it provides a general, though approximate, framework that is amenable to systematic improvements and flexible enough to incorporate the dynamical effects of a changing shape, different rheologies and complex rotational histories. To demonstrate the power of our technique, we investigate the non-equilibrium dynamics of rigid-plastic, spinning, prolate asteroids to watch the simultaneous histories of shape and spin rate for rubble piles. We have succeeded in recovering most results of Richardson et al. (Icarus 173 [2004], 349), who obtained equilibrium shapes by studying numerically the passage into equilibrium of aggregates containing discrete, interacting, frictionless, spherical particles. Our mainly analytical approach aids

  18. The stochastic link equilibrium strategy and algorithm for flow assignment in communication networks

    NASA Astrophysics Data System (ADS)

    Tao, Yang; Zhou, Xia

    2005-11-01

    Based on the mature user equilibrium (UE) theory in transportation field as well as the similarity of network flow between transportation and communication, in this paper, the user equilibrium theory was applied to communication networks, and how to apply the stochastic user equilibrium (SUE) to flow assigning in generalized communication networks was further studied. The stochastic link equilibrium (SLE) flow assignment strategy was proposed in this paper, the algorithm of SLE flow assignment was also provided. Both analyses and simulation based on the given algorithm proved that the optimal flow assignment in networks can be achieved by using this algorithm.

  19. LAPS discretization and solution of plasma equilibrium

    NASA Astrophysics Data System (ADS)

    Missanelli, Maria; Delzanno, Gian Luca; Guo, Zehua; Srinivasan, Bhuvana; Tang, Xianzhu

    2011-10-01

    LAPS provides spectral element discretization for solving steady state plasma profiles. Our initial focus is on its implementation for two dimensional open magnetic field equilibria in linear and toroidal geometries. The linear geometry is an axisymmetric magnetic mirror with anisotropic pressure. The toroidal case is a tokamak scrape-off layer plasma. Structured grids are produced by the grid generation package in LAPS. The spectral element discretization uses modal bases over quadrilateral elements. A Newton-Krylov solver implemented with the Portable, Extensible Toolkits for Scientific Computing PETSc is applied to iteratively converge the solution. Care has been taken in the code design to separate the grid generation, spectral element discretization, and (non)linear solver from the user-specified equilibrium equations, so the LAPS infrastructure can be easily used for different applications. Work supported by DOE OFES.

  20. 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.

  1. Approach to Equilibrium for the Stochastic NLS

    NASA Astrophysics Data System (ADS)

    Lebowitz, J. L.; Mounaix, Ph.; Wang, W.-M.

    2013-07-01

    We study the approach to equilibrium, described by a Gibbs measure, for a system on a d-dimensional torus evolving according to a stochastic nonlinear Schrödinger equation (SNLS) with a high frequency truncation. We prove exponential approach to the truncated Gibbs measure both for the focusing and defocusing cases when the dynamics is constrained via suitable boundary conditions to regions of the Fourier space where the Hamiltonian is convex. Our method is based on establishing a spectral gap for the non self-adjoint Fokker-Planck operator governing the time evolution of the measure, which is uniform in the frequency truncation N. The limit N →∞ is discussed.

  2. Equilibrium Structure of Tantalum Oxygen Clusters

    NASA Astrophysics Data System (ADS)

    Dalgic, S. Sentürk; Caliskan, M.

    2007-04-01

    We determine a refined model for the interionic interactions in TaOn clusters by an analysis of data on their molecular structures. The potential energy function of an ionic cluster we adopt is based on the interionic force model proposed by Akdeniz and Tosi. The microscopic model used for Tantalum oxygen clusters incorporates the Born Model of cohesion and shell model for vibrational motions and crystal defects. Electron shell deformability is described through the effective valences, the electric and overlap polarizabilities of the oxygens, the electric polarizability of the tantalum ions. The two different overlap repulsive energy form have been tested. The molecular structure of clusters in equilibrium have been shown. It has been found in a good agreement for the bond lengths and bond angles by comparing with those obtained by chemical structure calculations and experimental data Thus the applicability of interionic model is tested for transition metal oxide clusters.

  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. 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.

  5. 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

  6. 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

  7. 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.

  8. Development of equilibrium raindrop size distribution in natural rain.

    NASA Astrophysics Data System (ADS)

    Pio D'Adderio, Leo; Porcu, Federico; Tokay, Ali

    2015-04-01

    The NASA's Global Precipitation Measurement (GPM) mission dual-frequency precipitation radar retrieval has adopted a three-parameter gamma distribution to retrieve the raindrop size distribution (DSD) from dual-frequency precipitation radar (DPR) measurements. Recent analysis from disdrometric measurements collected during GPM ground validation (GV) field experiments shows that the three-parameter gamma distribution does not well fit the observed spectra in the presence of collisional break-up, i.e. when the DSD reaches the equilibrium stage. An automatic algorithm is used to select equilibrium DSD in six datasets for a total number of more than 12,000 minutes with rain rate higher than 5 mmh-1 collected from 2-DVD disdrometers. The algorithm is based on the analysis of the DSD slope in the interval 1.0-2.5 mm diameter. The 1-minute time series are studied in order to assess the conditions more favorable for equilibrium DSD to take place, showing the transition between the one-peak DSD to the 2-peak DSD, for selected case studies, over a wide range of rainrate values. The results are discussed in terms of precipitation type and intensity, showing a very rapid onset and dissipation of equilibrium DSD conditions. The temporal evolution of some DSD parameters is also analyzed, and, for two of the six datasets (MC3E and Wallops), was also possible to evaluate the small-scale spatial structure of equilibrium DSD.

  9. Regularized Mathematical Programs with Stochastic Equilibrium Constraints: Estimating Structural Demand Models

    DTIC Science & Technology

    2013-07-23

    equilibrium constraints involving only single-valued Lipschitz continuous functions. In addition, sampling has the further effect of replacing the...constraints, based on regularization, that replaces them by equilibrium constraints involving only single-valued Lipschitz continuous functions. In addition...only single-valued Lipschitz continuous functions. In addition, sampling has the further effect of replacing the ‘simplified’ equilibrium constraints by

  10. 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)

  11. SCREENED COULOMB FORMULATION OF THE IONIZATION EQUILIBRIUM EQUATION OF STATE,

    DTIC Science & Technology

    The ionization equilibrium equation of state (IEEOS) is formulated relative to the numerical solutions of the Schrodinger equation with the complete...for hydrogen and iron, where pressures at high densities and temperature are compared with pressures from the equation of state based upon the Thomas...IEEOS represents a significant improvement over the TFD equation of state . (Author)

  12. 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.)

  13. 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.

  14. Time-resolved measurements of equilibrium profiles in MST

    NASA Astrophysics Data System (ADS)

    Deng, B. H.; Brower, D. L.; Ding, W. X.; Yates, T. F.; Anderson, J. K.; Caspary, K.; McCollam, K. J.; Prager, S. C.; Reusch, J. A.; Sarff, J. S.; Craig, D.

    2007-11-01

    Based on the high-speed, three-wave, far-infrared polarimeter-interferometer measurement of Bpol profiles and external coil measurements of Btave and Btw, a new method is developed to derive Btor and other equilibrium profiles (J// and q) with high time resolution. Using Faraday's law, the inductive electric field (E//) profile is also deduced from the temporal derivatives of the time-resolved magnetic field profiles. The derived B(0) values have excellent agreement with direct measurements using a Motional Stark Effect (MSE) diagnostic. Evolution of equilibrium profiles during single sawtooth events in MST, both the slow linear ramp and crash phases, are presented. Profile scaling with plasma current Ip and reversal parameter F is also explored. MHD stability is tested from the spatial gradients of the J// and q profiles, and correlation with fluctuation mode amplitude is investigated. Future improvements to equilibrium reconstruction are expected by measuring Btor(r,t) directly via Cotton-Mouton interferometry.

  15. The use of Bayesian inversion to resolve plasma equilibrium

    SciTech Connect

    Hole, M. J.; Nessi, G. von; Pretty, D.; Howard, J.; Blackwell, B.; Svensson, J.; Appel, L. C.

    2010-10-15

    Recently, Bayesian probability theory has been used at a number of experiments to fold uncertainties and interdependencies in the diagnostic data and forward models, together with prior knowledge of the state of the plasma, to increase accuracy of inferred physics variables. A new probabilistic framework, MINERVA, based on Bayesian graphical models, has been used at JET and W7-AS to yield predictions of internal magnetic structure. A feature of the framework is the Bayesian inversion for poloidal magnetic flux without the need for an explicit equilibrium assumption. Building on this, we discuss results from a new project to develop Bayesian inversion tools that aim to (1) distinguish between competing equilibrium theories, which capture different physics, using the MAST spherical tokamak, and (2) test the predictions of MHD theory, particularly mode structure, using the H-1 Heliac. Specifically, we report on correction of the motional Stark effect, pickup coils, flux-loop constrained Bayesian inferred equilibrium for varying toroidal flux.

  16. The use of bayesian inversion to resolve plasma equilibrium.

    PubMed

    Hole, M J; von Nessi, G; Pretty, D; Howard, J; Blackwell, B; Svensson, J; Appel, L C

    2010-10-01

    Recently, bayesian probability theory has been used at a number of experiments to fold uncertainties and interdependencies in the diagnostic data and forward models, together with prior knowledge of the state of the plasma, to increase accuracy of inferred physics variables. A new probabilistic framework, MINERVA, based on bayesian graphical models, has been used at JET and W7-AS to yield predictions of internal magnetic structure. A feature of the framework is the bayesian inversion for poloidal magnetic flux without the need for an explicit equilibrium assumption. Building on this, we discuss results from a new project to develop bayesian inversion tools that aim to (1) distinguish between competing equilibrium theories, which capture different physics, using the MAST spherical tokamak, and (2) test the predictions of MHD theory, particularly mode structure, using the H-1 Heliac. Specifically, we report on correction of the motional Stark effect, pickup coils, flux-loop constrained bayesian inferred equilibrium for varying toroidal flux.

  17. V3FIT: Three-Dimensional MHD Equilibrium Reconstruction

    NASA Astrophysics Data System (ADS)

    Hanson, James D.; Shields, John; Hirshman, S. P.; Lazarus, E. A.; Lao, L.; Knowlton, S. F.

    2007-11-01

    V3FIT is a three-dimensional MHD equilibrium reconstruction code, based on the VMEC equilibrium code. V3FIT is a general and easily extensible reconstruction code, designed so that information from many types of diagnostics can be used to determine the equilibrium. The first diagnostics included in V3FIT were magnetic diagnostics. We will present results on reconstruction using microwave interferometers and polarimeters as diagnostics. We will also show comparisons between V3FIT and EFIT reconstructions using experimental data from the DIII-D tokamak. This work is supported in part by US DOE Grant DE-FG02-03ER54692B and a US DOE Postdoctoral Research Fellowship.

  18. 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.

  19. 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.

  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. Far from Equilibrium: The Gas Pendulum.

    ERIC Educational Resources Information Center

    Soltzberg, Leonard J.

    1986-01-01

    Discusses the importance of studying the far-from-equilibrium phenomena in college chemistry. Presents a system using the gas pendulum which displays all of the essential characteristics of dissipative systems. Promotes the use of the gas pendulum as a teaching example of a nonlinear far-from-equilibrium process. (TW)

  5. Equilibrium Tail Distribution Due to Touschek Scattering

    SciTech Connect

    Nash,B.; Krinsky, S.

    2009-05-04

    Single large angle Coulomb scattering is referred to as Touschek scattering. In addition to causing particle loss when the scattered particles are outside the momentum aperture, the process also results in a non-Gaussian tail, which is an equilibrium between the Touschek scattering and radiation damping. Here we present an analytical calculation for this equilibrium distribution.

  6. 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…

  7. Information-theoretic equilibrium and observable thermalization

    PubMed Central

    Anzà, F.; Vedral, V.

    2017-01-01

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

  8. 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.

  9. Information-theoretic equilibrium and observable thermalization

    NASA Astrophysics Data System (ADS)

    Anzà, F.; Vedral, V.

    2017-03-01

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

  10. Information-theoretic equilibrium and observable thermalization.

    PubMed

    Anzà, F; Vedral, V

    2017-03-07

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

  11. 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.

  12. 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.

  13. 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.

