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Sample records for chemical equilibrium modeling

  1. Chemical equilibrium modeling of detonation

    SciTech Connect

    Fried, Laurence E.; Bastea, Sorin

    2010-05-19

    Energetic materials are unique for having a strong exothermic reactivity, which has made them desirable for both military and commercial applications. Energetic materials are commonly divided into high explosives, propellants, and pyrotechnics. We will focus on high explosive (HE) materials here, although there is a great deal of commonality between the classes of energetic materials. Furthermore the history of HE materials is long, their condensed-phase chemical properties are poorly understood.

  2. Learning of Chemical Equilibrium through Modelling-Based Teaching

    ERIC Educational Resources Information Center

    Maia, Poliana Flavia; Justi, Rosaria

    2009-01-01

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

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

    ERIC Educational Resources Information Center

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

    2002-01-01

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

  4. 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.

  5. 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.

  6. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    SciTech Connect

    Yeh, G.T.; Iskra, G.A.; Szecsody, J.E.; Zachara, J.M.; Streile, G.P.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength.

  7. Exploring the Use of Multiple Analogical Models when Teaching and Learning Chemical Equilibrium

    ERIC Educational Resources Information Center

    Harrison, Allan G.; De Jong, Onno

    2005-01-01

    This study describes the multiple analogical models used to introduce and teach Grade 12 chemical equilibrium. We examine the teacher's reasons for using models, explain each model's development during the lessons, and analyze the understandings students derived from the models. A case study approach was used and the data were drawn from the…

  8. Efficient chemical equilibrium calculations for geochemical speciation and reactive transport modelling

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Blunt, Martin J.; LaForce, Tara C.

    2014-04-01

    Chemical equilibrium calculations are essential for many environmental problems. It is also a fundamental tool for chemical kinetics and reactive transport modelling, since these applications may require hundreds to billions equilibrium calculations in a single simulation. Therefore, an equilibrium method for such critical applications must be very efficient, robust and accurate. In this work we demonstrate the potential effectiveness of a novel Gibbs energy minimisation algorithm for reactive transport simulations. The algorithm includes strategies to converge from poor initial guesses; capabilities to specify non-linear equilibrium constraints such as pH of an aqueous solution and activity or fugacity of a species; a rigorous phase stability test to determine the unstable phases; and a strategy to boost the convergence speed of the calculations to quadratic rates, requiring only few iterations to converge. We use this equilibrium method to solve geochemical problems relevant to carbon storage in saline aquifers, where aqueous, gaseous and minerals phases are present. The problems are formulated to mimic the ones found in kinetics and transport simulations, where a sequence of equilibrium calculations are performed, each one using the previous solution as the initial guess. The efficiency and convergence rates of the calculations are presented, which require an average of 1-2 iterations. These results indicate that critical applications such as chemical kinetics and reactive transport modelling can potentially benefit by using this multiphase equilibrium algorithm.

  9. ORCHESTRA: an object-oriented framework for implementing chemical equilibrium models.

    PubMed

    Meeussen, Johannes C L

    2003-03-15

    This work presents a new object-oriented structure for chemical equilibrium calculations that is used in the modeling framework ORCHESTRA (Objects Representing CHEmical Speciation and TRAnsport). In contrast to standard chemical equilibrium algorithms, such as MINEQL, MINTEQ2A, PHREEQC, and ECOSAT, model equations are not hard-coded in the source code, but instead all equations are defined in text format and read by the ORCHESTRA calculation kernel at run time. This makes model definitions easily accessible and extendible by users. Furthermore, it results in a very compact and efficient calculation kernel that is easy to use as a submodel within mass transport or kinetic models. Finally, the object-oriented structure of the chemical model definitions makes it possible to implement a new object-oriented framework for implementing chemical models. This framework consists of three basic object types, entities, reactions, and phases, that form the building blocks from which other chemical models are composed. The hierarchical approach ensures consistent and compact model definitions and is illustrated here by discussing the implementation of a number of commonly used chemical models such as aqueous complexation, activity correction, precipitation, surface complexation ion exchange, and several more sophisticated adsorption models including electrostatic interactions, NICA, and CD-MUSIC. The ORCHESTRA framework is electronically available from www.macaulay.ac.uk/ORCHESTRA. PMID:12680672

  10. Exploring the use of multiple analogical models when teaching and learning chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Harrison, Allan G.; de Jong, Onno

    2005-12-01

    This study describes the multiple analogical models used to introduce and teach Grade 12 chemical equilibrium. We examine the teacher's reasons for using models, explain each model's development during the lessons, and analyze the understandings students derived from the models. A case study approach was used and the data were drawn from the observation of three consecutive Grade 12 lessons on chemical equilibrium, pre- and post-lesson interviews, and delayed student interviews. The key analogical models used in teaching were: the school dance; the sugar in a teacup; the pot of curry; and the busy highway. The lesson and interview data were subject to multiple, independent analyses and yielded the following outcomes: The teacher planned to use the students' prior knowledge wherever possible and he responded to student questions with stories and extended and enriched analogies. He planned to discuss where each analogy broke down but did not. The students enjoyed the teaching but built variable mental models of equilibrium and some of their analogical mappings were unreliable. A female student disliked masculine analogies, other students tended to see elements of the multiple models in isolation, and some did not recognize all the analogical mappings embedded in the teaching plan. Most students learned that equilibrium reactions are dynamic, occur in closed systems, and the forward and reverse reactions are balanced. We recommend the use of multiple analogies like these and insist that teachers always show where the analogy breaks down and carefully negotiate the conceptual outcomes.

  11. 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)

  12. Molecular finite-size effects in stochastic models of equilibrium chemical systems.

    PubMed

    Cianci, Claudia; Smith, Stephen; Grima, Ramon

    2016-02-28

    The reaction-diffusion master equation (RDME) is a standard modelling approach for understanding stochastic and spatial chemical kinetics. An inherent assumption is that molecules are point-like. Here, we introduce the excluded volume reaction-diffusion master equation (vRDME) which takes into account volume exclusion effects on stochastic kinetics due to a finite molecular radius. We obtain an exact closed form solution of the RDME and of the vRDME for a general chemical system in equilibrium conditions. The difference between the two solutions increases with the ratio of molecular diameter to the compartment length scale. We show that an increase in the fraction of excluded space can (i) lead to deviations from the classical inverse square root law for the noise-strength, (ii) flip the skewness of the probability distribution from right to left-skewed, (iii) shift the equilibrium of bimolecular reactions so that more product molecules are formed, and (iv) strongly modulate the Fano factors and coefficients of variation. These volume exclusion effects are found to be particularly pronounced for chemical species not involved in chemical conservation laws. Finally, we show that statistics obtained using the vRDME are in good agreement with those obtained from Brownian dynamics with excluded volume interactions. PMID:26931675

  13. Molecular finite-size effects in stochastic models of equilibrium chemical systems

    NASA Astrophysics Data System (ADS)

    Cianci, Claudia; Smith, Stephen; Grima, Ramon

    2016-02-01

    The reaction-diffusion master equation (RDME) is a standard modelling approach for understanding stochastic and spatial chemical kinetics. An inherent assumption is that molecules are point-like. Here, we introduce the excluded volume reaction-diffusion master equation (vRDME) which takes into account volume exclusion effects on stochastic kinetics due to a finite molecular radius. We obtain an exact closed form solution of the RDME and of the vRDME for a general chemical system in equilibrium conditions. The difference between the two solutions increases with the ratio of molecular diameter to the compartment length scale. We show that an increase in the fraction of excluded space can (i) lead to deviations from the classical inverse square root law for the noise-strength, (ii) flip the skewness of the probability distribution from right to left-skewed, (iii) shift the equilibrium of bimolecular reactions so that more product molecules are formed, and (iv) strongly modulate the Fano factors and coefficients of variation. These volume exclusion effects are found to be particularly pronounced for chemical species not involved in chemical conservation laws. Finally, we show that statistics obtained using the vRDME are in good agreement with those obtained from Brownian dynamics with excluded volume interactions.

  14. General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

    NASA Astrophysics Data System (ADS)

    Liu, Yen; Panesi, Marco; Sahai, Amal; Vinokur, Marcel

    2015-04-01

    This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model's accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

  15. General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures.

    PubMed

    Liu, Yen; Panesi, Marco; Sahai, Amal; Vinokur, Marcel

    2015-04-01

    This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model's accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

  16. General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

    SciTech Connect

    Liu, Yen Vinokur, Marcel; Panesi, Marco; Sahai, Amal

    2015-04-07

    This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model’s accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

  17. Chemical Equilibrium Modeling of Hanford Waste Tank Processing: Applications of Fundamental Science

    SciTech Connect

    Felmy, Andrew R.; Wang, Zheming; Dixon, David A.; Hess, Nancy J.

    2004-05-01

    The development of computational models based upon fundamental science is one means of quantitatively transferring the results of scientific investigations to practical application by engineers in laboratory and field situations. This manuscript describes one example of such efforts, specifically the development and application of chemical equilibrium models to different waste management issues at the U.S. Department of Energy (DOE) Hanford Site. The development of the chemical models is described with an emphasis on the fundamental science investigations that have been undertaken in model development followed by examples of different waste management applications. The waste management issues include the leaching of waste slurries to selective remove non-hazardous components and the separation of Sr90 and transuranics from the waste supernatants. The fundamental science contributions include: molecular simulations of the energetics of different molecular clusters to assist in determining the species present in solution, advanced synchrotron research to determine the chemical form of precipitates, and laser based spectroscopic studies of solutions and solids.

  18. Chemical Equilibrium Detonation

    NASA Astrophysics Data System (ADS)

    Bastea, Sorin; Fried, Laurence E.

    Energetic materials are unique for having a strong exothermic reactivity, which has made them desirable for both military and commercial applications. The fundamental principles outlined in this chapter pertain to the study of detonation in both gas-phase and condensed-phase energetic materials, but our main focus will be on the condensed ones, particularly on high explosives (HEs). They share many properties with other classes of condensed energetic compounds such as propellants and pyrotechnics, but a detailed understanding of detonation is especially important for numerous HE applications. The usage and study of HE materials goes back more than a century, but many questions remain to be answered, e.g., on their reaction pathways at high pressures and temperatures, chemical properties, etc.

  19. Basis invariant description of chemical equilibrium with implications for a recent axionic leptogenesis model

    NASA Astrophysics Data System (ADS)

    Shi, Bowen; Raby, Stuart

    2015-10-01

    We provide a systematic treatment of chemical equilibrium in the presence of a specific type of time dependent background. The type of time dependent background we consider appears, for example, in recently proposed axion/Majoron leptogenesis models [A. Kusenko, K. Schmitz, and T. T. Yanagida, Phys. Rev. Lett. 115, 011302 (2015) and M. Ibe and K. Kaneta, Phys. Rev. D 92, 035019 (2015)]. In describing the chemical equilibrium we use quantities which are invariant under redefinition of fermion phases (we refer to this redefinition as a change of basis for short In this paper, change of basis does not mean change of Lorentz frame. All calculations in this paper are performed in the center-of-momentum frame of the thermal plasma, i.e. the Lorentz frame in which the average momentum of particles is zero.), and therefore it is a basis invariant treatment. The change of the anomaly terms due to the change of the path integral measure [K. Fujikawa, Phys. Rev. Lett. 42, 1195 (1979) and K. Fujikawa, Phys. Rev. D 29, 285 (1984)] under a basis change is taken into account. We find it is useful to go back and forth between different bases, and there are insights which can be more easily obtained in one basis rather than another. A toy model is provided to illustrate the ideas. For the axion leptogenesis model [A. Kusenko, K. Schmitz, and T. T. Yanagida, Phys. Rev. Lett. 115, 011302 (2015)], our result suggests that at T >1013 GeV , when sphaleron processes decouple and ΓB +L≪H <ΓL (where H is the Hubble parameter at temperature T and ΓL is the Δ L =2 lepton number violating interaction rate), the amount of B -L created is controlled by the smallness of the sphaleron interaction rate, ΓB +L. Therefore it is not as efficient as described. In addition, we notice an interesting modification of gauge boson dispersion relations at subleading order.

  20. Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

    NASA Technical Reports Server (NTRS)

    Glass, Christopher E.

    1990-01-01

    The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

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

    NASA Technical Reports Server (NTRS)

    Grodzka, P.; Facemire, B.

    1977-01-01

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

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

    SciTech Connect

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

    2007-01-01

    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 NE equilibrium reactions and a set of reactive transport equations of M-NE 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. A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

    NASA Astrophysics Data System (ADS)

    Saaltink, Maarten W.; Vilarrasa, Victor; De Gaspari, Francesca; Silva, Orlando; Carrera, Jesús; Rötting, Tobias S.

    2013-12-01

    CO2 injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO2 into the brine. The resulting neutralization will drive further dissolution of both CO2 and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO2), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H2O-CO2-Na-Cl-CaCO3 system, so as to model CO2 injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO2 plume because the brine below the plume tends to reach

  4. Microscopic Simulation and Macroscopic Modeling for Thermal and Chemical Non-Equilibrium

    NASA Technical Reports Server (NTRS)

    Liu, Yen; Panesi, Marco; Vinokur, Marcel; Clarke, Peter

    2013-01-01

    This paper deals with the accurate microscopic simulation and macroscopic modeling of extreme non-equilibrium phenomena, such as encountered during hypersonic entry into a planetary atmosphere. The state-to-state microscopic equations involving internal excitation, de-excitation, dissociation, and recombination of nitrogen molecules due to collisions with nitrogen atoms are solved time-accurately. Strategies to increase the numerical efficiency are discussed. The problem is then modeled using a few macroscopic variables. The model is based on reconstructions of the state distribution function using the maximum entropy principle. The internal energy space is subdivided into multiple groups in order to better describe the non-equilibrium gases. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients. The modeling is completely physics-based, and its accuracy depends only on the assumed expression of the state distribution function and the number of groups used. The model makes no assumption at the microscopic level, and all possible collisional and radiative processes are allowed. The model is applicable to both atoms and molecules and their ions. Several limiting cases are presented to show that the model recovers the classical twotemperature models if all states are in one group and the model reduces to the microscopic equations if each group contains only one state. Numerical examples and model validations are carried out for both the uniform and linear distributions. Results show that the original over nine thousand microscopic equations can be reduced to 2 macroscopic equations using 1 to 5 groups with excellent agreement. The computer time is decreased from 18 hours to less than 1 second.

  5. A chemical model for generating the sources of mare basalts - Combined equilibrium and fractional crystallization of the lunar magmasphere

    NASA Technical Reports Server (NTRS)

    Snyder, Gregory A.; Taylor, Lawrence A.; Neal, Clive R.

    1992-01-01

    A chemical model for simulating the sources of the lunar mare basalts was developed by considering a modified mafic cumulate source formed during the combined equilibrium and fractional crystallization of a lunar magma ocean (LMO). The parameters which influence the initial LMO and its subsequent crystallization are examined, and both trace and major elements are modeled. It is shown that major elements tightly constrain the composition of mare basalt sources and the pathways to their creation. The ability of this LMO model to generate viable mare basalt source regions was tested through a case study involving the high-Ti basalts.

  6. 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.…

  7. Accounting for natural organic matter in aqueous chemical equilibrium models: a review of the theories and applications

    NASA Astrophysics Data System (ADS)

    Dudal, Yves; Gérard, Frédéric

    2004-08-01

    Soil organic matter consists of a highly complex and diversified blend of organic molecules, ranging from low molecular weight organic acids (LMWOAs), sugars, amines, alcohols, etc., to high apparent molecular weight fulvic and humic acids. The presence of a wide range of functional groups on these molecules makes them very reactive and influential in soil chemistry, in regards to acid-base chemistry, metal complexation, precipitation and dissolution of minerals and microbial reactions. Out of these functional groups, the carboxylic and phenolic ones are the most abundant and most influential in regards to metal complexation. Therefore, chemical equilibrium models have progressively dealt with organic matter in their calculations. This paper presents a review of six chemical equilibrium models, namely N ICA-Donnan, E Q3/6, G EOCHEM, M INTEQA2, P HREEQC and W HAM, in light of the account they make of natural organic matter (NOM) with the objective of helping potential users in choosing a modelling approach. The account has taken various faces, mainly by adding specific molecules within the existing model databases (E Q3/6, G EOCHEM, and P HREEQC) or by using either a discrete (W HAM) or a continuous (N ICA-Donnan and M INTEQA2) distribution of the deprotonated carboxylic and phenolic groups. The different ways in which soil organic matter has been integrated into these models are discussed in regards to the model-experiment comparisons that were found in the literature, concerning applications to either laboratory or natural systems. Much of the attention has been focused on the two most advanced models, W HAM and N ICA-Donnan, which are able to reasonably describe most of the experimental results. Nevertheless, a better knowledge of the humic substances metal-binding properties is needed to better constrain model inputs with site-specific parameter values. This represents the main axis of research that needs to be carried out to improve the models. In addition to

  8. Parameterization of the non-local thermodynamic equilibrium source function with chemical production by an equivalent two-level model

    NASA Astrophysics Data System (ADS)

    Zhu, Xun

    2003-07-01

    The classic two-level or equivalent two-level model that includes only the statistical equilibrium of radiative and thermal processes of excitation and quenching between two vibrational energy levels is extended by adding chemical production to the rate equations. The modifications to the non-local thermodynamic equilibrium source function and cooling rate are parameterized by ϕc, which characterizes the ratio of chemical production to collisional quenching. For applications of broadband emission of O3 at 9.6 μm, the non-LTE effect of chemical production on the cooling rate and limb emission is proportional to the ratio of O to O3. For a typical [O]/[O3], the maximum enhancements of limb radiance and cooling rate are about 15% 30% and 0.03 0.05 K day-1, respectively, both occurring near the mesopause regions. This suggests that the broadband limb radiance above ˜80 km is sensitive to O3 density but not sensitive to the direct cooling rate along the line-of-sight, which makes O3 retrieval feasible but the direct cooling rate retrieval difficult by using the O3 9.6 μm band limb emission.

  9. 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.

  10. Quantum chemical modeling of humic acid/air equilibrium partitioning of organic vapors.

    PubMed

    Niederer, Christian; Goss, Kai-Uwe

    2007-05-15

    Classical approaches for predicting soil organic matter partition coefficients of organic compounds require a calibration with experimental partition data and, for good accuracy, experimental compound descriptors. In this study we evaluate the quantum chemical model COSMO-RS in its COSMOtherm implementation for the prediction of about 200 experimental Leonardite humic acid/air partition coefficients without calibration or experimental compound descriptors, but simply based on molecular structures. For this purpose a Leonardite Humic Acid model monomer limited to 31 carbon atoms was derived from 13C NMR analysis, elemental analysis, and acidic function analysis provided in the literature. Altogether the COSMOtherm calculations showed a good performance and we conclude that it may become a very promising tool for the prediction of sorption in soil organic matter for compounds for which the molecular structure is the only reliable information available. COSMOtherm can be expected to be very robust with respectto new and complex compound structures because its calculations are based on a fundamental assessment of the underlying intermolecular forces. In contrast, other empirical models that are also based on the molecular structure of the sorbate have an application domain that is limited by their calibration data set that is often unknown to the user. PMID:17547191

  11. Chemical Equilibrium And Transport (CET)

    NASA Technical Reports Server (NTRS)

    Mcbride, B. J.

    1991-01-01

    Powerful, machine-independent program calculates theoretical thermodynamic properties of chemical systems. Aids in design of compressors, turbines, engines, heat exchangers, and chemical processing equipment.

  12. 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.

  13. Chemical equilibrium and reaction modeling of arsenic and selenium in soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The chemical processes and soil factors that affect the concentrations of As and Se in soil solution were discussed. Both elements occur in two redox states differing in toxicity and reactivity. Methylation and volatilization reactions occur in soils and can act as detoxification pathways. Precip...

  14. An Elementary Discussion of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    David, Carl W.

    1988-01-01

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

  15. Spreadsheet Templates for Chemical Equilibrium Calculations.

    ERIC Educational Resources Information Center

    Joshi, Bhairav D.

    1993-01-01

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

  16. Exploring Chemical and Thermal Non-equilibrium in Nitrogen Arcs

    NASA Astrophysics Data System (ADS)

    Ghorui, S.; Das, A. K.

    2012-12-01

    Plasma torches operating with nitrogen are of special importance as they can operate with usual tungsten based refractory electrodes and offer radical rich non-oxidizing high temperature environment for plasma chemistry. Strong gradients in temperature as well as species densities and huge convective fluxes lead to varying degrees of chemical non-equilibrium in associated regions. An axi-symmetric two-temperature chemical non-equilibrium model of a nitrogen plasma torch has been developed to understand the effects of thermal and chemical non-equilibrium in arcs. A 2-D finite volume CFD code in association with a non-equilibrium property routine enabled extraction of steady state self-consistent distributions of various plasma quantities inside the torch under various thermal and chemical non-equilibrium conditions. Chemical non-equilibrium has been incorporated through computation of diffusive and convective fluxes in each finite volume cell in every iteration and associating corresponding thermodynamic and transport properties through the scheme of 'chemical non-equilibrium parameter' introduced by Ghorui et. al. Recombination coefficient data from Nahar et. al. and radiation data from Krey and Morris have been used in the simulation. Results are presented for distributions of temperature, pressure, velocity, current density, electric potential, species densities and chemical non-equilibrium effects. Obtained results are compared with similar results under LTE.