  14. Comparison of equilibrium and non-equilibrium distribution coefficients for the human drug carbamazepine in soil.

    PubMed

    Williams, C F; Watson, J E; Nelson, S D

    2014-01-01

    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 the columns at 0.5, 1.0 and 1.5 mL min(-1) representing average linear velocities of 1.8, 3.5 and 5.3 cm h(-1) respectively. Each flow rate was replicated three times and three carbamazepine pulses were applied to each column resulting in a total of 9 columns with 27 total carbamazepine pulses. Breakthrough curves were used to determine KD using the parameter fitting software CXTFIT. Results indicate that as flow rate decreased from 5.3 to 1.8 cm h(-1), KD increased an average of 21%. Additionally, KD determined by column leaching (14.7-22.7 L kg(-1)) was greater than KD determined by a 2h batch equilibrium adsorption (12.6 L kg(-1)). Based on these KD's carbamazepine would be generally characterized as non-mobile in the soil investigated. However, repeated carbamazepine applications resulted in an average 22% decrease in KD between the first and third applications. Decreasing KD is attributed to differences in sorption site kinetics and carbamazepine residence time in contact with the soil. This would indicate that the repeated use of reclaimed wastewater at high application rates for long-term irrigation or groundwater recharge has the potential to lead to greater transport of carbamazepine than KD determined by batch equilibrium would predict.

  15. 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…

  16. 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)

  17. 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).

  18. 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…

  19. 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.

  20. A general framework for ion equilibrium calculations in compacted bentonite

    NASA Astrophysics Data System (ADS)

    Birgersson, Martin

    2017-03-01

    An approach for treating chemical equilibrium between compacted bentonite and aqueous solutions is presented. The treatment is based on conceptualizing bentonite as a homogeneous mixture of water and montmorillonite, and assumes Gibbs-Donnan membrane equilibrium across interfaces to external solutions. An equation for calculating the electrostatic potential difference between bentonite and external solution (Donnan potential) is derived and solved analytically for some simple systems. The solutions are furthermore analyzed in order to illuminate the general mechanisms of ion equilibrium and their relation to measurable quantities. A method is suggested for estimating interlayer activity coefficients based on the notion of an interlayer ionic strength. Using this method, several applications of the framework are presented, giving a set of quantitative predictions which may be relatively simply tested experimentally, e.g.: (1) the relative amount of anions entering the bentonite depends approximately on the square-root of the external concentration for a 1:2 salt (e.g. CaCl2). For a 1:1 salt (e.g. NaCl) the dependence is approximately linear, and for a 1:2 salt (e.g. Na2SO4) the dependence is approximately quadratic. (2) Bentonite contains substantially more nitrate as compared to chloride if equilibrated with the two salt solutions at equal external concentration. (3) Potassium bentonite generally contains more anions as compared to sodium bentonite if equilibrated at the same external concentration. (4) The anion concentration ratio in two bentonite samples of different cations (but with the same density and cation exchange capacity) resembles the ion exchange selectivity coefficient for that specific cation pair. The results show that an adequate treatment of chemical equilibrium between interlayers and bulk solutions are essential when modeling compacted bentonite, and that activity corrections generally are required for relevant ion equilibrium calculations. It

  1. Temperature lapse rates at restricted thermodynamic equilibrium. Part II: Saturated air and further discussions

    NASA Astrophysics Data System (ADS)

    Björnbom, Pehr

    2016-03-01

    In the first part of this work equilibrium temperature profiles in fluid columns with ideal gas or ideal liquid were obtained by numerically minimizing the column energy at constant entropy, equivalent to maximizing column entropy at constant energy. A minimum in internal plus potential energy for an isothermal temperature profile was obtained in line with Gibbs' classical equilibrium criterion. However, a minimum in internal energy alone for adiabatic temperature profiles was also obtained. This led to a hypothesis that the adiabatic lapse rate corresponds to a restricted equilibrium state, a type of state in fact discussed already by Gibbs. In this paper similar numerical results for a fluid column with saturated air suggest that also the saturated adiabatic lapse rate corresponds to a restricted equilibrium state. The proposed hypothesis is further discussed and amended based on the previous and the present numerical results and a theoretical analysis based on Gibbs' equilibrium theory.

  2. 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

  3. 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.

  4. 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)

  5. 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

  6. 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.

  7. 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.

  8. New aspects of the equilibrium pole tide

    NASA Technical Reports Server (NTRS)

    Dickman, S. R.; Steinberg, D. J.

    1986-01-01

    A new spherical harmonic algorithm is developed for the calculation of the loading and self-gravitating equilibrium pole tide. Based on a suggestion of Dahlen (1976), this approach minimizes the distortions in tide height caused by an incomplete representation of the ocean function. With slight modification this approach easily could be used to compute self-gravitating and loading lunisolar tides as well. Using the algorithm, the static pole tide is compared with tide observations at a variety of locations around the world, and statistically significant evidence for pole tide enhancements is found in midocean as well as the shallow seas. Also included is a reinvestigation of the effect of the static tide on the Chandler-wobble period. The difference between the wobble period of an oceanless elastic earth with a fluid core (Smith and Dahlen, 1981) and the period of an earth minus static oceans yields a 7.4-day discrepancy. It is concluded from tide observations that much of the discrepancy can probably be accounted for by nonequilibrium pole-tide behavior in the deep oceans.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Equilibrium and Non-Equilibrium Condensation Phenomena in Tuneable 3D and 2D Bose Gases

    DTIC Science & Technology

    2016-04-01

    equilibrium and non-equilibrium many-body phenomena, trapping ultracold atomic gases in different geometries including both 3 and 2 spatial dimensions...box trap we created the world’s first atomic BEC in a quasi-uniform potential. 15. SUBJECT TERMS EOARD, Bose gas, ultracold, condensation, equilibrium... atom trap, Bose-Einstein condensate 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT SAR 18. NUMBER OF PAGES 3 19a. NAME OF RESPONSIBLE

  15. 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

  16. EAST equilibrium current profile reconstruction using polarimeter-interferometer internal measurement constraints

    NASA Astrophysics Data System (ADS)

    Qian, J. P.; Lao, L. L.; Liu, H. Q.; Ding, W. X.; Zeng, L.; Luo, Z. P.; Ren, Q. L.; Huang, Y.; Huang, J.; Brower, D. L.; Hanada, K.; Chen, D. L.; Sun, Y. W.; Shen, B.; Gong, X. Z.; Xiao, B. J.; Wan, B. N.

    2017-03-01

    The first equilibrium reconstruction of EAST current-density profile based on internal Faraday rotation measurements provided by the POlarimeter-INTerferometer (POINT) diagnostic is demonstrated using the EFIT equilibrium reconstruction code. EFIT incorporates 11 simultaneous line-integrated density and Faraday effect measurements from POINT to self-consistently reconstruct the equilibrium toroidal current density profile using a Faraday rotation reconstruction algorithm. It is shown that the POINT measurements can be applied to improve the accuracy of core plasma current density and q profile on EAST. Comparisons of magnetic surfaces and the q profile reconstructed using external magnetic data against those using magnetic and POINT data are presented. Equilibrium reconstructions using POINT data are found to be consistent with sawtooth phenomena. The sensitivity of equilibrium reconstruction to POINT measurements indicates Faraday rotation provides important constraints for determining the current profile.

  17. 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.

  18. Classifying magnetic and superfluid equilibrium states in magnets with the spin s = 1

    NASA Astrophysics Data System (ADS)

    Kovalevskii, M. Yu.

    2016-03-01

    Based on the method of quasiaverages, we classify magnetic and superfluid equilibrium states in magnets with the spin s = 1. Under certain simplifications, assumptions about the residual symmetry of degenerate states and the transformation properties of order parameter operators under transformations generated by additive integrals of motions lead to linear algebraic equations for a classification of the equilibrium means of the order parameters. We consider different cases of the magnetic SO(3) or SU(3) symmetry breaking and obtain solutions for the vector and tensor order parameters for particular forms of the parameters of the residual symmetry generators. We study the equilibriums of magnets with simultaneously broken phase and magnetic symmetries. We find solutions of the classification equations for superfluid equilibrium states and establish relations between the parameters of the residual symmetry generator that allow the thermodynamic coexistence of nonzero equilibrium means of the order parameters.

  19. 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.

  20. Equilibrium and non-equilibrium emission of complex fragments

    SciTech Connect

    Bowman, D.R.

    1989-08-01

    Complex fragment emission (Z{gt}2) has been studied in the reactions of 50, 80, and 100 MeV/u {sup 139}La + {sup 12}C, and 80 MeV/u {sup 139}La + {sup 27}Al, {sup nat}Cu, and {sup 197}Au. Charge, angle, and energy distributions were measured inclusively and in coincidence with other complex fragments, and were used to extract the source rapidities, velocity distributions, and cross sections. The experimental emission velocity distributions, charge loss distributions, and cross sections have been compared with calculations based on statistical compound nucleus decay. The binary signature of the coincidence events and the sharpness of the velocity distributions illustrate the primarily 2-body nature of the {sup 139}La + {sup 12}C reaction mechanism between 50 and 100 MeV/u. The emission velocities, angular distributions, and absolute cross sections of fragments of 20{le}Z{le}35 at 50 MeV/u, 19{le}Z{le}28 at 80 MeV/u, and 17{le}Z{le}21 at 100 MeV/u indicate that these fragments arise solely from the binary decay of compound nuclei formed in incomplete fusion reactions in which the {sup 139}La projectile picks up about one-half of the {sup 12}C target. In the 80 MeV/u {sup 139}La + {sup 27}Al, {sup nat}Cu, and {sup 197}Au reactions, the disappearance of the binary signature in the total charge and velocity distributions suggests and increase in the complex fragment and light charged particle multiplicity with increasing target mass. As in the 80 and 100 MeV/u {sup 139}La + {sup 12}C reactions, the lighter complex fragments exhibit anisotropic angular distributions and cross sections that are too large to be explained exclusively by statistical emission. 143 refs., 67 figs.

  1. On equilibrium structures of the water molecule

    NASA Astrophysics Data System (ADS)

    Császár, Attila G.; Czakó, Gábor; Furtenbacher, Tibor; Tennyson, Jonathan; Szalay, Viktor; Shirin, Sergei V.; Zobov, Nikolai F.; Polyansky, Oleg L.

    2005-06-01

    Equilibrium structures are fundamental entities in molecular sciences. They can be inferred from experimental data by complicated inverse procedures which often rely on several assumptions, including the Born-Oppenheimer approximation. Theory provides a direct route to equilibrium geometries. A recent high-quality ab initio semiglobal adiabatic potential-energy surface (PES) of the electronic ground state of water, reported by Polyansky et al. [Polyansky et al.Science 299, 539 (2003)] and called CVRQD here, is analyzed in this respect. The equilibrium geometries resulting from this direct route are deemed to be of higher accuracy than those that can be determined by analyzing experimental data. Detailed investigation of the effect of the breakdown of the Born-Oppenheimer approximation suggests that the concept of an isotope-independent equilibrium structure holds to about 3×10-5Å and 0.02° for water. The mass-independent [Born-Oppenheimer (BO)] equilibrium bond length and bond angle on the ground electronic state PES of water is reBO=0.95782Å and θeBO=104.485°, respectively. The related mass-dependent (adiabatic) equilibrium bond length and bond angle of H2O16 is read=0.95785Å and θead=104.500°, respectively, while those of D2O16 are read=0.95783Å and θead=104.490°. Pure ab initio prediction of J =1 and 2 rotational levels on the vibrational ground state by the CVRQD PESs is accurate to better than 0.002cm-1 for all isotopologs of water considered. Elaborate adjustment of the CVRQD PESs to reproduce all observed rovibrational transitions to better than 0.05cm-1 (or the lower ones to better than 0.0035cm-1) does not result in noticeable changes in the adiabatic equilibrium structure parameters. The expectation values of the ground vibrational state rotational constants of the water isotopologs, computed in the Eckart frame using the CVRQD PESs and atomic masses, deviate from the experimentally measured ones only marginally, especially for A0 and B0. The

  2. Aerospace Applications of Non-Equilibrium Plasma

    NASA Technical Reports Server (NTRS)

    Blankson, Isaiah M.

    2016-01-01

    Nonequilibrium plasma/non-thermal plasma/cold plasmas are being used in a wide range of new applications in aeronautics, active flow control, heat transfer reduction, plasma-assisted ignition and combustion, noise suppression, and power generation. Industrial applications may be found in pollution control, materials surface treatment, and water purification. In order for these plasma processes to become practical, efficient means of ionization are necessary. A primary challenge for these applications is to create a desired non-equilibrium plasma in air by preventing the discharge from transitioning into an arc. Of particular interest is the impact on simulations and experimental data with and without detailed consideration of non-equilibrium effects, and the consequences of neglecting non-equilibrium. This presentation will provide an assessment of the presence and influence of non-equilibrium phenomena for various aerospace needs and applications. Specific examples to be considered will include the forward energy deposition of laser-induced non-equilibrium plasmoids for sonic boom mitigation, weakly ionized flows obtained from pulsed nanosecond discharges for an annular Hall type MHD generator duct for turbojet energy bypass, and fundamental mechanisms affecting the design and operation of novel plasma-assisted reactive systems in dielectric liquids (water purification, in-pipe modification of fuels, etc.).

  3. Equilibrium radiative heating tables for aerobraking in the Martian atmosphere

    NASA Technical Reports Server (NTRS)

    Hartung, Lin C.; Sutton, Kenneth; Brauns, Frank

    1990-01-01

    Studies currently underway for Mars missions often envision the use of aerobraking for orbital capture at Mars. These missions generally involve blunt-nosed vehicles to dissipate the excess energy of the interplanetary transfer. Radiative heating may be of importance in these blunt-body flows because of the highly energetic shock layer around the blunt nose. In addition, the Martian atmosphere contains CO2, whose dissociation products are known to include strong radiators. An inviscid, equilibrium, stagnation point, radiation-coupled flow-field code has been developed for investigating blunt-body atmospheric entry. The method has been compared with ground-based and flight data for air, and reasonable agreement has been found. In the present work, the method was applied to a matrix of conditions in the Martian atmosphere. These conditions encompass most trajectories of interest for Mars exploration spacecraft. The predicted equilibrium radiative heating to the stagnation point of the vehicle is presented.

  4. 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.

  5. Interfaces at equilibrium: A guide to fundamentals.

    PubMed

    Marmur, Abraham

    2016-05-20

    The fundamentals of the thermodynamics of interfaces are reviewed and concisely presented. The discussion starts with a short review of the elements of bulk thermodynamics that are also relevant to interfaces. It continues with the interfacial thermodynamics of two-phase systems, including the definition of interfacial tension and adsorption. Finally, the interfacial thermodynamics of three-phase (wetting) systems is discussed, including the topic of non-wettable surfaces. A clear distinction is made between equilibrium conditions, in terms of minimizing energies (internal, Gibbs or Helmholtz), and equilibrium indicators, in terms of measurable, intrinsic properties (temperature, chemical potential, pressure). It is emphasized that the equilibrium indicators are the same whatever energy is minimized, if the boundary conditions are properly chosen. Also, to avoid a common confusion, a distinction is made between systems of constant volume and systems with drops of constant volume.

  6. KSTAR Equilibrium Reconstruction with EFIT Code

    NASA Astrophysics Data System (ADS)

    You, Kwang-Il; Lee, D. K.; Hahn, S. H.; Lao, L. L.

    2007-11-01

    For application to the KSTAR (Korea Superconducting Tokamak Advanced Research) device, we have made some modification to the EFIT code and installed it on our computing system. The main function of EFIT is reconstruction of plasma equilibrium using discharge data. After every discharge, the code will be automatically run for a chosen time array and the results will be stored in the same way as experimental data will be. An MDSplus system will be used as the data storage for KSTAR; therefore, the EFIT reads experimental data from the MDSplus server and writes the results to it. We have added some subroutines to EFIT for direct link with the MDSplus server and also converted EFIT to Fortran 95 form. Test runs of the code will be made by using plasma simulator in the KSTAR plasma control system. This paper will also present some results of equilibrium data obtained with the equilibrium mode of EFIT.

  7. Equilibrium reconstruction using EFIT code for KSTAR

    NASA Astrophysics Data System (ADS)

    You, Kwang-Il; Lee, D. K.; Jeon, Y. M.; Hahn, S. H.; Lao, L. L.

    2006-10-01

    For application to the KSTAR (Korea Superconducting Tokamak Advanced Research) device, we have made some modification to the EFIT code and installed it on our computing system. The main function of EFIT is reconstruction of plasma equilibrium using discharge data. After every discharge, the code will be run for a chosen time array and the results will be stored in the same way as experimental data will be. An MDSplus system will be used as the data storage for KSTAR; therefore, the EFIT reads experimental data from the MDSplus server and writes the results to it. We have added some subroutines to EFIT for direct link with the MDSplus server and also converted it to Fortran 95 form. Test runs of the code will be made by using the KSTAR plasma control system. This paper will also present results of equilibrium data obtained with the equilibrium mode of EFIT.

  8. Pions in and out of equilibrium

    SciTech Connect

    Gavin, S.

    1991-12-01

    Can final state scattering wrestle the secondaries in nucleus-nucleus collisions into a fluid state near local thermal equilibrium What do the pion p{sub T} spectra measured in pp, pA and SPS light ion experiments already tell us about the approach to equilibrium To begin to address these questions, we must face the nonequilibrium nature of hadronic evolution in the late stages of these collisions. I will outline efforts to apply transport theory to the nonequilibrium pion fluid at midrapidity focusing on two phenomena: partial thermalization and pion conservation.

  9. Pions in and out of equilibrium

    SciTech Connect

    Gavin, S.

    1991-12-01

    Can final state scattering wrestle the secondaries in nucleus-nucleus collisions into a fluid state near local thermal equilibrium? What do the pion p{sub T} spectra measured in pp, pA and SPS light ion experiments already tell us about the approach to equilibrium? To begin to address these questions, we must face the nonequilibrium nature of hadronic evolution in the late stages of these collisions. I will outline efforts to apply transport theory to the nonequilibrium pion fluid at midrapidity focusing on two phenomena: partial thermalization and pion conservation.

  10. 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)

  11. 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.

  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. 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.

  14. Equilibrium properties of hybrid field reversed configurations

    NASA Astrophysics Data System (ADS)

    Tuszewski, M.; Gupta, D.; Gupta, S.; Onofri, M.; Osin, D.; Deng, B. H.; Dettrick, S. A.; Hubbard, K.; Gota, H.

    2017-01-01

    Field Reversed Configurations (FRCs) heated by neutral beam injection may include a large fast ion pressure that significantly modifies the equilibrium. A new analysis is required to characterize such hybrid FRCs, as the simple relations used up to now prove inaccurate. The substantial contributions of fast ions to FRC radial pressure balance and diamagnetism are described. A simple model is offered to reconstruct more accurately the equilibrium parameters of elongated hybrid FRCs. Further modeling requires new measurements of either the magnetic field or the plasma pressure.

  15. Isodynamic axisymmetric equilibrium near the magnetic axis

    NASA Astrophysics Data System (ADS)

    Arsenin, V. V.

    2013-08-01

    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).

  16. Equilibrium stellar systems with genetic algorithms

    NASA Astrophysics Data System (ADS)

    Gularte, E.; Carpintero, D. D.

    In 1979, M Schwarzschild showed that it is possible to build an equilibrium triaxial stellar system. However, the linear programmation used to that goal was not able to determine the uniqueness of the solution, nor even if that solution was the optimum one. Genetic algorithms are ideal tools to find a solution to this problem. In this work, we use a genetic algorithm to reproduce an equilibrium spherical stellar system from a suitable set of predefined orbits, obtaining the best solution attainable with the provided set. FULL TEXT IN SPANISH

  17. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class airman... by, or that may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  18. 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...

  19. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class airman..., vertigo or a disturbance of equilibrium....

  20. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class airman... by, or that may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  1. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class airman... may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  2. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class airman..., vertigo or a disturbance of equilibrium....

  3. 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...

  4. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class airman... may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  5. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class airman... by, or that may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  6. 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...

  7. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class airman... by, or that may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  8. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class airman... may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class airman..., vertigo or a disturbance of equilibrium....

  10. 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...

  11. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class airman... may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  12. 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...

  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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a third-class airman... by, or that may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  14. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class airman..., vertigo or a disturbance of equilibrium....

  15. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a second-class airman..., vertigo or a disturbance of equilibrium....

  16. 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..., nose, throat, and equilibrium. Ear, nose, throat, and equilibrium standards for a first-class airman... may reasonably be expected to be manifested by, vertigo or a disturbance of equilibrium....

  17. 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.

  18. 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…

  19. ON THE EQUILIBRIUM STRUCTURE OF SIMPLE LIQUIDS

    DTIC Science & Technology

    It is shown that the repulsive (not merely the positive) portion of the Lennard - Jones potential quantitatively dominates the equilibrium structure of...the Lennard - Jones liquid. A simple and accurate approximation for the radial distribution function at high densities is presented.

  20. Phase equilibrium measurements on twelve binary mixtures

    SciTech Connect

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

    1996-11-01

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

  1. 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…

  2. 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.

  3. 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…

  4. 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…

  5. 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)

  6. Payload specialists Patrick Baudry conducts equilibrium experiments

    NASA Technical Reports Server (NTRS)

    1985-01-01

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

  7. Non-equilibrium spatial dynamics of ecosystems.

    PubMed

    Guichard, Frederic; Gouhier, Tarik C

    2014-09-01

    Ecological systems show tremendous variability across temporal and spatial scales. It is this variability that ecologists try to predict and that managers attempt to harness in order to mitigate risk. However, the foundations of ecological science and its mainstream agenda focus on equilibrium dynamics to describe the balance of nature. Despite a rich body of literature on non-equilibrium ecological dynamics, we lack a well-developed set of predictions that can relate the spatiotemporal heterogeneity of natural systems to their underlying ecological processes. We argue that ecology needs to expand its current toolbox for the study of non-equilibrium ecosystems in order to both understand and manage their spatiotemporal variability. We review current approaches and outstanding questions related to the study of spatial dynamics and its application to natural ecosystems, including the design of reserves networks. We close by emphasizing the importance of ecosystem function as a key component of a non-equilibrium ecological theory, and of spatial synchrony as a central phenomenon for its inference in natural systems.

  8. 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…

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Equilibrium defects and solute site preferences in intermetallics: I. thermodynamics

    NASA Astrophysics Data System (ADS)

    Collins, Gary S.; Zacate, Matthew O.

    2001-03-01

    A model was developed to describe equilibrium defects and site preferences of dilute solute atoms in compounds having the CsCl and Ni_2Al3 structures. Equilibrium defects considered were combinations of elementary point defects that preserve the composition. Equilibria among possible defect combinations were combined with appropriate equations of constraint to obtain defect concentrations as a function of temperature and possible deviation from the stoichiometric composition. As an application, site-energies of defects and solutes in AB and A_2B_3) systems were estimated using Miedema's empirical model, with A=(Ni, Pd, Pt) and B= (Al, Ga, In). Dominant equilibrium defects in the respective systems were found to be the "triple defect" (2V_A+ A_B) and "octal defect" (5V_A+ 3A_B). Site preferences were found to depend on concentrations of intrinsic defects as well as on site-energy differences, and results reveal how preferences generally depend on temperature and composition. Consider solute S which, based on site energies, prefers to replace atom B. It is found that S always occupies B-sites in B-deficient alloys. In B-rich alloys, however, S may or may not occupy B-sites, depending on site-energy differences and the formation energies of equilibrium defects. For a solute that prefers to replace atom A, analogous results are obtained but with A replacing B in the three preceding sentences. This work was supported in part by the NSF under grant DMR 96-12306.

  16. Equilibrium and Sudden Events in Chemical Evolution

    NASA Astrophysics Data System (ADS)

    Weinberg, David H.; Andrews, Brett H.; Freudenburg, Jenna

    2017-03-01

    We present new analytic solutions for one-zone (fully mixed) chemical evolution models that incorporate a realistic delay time distribution for Type Ia supernovae (SNe Ia) and can therefore track the separate evolution of α-elements produced by core collapse supernovae (CCSNe) and iron peak elements synthesized in both CCSNe and SNe Ia. Our solutions allow constant, exponential, or linear–exponential ({{te}}-t/{τ {sfh}}) star formation histories, or combinations thereof. In generic cases, α and iron abundances evolve to an equilibrium at which element production is balanced by metal consumption and gas dilution, instead of continuing to increase over time. The equilibrium absolute abundances depend principally on supernova yields and the outflow mass loading parameter η, while the equilibrium abundance ratio [α /{Fe}] depends mainly on yields and secondarily on star formation history. A stellar population can be metal-poor either because it has not yet evolved to equilibrium or because high outflow efficiency makes the equilibrium abundance itself low. Systems with ongoing gas accretion develop metallicity distribution functions (MDFs) that are sharply peaked, while “gas starved” systems with rapidly declining star formation, such as the conventional “closed box” model, have broadly peaked MDFs. A burst of star formation that consumes a significant fraction of a system’s available gas and retains its metals can temporarily boost [α /{Fe}] by 0.1–0.3 dex, a possible origin for rare, α-enhanced stars with intermediate age and/or high metallicity. Other sudden transitions in system properties can produce surprising behavior, including backward evolution of a stellar population from high to low metallicity.