  17. Binding of Iron(III) to Organic Soils: Exafs Spectroscopy And Chemical Equilibrium Modeling

    SciTech Connect

    Gustafsson, J.P.; Persson, I.; Kleja, D.B.; Schaik, J.W.J.van

    2007-07-09

    The complexation of iron(III) to soil organic matter is important for the binding of trace metals in natural environments because of competition effects. In this study, we used extended X-ray absorption fine structure (EXAFS) spectroscopy to characterize the binding mode for iron(III) in two soil samples from organic mor layers, one of which was also treated with iron(III). In most cases the EXAFS spectra had three significant contributions, inner-core Fe-O/N interactions at about 2.02(2) angstroms, Fe-C interactions in the second scattering shell at 3.00(4) angstroms, and a mean Fe-Fe distance at 3.37(3) angstroms. One untreated sample showed features typical for iron (hydr)oxides; however, after treatment of iron(III) the EXAFS spectrum was dominated by organically complexed iron. The presence of a Fe-Fe distance in all samples showed that the major part of the organically complexed iron was hydrolyzed, most likely in a mixture of complexes with an inner core of (O{sub 5}Fe){sub 2}O and (O{sub 5}Fe){sub 3}O. These results were used to constrain a model for metal-humic complexation, the Stockholm Humic Model (SHM). The model was able to describe iron(III) binding very well at low pH considering only one dimeric iron(III)-humic complex. The competition effect on trace metals was also well described.

  18. The Monte Carlo Integration Computer as an Instructional Model for the Simulation of Equilibrium and Kinetic Chemical Processes: The Development and Evaluation of a Teaching Aid.

    ERIC Educational Resources Information Center

    Wood, Dean Arthur

    A special purpose digital computer which utilizes the Monte Carlo integration method of obtaining simulations of chemical processes was developed and constructed. The computer, designated as the Monte Carlo Integration Computer (MCIC), was designed as an instructional model for the illustration of kinetic and equilibrium processes, and was…

  19. Computational non-chemically equilibrium model on the current zero simulation in a model N2 circuit breaker under the free recovery condition

    NASA Astrophysics Data System (ADS)

    Sun, Hao; Tanaka, Yasunori; Tomita, Kentaro; Wu, Yi; Rong, Mingzhe; Uesugi, Yoshihiko; Ishijima, Tatsuo

    2016-02-01

    A non-chemically equilibrium (non-CE) model was established to investigate the N2 arc plasma in the decaying phase during the arc interruption, and was validated by comparison with the experimental results based on laser Thomson scattering. Unlike the conventional model assuming the local thermodynamic equilibrium (LTE), in this non-CE model, the magneto-hydro-dynamics (MHD) method was coupled with the reaction kinetics to obtain the time-dependent species compositions and properties. The current calculation took into account five species in hot gas and 22 chemical reactions in total. The time-dependent species compositions of hot N2 were derived from the mass conservation equation for each species, considering the effect of the convection, diffusion and the chemical reaction. The influence of the non-CE compositions on the arc decaying behavior was realized by updating the thermodynamic and transport properties at each iterative step. The results indicate that the non-CE model can result in the departure of the arc decaying behavior from the LTE model, because it alters the time evolution of the species composition and consequently changes the thermodynamic and transport properties. At the edge of the arc, the time evolutions of the species are dominant by both the diffusion and the chemical reactions while at the center of the arc they are mainly influenced by the chemical reactions. Generally, the non-CE effect can lead to the delay of all the particles’ variations, particularly the electron decay, so that the arc interruption performance will be reduced compared with that in the LTE model.

  20. 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.

  1. 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.

  2. 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…

  3. Measurement and estimation of ammonia emissions from lagoon-atmosphere interface using a coupled mass transfer and chemical reactions model, and an equilibrium model

    NASA Astrophysics Data System (ADS)

    Bajwa, Kanwardeep S.; Aneja, Viney P.; Pal Arya, S.

    Ammonia has recently gained importance for its increasing atmospheric concentrations and its role in the formation of aerosols. The anaerobic lagoon and spray method, commonly used for waste storage and disposal in confined animal feeding operations (CAFO), is a significant source of ammonia emissions. An accurate emission model for ammonia from aqueous surfaces can help in the development of emission factors. Data collected from field measurements made at hog waste lagoons in south eastern North Carolina, using the flow through dynamic chamber technique, were used to evaluate the Coupled mass transfer and Chemical reactions model and Equilibrium model developed by Aneja et al. [2001a. Measurement and modeling of ammonia emissions at waste treatment lagoon-Atmospheric Interface. Water, Air and Soil pollution: Focus 1, 177-188]. Sensitivity analysis shows that ammonia flux increases exponentially with lagoon temperature and pH, but a linear increase was observed with an increase in total ammoniacal nitrogen (TAN). Ammonia flux also shows a nonlinear increase with increasing wind speed. Observed ammonia fluxes were generally lower in the cold season than in the warm season when lagoon temperatures are higher. About 41% of the equilibrium model predictions and 43% of the Coupled model predictions are found to be within a factor of two of the observed fluxes. Several model performance statistics were used to evaluate the performance of the two models against the observed flux data. These indicate that the simpler Equilibrium model does as well as the Coupled model. The possible effects of the "artificial" environment within the chamber, which is different from that in the ambient atmospheric conditions above the open lagoon surface, on the measured fluxes are also recognized.

  4. THE ABUNDANCE OF MOLECULAR HYDROGEN AND ITS CORRELATION WITH MIDPLANE PRESSURE IN GALAXIES: NON-EQUILIBRIUM, TURBULENT, CHEMICAL MODELS

    SciTech Connect

    Mac Low, Mordecai-Mark; Glover, Simon C. O. E-mail: glover@uni-heidelberg.de

    2012-02-20

    Observations of spiral galaxies show a strong linear correlation between the ratio of molecular to atomic hydrogen surface density R{sub mol} and midplane pressure. To explain this, we simulate three-dimensional, magnetized turbulence, including simplified treatments of non-equilibrium chemistry and the propagation of dissociating radiation, to follow the formation of H{sub 2} from cold atomic gas. The formation timescale for H{sub 2} is sufficiently long that equilibrium is not reached within the 20-30 Myr lifetimes of molecular clouds. The equilibrium balance between radiative dissociation and H{sub 2} formation on dust grains fails to predict the time-dependent molecular fractions we find. A simple, time-dependent model of H{sub 2} formation can reproduce the gross behavior, although turbulent density perturbations increase molecular fractions by a factor of few above it. In contradiction to equilibrium models, radiative dissociation of molecules plays little role in our model for diffuse radiation fields with strengths less than 10 times that of the solar neighborhood, because of the effective self-shielding of H{sub 2}. The observed correlation of R{sub mol} with pressure corresponds to a correlation with local gas density if the effective temperature in the cold neutral medium of galactic disks is roughly constant. We indeed find such a correlation of R{sub mol} with density. If we examine the value of R{sub mol} in our local models after a free-fall time at their average density, as expected for models of molecular cloud formation by large-scale gravitational instability, our models reproduce the observed correlation over more than an order-of-magnitude range in density.

  5. 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…

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

    SciTech Connect

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

    2011-05-20

    We examine both processes of ionization by electron and heavy-particle impact in spatially uniform plasmas at rest in the absence of external forces. A singular perturbation analysis is used to study the following physical scenario, in which thermal relaxation becomes much slower than chemical reactions. First, electron-impact ionization is investigated. The dynamics of the system rapidly becomes close to a slow dynamics manifold that allows for defining a unique chemical quasi-equilibrium for two-temperature plasmas and proving that the second law of thermodynamics is satisfied. Then, all ionization reactions are taken into account simultaneously, leading to a surprising conclusion: the inner layer for short time scale (or time boundary layer) directly leads to thermal equilibrium. Global thermo-chemical equilibrium is reached within a short time scale, involving only chemical reactions, even if thermal relaxation through elastic collisions is assumed to be slow.

  7. 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.

  8. 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"…

  9. Development of Accurate Chemical Equilibrium Models for the Hanford Waste Tanks: New Thermodynamic Measurements and Model Applications

    SciTech Connect

    Felmy, Andrew R.; Mason, Marvin; Qafoku, Odeta; Xia, Yuanxian; Wang, Zheming; MacLean, Graham

    2003-03-27

    Developing accurate thermodynamic models for predicting the chemistry of the high-level waste tanks at Hanford is an extremely daunting challenge in electrolyte and radionuclide chemistry. These challenges stem from the extremely high ionic strength of the tank waste supernatants, presence of chelating agents in selected tanks, wide temperature range in processing conditions and the presence of important actinide species in multiple oxidation states. This presentation summarizes progress made to date in developing accurate models for these tank waste solutions, how these data are being used at Hanford and the important challenges that remain. New thermodynamic measurements on Sr and actinide complexation with specific chelating agents (EDTA, HEDTA and gluconate) will also be presented.

  10. Chemical heterogeneities in the mantle: The equilibrium thermodynamic approach

    NASA Astrophysics Data System (ADS)

    Tirone, M.; Buhre, S.; Schmück, H.; Faak, K.

    2016-02-01

    This study attempts to answer a simple and yet fundamental question in relation to our understanding of the chemical evolution of deep Earth and planetary interiors. Given two initially separate assemblages (lithologies) in chemical equilibrium can we predict the chemical and mineralogical compositions of the two assemblages when they are put together to form a new equilibrated system? Perhaps a common perception is that given sufficient time, the two assemblages will homogenize chemically and mineralogically, however from a chemical thermodynamic point of view, this is not the case. Certain petrological differences in terms of bulk composition, mineralogy and mineral abundance remain unless other processes, like melting or mechanical mixing come into play. While there is not a standard procedure to address this problem, in this study it is shown that by applying chemical thermodynamic principles and some reasonable assumptions, it is possible to determine the equilibrium composition of each of the two assemblages. Some examples that consider typical mantle rocks, peridotite, lherzolite, dunite and eclogite described by simplified chemical systems are used to illustrate the general approach. A preliminary application to evaluate the effect of melting a heterogeneous mantle in complete chemical equilibrium using a thermodynamic formulation coupled with a two-phase geodynamic model shows that major element composition of the melt product generated by different peridotites is very similar. This may explain the relative homogeneity of major elements of MORBs which could be the product of melting a relatively uniform mantle, as commonly accepted, or alternatively a peridotitic mantle with different compositions but in chemical equilibrium.

  11. 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.

  12. 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. PMID:27116566

  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. 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)

  15. 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…

  16. Sparse Partial Equilibrium Tables in Chemically Resolved Reactive Flow

    SciTech Connect

    Vitello, P; Fried, L E; Pudliner, B; McAbee, T

    2003-07-14

    The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and hydrodynamics. Unfortunately, little is known concerning the detailed chemical kinetics of detonations in energetic materials. CHEETAH uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. CHEETAH supports a wide range of elements and condensed detonation products and can also be applied to gas detonations. A sparse hash table of equation of state values, called the ''cache'' is used in CHEETAH to enhance the efficiency of kinetic reaction calculations. For large-scale parallel hydrodynamic calculations, CHEETAH uses MPI communication to updates to the cache. We present here details of the sparse caching model used in the CHEETAH. To demonstrate the efficiency of modeling using a sparse cache model we consider detonations in energetic materials.

  17. Sparse Partial Equilibrium Tables in Chemically Resolved Reactive Flow

    NASA Astrophysics Data System (ADS)

    Vitello, Peter; Fried, Laurence E.; Pudliner, Brian; McAbee, Tom

    2004-07-01

    The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and hydrodynamics. Unfortunately, little is known concerning the detailed chemical kinetics of detonations in energetic materials. CHEETAH uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. CHEETAH supports a wide range of elements and condensed detonation products and can also be applied to gas detonations. A sparse hash table of equation of state values is used in CHEETAH to enhance the efficiency of kinetic reaction calculations. For large-scale parallel hydrodynamic calculations, CHEETAH uses parallel communication to updates to the cache. We present here details of the sparse caching model used in the CHEETAH coupled to an ALE hydrocode. To demonstrate the efficiency of modeling using a sparse cache model we consider detonations in energetic materials.

  18. Teaching Chemical Equilibrium and Thermodynamics in Undergraduate General Chemistry Classes.

    ERIC Educational Resources Information Center

    Banerjee, Anil C.

    1995-01-01

    Discusses some of the conceptual difficulties encountered by undergraduate students in learning certain aspects of chemical equilibrium and thermodynamics. Discusses teaching strategies for dealing with these difficulties. (JRH)

  19. Boltzmann equation solver adapted to emergent chemical non-equilibrium

    SciTech Connect

    Birrell, Jeremiah; Wilkening, Jon; Rafelski, Johann

    2015-01-15

    We present a novel method to solve the spatially homogeneous and isotropic relativistic Boltzmann equation. We employ a basis set of orthogonal polynomials dynamically adapted to allow for emergence of chemical non-equilibrium. Two time dependent parameters characterize the set of orthogonal polynomials, the effective temperature T(t) and phase space occupation factor ϒ(t). In this first paper we address (effectively) massless fermions and derive dynamical equations for T(t) and ϒ(t) such that the zeroth order term of the basis alone captures the particle number density and energy density of each particle distribution. We validate our method and illustrate the reduced computational cost and the ability to easily represent final state chemical non-equilibrium by studying a model problem that is motivated by the physics of the neutrino freeze-out processes in the early Universe, where the essential physical characteristics include reheating from another disappearing particle component (e{sup ±}-annihilation)

  20. Non-equilibrium effects in high temperature chemical reactions

    NASA Technical Reports Server (NTRS)

    Johnson, Richard E.

    1987-01-01

    Reaction rate data were collected for chemical reactions occurring at high temperatures during reentry of space vehicles. The principle of detailed balancing is used in modeling kinetics of chemical reactions at high temperatures. Although this principle does not hold for certain transient or incubation times in the initial phase of the reaction, it does seem to be valid for the rates of internal energy transitions that occur within molecules and atoms. That is, for every rate of transition within the internal energy states of atoms or molecules, there is an inverse rate that is related through an equilibrium expression involving the energy difference of the transition.

  1. Chemical Equilibrium Models for the S3 State of the Oxygen-Evolving Complex of Photosystem II.

    PubMed

    Isobe, Hiroshi; Shoji, Mitsuo; Shen, Jian-Ren; Yamaguchi, Kizashi

    2016-01-19

    We have performed hybrid density functional theory (DFT) calculations to investigate how chemical equilibria can be described in the S3 state of the oxygen-evolving complex in photosystem II. For a chosen 340-atom model, 1 stable and 11 metastable intermediates have been identified within the range of 13 kcal mol(-1) that differ in protonation, charge, spin, and conformational states. The results imply that reversible interconversion of these intermediates gives rise to dynamic equilibria that involve processes with relocations of protons and electrons residing in the Mn4CaO5 cluster, as well as bound water ligands, with concomitant large changes in the cluster geometry. Such proton tautomerism and redox isomerism are responsible for reversible activation/deactivation processes of substrate oxygen species, through which Mn-O and O-O bonds are transiently ruptured and formed. These results may allow for a tentative interpretation of kinetic data on substrate water exchange on the order of seconds at room temperature, as measured by time-resolved mass spectrometry. The reliability of the hybrid DFT method for the multielectron redox reaction in such an intricate system is also addressed. PMID:26717045

  2. Use of a chemical equilibrium model to describe surface properties and uptake of cadmium, strontium, and lead by Chlorella (UTEX 252)

    SciTech Connect

    Hassett, J.M.

    1988-01-01

    Metal-aquatic biota interactions are important in both natural and engineered systems. In this study, the uptake of cadmium, strontium and lead by the unicellular green alga Chlorella (UTEX 252) was investigated. Variables included metal concentration, pH, and ionic strength. Data gathered included dry weights (mg/l), cell counts (cells/ml), electrophoretic mobilities (EPMs, {mu}m/sec/V/cm) of metal-free and metal-exposed cells, and metal uptake - difference in concentration in filtrate of cell-metal and cell-free metal solutions. Derived data included cell volumes and surface area, uptake on a {mu}M/m{sup 2} basis, {zeta}-potentials, diffuse layer potentials and charge densities. Typical uptake values were 1.1, 5.2, and 6 {mu}M/m{sup 2} for Cd, Pb, and Sr, respectively, from solutions of pH 6, ionic strength 0.02M, and metal concentration 10{sup {minus}4} M. Cell EPMs were insensitive to metal; under certain conditions, however, (pM > 4, pH > 8), cadmium exposed cells exhibited a reversal in surface charge from negative to positive. The chemical equilibrium model MINEQL1 + STANFORD was used to model algal surface properties and metal uptake. Input data included site pK, density, and {Delta}pK, estimated from EPM-pH data. The model described surface properties of Chlorella (UTEX 252) as judged by a close fit of {zeta}-potentials and model-derived diffuse layer potentials. Metal uptake was modelled by adjusting site density and/or metal-surface site equilibrium constants. Attempts to model surface properties and metal uptake simultaneously were not successful.

  3. The Lewis Chemical Equilibrium Program with parametric study capability

    NASA Technical Reports Server (NTRS)

    Sevigny, R.

    1981-01-01

    The program was developed to determine chemical equilibrium in complex systems. Using a free energy minimization technique, the program permits calculations such as: chemical equilibrium for assigned thermodynamic states; theoretical rocket performance for both equilibrium and frozen compositions during expansion; incident and reflected shock properties; and Chapman-Jouget detonation properties. It is shown that the same program can handle solid coal in an entrained flow coal gasification problem.

  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. Conceptual Integration of Chemical Equilibrium by Prospective Physical Sciences Teachers

    ERIC Educational Resources Information Center

    Ganaras, Kostas; Dumon, Alain; Larcher, Claudine

    2008-01-01

    This article describes an empirical study concerning the mastering of the chemical equilibrium concept by prospective physical sciences teachers. The main objective was to check whether the concept of chemical equilibrium had become an integrating and unifying concept for them, that is to say an operational and functional knowledge to explain and…

  6. Prediction of chemical speciation in stabilized/solidified wastes using a general chemical equilibrium model. 2: Doped waste contaminants in cement porewaters

    SciTech Connect

    Park, J.Y.; Batchelor, B.

    1999-01-01

    In the previous paper, SOLTEQ demonstrated its ability to represent chemical speciation in the pure s/s binder systems. The objective of this paper is to provide a method for representing doped waste contaminants in SOLTEQ so that their speciation can be determined. To evaluate this method, model predictions were compared with measured concentrations in the porewaters expressed from cement pastes doped with various metal salts. Among doped metals, only mercury showed concentrations that indicated primary control by precipitation. The other metals, such as Cr(VI), Cd, Pb, and Na, showed behaviors that imply sorption as a major immobilization mechanism. The Langmuir isotherm was found to be well suited to describe the sorption of Na{sup +} ions onto the effective surface of CSH. To support the sorption of metal anions onto presumably negatively charged silica surface in cement porewater, a hypothesis of super-equivalent adsorption is proposed.

  7. Chemical Equilibrium Composition of Aqueous Systems

    Energy Science and Technology Software Center (ESTSC)

    1996-12-30

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

  8. Chemical equilibrium model for interfacial activity of crude oil in aqueous alkaline solution: the effects of pH, alkali and salt

    SciTech Connect

    Chan, M.; Yen, T.F.

    1980-11-01

    A chemical equilibrium model for interfacial activity of crude in aqueous alkaline solution is proposed. The model predicts the observed effects of pH and concentrations of alkali and salt on the interfacial tension (IFT). The model proposed was shown to describe the observed effects of acid content, pH, and sodium ions on the interfacial activity of crude oil in water. Once the pH of the interface reaches the pKa of the acids, sometimes with the help of addition of some salt, the IFT experiences a sudden steep drop to the range of 10/sup -2/ dynes/cm. After that, further addition of sodium either in the form of NaOH or NaCl is going to increase the IFT due to a shift of equilibriumn to the formation of undissociated soap. This was confirmed by the difference in the observed effect of sodium on the IFT of the extracted soap molecules which are dissociated easily and those which are associated highly and precipitated easily. These soap molecules have dissociation constant values ranging from below 10/sup -2/ to above one. 13 references.

  9. Modeling equilibrium Fe isotope fractionation

    NASA Astrophysics Data System (ADS)

    Anbar, A.; Jarzecki, A.; Spiro, T.

    2003-04-01

    Research into the stable isotope biogeochemistry of Fe and other transition metals has been driven primarily by analytical innovations which have revealed significant isotope effects in nature and the laboratory. Further development of these new isotope systems requires complementary theoretical research to guide analytical efforts. The results of the first such studies show some discrepancies with experiments. For example, Johnson et al. (2002) report an experimentally-determined 56Fe/54Fe equilibrium fractionation factor between Fe(II) and Fe(III) aquo complexes of ˜1.0025. This effect is ˜50% smaller than predicted theoretically by Schauble et al. (2001). It is important to resolve such discrepancies. Equilibrium isotope fractionation factors can be predicted from vibrational spectroscopic data of isotopically-substituted complexes, or from theoretical predictions of some or all of these frequencies obtained using force field models. The pioneering work of Schauble et al. (2001) utilized a modified Urey-Bradley force field (MUBFF) model. This approach is limiting in at least three ways: First, it is not ab initio, requiring as input some measured vibrational frequencies. Such data are not always available, or may have significant uncertainties. Second, the MUBFF does not include potentially important effects of solvent interaction. Third, because it makes certain assumptions about molecular symmetry, the MUBFF-based approach is not able to model the spectra of mixed-ligand complexes. To address these limitations, we are evaluating the use of density functional theory (DFT) as an ab initio method to predict vibrational frequencies of isotopically-substituted complexes and, hence, equilibrium fractionation factors. In a preliminary examination of the frequency shift upon isotope substitution of the bending and asymmetric stretching modes of the tetrahedral FeCl_42- complex, we find substantial differences between MUBFF and DFT predictions. Results for other Fe

  10. A Better Way of Dealing with Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Tykodi, Ralph J.

    1986-01-01

    Discusses how to address the concept of chemical equilibrium through the use of thermodynamic activities. Describes the advantages of setting up an equilibrium constant in terms of activities and demonstrates how to approximate those activities by practical measures such as partial pressures, mole fractions, and molar concentrations. (TW)

  11. Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Hunt, J. L.; Boney, L. R.