  17. Equilibrium studies on the formaldehyde reaction with native DNA.

    PubMed

    Shikama, K; Miura, K I

    1976-03-16

    Equilibrium analysis of the reaction of formaldehyde with native calf thymus DNA was carried out at temperatures below the thermal transition zone by the spectrophotometric method. The apparent equilibrium constant, Kconf., for the conformational opening and closing reaction of base pairs along the double-helical chain, was measured in various concentrations of formaldehyde, and these values were extrapolated to the zero concentration. The value of KOconf. thus obtained in the absence of the chemical probe was 0.12 in 5 mM 2-(N-morpholino)ethane sulfonic acid buffer (Mes), and 0.003 in 0.15 M NaCl plus 5 mM Mes, pH 7.0, at 50 degrees C. These results make it possible to calculate roughly that 230 base pairs and 7 base pairs are open respectively, at 50 degrees C in the native DNA molecule composed of 2300 base pairs, using Mr = 1.5 x 10(6) for the sample used. This conformational reaction was also characterized by the following thermodynamic parameters: deltaGOconf. = 1.36 kcal - mol-1 (5.68 kJ - mol-1), deltaHOconf. = 36.8 kcal - mol-1 (154 kJ - mol-1), and deltaSOconf. = 110 cal - mol-1 - K-1 (460 J - mol-1 - K-1) in 5 mM Mes, pH 7.0, at 50 degrees C, and the nature of the 'breathing' of base pairs was discussed.

  18. Devils Hole paleotemperatures and implications for oxygen isotope equilibrium fractionation

    NASA Astrophysics Data System (ADS)

    Kluge, Tobias; Affek, Hagit P.; Dublyansky, Yuri; Spötl, Christoph

    2014-08-01

    Subaqueous calcite in Devils Hole, Nevada, was growing continuously from slightly super-saturated groundwater, providing a 570 kyr-long δO18 paleoclimate record. Due to its very slow growth it has been assumed to have grown under conditions of isotopic equilibrium. However, its Holocene δO18 value is 1.5‰ higher than predicted by laboratory-precipitation-based oxygen isotope thermometer calibrations. The suggestion that Devils Hole calcite anchors the isotope thermometer to more 18O-enriched values has stirred a debate as to which paleothermometer calibration is relevant for paleoclimate and casts doubt on the validity of δO18-based paleotemperatures. We used clumped isotopes to test the assumptions of the Devils Hole alternative 18O-thermometer. Carbonate clumped isotopes are a temperature proxy that measures the abundance of 13Csbnd 18O bonds in CaCO3. This proxy is independent of the water composition and therefore gives independent estimates of temperatures when calcite forms at thermodynamic and isotopic equilibrium. We find that Devils Hole water paleotemperatures were constant at 30.6±2.6 °C between 27 and 180 ka, similarly to the modern groundwater temperature of 32.8-34.3 °C. The proximity of the Devils Hole clumped isotope data to values expected based on modern groundwater temperatures supports the notion that Devils Hole calcite grew under equilibrium conditions. Therefore, the commonly used laboratory-based δO18-temperature calibrations should be reconsidered. The constant water temperature over the glacial-interglacial cycles indicates that the long Devils Hole δO18 record reflects only variations in the groundwater δO18 values and as such, represents a valuable archive of paleoclimate and isotope paleohydrology.

  19. Modelling non-equilibrium thermodynamic systems from the speed-gradient principle.

    PubMed

    Khantuleva, Tatiana A; Shalymov, Dmitry S

    2017-03-06

    The application of the speed-gradient (SG) principle to the non-equilibrium distribution systems far away from thermodynamic equilibrium is investigated. The options for applying the SG principle to describe the non-equilibrium transport processes in real-world environments are discussed. Investigation of a non-equilibrium system's evolution at different scale levels via the SG principle allows for a fresh look at the thermodynamics problems associated with the behaviour of the system entropy. Generalized dynamic equations for finite and infinite number of constraints are proposed. It is shown that the stationary solution to the equations, resulting from the SG principle, entirely coincides with the locally equilibrium distribution function obtained by Zubarev. A new approach to describe time evolution of systems far from equilibrium is proposed based on application of the SG principle at the intermediate scale level of the system's internal structure. The problem of the high-rate shear flow of viscous fluid near the rigid plane plate is discussed. It is shown that the SG principle allows closed mathematical models of non-equilibrium processes to be constructed.This article is part of the themed issue 'Horizons of cybernetical physics'.

  20. Modelling non-equilibrium thermodynamic systems from the speed-gradient principle

    NASA Astrophysics Data System (ADS)

    Khantuleva, Tatiana A.; Shalymov, Dmitry S.

    2017-03-01

    The application of the speed-gradient (SG) principle to the non-equilibrium distribution systems far away from thermodynamic equilibrium is investigated. The options for applying the SG principle to describe the non-equilibrium transport processes in real-world environments are discussed. Investigation of a non-equilibrium system's evolution at different scale levels via the SG principle allows for a fresh look at the thermodynamics problems associated with the behaviour of the system entropy. Generalized dynamic equations for finite and infinite number of constraints are proposed. It is shown that the stationary solution to the equations, resulting from the SG principle, entirely coincides with the locally equilibrium distribution function obtained by Zubarev. A new approach to describe time evolution of systems far from equilibrium is proposed based on application of the SG principle at the intermediate scale level of the system's internal structure. The problem of the high-rate shear flow of viscous fluid near the rigid plane plate is discussed. It is shown that the SG principle allows closed mathematical models of non-equilibrium processes to be constructed. This article is part of the themed issue 'Horizons of cybernetical physics'.

  1. Spontaneous Formation of Closed-Field Torus Equilibrium via Current Jump Observed in an Electron-Cyclotron-Heated Plasma

    SciTech Connect

    Yoshinaga, T.; Uchida, M.; Tanaka, H.; Maekawa, T.

    2006-03-31

    Spontaneous current jump resulting in the formation of closed field equilibrium has been observed in electron-cyclotron-heated toroidal plasmas under steady external fields composed of a toroidal field and a relatively weak vertical field in the low aspect ratio torus experiment device. This bridges the gap between the open field equilibrium maintained by a pressure-driven current in the external field and the closed field equilibrium at a larger current. Experimental results and theoretical analyses suggest a current jump model that is based on the asymmetric electron confinement along the field line appearing upon simultaneous transitions of field topology and equilibrium.

  2. 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.

  3. Spectra from pair-equilibrium plasmas

    NASA Technical Reports Server (NTRS)

    Zdziarski, A. A.

    1984-01-01

    A numerical model of relativistic nonmagnetized plasma with uniform temperature and electron density distributions is considered, and spectra from plasma in pair equilibrium are studied. A range of dimensionless temperature (T) greater than about 0.2 is considered. The spectra from low pair density plasmas in pair equilibrium vary from un-Comptonized bremsstrahlung spectra at Thomson cross section tau(N) much less than one to Comptonized bremsstrahlung spectra with tau(N) over one. For high pair density plasmas the spectra are flat for T greater than about one, and have broad intensity peaks at energy roughly equal to 3T for T less than one. In the latter region the total luminosity is approximately twice the annihilation luminosity. All spectra are flat in the X-ray region, in contradiction to observed AGN spectra. For dimensionless luminosity greater than about 100, the cooling time becomes shorter than the Thomson time.

  4. Fluctuation theorem for constrained equilibrium systems.

    PubMed

    Gilbert, Thomas; Dorfman, J Robert

    2006-02-01

    We discuss the fluctuation properties of equilibrium chaotic systems with constraints such as isokinetic and Nosé-Hoover thermostats. Although the dynamics of these systems does not typically preserve phase-space volumes, the average phase-space contraction rate vanishes, so that the stationary states are smooth. Nevertheless, finite-time averages of the phase-space contraction rate have nontrivial fluctuations which we show satisfy a simple version of the Gallavotti-Cohen fluctuation theorem, complementary to the usual fluctuation theorem for nonequilibrium stationary states and appropriate to constrained equilibrium states. Moreover, we show that these fluctuations are distributed according to a Gaussian curve for long enough times. Three different systems are considered here: namely, (i) a fluid composed of particles interacting with Lennard-Jones potentials, (ii) a harmonic oscillator with Nosé-Hoover thermostatting, and (iii) a simple hyperbolic two-dimensional map.

  5. Fluctuation theorem for constrained equilibrium systems

    NASA Astrophysics Data System (ADS)

    Gilbert, Thomas; Dorfman, J. Robert

    2006-02-01

    We discuss the fluctuation properties of equilibrium chaotic systems with constraints such as isokinetic and Nosé-Hoover thermostats. Although the dynamics of these systems does not typically preserve phase-space volumes, the average phase-space contraction rate vanishes, so that the stationary states are smooth. Nevertheless, finite-time averages of the phase-space contraction rate have nontrivial fluctuations which we show satisfy a simple version of the Gallavotti-Cohen fluctuation theorem, complementary to the usual fluctuation theorem for nonequilibrium stationary states and appropriate to constrained equilibrium states. Moreover, we show that these fluctuations are distributed according to a Gaussian curve for long enough times. Three different systems are considered here: namely, (i) a fluid composed of particles interacting with Lennard-Jones potentials, (ii) a harmonic oscillator with Nosé-Hoover thermostatting, and (iii) a simple hyperbolic two-dimensional map.

  6. Adaptive resolution simulation in equilibrium and beyond

    NASA Astrophysics Data System (ADS)

    Wang, H.; Agarwal, A.

    2015-09-01

    In this paper, we investigate the equilibrium statistical properties of both the force and potential interpolations of adaptive resolution simulation (AdResS) under the theoretical framework of grand-canonical like AdResS (GC-AdResS). The thermodynamic relations between the higher and lower resolutions are derived by considering the absence of fundamental conservation laws in mechanics for both branches of AdResS. In order to investigate the applicability of AdResS method in studying the properties beyond the equilibrium, we demonstrate the accuracy of AdResS in computing the dynamical properties in two numerical examples: The velocity auto-correlation of pure water and the conformational relaxation of alanine dipeptide dissolved in water. Theoretical and technical open questions of the AdResS method are discussed in the end of the paper.

  7. Spatial distribution of thermal energy in equilibrium.

    PubMed

    Bar-Sinai, Yohai; Bouchbinder, Eran

    2015-06-01

    The equipartition theorem states that in equilibrium, thermal energy is equally distributed among uncoupled degrees of freedom that appear quadratically in the system's Hamiltonian. However, for spatially coupled degrees of freedom, such as interacting particles, one may speculate that the spatial distribution of thermal energy may differ from the value predicted by equipartition, possibly quite substantially in strongly inhomogeneous or disordered systems. Here we show that for systems undergoing simple Gaussian fluctuations around an equilibrium state, the spatial distribution is universally bounded from above by 1/2k(B)T. We further show that in one-dimensional systems with short-range interactions, the thermal energy is equally partitioned even for coupled degrees of freedom in the thermodynamic limit and that in higher dimensions nontrivial spatial distributions emerge. Some implications are discussed.

  8. Cosmic curvature from de Sitter equilibrium cosmology.

    PubMed

    Albrecht, Andreas

    2011-10-07

    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.

  9. 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

  10. 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.

  11. Equilibrium Reconstruction of KSTAR First Plasma

    NASA Astrophysics Data System (ADS)

    You, K.-I.; Lee, D. K.; Park, B. H.; Lee, S. G.; Bak, J. G.; Seo, S. H.; Hahn, S. H.; Lao, L. L.

    2008-11-01

    To reconstruct the plasma equilibrium of KSTAR (Korea Superconducting Tokamak Advanced Research), we have made some modification to the EFIT code and installed it on our computing system. An MDSplus system is used for the data storage of KSTAR; thus, the EFIT reads experimental data from the MDSplus server and writes the results to it. We have modified some subroutines of the EFIT code for direct link with the MDSplus server. KSTAR PF and TF coil systems use a CICC (Cable-In-Conduit Conductor) type superconductor. The CICC jacket material for most PF and all TF coils is Incoloy 908, which is a magnetic material with relative magnetic permeability greater than 10 in low external field. The Incoloy 908 effects should, therefore, be considered in analyzing the magnetic diagnostics data. In this paper, we present our efforts to reconstruct the plasma equilibrium with EFIT code, including the compensation of Incoloy 908 effects.