    1973-01-01

    Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

  12. 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…

  13. 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…

  14. Thermal Conductivity of Gas Mixtures in Chemical Equilibrium

    NASA Technical Reports Server (NTRS)

    Brokaw, Richard S.

    1960-01-01

    The expression for the thermal conductivity of gas mixtures in chemical equilibrium is presented in a simpler and less restrictive form. This new form is shown to be equivalent to the previous equations.

  15. Speleothems as Examples of Chemical Equilibrium Processes.

    ERIC Educational Resources Information Center

    Wilson, James R.

    1984-01-01

    The chemical formation of speleothems such as stalactites and stalagmites is poorly understood by introductory geology instructors and misrepresented in most textbooks. Although evaporation may be a controlling factor in some caves, it is necessary to consider chemical precipitation as more important in controlling the diagenesis of calcium…

  16. 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…

  17. Wave propagation in a quasi-chemical equilibrium plasma

    NASA Technical Reports Server (NTRS)

    Fang, T.-M.; Baum, H. R.

    1975-01-01

    Wave propagation in a quasi-chemical equilibrium plasma is studied. The plasma is infinite and without external fields. The chemical reactions are assumed to result from the ionization and recombination processes. When the gas is near equilibrium, the dominant role describing the evolution of a reacting plasma is played by the global conservation equations. These equations are first derived and then used to study the small amplitude wave motion for a near-equilibrium situation. Nontrivial damping effects have been obtained by including the conduction current terms.

  18. 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.

  19. 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.

  20. QUANTITATIVE ANALYSIS OF AQUEOUS SPECIES USING RAMAN SPECTROMETRY AND EQUILIBRIUM MODEL CALCULATIONS

    EPA Science Inventory

    An analytical approach of quantifying various chemical species, using Raman spectrometry in conjunction with equilibrium modeling, has been tested on aqueous solutions containing Nd, Cu, and dipicolinic acid. Equilibrium modeling was used to select optimum conditions in simple so...

  1. Temporal assessment of copper speciation, bioavailability and toxicity in UK freshwaters using chemical equilibrium and biotic ligand models: Implications for compliance with copper environmental quality standards.

    PubMed

    Lathouri, Maria; Korre, Anna

    2015-12-15

    Although significant progress has been made in understanding how environmental factors modify the speciation, bioavailability and toxicity of metals such as copper in aquatic environments, the current methods used to establish water quality standards do not necessarily consider the different geological and geochemical characteristics of a given site and the factors that affect copper fate, bioavailability potential and toxicity. In addition, the temporal variation in the concentration and bioavailable metal fraction is also important in freshwater systems. The work presented in this paper illustrates the temporal and seasonal variability of a range of water quality parameters, and Cu speciation, bioavailability and toxicity at four freshwaters sites in the UK. Rivers Coquet, Cree, Lower Clyde and Eden (Kent) were selected to cover a broad range of different geochemical environments and site characteristics. The monitoring data used covered a period of around six years at almost monthly intervals. Chemical equilibrium modelling was used to study temporal variations in Cu speciation and was combined with acute toxicity modelling to assess Cu bioavailability for two aquatic species, Daphnia magna and Daphnia pulex. The estimated copper bioavailability, toxicity levels and the corresponding ecosystem risks were analysed in relation to key water quality parameters (alkalinity, pH and DOC). Although copper concentrations did not vary much during the sampling period or between the seasons at the different sites; copper bioavailability varied markedly. In addition, through the chronic-Cu BLM-based on the voluntary risk assessment approach, the potential environmental risk in terms of the chronic toxicity was assessed. A much higher likelihood of toxicity effects was found during the cold period at all sites. It is suggested that besides the metal (copper) concentration in the surface water environment, the variability and seasonality of other important water quality

  2. Mathematical modeling of non-equilibrium sorption

    NASA Astrophysics Data System (ADS)

    Kaliev, Ibragim A.; Mukhambetzhanov, Saltanbek T.; Sabitova, Gulnara S.; Sakhit, Anghyz E.

    2016-08-01

    We consider the system of equations modeling the process of non-equilibrium sorption. Difference approximation of differential problem by the implicit scheme is formulated. The solution of the difference problem is constructed using the sweep method. Based on the numerical results we can conclude the following: when the relaxation time decreases to 0, then the solution of non-equilibrium problem tends with increasing time to solution of the equilibrium problem.

  3. 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

  4. From Chemical Forces to Chemical Rates: A Historical/Philosophical Foundation for the Teaching of Chemical Equilibrium

    ERIC Educational Resources Information Center

    Quilez, Juan

    2009-01-01

    With this paper, our main aim is to contribute to the realisation of the chemical reactivity concept, tracing the historical evolution of the concept of chemical affinity that eventually supported the concept of chemical equilibrium. We will concentrate on searching for the theoretical grounds of three key chemical equilibrium ideas: "incomplete…

  5. Developing Secondary Students' Conceptions of Chemical Reactions: The Introduction of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Van Driel, Jan H.; De Vos, Wobbe; Verloop, Nico; Dekkers, Hetty

    1998-01-01

    Describes an empirical study concerning the introduction of the concept of chemical equilibrium in chemistry classrooms in a way which challenges students' initial conceptions of chemical reactions. Contains 23 references. (DDR)

  6. Chemical-equilibrium calculations for aqueous geothermal brines

    SciTech Connect

    Kerrisk, J.F.

    1981-05-01

    Results from four chemical-equilibrium computer programs, REDEQL.EPAK, GEOCHEM, WATEQF, and SENECA2, have been compared with experimental solubility data for some simple systems of interest with geothermal brines. Seven test cases involving solubilities of CaCO/sub 3/, amorphous SiO/sub 2/, CaSO/sub 4/, and BaSO/sub 4/ at various temperatures from 25 to 300/sup 0/C and in NaCl or HCl solutions of 0 to 4 molal have been examined. Significant differences between calculated results and experimental data occurred in some cases. These differences were traced to inaccuracies in free-energy or equilibrium-constant data and in activity coefficients used by the programs. Although currently available chemical-equilibrium programs can give reasonable results for these calculations, considerable care must be taken in the selection of free-energy data and methods of calculating activity coefficients.

  7. Treating Chemical Equilibrium Mathematically in Secondary Schools: A Preliminary Investigation.

    ERIC Educational Resources Information Center

    Case, James B.

    This report presents the procedures, results, and conclusions of a study to determine the characteristics of secondary school chemistry students who were successful in grasping a mathematical approach to learning chemical equilibrium. Subjects were eighty-nine students enrolled in chemistry at a rural-suburban high school; each student had…

  8. Modified NASA-Lewis chemical equilibrium code for MHD applications

    NASA Technical Reports Server (NTRS)

    Sacks, R. A.; Geyer, H. K.; Grammel, S. J.; Doss, E. D.

    1979-01-01

    A substantially modified version of the NASA-Lewis Chemical Equilibrium Code was recently developed. The modifications were designed to extend the power and convenience of the Code as a tool for performing combustor analysis for MHD systems studies. The effect of the programming details is described from a user point of view.

  9. Computer program determines chemical composition of physical system at equilibrium

    NASA Technical Reports Server (NTRS)

    Kwong, S. S.

    1966-01-01

    FORTRAN 4 digital computer program calculates equilibrium composition of complex, multiphase chemical systems. This is a free energy minimization method with solution of the problem reduced to mathematical operations, without concern for the chemistry involved. Also certain thermodynamic properties are determined as byproducts of the main calculations.

  10. Chemical equilibrium of ablation materials including condensed species

    NASA Technical Reports Server (NTRS)

    Stroud, C. W.; Brinkley, K. L.

    1975-01-01

    Equilibrium is determined by finding chemical composition with minimum free energy. Method of steepest descent is applied to quadratic representation of free-energy surface. Solution is initiated by selecting arbitrary set of mole fractions, from which point on free-energy surface is computed.

  11. 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.

  12. Chemical Equilibrium and Polynomial Equations: Beware of Roots.

    ERIC Educational Resources Information Center

    Smith, William R.; Missen, Ronald W.

    1989-01-01

    Describes two easily applied mathematical theorems, Budan's rule and Rolle's theorem, that in addition to Descartes's rule of signs and intermediate-value theorem, are useful in chemical equilibrium. Provides examples that illustrate the use of all four theorems. Discusses limitations of the polynomial equation representation of chemical…

  13. Computer Series, 108. Computer Simulation of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Cullen, John F., Jr.

    1989-01-01

    Presented is a computer simulation called "The Great Chemical Bead Game" which can be used to teach the concepts of equilibrium and kinetics to introductory chemistry students more clearly than through an experiment. Discussed are the rules of the game, the application of rate laws and graphical analysis. (CW)

  14. Problem Solving and Chemical Equilibrium: Successful versus Unsuccessful Performance.

    ERIC Educational Resources Information Center

    Camacho, Moises; Good, Ron

    1989-01-01

    Describes the problem-solving behaviors of experts and novices engaged in solving seven chemical equilibrium problems. Lists 27 behavioral tendencies of successful and unsuccessful problem solvers. Discusses several implications for a problem solving theory, think-aloud techniques, adequacy of the chemistry domain, and chemistry instruction.…

  15. Concept Maps about Chemical Equilibrium and Students' Achievement Scores.

    ERIC Educational Resources Information Center

    Wilson, Jan

    1996-01-01

    Examines relationships between structural characteristics of students' concept maps about chemical equilibrium and independent measures of their achievement in chemistry. Results indicate significant relationships between multidimensional scaling coordinates and test scores of recall of knowledge and its application and also reveal structural…

  16. Parameter uncertainty in chemical equilibrium calculations using fuzzy set theory

    NASA Astrophysics Data System (ADS)

    Schulz, K.; Huwe, B.; Peiffer, S.

    1999-04-01

    A method based on fuzzy set theory is presented to incorporate imprecise thermodynamic parameters into chemical equilibrium calculations of aqueous systems. Imprecision may arise from uncertainties in experimental parameter determination as well as from inconsistency of available data in the literature. Fuzzy numbers with different shapes of membership functions are used to express imprecision in a non-probabilistic sense. A solution algorithm for a system of nonlinear algebraic equations calculating the chemical equilibrium composition is combined with level set operations to solve the fuzzy chemical equlibrium problem. The method results in multiple minimizing/maximizing procedures from which the membership functions of equilibrium species concentrations are determined. An application of the proposed method to an aqueous cadmium-sulfide system illustrates the acquisition of membership functions for the thermodynamic constants out of given information. Stochastic information on measurement data are appropriately transformed into fuzzy numbers to allow for the combined calculation of different kinds of uncertainty. The results of four calculation scenarios show their strong impact on the resulting membership functions of chemical equilibrium composition and are discussed in the context of data evaluation and decision making in geochemistry.

  17. Pre-equilibrium approximation in chemical and photophysical kinetics

    NASA Astrophysics Data System (ADS)

    Rae, Margaret; Berberan-Santos, Mário N.

    2002-07-01

    For most mechanisms of chemical reactions and molecular photophysical processes the time evolution of the concentration of the intervening species cannot be obtained analytically. The pre-equilibrium approximation is one of several useful approximation methods that allow the derivation of explicit solutions and simplify numerical solutions. In this work, a general view of the pre-equilibrium approximation is presented, along with the respective analytical solution. It is also shown that the kinetic behavior of systems subject to pre-equilibration can be obtained by the application of perturbation theory. Several photophysical systems are discussed, including excimer formation, thermally activated delayed fluorescence, and external-heavy atom quenching of luminescence.

  18. The Fossil Fuel Combustion Waste Leaching Code -- including the GMIN chemical equilibrium model and the HELP water balance model. Volume 2, Technical manual for the FOWL-GH{trademark} code

    SciTech Connect

    Rai, D.

    1993-12-01

    This document is a technical reference manual for FOWL-GH{trademark}, the FOssil Fuel Combustion Waste Leaching Code. FOWL-GH{trademark} predicts the chemical composition of fifteen chemical constituents (Ba, Ca, Cd, CO{sub 3} Cr, Cu, Mo, SO{sub 4}, Sr, As, B, Ni, Se, Zn, and total dissolved solids), plus the pH (H{sup +}), as a function of time at electric utility by-product disposal sites. Boron and Zn are considered only in the ponded site option. These sites may contain fly ash, bottom ash, or flue gas desulfurization (FGD) sludges. FOWL-GH{trademark} considers both landfill and slurry pond disposal sites. FOWL-GH{trademark} is a completely restructured and recoded version of the original FOWL{trademark} model. The major improvements in FOWL-GH{trademark} are the inclusion of a chemical equilibrium model (GMIN) to perform the geochemical calculations, a recoded version of the Hydrologic Evaluation of Landfill Performance (HELP) model for water-balance calculations at landfill sites, the capability to model slurry pond sites, an enhanced user-oriented interface, improved mechanistic (thermodynamic) and empirical data for several elements, and the capability to model concentrations of highly soluble salts. This manual describes the scientific basis for the calculations in FOWL-GH{trademark}. An overview of the structure of the model is also provided. The reliability of the geochemical-module calculations is demonstrated by an extensive comparison of model calculations with experimental data from laboratory batch experiments and data collected at field disposal sites. The results show good agreement with the experimental and field data for most of the chemical constituents included in the model.

  19. Clouds Composition in Super-Earth Atmospheres: Chemical Equilibrium Calculations

    NASA Astrophysics Data System (ADS)

    Kempton, Eliza M.-R.; Mbarek, Rostom

    2015-12-01

    Attempts to determine the composition of super-Earth atmospheres have so far been plagued by the presence of clouds. Yet the theoretical framework to understand these clouds is still in its infancy. For the super-Earth archetype GJ 1214b, KCl, Na2S, and ZnS have been proposed as condensates that would form under the condition of chemical equilibrium, if the planet’s atmosphere has a bulk composition near solar. Condensation chemistry calculations have not been presented for a wider range of atmospheric bulk composition that is to be expected for super-Earth exoplanets. Here we provide a theoretical context for the formation of super-Earth clouds in atmospheres of varied composition by determining which condensates are likely to form, under the assumption of chemical equilibrium. We model super-Earth atmospheres assuming they are formed by degassing of volatiles from a solid planetary core of chondritic material. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350-3,000 K. Clouds should form along the temperature-pressure boundaries where the condensed species appear in our calculations. The super-Earth atmospheres that we study range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solar and super-solar, thereby spanning a diverse range of atmospheric composition that is appropriate for low-mass exoplanets. Some condensates appear across all of our models. However, the majority of condensed species appear only over specific ranges of H:O and C:O ratios. We find that for GJ 1214b, KCl is the primary cloud-forming condensate at solar composition, in agreement with previous work. However, for oxidizing atmospheres, where H:O is less than unity, K2SO4 clouds form instead. For carbon-rich atmospheres with super-solar C:O ratios, graphite clouds additionally appear. At

  20. MCNP modelling of the PBMR equilibrium core

    SciTech Connect

    Albornoz, F.; Korochinsky, S.

    2006-07-01

    A complete MCNP model of the PBMR equilibrium core is presented, which accounts for the same fuel regions defined in the PBMR core management code, as well as for complete fuel and reflector temperature distributions. This comprehensive 3D model is the means to calculate and characterize the neutron and photon boundary sources of the equilibrium core, and is also used to support some specific core neutronic studies needing detailed geometry modelling. Due to the geometrical modelling approach followed, an unrealistic partial cutting of fuel kernels and pebbles is introduced in the model. The variations introduced by this partial cutting both on the packing fraction and on the uranium load of the modelled core and its corresponding effect on core reactivity and flux levels, have been investigated and quantified. A complete set of high-temperature cross-section data was applied to the calculation of the PBMR equilibrium core, and its effect on the calculated core reactivity is also reported. (authors)

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

    PubMed

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

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting. PMID:27147197

  2. The Fossil Fuel Combustion Waste Leaching Code -- including the GMIN chemical equilibrium model and the HELP water balance model. Volume 1: User`s guide for the FOWL-GH{trademark} code

    SciTech Connect

    Rai, D.

    1993-12-01

    This document is a user`s manual for FOWL-GH{trademark}, the FOssil Fuel Combustion Waste Leaching Code. The necessary input data, model output, installation procedures, and example test cases for FOWL-GH{trademark} are described in this manual. FOWL-GH{trademark} predicts the chemical composition of fifteen chemical constituents (Ba, Ca, Cd, CO{sub 3}, Cr, CU, Mo, SO{sub 4}, Sr, Zn, As, B, Ni, Se, and the total dissolved solids), plus the pH (H{sup +}), as a function of time at electric utility by-product disposal sites. These sites may contain fly ash, bottom ash, or flue gas desulfurization sludges. FOWL-GH{trademark} considers both landfill and slurry-pond disposal sites. FOWL-GH{trademark} is a completely restructured and recoded version of the original FOWL{trademark} model. The major improvements in FOWL-GH{trademark} are the inclusion of a chemical equilibrium model (GMIN) to perform the geochemical calculations, a recoded version of the Hydrologic Evaluation of Landfill Performance (HELP) model for water-balance calculations at landfill sites, the capability to model slurry-pond sites, an enhanced user-oriented interface, improved mechanistic (thermodynamic) and empirical data for several elements, and the capability to model concentrations of highly soluble salts. The actual implementation of these features is described in the accompanying technical manual (Felmy et al. 1993). FOWL-GH{trademark} distributed in executable form for IBM-compatible personal computers by the Electric Power Software Center through an Electric Power Research Institute, Inc. (EPRI) license.

  3. Geometric programming, chemical equilibrium, and the anti-entropy function.

    PubMed

    Duffin, R J; Zener, C

    1969-07-01

    THE CULMINATION OF THIS PAPER IS THE FOLLOWING DUALITY PRINCIPLE OF THERMODYNAMICS: maximum S = minimum S(*). (1) The left side of relation (1) is the classical characterization of equilibrium. It says to maximize the entropy function S with respect to extensive variables which are subject to certain constraints. The right side of (1) is a new characterization of equilibrium and concerns minimization of an anti-entropy function S(*) with respect to intensive variables. Relation (1) is applied to the chemical equilibrium of a mixture of gases at constant temperature and volume. Then (1) specializes to minimum F = maximum F(*), (2) where F is the Helmholtz function for free energy and F(*) is an anti-Helmholtz function. The right-side of (2) is an unconstrained maximization problem and gives a simplified practical procedure for calculating equilibrium concentrations. We also give a direct proof of (2) by the duality theorem of geometric programming. The duality theorem of geometric programming states that minimum cost = maximum anti-cost. (30). PMID:16591769

  4. 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…

  5. Chemical equilibrium in high pressure molecular fluid mixtures

    SciTech Connect

    Shaw, M.S.

    1993-09-01

    The N{sub atoms}PT Monte Carlo simulation method has been reformulated to incorporate multiple species and chemical reactions with changes in total number of molecules. While maintaining a constant number of each type of atom, the number of molecules is changed by turning on and off the interactions of any particular position with other molecules. Chemical reactions are allowed as a correlated move of atoms to differnt molecular locations. Equilibrium chemical composition is determined as an average over the simulation along with equation of state quantities. A large set of simulations has been made with the system N{sub 2} + O{sub 2} {rightleftharpoons} NO covering a wide range in P and T. Both Hugoniot states and the CJ point have been determined and are shown to be sensitive to the potentials between unlike species.

  6. 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…

  7. Students' and Teachers' Misapplication of Le Chatelier's Principle: Implications for the Teaching of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Quilez-Pardo, Juan; Solaz-Portoles, Joan Josep

    1995-01-01

    Study of strategies and procedures of 170 students and 40 teachers when solving chemical equilibrium problems found misconceptions emerging through: misapplication of Le Chatelier's Principle, use of rote-learning recall, incorrect control of variables, limited use of chemical equilibrium law, lack of mastery of chemical equilibrium principles,…

  8. Early quark production and approach to chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Gelfand, D.; Hebenstreit, F.; Berges, J.

    2016-04-01

    We perform real-time lattice simulations of out-of-equilibrium quark production in non-Abelian gauge theory in 3 +1 dimensions. Our simulations include the backreaction of quarks onto the dynamical gluon sector, which is particularly relevant for strongly correlated quarks. We observe fast isotropization and universal behavior of quarks and gluons at weak coupling and establish a quantitative connection to previous pure glue results. In order to understand the strongly correlated regime, we perform simulations for a large number of flavors and compare them to those obtained with two light quark flavors. By doing this we are able to provide estimates of the chemical equilibration time.

  9. Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Horowitz, Jordan M.

    2015-07-01

    The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

  10. Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium

    SciTech Connect

    Horowitz, Jordan M.

    2015-07-28

    The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

  11. Concept maps about chemical equilibrium and students' achievement scores

    NASA Astrophysics Data System (ADS)

    Wilson, Jan

    1996-06-01

    The purpose of this study was to examine relationships between structural characteristics of students' concept maps about chemical equilibrium and independent measures of their achievement in chemistry. Fifty students in 1991 and seventy students in 1992 completed a concept-mapping task using twenty-four specified concepts. Using similarities in concept map structure, based on the presence or absence of linked pairs of concepts, non-metric multidimensional scaling (MDS) was used to plot the location of the concept maps in coordinate space. The distribution of maps was based on differences in their structure, but also reflected levels of student achievement on independent tests. The relationship between the coordinate location of each student's maps and his or her test scores on independent chemistry achievement tests was sought by canonical correlation analysis of the 1991 data set. This revealed significant relationships between the MDS coordinates and test scores of recall of knowledge and its application. Multiple regression analysis of sixty-one students' maps from the 1992 data set against their percentile rank scores on a national chemistry quiz revealed significant relationships. The results are interpreted as revealing structural differences in conceptual organisation about chemical equilibrium among students with different levels of achievement and thus relative expertise in the domain. The significant relationship between map structure and cognitive process scores in chemistry also supports the view that the organisation of declarative knowledge influences its accessibility in cognitive tasks.