  12. 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

  13. Molecular equilibrium with condensation. [in astrophysics

    NASA Technical Reports Server (NTRS)

    Sharp, C. M.; Huebner, W. F.

    1990-01-01

    Minimization of the Gibbs energy of formation for species of chemical elements and compounds in their gas and condensed phases determines their relative abundances in a mixture in chemical equilibrium. The procedure is more general and more powerful than previous abundance determinations in multiphase astrophysical mixtures. Some results for astrophysical equations of state are presented, and the effects of condensation on opacity are briefly indicated.

  14. Flux Jacobian Matrices For Equilibrium Real Gases

    NASA Technical Reports Server (NTRS)

    Vinokur, Marcel

    1990-01-01

    Improved formulation includes generalized Roe average and extension to three dimensions. Flux Jacobian matrices derived for use in numerical solutions of conservation-law differential equations of inviscid flows of ideal gases extended to real gases. Real-gas formulation of these matrices retains simplifying assumptions of thermodynamic and chemical equilibrium, but adds effects of vibrational excitation, dissociation, and ionization of gas molecules via general equation of state.

  15. Equilibrium Configuration of Φ4 Oscillatons

    NASA Astrophysics Data System (ADS)

    Valdez-Alvarado, Susana; Becerril, Ricardo; Ureña-López, L. Arturo

    2010-07-01

    We search for equilibrium configurations of the (coupled) Einstein-Klein-Gordon equations for the case of a real scalar field endowed with a quartic self-interaction potential. The resulting solutions are the generalizations of the (massive) oscillating soliton stars, the so-called oscillatons. Among other parameters, we estimate the mass curve of the configurations, and determine their critical mass for different values of the quartic interaction.

  16. Oxygen equilibrium of brachiopod Lingula hemerythrin.

    PubMed

    MANWELL, C

    1960-08-26

    In contrast to hemerythrin from five different species of sipunculid worms, ecardine brachiopod Lingula hemerythrin has an oxygen equilibrium which is reversibly altered by pH changes, both the oxygen affinity (Bohr effect) and the interactions between oxygen-binding centers being a function of pH. The significance of these phenomena is discussed in view of the phylogenetic distribution of hemerythrin and the function of respiratory pigments.

  17. Contact angle measurements under thermodynamic equilibrium conditions.

    PubMed

    Lages, Carol; Méndez, Eduardo

    2007-08-01

    The precise control of the ambient humidity during contact angle measurements is needed to obtain stable and valid data. For a such purpose, a simple low-cost device was designed, and several modified surfaces relevant to biosensor design were studied. Static contact angle values for these surfaces are lower than advancing contact angles published for ambient conditions, indicating that thermodynamic equilibrium conditions are needed to avoid drop evaporation during the measurements.

  18. Stationary equilibrium singularity distributions in the plane

    NASA Astrophysics Data System (ADS)

    Newton, P. K.; Ostrovskyi, V.

    2012-02-01

    We characterize all stationary equilibrium point singularity distributions in the plane of logarithmic type, allowing for real, imaginary or complex singularity strengths. The dynamical system follows from the assumption that each of the N singularities moves according to the flow field generated by all the others at that point. For strength vector \\vec{\\Gamma} \\in {\\Bbb R}^N , the dynamical system is the classical point vortex system obtained from a singular discrete representation of the vorticity field from ideal, incompressible fluid flow. When \\vec{\\Gamma} \\in \\Im , it corresponds to a system of sources and sinks, whereas when \\vec{\\Gamma} \\in {\\Bbb C}^N the system consists of spiral sources and sinks discussed in Kochin et al (1964 Theoretical Hydromechanics 1 (London: Interscience)). We formulate the equilibrium problem as one in linear algebra, A \\vec{\\Gamma} = 0 , A \\in {\\Bbb C}^{N \\times N} , \\vec{\\Gamma} \\in {\\Bbb C}^N , where A is a N × N complex skew-symmetric configuration matrix which encodes the geometry of the system of interacting singularities. For an equilibrium to exist, A must have a kernel and \\vec{\\Gamma} must be an element of the nullspace of A. We prove that when N is odd, A always has a kernel, hence there is a choice of \\vec{\\Gamma} for which the system is a stationary equilibrium. When N is even, there may or may not be a non-trivial nullspace of A, depending on the relative position of the points in the plane. We provide examples of evenly and randomly distributed points on curves such as circles, figure eights, flower-petal configurations and spirals. We then show how to classify the stationary equilibria in terms of the singular spectrum of A.

  19. The traffic equilibrium problem with nonadditive path costs

    SciTech Connect

    Gabriel, S.A.; Bernstein, D.

    1995-08-21

    In this paper the authors present a version of the (static) traffic equilibrium problem in which the cost incurred on a path is not simply the sum of the costs on the arcs that constitute that path. The authors motivate this nonadditive version of the problem by describing several situations in which the classical additivity assumption fails. They also present an algorithm for solving nonadditive problems that is based on the recent NE/SQP algorithm, a fast and robust method for the nonlinear complementarity problem. Finally, they present a small example that illustrates both the importance of using nonadditive costs and the effectiveness of the NE/SQP method.

  20. ORMEC: a three-dimensional MHD spectral inverse equilibrium code

    SciTech Connect

    Hirshman, S.P.; Hogan, J.T.

    1986-02-01

    The Oak Ridge Moments Equilibrium Code (ORMEC) is an efficient computer code that has been developed to calculate three-dimensional MHD equilibria using the inverse spectral method. The fixed boundary formulation, which is based on a variational principle for the spectral coefficients (moments) of the cylindrical coordinates R and Z, is described and compared with the finite difference code BETA developed by Bauer, Betancourt, and Garabedian. Calculations for the Heliotron, Wendelstein VIIA, and Advanced Toroidal Facility (ATF) configurations are performed to establish the accuracy and mesh convergence properties for the spectral method. 16 refs., 13 figs.

  1. 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.

  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. 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.

  4. Equilibrium Gold Nanoclusters Quenched with Biodegradable Polymers

    PubMed Central

    Murthy, Avinash K.; Stover, Robert J.; Borwankar, Ameya U.; Nie, Golay D.; Gourisankar, Sai; Truskett, Thomas M.; Sokolov, Konstantin V.; Johnston, Keith P.

    2013-01-01

    Although sub-100 nm nanoclusters of metal nanoparticles are of interest in many fields including biomedical imaging, sensors and catalysis, it has been challenging to control their morphologies and chemical properties. Herein, a new concept is presented to assemble equilibrium Au nanoclusters of controlled size by tuning the colloidal interactions with a polymeric stabilizer, PLA(1k)-b-PEG(10k)-b-PLA(1k). The nanoclusters form upon mixing a dispersion of ~5 nm Au nanospheres with a polymer solution followed by partial solvent evaporation. A weakly adsorbed polymer quenches the equilibrium nanocluster size and provides steric stabilization. Nanocluster size is tuned from ~20 nm to ~40 nm by experimentally varying the final Au nanoparticle concentration and the polymer/Au ratio, along with the charge on the initial Au nanoparticle surface. Upon biodegradation of the quencher, the nanoclusters reversibly and fully dissociate to individual ~5 nm primary particles. Equilibrium cluster size is predicted semi-quantitatively with a free energy model that balances short-ranged depletion and van der Waals attractions with longer-ranged electrostatic repulsion, as a function of the Au and polymer concentrations. The close spacings of the Au nanoparticles in the clusters produce strong NIR extinction over a broad range of wavelengths from 650 to 900 nm, which is of practical interest in biomedical imaging. PMID:23230905

  5. [New relations for steady-state enzyme kinetics and their application to rapid equilibrium assumption].

    PubMed

    Vrzheshch, P V

    2013-01-01

    With the use of a graph theory new relations for steady-state enzyme kinetics are derived and strictly proved for the arbitrary mechanism of an enzyme-catalysed reaction containing a reversible segment. Using these relations, a general principle for rapid equilibrium assumption is formulated and proved: the reversible bound segment can be considered as an equilibrium segment only when the values of the base trees that are not proper to this segment can be neglected (within a prescribed accuracy) in relation to the values of the base trees that belong to this segment. In contrast with the foreign base trees the base trees that are proper to the segment have the following properties: the tree that is directed to the base within this segment does not contain the edges leaving this segment; and the tree that is directed to the base outside the segment contains only one edge leaving this segment. Equilibrium variations are assessed for steady-state intermediates concentrations of the equilibrium segment, numerical expressions are obtained for the accuracy of determination of the intermediates concentrations as well as for the accuracy of determination of the rate of enzyme-catalysed reaction in case of using rapid equilibrium assumption.

  6. Equilibrium selectivity alone does not create K+-selective ion conduction in K+ channels

    NASA Astrophysics Data System (ADS)

    Liu, Shian; Lockless, Steve W.

    2013-11-01

    Potassium (K+) channels are selective for K+ over Na+ ions during their transport across membranes. We and others have previously shown that tetrameric K+ channels are primarily occupied by K+ ions in their selectivity filters under physiological conditions, demonstrating the channel’s intrinsic equilibrium preference for K+ ions. Based on this observation, we hypothesize that the preference for K+ ions over Na+ ions in the filter determines its selectivity during ion conduction. Here, we ask whether non-selective cation channels, which share an overall structure and similar individual ion-binding sites with K+ channels, have an ion preference at equilibrium. The variants of the non-selective Bacillus cereus NaK cation channel we examine are all selective for K+ over Na+ ions at equilibrium. Thus, the detailed architecture of the K+ channel selectivity filter, and not only its equilibrium ion preference, is fundamental to the generation of selectivity during ion conduction.

  7. Emission properties of non-equilibrium krypton plasma in the water-window region

    NASA Astrophysics Data System (ADS)

    Zakharov, Vassily S.

    2017-01-01

    The line emission properties of non-equilibrium krypton plasma are examined and the optimal emission temperature conditions for soft x-ray emission output in the water-window region are explored. The kinetic parameters for non-equilibrium plasma including major inelastic ion interaction processes, radiation and emission data are obtained with an approach based on the Hartree-Fock-Slater (HFS) quantum-statistical model and a distorted wave approximation. A nonmaxwellian electron distribution is used as well for calculating collisional rates. At a temperature of 70 eV the emission spectral efficiency for Kr equilibrium plasma is about 10%, and it jumps to a value greater than 70% at 100 eV. A similar spectral efficiency is achieved at a lower temperature e.g. 80 eV in non-equilibrium plasma with 7.5 keV fast electron average energy.

  8. 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.

  9. 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

  10. Non-equilibrium mechanisms of light in the microwave region

    NASA Astrophysics Data System (ADS)

    Mortenson, Juliana H. J.

    2011-09-01

    Quantum mechanics and quantum chemistry have taught for more than 100 years that "photons" associated with microwaves cannot exert photochemical effects because their "photon energies" are smaller than chemical bond energies. Those quantum theories have been strongly contradicted within the last few decades by physical experiments demonstrating non-equilibrium, photochemical and photomaterial activity by microwaves. Reactions among scientists to these real physical models and proofs have varied from disbelief and denial, to acceptance of the real physical phenomena and demands for revisions to quantum theory. At the previous "Nature of Light" meeting, an advance in the foundations of quantum mechanics was presented. Those discoveries have revealed the source of these conflicts between quantum theory and microwave experiments. Critical variables and constants were missing from quantum theory due to a minor mathematical inadvertence in Planck's original quantum work. As a result, erroneous concepts were formed nearly a century ago regarding the energetics and mechanisms of lower frequency light, such as in the microwave region. The new discoveries have revealed that the traditional concept of "photons" mistakenly attributed elementary particle status to what is actually an arbitrarily time-based collection of sub-photonic, elementary particles. In a mathematical dimensional sense, those time-based energy measurements cannot be mathematically equivalent to bond energies as historically believed. Only an "isolated quantity of energy", as De Broglie referred to it, can be equivalent to bond energy. With the aid of the new variables and constants, the non-equilibrium mechanisms of light in the microwave region can now be described. They include resonant absorption, splitting frequency stimulation leading to electronic excitation, and resonant acoustic transduction. Numerous practical engineering applications can be envisioned for non-equilibrium microwaves.

  11. 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.

  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. 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)

  14. 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)

  15. 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

  16. 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.