  12. Network representations of knowledge about chemical equilibrium: Variations with achievement

    NASA Astrophysics Data System (ADS)

    Wilson, Janice M.

    This study examined variation in the organization of domain-specific knowledge by 50 Year-12 chemistry students and 4 chemistry teachers. The study used nonmetric multidimensional scaling (MDS) and the Pathfinder network-generating algorithm to investigate individual and group differences in student concepts maps about chemical equilibrium. MDS was used to represent the individual maps in two-dimensional space, based on the presence or absence of paired propositional links. The resulting separation between maps reflected degree of hierarchical structure, but also reflected independent measures of student achievement. Pathfinder was then used to produce semantic networks from pooled data from high and low achievement groups using proximity matrices derived from the frequencies of paired concepts. The network constructed from maps of higher achievers (coherence measure = 0.18, linked pairs = 294, and number of subjects = 32) showed greater coherence, more concordance in specific paired links, more important specific conceptual relationships, and greater hierarchical organization than did the network constructed from maps of lower achievers (coherence measure = 0.12, linked pairs = 552, and number of subjects = 22). These differences are interpreted in terms of qualitative variation in knowledge organization by two groups of individuals with different levels of relative expertise (as reflected in achievement scores) concerning the topic of chemical equilibrium. The results suggest that the technique of transforming paired links in concept maps into proximity matrices for input to multivariate analyses provides a suitable methodology for comparing and documenting changes in the organization and structure of conceptual knowledge within and between individual students.

  13. Application of a coupled ecosystem-chemical equilibrium model, DayCent-Chem, to stream and soil chemistry in a Rocky Mountain watershed

    USGS Publications Warehouse

    Hartman, M.D.; Baron, J.S.; Ojima, D.S.

    2007-01-01

    Atmospheric deposition of sulfur and nitrogen species have the potential to acidify terrestrial and aquatic ecosystems, but nitrate and ammonium are also critical nutrients for plant and microbial productivity. Both the ecological response and the hydrochemical response to atmospheric deposition are of interest to regulatory and land management agencies. We developed a non-spatial biogeochemical model to simulate soil and surface water chemistry by linking the daily version of the CENTURY ecosystem model (DayCent) with a low temperature aqueous geochemical model, PHREEQC. The coupled model, DayCent-Chem, simulates the daily dynamics of plant production, soil organic matter, cation exchange, mineral weathering, elution, stream discharge, and solute concentrations in soil water and stream flow. By aerially weighting the contributions of separate bedrock/talus and tundra simulations, the model was able to replicate the measured seasonal and annual stream chemistry for most solutes for Andrews Creek in Loch Vale watershed, Rocky Mountain National Park. Simulated soil chemistry, net primary production, live biomass, and soil organic matter for forest and tundra matched well with measurements. This model is appropriate for accurately describing ecosystem and surface water chemical response to atmospheric deposition and climate change. ?? 2006 Elsevier B.V. All rights reserved.

  14. 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

    2016-01-01

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies. PMID:26786848

  15. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

    NASA Astrophysics Data System (ADS)

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-01

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

  16. 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

  17. MANE: A MULTIPHASE, AQUEOUS, NON-STEADY STATE EQUILIBRIUM MODEL FOR SIMULATING SOIL-WATER INTERACTIONS

    EPA Science Inventory

    A variety of chemical equilibrium models have been developed to help assess environmental chemistry problems, but few were specifically developed as research and teaching tools for use in conjunction with soil chemistry experiments. MANE model was developed to calculate equilibri...

  18. Minimizing the Free Energy: A Computer Method for Teaching Chemical Equilibrium Concepts.

    ERIC Educational Resources Information Center

    Heald, Emerson F.

    1978-01-01

    Presents a computer method for teaching chemical equilibrium concepts using material balance conditions and the minimization of the free energy. Method for the calculation of chemical equilibrium, the computer program used to solve equilibrium problems and applications of the method are also included. (HM)

  19. 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.

  20. Transport Coefficients for the NASA Lewis Chemical Equilibrium Program

    NASA Technical Reports Server (NTRS)

    Svehla, Roger A.

    1995-01-01

    The new transport property data that will be used in the NASA Lewis Research Center's Chemical Equilibrium and Applications Program (CEA) is presented. It complements a previous publication that documented the thermodynamic and transport property data then in use. Sources of the data and a brief description of the method by which the data were obtained are given. Coefficients to calculate the viscosity, thermal conductivity, and binary interactions are given for either one, or usually, two temperature intervals, typically 300 to 1000 K and 1000 to 5000 K. The form of the transport equation is the same as used previously. The number of species was reduced from the previous database. Many species for which the data were estimated were eliminated from the database. Some ionneutral interactions were added.

  1. Incorporation of a Chemical Equilibrium Equation of State into LOCI-Chem

    NASA Technical Reports Server (NTRS)

    Cox, Carey F.

    2005-01-01

    Renewed interest in development of advanced high-speed transport, reentry vehicles and propulsion systems has led to a resurgence of research into high speed aerodynamics. As this flow regime is typically dominated by hot reacting gaseous flow, efficient models for the characteristic chemical activity are necessary for accurate and cost effective analysis and design of aerodynamic vehicles that transit this regime. The LOCI-Chem code recently developed by Ed Luke at Mississippi State University for NASA/MSFC and used by NASA/MSFC and SSC represents an important step in providing an accurate, efficient computational tool for the simulation of reacting flows through the use of finite-rate kinetics [3]. Finite rate chemistry however, requires the solution of an additional N-1 species mass conservation equations with source terms involving reaction kinetics that are not fully understood. In the equilibrium limit, where the reaction rates approach infinity, these equations become very stiff. Through the use of the assumption of local chemical equilibrium the set of governing equations is reduced back to the usual gas dynamic equations, and thus requires less computation, while still allowing for the inclusion of reacting flow phenomenology. The incorporation of a chemical equilibrium equation of state module into the LOCI-Chem code was the primary objective of the current research. The major goals of the project were: (1) the development of a chemical equilibrium composition solver, and (2) the incorporation of chemical equilibrium solver into LOCI-Chem. Due to time and resource constraints, code optimization was not considered unless it was important to the proper functioning of the code.

  2. 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)

  3. Equilibrium Model of Precipitation in Microalloyed Steels

    NASA Astrophysics Data System (ADS)

    Xu, Kun; Thomas, Brian G.; O'Malley, Ron

    2011-02-01

    The formation of precipitates during thermal processing of microalloyed steels greatly influences their mechanical properties. Precipitation behavior varies with steel composition and temperature history and can lead to beneficial grain refinement or detrimental transverse surface cracks. This work presents an efficient computational model of equilibrium precipitation of oxides, sulfides, nitrides, and carbides in steels, based on satisfying solubility limits including Wagner interaction between elements, mutual solubility between precipitates, and mass conservation of alloying elements. The model predicts the compositions and amounts of stable precipitates for multicomponent microalloyed steels in liquid, ferrite, and austenite phases at any temperature. The model is first validated by comparing with analytical solutions of simple cases, predictions using the commercial package JMat-PRO, and previous experimental observations. Then it is applied to track the evolution of precipitate amounts during continuous casting of two commercial steels (1004 LCAK and 1006Nb HSLA) at two different casting speeds. This model is easy to modify to incorporate other precipitates, or new thermodynamic data, and is a useful tool for equilibrium precipitation analysis.

  4. Computer program for calculation of complex chemical equilibrium compositions and applications. Part 1: Analysis

    NASA Technical Reports Server (NTRS)

    Gordon, Sanford; Mcbride, Bonnie J.

    1994-01-01

    This report presents the latest in a number of versions of chemical equilibrium and applications programs developed at the NASA Lewis Research Center over more than 40 years. These programs have changed over the years to include additional features and improved calculation techniques and to take advantage of constantly improving computer capabilities. The minimization-of-free-energy approach to chemical equilibrium calculations has been used in all versions of the program since 1967. The two principal purposes of this report are presented in two parts. The first purpose, which is accomplished here in part 1, is to present in detail a number of topics of general interest in complex equilibrium calculations. These topics include mathematical analyses and techniques for obtaining chemical equilibrium; formulas for obtaining thermodynamic and transport mixture properties and thermodynamic derivatives; criteria for inclusion of condensed phases; calculations at a triple point; inclusion of ionized species; and various applications, such as constant-pressure or constant-volume combustion, rocket performance based on either a finite- or infinite-chamber-area model, shock wave calculations, and Chapman-Jouguet detonations. The second purpose of this report, to facilitate the use of the computer code, is accomplished in part 2, entitled 'Users Manual and Program Description'. Various aspects of the computer code are discussed, and a number of examples are given to illustrate its versatility.

  5. From Chemical Forces to Chemical Rates: A Historical/Philosophical Foundation for the Teaching of Chemical Equilibrium

    NASA Astrophysics Data System (ADS)

    Quílez, Juan

    2009-09-01

    With this paper, our main aim is to contribute to the realisation of the chemical reactivity concept, tracing the historical evolution of the concept of chemical affinity that eventually supported the concept of chemical equilibrium. We will concentrate on searching for the theoretical grounds of three key chemical equilibrium ideas: ‚incomplete reaction’, ‚reversibility’ and ‚dynamics’. In addition, the paper aims to promote teachers’ philosophical/historical chemical knowledge. The starting point of this historical reconstruction will be the state of the art in the construction of the first affinity tables, based on the concept of elective affinities, during the 18th century. Berthollet reworked this idea, considering that the amount of the substances involved in a reaction was a key factor accounting for the chemical forces. Guldberg and Waage attempted to measure those forces, formulating the first affinity mathematical equations. Afterwards, the first ideas providing a molecular interpretation of the macroscopic properties of equilibrium reactions are presented. Eventually, theoretical chemists integrated previous findings into a new field: thermodynamics. This historical approach may serve as a base for an appropriate sequencing of the teaching and learning of chemical equilibrium. Hence, this paper tries to go beyond the simple development of teachers’ conceptions of the nature of chemistry, for it gives suggestions about how teachers may translate such understandings into classroom practice.

  6. Modeling of turbulent chemical reaction

    NASA Technical Reports Server (NTRS)

    Chen, J.-Y.