  17. 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.

  18. Phase equilibrium in coal liquefaction processes. Final report

    SciTech Connect

    Chao, K.C.

    1984-08-01

    Gas-liquid equilibrium data have been determined in simulation of coal liquefaction process conditions in mixtures of light gases + heavy hydrocarbons to add to the accumulated data previously reported in EPRI AP-1593. The mixture systems newly investigated are: methane + 9,10 dihydrophenanthrene; hydrogen + methane + 1-methylnaphthalene; hydrogen + carbon dioxide + tetralin; hydrogen + carbon dioxide + 1-methynaphthalene; hydrogen + carbon dioxide + quinoline; nitrogen + tetralin, + n-hexadecane, + 1-methylnaphthalene, + quinoline, and + m-cresol. Correlations for the solubilities of methane and carbon dioxide have been developed from the data based on the use of solubility parameter. The solubility of hydrogen was correlated in EPRI AP-1593. Two equations of state are developed for the description of both the gas solubility and the vaporization of the heavy oil. The Chain-of-Rotators (COR) equation of state explicitly accounts for the rotational molecular motion contribution to the pressure of a fluid. The Cubic-Chain-of-Rotators (CCOR) equation is obtained upon simplifying the COR equation. Interaction constants in the CCOR equation have been determined for the light gases with the heavy hydrocarbons based on data from this project, and the constants are correlated. Equilibrium flash vaporization has been experimentally determined for three coal liquids and for their mixtures with hydrogen. The data are correlated with the CCOR equation of state. 74 figures, 46 tables.

  19. An Equilibrium and Kinetic Investigation of Salt-Cycloamylose Complexes

    DTIC Science & Technology

    1976-12-08

    Coneinut on reverse aide It necessary and identify by blo * number) Equilibrium constants inorganic anions Rate constants Ultrasonic relaxation Inclusion...The equilibrium constants and rate constants for the formation of inclusion complexes of cycloheptaamylose with small inorganic anions were measured by...of cyclo- amylose chemistry. Recently, equilibrium constants for cyclohexaamylose, sometimes denoted by a-CD, with various Tnorganic salts were

  20. 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…

  1. On the Chermnykh-Like Problems: II. The Equilibrium Points

    NASA Astrophysics Data System (ADS)

    Yeh, Li-Chin; Jiang, Ing-Guey

    2006-12-01

    Motivated by Papadakis (2005a, b), we study a Chermnykh-like problem, in which an additional gravitational potential from the belt is included. In addition to the usual five equilibrium points (three collinear and two triangular points), there are some new equilibrium points for this system. We studied the conditions for the existence of these new equilibrium points both analytically and numerically.

  2. 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"…

  3. 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.

  4. Thermo-chemical dynamics and chemical quasi-equilibrium of plasmas in thermal non-equilibrium

    NASA Astrophysics Data System (ADS)

    Massot, Marc; Graille, Benjamin; Magin, Thierry E.

    2011-05-01

    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.

  5. Modeling Equilibrium of microRNA Expression

    PubMed Central

    Chan, Lawrence W. C.

    2011-01-01

    MicroRNAs are a class of non-coding RNAs and the dysregulated expression of these short RNA molecules was frequently observed in cancer cells. The steady state level of microRNA concentration may differentiate the biological function of the cells between normal and impaired. To understand the steady state or equilibrium of microRNAs, their interactions with transcription factors and target genes need to be explored and visualized through prediction and network analysis algorithms. This article discusses the application of mathematical model for simulating the dynamics of network feedback loop so as to decipher the mechanism of microRNA regulation. PMID:22303331

  6. Equilibrium field coil concepts for INTOR

    SciTech Connect

    Strickler, D.J.; Peng, Y.K.M.; Brown, T.G.

    1981-08-01

    Methods are presented for reducing ampere-turn requirements in the EF coil system. It is shown that coil currents in an EF coil system external to the toroidal field coils can be substantially reduced by relaxing the triangularity of a D-shaped plasma. Further reductions are realized through a hybrid EF coil system using both internal and external coils. Equilibrium field coils for a poloidally asymmetric, single-null INTOR configuration are presented. It is shown that the shape of field lines in the plasma scrapeoff region and divertor channel improves as triangularity is reduced, but it does so at the possible expense of achievable stable beta values.

  7. 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

  8. 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.

  9. Microscopic theory of equilibrium polariton condensates

    NASA Astrophysics Data System (ADS)

    Xue, Fei; Wu, Fengcheng; Xie, Ming; Su, Jung-Jung; MacDonald, A. H.

    2016-12-01

    We present a microscopic theory of the equilibrium polariton condensate state of a semiconductor quantum well in a planar optical cavity. The theory accounts for the adjustment of matter excitations to the presence of a coherent photon field, predicts effective polariton-polariton interaction strengths that are weaker and condensate exciton fractions that are smaller than in the commonly employed exciton-photon model, and yields effective Rabi coupling strengths that depend on the detuning of the cavity-photon energy relative to the bare exciton energy. The dressed quasiparticle bands that appear naturally in the theory provide a mechanism for electrical manipulation of polariton condensates.

  10. Asteroid Shapes Are Always Close To Fluid Equilibrium

    NASA Astrophysics Data System (ADS)

    Tanga, Paolo; Comito, C.; Hestroffer, D.; Richardson, D. C.

    2010-10-01

    The simple evidence that asteroid are composed by solid rocks suggests that their shape can be rather far from the theoretical equilibrium for rotating fluid bodies. The possible fragmented ("rubble-pile") nature of most of them has suggested interpretations based on elasto-plastic models (such as the Mohr-Coulomb theory) that take into account the static behavior of a granular structure. However, these approaches did not incorporate explicitly the possible evolution of shapes in time due to external factors such as crater forming impacts or tidal deformations. We revisited the theory of equilibrium shapes for fluids, quantitatively evaluating - by appropriate metrics - the distance of the observed shapes from fluid equilibrium. This distance turns out to be much smaller than previously expected. On the basis of this evidence, we simulated numerically the evolution of gravitational aggregates having a small degree of internal friction, consistent with the theoretical findings. Our results offer a global scenario for the evolution of asteroid shapes under the action of gradual stresses due to minor impacts, tidal forces and seismic shaking. We show that actual asteroid shapes are consistent with the evolution of aggregates tending towards minimum free energy states. We are able to explain the samples of observed shapes obtained by different techniques. Our findings strongly support a highly porous and fragmented nature for most asteroids, at least in an external layer. Reference: Tanga et al. 2009: ApJ Letters, 706, 1, L197-L202 Acknowledgments: PT and CC have been supported by the "Programme Nationale de Planetologie" of France; DCR acknowledges support by the NASA (grant no. NNX08AM39G issued through the Office of Space Science) and by the NSF (grant no. AST0708110).

  11. 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.

  12. Understanding atom transfer radical polymerization: effect of ligand and initiator structures on the equilibrium constants.

    PubMed

    Tang, Wei; Kwak, Yungwan; Braunecker, Wade; Tsarevsky, Nicolay V; Coote, Michelle L; Matyjaszewski, Krzysztof

    2008-08-13

    Equilibrium constants in Cu-based atom transfer radical polymerization (ATRP) were determined for a wide range of ligands and initiators in acetonitrile at 22 degrees C. The ATRP equilibrium constants obtained vary over 7 orders of magnitude and strongly depend on the ligand and initiator structures. The activities of the Cu(I)/ligand complexes are highest for tetradentate ligands, lower for tridentate ligands, and lowest for bidentate ligands. Complexes with tripodal and bridged ligands (Me6TREN and bridged cyclam) tend to be more active than those with the corresponding linear ligands. The equilibrium constants are largest for tertiary alkyl halides and smallest for primary alkyl halides. The activities of alkyl bromides are several times larger than those of the analogous alkyl chlorides. The equilibrium constants are largest for the nitrile derivatives, followed by those for the benzyl derivatives and the corresponding esters. Other equilibrium constants that are not readily measurable were extrapolated from the values for the reference ligands and initiators. Excellent correlations of the equilibrium constants with the Cu(II/I) redox potentials and the carbon-halogen bond dissociation energies were observed.

  13. 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;

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

    PubMed

    Niu, Yuanling; Wang, Yue; Zhou, Da

    2015-12-07

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

  15. 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

    2015-10-06

    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.

  16. 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.

  17. Dynamics of Charged Particles in an Adiabatic Thermal Beam Equilibrium

    NASA Astrophysics Data System (ADS)

    Chen, Chiping; Wei, Haofei

    2010-11-01

    Charged-particle motion is studied in the self-electric and self-magnetic fields of a well-matched, intense charged-particle beam and an applied periodic solenoidal magnetic focusing field. The beam is assumed to be in a state of adiabatic thermal equilibrium. The phase space is analyzed and compared with that of the well-known Kapchinskij-Vladimirskij (KV)-type beam equilibrium. It is found that the widths of nonlinear resonances in the adiabatic thermal beam equilibrium are narrower than those in the KV-type beam equilibrium. Numerical evidence is presented, indicating almost complete elimination of chaotic particle motion in the adiabatic thermal beam equilibrium.

  18. 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.

  19. 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.

  20. Equilibrium stellar systems with spindle singularities

    NASA Technical Reports Server (NTRS)

    Shapiro, Stuart L.; Teukolsky, Saul A.

    1992-01-01

    Equilibrium sequences of axisymmetric Newtonian clusters that tend toward singular states are constructed. The distribution functions are chosen to be of the form f = f(E, Jz). The numerical method then determines the density and gravitational potential self-consistently to satisfy Poisson's equation. For the prolate models, spindle singularities arise from the depletion of angular momentum near the symmetry axis. While the resulting density enhancement is confined to the region near the axis, the influence of the spindle extends much further out through its tidal gravitational field. Centrally condensed prolate clusters may contain strong-field regions even though the spindle mass is small and the mean cluster eccentricity is not extreme. While the calculations performed here are entirely Newtonian, the issue of singularities is an important topic in general relativity. Equilibrium solutions for relativistic star clusters can provide a testing ground for exploring this issue. The methods used in this paper for building nonspherical clusters can be extended to relativistic systems.

  1. 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.

  2. 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

  3. Non-equilibrium modelling of transferred arcs

    NASA Astrophysics Data System (ADS)

    Haidar, J.

    1999-02-01

    A two-temperature, variable-density, arc model has been developed for description of high-current free-burning arcs, including departures from thermodynamic and chemical equilibrium in the plasma. The treatment includes the arc, the anode and the cathode and considers the separate energy balance of the electrons and the heavy particles, together with the continuity equations for these species throughout the plasma. The output includes a two-dimensional distribution for the temperatures and densities both of the electrons and of the heavy particles, plasma velocity, current density and electrical potential throughout the arc. For a 200 A arc in pure argon at 1 atm, we calculate large differences between the temperatures of the electrons and the heavy particles in the plasma region near the cathode tip, together with large departures from local chemical plasma equilibrium. In the main body of the arc at high plasma temperatures, we predict minor differences between the temperatures of the electrons and the heavy particles, which are inconsistent with recent measurements using laser-scattering techniques showing differences of up to several thousand degrees. However, we find that, for the region in front of the cathode tip, the ground-state level of the neutral atoms is overpopulated relative to the corresponding populations under conditions of LTE, in agreement with experimental observations. These departures from LTE are caused by the injection of a large mass flow of cold gas into the arc core due to arc constriction at the tip of the cathode.

  4. Accurate equilibrium structures for piperidine and cyclohexane.

    PubMed

    Demaison, Jean; Craig, Norman C; Groner, Peter; Écija, Patricia; Cocinero, Emilio J; Lesarri, Alberto; Rudolph, Heinz Dieter

    2015-03-05

    Extended and improved microwave (MW) measurements are reported for the isotopologues of piperidine. New ground state (GS) rotational constants are fitted to MW transitions with quartic centrifugal distortion constants taken from ab initio calculations. Predicate values for the geometric parameters of piperidine and cyclohexane are found from a high level of ab initio theory including adjustments for basis set dependence and for correlation of the core electrons. Equilibrium rotational constants are obtained from GS rotational constants corrected for vibration-rotation interactions and electronic contributions. Equilibrium structures for piperidine and cyclohexane are fitted by the mixed estimation method. In this method, structural parameters are fitted concurrently to predicate parameters (with appropriate uncertainties) and moments of inertia (with uncertainties). The new structures are regarded as being accurate to 0.001 Å and 0.2°. Comparisons are made between bond parameters in equatorial piperidine and cyclohexane. Another interesting result of this study is that a structure determination is an effective way to check the accuracy of the ground state experimental rotational constants.

  5. Kinetic and equilibrium measurements of coal drying

    SciTech Connect

    Heller, A.; Elliott, G.R.B.

    1980-01-01

    The retention, attachment, and release of water (sorption, adsorption, and desorption) in Fruitland subbituminous coal are shown to be very complex phenomena. The vapor pressure and thermodynamic activity of water in the coal at about 315 K vary sharply with composition. Removal of 60% of the water initially present reduces the vapor pressure by about 60%. The total moisture content of saturated coal also varies with temperature. A 10 K rise in temperature reduces the sorbed water by about 8%. There is strong hysteresis in the sorption behavior; water which is desorbed by reducing the vapor pressure over a coal sample is not fully replaced by adsorption when the vapor pressure is returned to its original level. These measurements of desorption and adsorption reflect stable and metastable equilibria. Kinetic measurements are reported for approach to a new equilibrium if the vapor pressure over the coal is reduced. The kinetic measurements reflect the shape of the pores while equilibrium vapor pressures reflect how tightly the water is bound in the pores. Both types of measurement show changes in behavior at the same compositions. Implications of these results for UCG are discussed.

  6. 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.

  7. PROCEDURES FOR THE DERIVATION OF EQUILIBRIUM ...

    EPA Pesticide Factsheets

    This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations for 32 nonionic organic chemicals in sediment which are protective of the presence of freshwater and marine benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it accounts for the varying biological availability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms. EqP can be used to calculate ESBs for any toxicity endpoint for which there are water-only toxicity data; it is not limited to any single effect endpoint. For the purposes of this document, ESBs for 32 nonionic organic chemicals, including several low molecular weight aliphatic and aromatic compounds, pesticides, and phthalates, were derived using Final Chronic Values (FCV) from Water Quality Criteria (WQC) or Secondary Chronic Values (SCV) derived from existing toxicological data using the Great Lakes Water Quality Initiative (GLI) or narcosis theory approaches. These values are intended to be the concentration of each chemical in water that is protective of the presence of aquatic life. For nonionic organic chemicals demonstrating a narcotic mode of action, ESBs derived using the GLI approach specifically for fres

  8. Entanglement equilibrium for higher order gravity

    NASA Astrophysics Data System (ADS)

    Bueno, Pablo; Min, Vincent S.; Speranza, Antony J.; Visser, Manus R.

    2017-02-01

    We show that the linearized higher derivative gravitational field equations are equivalent to an equilibrium condition on the entanglement entropy of small spherical regions in vacuum. This extends Jacobson's recent derivation of the Einstein equation using entanglement to include general higher derivative corrections. The corrections are naturally associated with the subleading divergences in the entanglement entropy, which take the form of a Wald entropy evaluated on the entangling surface. Variations of this Wald entropy are related to the field equations through an identity for causal diamonds in maximally symmetric spacetimes, which we derive for arbitrary higher derivative theories. If the variations are taken holding fixed a geometric functional that we call the generalized volume, the identity becomes an equivalence between the linearized constraints and the entanglement equilibrium condition. We note that the fully nonlinear higher curvature equations cannot be derived from the linearized equations applied to small balls, in contrast to the situation encountered in Einstein gravity. The generalized volume is a novel result of this work, and we speculate on its thermodynamic role in the first law of causal diamond mechanics, as well as its possible application to holographic complexity.

  9. Gravitational stability computed through the limit equilibrium method revisited

    NASA Astrophysics Data System (ADS)

    Tinti, Stefano; Manucci, Anna

    2006-01-01

    The stability of slopes is a problem of great relevance for geologists and geophysicists as well as for geotechnical and geoenvironmental engineers. The classical approaches are the method of limit equilibrium, and the finite-element and finite-difference analyses of deformations. Since the former is computationally simpler and less expensive, it is more widely used in common practice, though it has some weakness points from a theoretical point of view. Essential in this technique is the definition and computation of the factor of safety F for the slope, a parameter indicating that the slope is stable, if it is larger than unity. The method is known to have not a unique solution, but it is common belief that the safety factors associated with all the solutions fulfilling the basic equilibrium equations do not differ more than 5-10 per cent from each other, which is a range of variability considered acceptable by most. Here the non-uniqueness of the solution is discussed, and it is shown that the magnitude range of F can be so large as to undermine the meaning of the safety factor criterion. The classical limit equilibrium methods based on the assumptions of cutting the sliding body into a set of vertical slices are revised, and the new concept of minimum lithostatic deviation (MLD) is introduced as a means to mitigate the effect of non-uniqueness. The paper suggests that the proper solution to the problem is the one that satisfies the equilibrium equations and minimizes the lithostatic deviation that is defined here as the ratio of the average intensity of the interslice forces and the total weight of the body. Accordingly, the factor of safety F associated with such a solution is suggested to be the value appropriate to evaluate the stability of the slope. Remarkably, the MLD principle gives us the means to introduce a completely revolutionary approach to study stability. We derive expressions that account for gravitational loading, and for additional effects such

  10. Equilibrium Fluctuation Relations for Voltage Coupling in Membrane Proteins

    PubMed Central

    Kim, Ilsoo; Warshel, Arieh

    2015-01-01

    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 reaction coordinate of “voltage coupling”, we investigate several interconnected free energy relations between these two conformational states, considering voltage activation of ion channels. The free energy difference at zero membrane potential (i.e., between the two “non-equilibrium” conformational states) is shown to be equivalent to the free energy difference between the two “equilibrium” conformational states along the one-dimensional reaction coordinate of voltage coupling. Furthermore, the requirement that the application of linear response approximation to the free energy functions (free energies) of voltage coupling should satisfy the general free energy relations, yields a novel expression for the gating charge in terms of other experimentally measurable quantities. This connection is familiar in statistical mechanics, known as the equilibrium fluctuation-response relation. The theory is illustrated by considering the movement of a unit charge within the membrane under the influence of an external potential, 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 two conformational states, which allow for quantitative estimations of an equilibrium free energy difference, a free energy of barrier, and the voltage dependency of channel activation (Q-V curve) for the unit charge movement. In addition, our analysis offers a quantitative rationale for the correlation between the free

  11. 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.

  12. Microscopic versus macroscopic approaches to non-equilibrium systems

    NASA Astrophysics Data System (ADS)

    Derrida, Bernard

    2011-01-01

    The one-dimensional symmetric simple exclusion process (SSEP) is one of the very few exactly soluble models of non-equilibrium statistical physics. It describes a system of particles which diffuse with hard core repulsion on a one-dimensional lattice in contact with two reservoirs of particles at unequal densities. The goal of this paper is to review the two main approaches which lead to the exact expression of the large deviation functional of the density of the SSEP in its steady state: a microscopic approach (based on the matrix product ansatz and an additivity property) and a macroscopic approach (based on the macroscopic fluctuation theory of Bertini, De Sole, Gabrielli, Jona-Lasinio and Landim).

  13. Bayesian methods for examining Hardy-Weinberg equilibrium.

    PubMed

    Wakefield, Jon

    2010-03-01

    Testing for Hardy-Weinberg equilibrium is ubiquitous and has traditionally been carried out via frequentist approaches. However, the discreteness of the sample space means that uniformity of p-values under the null cannot be assumed, with enumeration of all possible counts, conditional on the minor allele count, offering a computationally expensive way of p-value calibration. In addition, the interpretation of the subsequent p-values, and choice of significance threshold depends critically on sample size, because equilibrium will always be rejected at conventional levels with large sample sizes. We argue for a Bayesian approach using both Bayes factors, and the examination of posterior distributions. We describe simple conjugate approaches, and methods based on importance sampling Monte Carlo. The former are convenient because they yield closed-form expressions for Bayes factors, which allow their application to a large number of single nucleotide polymorphisms (SNPs), in particular in genome-wide contexts. We also describe straightforward direct sampling methods for examining posterior distributions of parameters of interest. For large numbers of alleles at a locus we resort to Markov chain Monte Carlo. We discuss a number of possibilities for prior specification, and apply the suggested methods to a number of real datasets.

  14. Determination of reversible protein equilibrium association coefficients using light scattering

    NASA Astrophysics Data System (ADS)

    Larkin, Michael

    2009-03-01

    The characterization in solution of reversible protein associations as well as associations between proteins and small molecules is essential in many areas of science. Understanding cellular function or developing and formulating pharmaceuticals or other biologically active materials often requires quantitation of such associations. Most pharmaceuticals have functionality due solely to association with molecules within the body, and the discovery and accurate characterization of these associations is a key element for pharmaceutical development. Unfortunately, most methods used to measure associations of proteins require either immobilizing the protein on a surface (e.g. surface plasmon resonance), which potentially alters the protein characteristics, or require considerable time and effort and large quantities of sample (e.g. analytical ultracentrifugation, isothermal titration calorimetry). Light scattering based measurements of reversible association coefficients require much less sample and may be performed much more rapidly than other free solution techniques. In this talk I describe how static and dynamic light scattering may each independently be used to measure equilibrium association coefficients between proteins in free solution, and may also be used to observe and quantitate the association of small molecules with them. I present background theory for both static and dynamic light scattering measurements of equilibrium associations, and examples of measurements made of both model systems and of systems with commercial relevance in the pharmaceutical industry.

  15. Electrostatic interaction of two charged macroparticles in an equilibrium plasma

    NASA Astrophysics Data System (ADS)

    Filippov, A. V.; Pal', A. F.; Starostin, A. N.

    2015-11-01

    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.

  16. 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.

  17. Universality in equilibrium and away from it: A personal perspective

    SciTech Connect

    Munoz, Miguel A.

    2011-03-24

    In this talk/paper I discuss the concept of universality in phase transitions and the question of whether universality classes are more robust in equilibrium than away from it. In both of these situations, the main ingredients determining universality are symmetries, conservation laws, the dimension of the space and of the order-parameter and the presence of long-range interactions or quenched disorder. The existence of detailed-balance and fluctuation-dissipation theorems imposes severe constraints on equilibrium systems, allowing to define universality classes in a very robust way; instead, non-equilibrium allows for more variability. Still, quite robust non-equilibrium universality classes have been identified in the last decades. Here, I discuss some examples in which (i) non-equilibrium phase transitions are simply controlled by equilibrium critical points, i.e. non-equilibrium ingredients turn out to be irrelevant in the renormalization group sense and (ii) non-equilibrium situations in which equilibrium seems to come out of the blue, generating an adequate effective description of intrinsically non-equilibrium problems. Afterwards, I shall describe different genuinely non-equilibrium phase transitions in which introducing small, apparently innocuous changes (namely: presence or absence of an underlying lattice, parity conservation in the overall number of particles, existence of an un-accessible vacuum state, deterministic versus stochastic microscopic rules, presence or absence of a Fermionic constraint), the critical behavior is altered, making the case for lack of robustness. However, it will be argued that in all these examples, there is an underlying good reason (in terms of general principles) for universality to be altered. The final conclusions are that: (i) robust universality classes exist both in equilibrium and non-equilibrium; (ii) symmetry and conservation principles are crucial in both, (iii) non-equilibrium allows for more variability (i

  18. Equilibrium and non-equilibrium cluster phases in colloids with competing interactions.

    PubMed

    Mani, Ethayaraja; Lechner, Wolfgang; Kegel, Willem K; Bolhuis, Peter G

    2014-07-07

    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.

  19. 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...

  20. IEFIT - An Interactive Approach to High Temperature Fusion Plasma Magnetic Equilibrium Fitting

    SciTech Connect

    Peng, Q.; Schachter, J.; Schissel, D.P.; Lao, L.L.

    1999-06-01

    An interactive IDL based wrapper, IEFIT, has been created for the magnetic equilibrium reconstruction code EFIT written in FORTRAN. It allows high temperature fusion physicists to rapidly optimize a plasma equilibrium reconstruction by eliminating the unnecessarily repeated initialization in the conventional approach along with the immediate display of the fitting results of each input variation. It uses a new IDL based graphics package, GaPlotObj, developed in cooperation with Fanning Software Consulting, that provides a unified interface with great flexibility in presenting and analyzing scientific data. The overall interactivity reduces the process to minutes from the usual hours.

  1. Balance mass flux and ice velocity across the equilibrium line in drainage systems of Greenland

    NASA Astrophysics Data System (ADS)

    Zwally, H. Jay; Giovinetto, Mario B.

    2001-12-01

    Estimates of balance mass flux and depth-averaged ice velocity through the cross section aligned with the equilibrium line are produced for each of six drainage systems in Greenland. The estimates are based on a model equilibrium line fitted to field data and on a revised distribution of surface mass balance for the conterminous ice sheet. Ice drainage divides and six major drainage systems are delineated using surface topography from ERS radar altimeter data. Ice thicknesses at the equilibrium line and throughout each drainage system are based on the latest compilation of airborne radar sounding data described elsewhere. The net accumulation rate in the area bounded by the equilibrium line is 399 Gt a-1, and net ablation rate in the remaining area is 231 Gt a-1. Excluding an east central coastal ridge reduces the net accumulation rate to 397 Gt a-1, with a range from 42 to 121 Gt a-1 for the individual drainage systems. The mean balance mass flux and depth-averaged ice velocity at the cross-section aligned with the modeled equilibrium line are 0.1011 Gt km-2 a-1 and 0.111 km a-1, respectively, with little variation in these values from system to system. In contrast, the mean mass discharge per unit length along the equilibrium line ranges from one half to double the overall mean rate of 0.0468 Gt km-1 a-1. The ratio of the ice mass in the area bounded by the equilibrium line to the rate of mass output implies an effective exchange time of approximately 6 ka for total mass exchange. The range of exchange times, from a low of 3 ka in the SE drainage system to 14 ka in the NE, suggests a rank as to which regions of the ice sheet may respond more rapidly to climate fluctuations.

  2. 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.

  3. A model for predicting contaminant removal by adsorption within the International Space Station water processor: 1. Multicomponent equilibrium modeling.

    PubMed

    Bulloch, J L; Hand, D W; Crittenden, J C

    1998-01-01

    A thermodynamic model is developed to predict adsorption equilibrium in the International Space Station water processor's multifiltration beds. The model predicts multicomponent adsorption equilibrium behavior using single-component isotherm parameters and fictitious components representing the background matrix. The fictitious components are determined by fitting total organic carbon and tracer isotherms with the ideal adsorbed solution theory. Multicomponent isotherms using a wastewater with high surfactant and organic compound concentrations are used to validate the equilibrium description on a coconut-shell-based granular activated carbon (GAC), coal-based GAC, and a polymeric adsorbent.

  4. Deformation of the benzene ring upon fluorination: equilibrium structures of all fluorobenzenes

    NASA Astrophysics Data System (ADS)

    Demaison, Jean; Rudolph, Heinz Dieter; Császár, Attila G.

    2013-07-01

    Born-Oppenheimer equilibrium structure (r BO e) estimates are reported for benzene and all 12 possible fluorobenzenes, based on geometry optimizations performed at the coupled cluster level of electronic structure theory including single and double excitations augmented by a perturbational estimate of the effects of connected triple excitations [CCSD(T)] and Gaussian basis sets of at least triple zeta quality. Furthermore, accurate semiexperimental equilibrium (r SE e) structures are determined for C6H6, C6H5F, and 1,2- and 1,3-difluorobenzene. They are obtained through a least-squares structural refinement procedure based on equilibrium rotational constants of as many isotopologues as feasible, determined by correcting experimental vibrationally averaged ground-state rotational constants with computed ab initio vibration-rotation interaction constants and electronic g-factors, and using a few structural constraints based on the best r BO e estimates. The r BO e and r SE e equilibrium structures are in excellent agreement with each other for the four semirigid molecules but in almost all cases they differ significantly from previously determined equilibrium structure estimates based on rotational spectroscopy or gas electron diffraction. The nature of deformations of the benzene ring induced by a single fluorine substitution can be characterized as follows: (a) the strongest effect is the pushing of the ipso carbon atom toward the ring center resulting in a deformation at the ipso [by +2.7(1)°] and ortho [-1.7(1)°] CCC angles, (b) a simultaneous decrease in the ortho CC bond length of the benzene ring by 0.009 Å and (c) a decrease of all the CH bond lengths. Additivity relations concerning the F substitution effects are obtained based on the equilibrium structures of all possible fluorobenzenes.

  5. 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...

  6. The Equilibrium Between Titanium Ions and Titanium Metal in NaCl-KCl Equimolar Molten Salt

    NASA Astrophysics Data System (ADS)

    Wang, Qiuyu; Song, Jianxun; Hu, Guojing; Zhu, Xiaobo; Hou, Jungang; Jiao, Shuqiang; Zhu, Hongmin

    2013-08-01

    The equilibrium between metallic titanium and titanium ions, 3Ti2+ ⇌ 2Ti3+ + Ti, in NaCl-KCl equimolar molten salt was reevaluated. At a fixed temperature and an initial concentration of titanium chloride, the equilibrium was achieved by adding an excess amount of sponge titanium in assistant with bubbling of argon into the molten salt. The significance of this work is that the accurate concentrations of titanium ions have been obtained based on a reliable approach for taking samples. Furthermore, the equilibrium constant {{K}}_{{C}} = (x_{{{{Ti}}^{{ 3 { + }}} }}^{{eql}} )3 /(x_{{{{Ti}}^{{ 2 { + }}} }}^{{eql}} )2 was calculated through the best-fitting method under the consideration of the TiOCl dissolution. Indeed, the final results have disclosed that the stable value of KC could be achieved based on all modifications.

  7. Non-equilibrium assembly of microtubules: from molecules to autonomous chemical robots.

    PubMed

    Hess, H; Ross, Jennifer L

    2017-03-22

    Biological systems have evolved to harness non-equilibrium processes from the molecular to the macro scale. It is currently a grand challenge of chemistry, materials science, and engineering to understand and mimic biological systems that have the ability to autonomously sense stimuli, process these inputs, and respond by performing mechanical work. New chemical systems are responding to the challenge and form the basis for future responsive, adaptive, and active materials. In this article, we describe a particular biochemical-biomechanical network based on the microtubule cytoskeletal filament - itself a non-equilibrium chemical system. We trace the non-equilibrium aspects of the system from molecules to networks and describe how the cell uses this system to perform active work in essential processes. Finally, we discuss how microtubule-based engineered systems can serve as testbeds for autonomous chemical robots composed of biological and synthetic components.

  8. Interpolative Hyperbolic Realizable Moment Closures for Non-Equilibrium Flows with Heat Transfer

    NASA Astrophysics Data System (ADS)

    Tensuda, Boone Rudy

    The predictive capabilities of a novel, 14-moment, maximum-entropy-based, interpolative closure are explored for multi-dimensional non-equilibrium flows of a monatomic gas with heat transfer. Unlike the maximum-entropy closure on which it is based, the interpolative closure provides closed-form expressions for the closing fluxes while retaining a large region of hyperbolicity. Properties of the moment system are explored via a dispersion analysis and an implicit finite-volume solution procedure is proposed. Multi-dimensional applications of the closure are then examined for several canonical non-equilibrium flow problems in order to provide an assessment of its capabilities. The predictive capabilities of the closure were found to surpass those of the 10-moment Gaussian closure. It was also found to predict interesting non-equilibrium phenomena, such as counter-gradient heat flux. The proposed implicit solver showed improved computational performance compared to the previously studied semi-implicit technique.

  9. 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.

  10. Fluctuations in Hertz chains at equilibrium

    NASA Astrophysics Data System (ADS)

    Przedborski, Michelle; Sen, Surajit; Harroun, Thad A.

    2017-03-01

    We examine the long-term behavior of nonintegrable, energy-conserved, one-dimensional systems of macroscopic grains interacting via a contact-only generalized Hertz potential and held between stationary walls. Such systems can be set up to have no phononic background excitation and represent examples of a sonic vacuum. Existing dynamical studies showed the absence of energy equipartitioning in such systems, hence their long-term dynamics was described as quasiequilibrium. Here we show that these systems do in fact reach thermal equilibrium at sufficiently long times, as indicated by the calculated heat capacity. As a by-product, we show how fluctuations of system quantities, and thus the distribution functions, are influenced by the Hertz potential. In particular, the variance of the system's kinetic energy probability density function is reduced by a factor related to the contact potential.

  11. 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.

  12. 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.

  13. 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.

  14. Kinetics of allophycocyanin's trimer-monomer equilibrium.

    PubMed

    Huang, C; Berns, D S; MacColl, R

    1987-01-13

    Kinetic studies of the dissociation of allophycocyanin trimers to monomers have been performed by using stopped-flow techniques. The dissociation was monitored by two techniques: by light scattering to observe the molecular weight changes directly and by 650-nm absorbance to observe the linkage of quaternary structure to spectra. The light-scattering experiments showed a simple exponential decay of trimers to monomers with a dissociation constant of 0.23 s-1. The absorption changes were complex, with two processes occurring. The faster absorption change appeared to be almost simultaneous with the molecular weight change (about 0.27 s-1) and was perhaps totally coordinated with it. The slower absorption change (0.071 s-1) was possibly a result of a conformational change in the chromophore arising during the conversion from newly dissociated monomers to equilibrium monomers.

  15. Radiative equilibrium model of Titan's atmosphere

    NASA Astrophysics Data System (ADS)

    Samuelson, R. E.

    1983-02-01

    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.

  16. From interacting particles to equilibrium statistical ensembles

    NASA Astrophysics Data System (ADS)

    Ilievski, Enej; Quinn, Eoin; Caux, Jean-Sébastien

    2017-03-01

    We argue that a particle language provides a conceptually simple framework for the description of anomalous equilibration in isolated quantum systems. We address this paradigm in the context of integrable models, which are those where particles scatter completely elastically and are stable against decay. In particular, we demonstrate that a complete description of equilibrium ensembles for interacting integrable models requires a formulation built from the mode occupation numbers of the underlying particle content, mirroring the case of noninteracting particles. This yields an intuitive physical interpretation of generalized Gibbs ensembles, and reconciles them with the microcanonical ensemble. We explain how previous attempts to identify an appropriate ensemble overlooked an essential piece of information, and provide explicit examples in the context of quantum quenches.

  17. Equilibrium Phase Behavior of Polydisperse Hard Spheres

    NASA Astrophysics Data System (ADS)

    Fasolo, Moreno; Sollich, Peter

    2003-08-01

    We calculate the phase behavior of hard spheres with size polydispersity, using accurate free energies for the fluid and solid phases. Cloud and shadow curves are found exactly by the moment free energy method, but we also compute the complete phase diagram, taking full account of fractionation. In contrast to earlier, simplified treatments we find no point of equal concentration between fluid and solid or reentrant melting at higher densities. Rather, the fluid cloud curve continues to the largest polydispersity that we study (14%); from the equilibrium phase behavior a terminal polydispersity can thus be defined only for the solid, where we find it to be around 7%. At sufficiently large polydispersity, fractionation into several solid phases can occur, consistent with previous approximate calculations; we find, in addition, that coexistence of several solids with a fluid phase is also possible.

  18. The equilibrium size distribution of rouleaux.

    PubMed Central

    Perelson, A S; Wiegel, F W

    1982-01-01

    Rouleaux are formed by the aggregation of red blood cells in the presence of macromolecules that bridge the membranes of adherent erythrocytes. We compute the size and degree of branching of rouleaux for macroscopic systems in thermal equilibrium in the absence of fluid flow. Using techniques from statistical mechanics, analytical expressions are derived for (a) the average number of rouleaux consisting of n cells and having m branch points; (b) the average number of cells per rouleau; (c) the average number of branch points per rouleau; and (d) the number of rouleaux with n cells, n = 1, 2, ..., in a system containing a total of N cells. We also present the results of numerical evaluations to establish the validity of asymptotic expressions that simplify our formal analytic results. Images FIGURE 1 PMID:7059653

  19. Phase-field model of oxidation: Equilibrium

    NASA Astrophysics Data System (ADS)

    Sherman, Q. C.; Voorhees, P. W.

    2017-03-01

    A phase-field model of an oxide relevant to corrosion resistant alloys for film thicknesses below the Debye length LD, where charge neutrality in the oxide does not occur, is formulated. The phase-field model is validated in the Wagner limit using a sharp interface Gouy-Chapman model for the electrostatic double layer. The phase-field simulations show that equilibrium oxide films below the Wagner limit are charged throughout due to their inability to electrostatically screen charge over the length of the film, L . The character of the defect and charge distribution profiles in the oxide vary depending on whether reduced oxygen adatoms are present on the gas-oxide interface. The Fermi level in the oxide increases for thinner films, approaching the Fermi level of the metal in the limit L /LD→0 , which increases the driving force for adsorbed oxygen reduction at the gas-oxide interface.

  20. 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.