    1995-01-01

    Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

  7. Theory of Chemical Modeling

    NASA Astrophysics Data System (ADS)

    Kühn, Michael

    In order to deal with the complexity of natural systems simplified models are employed to illustrate the principal and regulatory factors controlling a chemical system. Following the aphorism of Albert Einstein: Everything should be made as simple as possible, but not simpler, models need not to be completely realistic to be useful (Stumm and Morgan 1996), but need to meet a successful balance between realism and practicality. Properly constructed, a model is neither too simplified that it is unrealistic nor too detailed that it cannot be readily evaluated and applied to the problem of interest (Bethke 1996). The results of a model have to be at least partially observable or experimentally verifiable (Zhu and Anderson 2002). Geochemical modeling theories are presented here in a sequence of increasing complexity from geochemical equilibrium models to kinetic, reaction path, and finally coupled transport and reaction models. The description is far from complete but provides the needs for the set up of reactive transport models of hydrothermal systems as done within subsequent chapters. Extensive reviews of geochemical models in general can be found in the literature (Appelo and Postma 1999, Bethke 1996, Melchior and Bassett 1990, Nordstrom and Ball 1984, Paschke and van der Heijde 1996).

  8. Closure conditions for non-equilibrium multi-component models

    NASA Astrophysics Data System (ADS)

    Müller, S.; Hantke, M.; Richter, P.

    2016-07-01

    A class of non-equilibrium models for compressible multi-component fluids in multi-dimensions is investigated taking into account viscosity and heat conduction. These models are subject to the choice of interfacial pressures and interfacial velocity as well as relaxation terms for velocity, pressure, temperature and chemical potentials. Sufficient conditions are derived for these quantities that ensure meaningful physical properties such as a non-negative entropy production, thermodynamical stability, Galilean invariance and mathematical properties such as hyperbolicity, subcharacteristic property and existence of an entropy-entropy flux pair. For the relaxation of chemical potentials, a two-component and a three-component models for vapor-water and gas-water-vapor, respectively, are considered.

  9. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a ``glass like`` material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  10. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a glass like'' material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  11. Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

  12. The Lack of Chemical Equilibrium does not Preclude the Use of the Classical Nucleation Theory in Circumstellar Outflows

    NASA Technical Reports Server (NTRS)

    Paquette, John A.; Nuth, Joseph A., III

    2011-01-01

    Classical nucleation theory has been used in models of dust nucleation in circumstellar outflows around oxygen-rich asymptotic giant branch stars. One objection to the application of classical nucleation theory (CNT) to astrophysical systems of this sort is that an equilibrium distribution of clusters (assumed by CNT) is unlikely to exist in such conditions due to a low collision rate of condensable species. A model of silicate grain nucleation and growth was modified to evaluate the effect of a nucleation flux orders of magnitUde below the equilibrium value. The results show that a lack of chemical equilibrium has only a small effect on the ultimate grain distribution.

  13. Cross-coupling effects in chemically non-equilibrium viscous compressible flows

    NASA Astrophysics Data System (ADS)

    Kustova, E. V.; Giordano, D.

    2011-01-01

    A closed self-consistent description of a one-temperature non-equilibrium reacting flow is presented on the basis of the kinetic theory methods. A general case including internal degrees of freedom, dissociation-recombination and exchange reactions, and arbitrary values of affinities of chemical reactions is considered. Chemical-reaction rates and mean normal stress in viscous compressible flows are studied and a symmetric cross coupling between these terms is found. It is shown that the rate of each chemical reaction and the mean normal stress depend on velocity divergence and affinities of all chemical reactions; the law of mass action is violated in viscous flows. The results obtained in the frame of linear irreversible thermodynamics can be deduced from the proposed model for the particular case of small affinities. The reciprocal Onsager-Casimir relations are verified, the symmetry of kinetic coefficients is demonstrated, and the entropy production in a viscous flow is studied.

  14. Clouds in Super-Earth Atmospheres: Chemical Equilibrium Calculations

    NASA Astrophysics Data System (ADS)

    Mbarek, Rostom; Kempton, Eliza M.-R.

    2016-08-01

    Recent studies have unequivocally proven the existence of clouds in super-Earth atmospheres. Here we provide a theoretical context for the formation of super-Earth clouds by determining which condensates are likely to form under the assumption of chemical equilibrium. We study super-Earth atmospheres of diverse bulk composition, which are assumed to form by outgassing from a solid core of chondritic material, following Schaefer & Fegley. The super-Earth atmospheres that we study arise from planetary cores made up of individual types of chondritic meteorites. They range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solar and super-solar, thereby spanning a range of atmospheric composition that is appropriate for low-mass exoplanets. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of formation for over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350–3000 K. Clouds should form along the temperature–pressure boundaries where the condensed species appear in our calculation. We find that the composition of condensate clouds depends strongly on both the H:O and C:O ratios. For the super-Earth archetype GJ 1214b, KCl and ZnS are the primary cloud-forming condensates at solar composition, in agreement with previous work. However, for oxidizing atmospheres, K2SO4 and ZnO condensates are favored instead, and for carbon-rich atmospheres with super-solar C:O ratios, graphite clouds appear. For even hotter planets, clouds form from a wide variety of rock-forming and metallic species.

  15. The Adverse Effects of Le Chatelier's Principle on Teacher Understanding of Chemical Equilibrium

    ERIC Educational Resources Information Center

    Cheung, Derek

    2009-01-01

    Although the scientific inadequacy of Le Chatelier's principle has long been documented in the literature, the principle is still treated as a central concept of chemical equilibrium by textbook writers and teachers in many countries. In the past, researchers' interest has focused on student misconceptions about chemical equilibrium and has…

  16. Identification and Analysis of Student Conceptions Used To Solve Chemical Equilibrium Problems.

    ERIC Educational Resources Information Center

    Voska, Kirk W.; Heikkinen, Henry W.

    2000-01-01

    Identifies and quantifies the chemistry conceptions used by students when solving chemical equilibrium problems requiring application of LeChatelier's Principle, and explores the feasibility of designing a paper and pencil test to accomplish these purposes. Eleven prevalent incorrect student conceptions about chemical equilibrium were identified…

  17. 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)

  18. 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…

  19. Teachers' Misconceptions about the Effects of Addition of More Reactants or Products on Chemical Equilibrium

    ERIC Educational Resources Information Center

    Cheung, Derek; Ma, Hong-jia; Yang, Jie

    2009-01-01

    The importance of research on misconceptions about chemical equilibrium is well recognized by educators, but in the past, researchers' interest has centered on student misconceptions and has neglected teacher misconceptions. Focusing on the effects of adding more reactants or products on chemical equilibrium, this article discusses the various…

  20. Promoting Pre-Service Elementary Students' Understanding of Chemical Equilibrium through Discussions in Small Groups

    ERIC Educational Resources Information Center

    Bilgin, Ibrahim

    2006-01-01

    The purpose of this study was to investigate the effectiveness of small group discussion on students' conceptual understanding of chemical equilibrium. Students' understanding of chemical equilibrium concepts was measured using the Misconception Identification Test. The test consisted of 30 items and administered as pre-posttests to a total of 81…

  1. Equilibrium Chemistry Calculations for Model Hot-Jupiter Atmospheres

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

    Every planet in our solar system has different elemental abundances from our sun's. It is thus necessary to explore a variety of elemental abundances when investigating exoplanet atmospheres. Composition is key to unraveling a planet's formation history and determines the radiative behavior of an atmosphere, including its spectrum (Moses et al. 2013). We consider here two commonly discussed situations: [C]/[O] > 1 and 10x and 100x heavy-element enrichment. For planets above 1200 K, equilibrium chemistry is a valid starting point in atmospheric analysis. For HD 209458b, this assumption was verified by comparing the results of a robust kinetics code (non-ideal behavior) to the results of an equilibrium chemistry code (ideal behavior). Both codes output similar results for the dayside of the planet (Agundez et al. 2012). Using NASA's open-source Chemical Equilibrium Abundances code (McBride and Gordon 1996), we calculate the molecular abundances of species of interest across the dayside of model planets with a range of: elemental abundance profiles, degree of redistribution, relevant substellar temperatures, and pressures. We then explore the compositional gradient of each model planet atmosphere layer using synthetic abundance images of target spectroscopic species (water, methane, carbon monoxide). This work was supported by the NASA Planetary Atmospheres grant NNX12AI69G and NASA Astrophysics Data Analysis Program NNX13AF38G.

  2. Chemical evolution of the Earth: Equilibrium or disequilibrium process?

    NASA Technical Reports Server (NTRS)

    Sato, M.

    1985-01-01

    To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

  3. Modeling rocky coastline evolution and equilibrium

    NASA Astrophysics Data System (ADS)

    Limber, P. W.; Murray, A. B.

    2010-12-01

    Many of the world’s rocky coastlines exhibit planform roughness in the form of alternating headlands and embayments. Along cliffed coasts, it is often assumed that headlands consist of rock that is more resistant to wave attack than in neighboring bays, because of either structural or lithologic variations. Bays would then retreat landward faster than headlands, creating the undulating planform profiles characteristic of a rocky coastal landscape. While the interplay between alongshore rock strength and nearshore wave energy is, in some circumstances, a fundamental control on coastline shape, beach sediment is also important. Laboratory experiments and field observations have shown that beach sediment, in small volumes, can act as an abrasive tool to encourage sea cliff retreat. In large volumes, though, sediment discourages wave attack on the cliff face, acting as a protective barrier. This nonlinearity suggests a means for headland persistence, even without alongshore variations in rock strength: bare-rock headlands could retreat more slowly than, or at the same rate as, neighboring sediment-filled embayments because of alongshore variations in the availability of beach sediment. Accordingly, nearshore sediment dynamics (i.e. sediment production from sea cliff retreat and alongshore sediment transport) could promote the development of autogenic planform geometry. To explore these ideas, we present numerical and analytical modeling of large-scale (> one kilometer) and long-term (millennial-scale) planform rocky coastline evolution, in which sediment is supplied by both sea cliff erosion and coastal rivers and is distributed by alongshore sediment transport. We also compare model predictions with real landscapes. Previously, our modeling exercises focused on a basic rocky coastline configuration where lithologically-homogeneous sea cliffs supplied all beach sediment and maintained a constant alongshore height. Results showed that 1) an equilibrium alongshore

  4. Formation of nitric acid hydrates - A chemical equilibrium approach

    NASA Technical Reports Server (NTRS)

    Smith, Roland H.

    1990-01-01

    Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

  5. An Evaluation of the Venous Equilibrium Model for Hepatic Clearance using Isolated Perfused Rainbow Trout Livers

    EPA Science Inventory

    The venous equilibrium model is widely used to describe hepatic clearance (CLH) of chemicals metabolized by the liver. If chemical delivery to the tissue does not limit CLH, this model predicts that CLH will approximately equal the product of intrinsic metabolic clearance and a t...

  6. Equilibrium statistical-thermal models in high-energy physics

    NASA Astrophysics Data System (ADS)

    Tawfik, Abdel Nasser

    2014-05-01

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

  7. A study of diurnal variations of PM2.5 acidity and related chemical species using a new thermodynamic equilibrium model.

    PubMed

    Behera, Sailesh N; Betha, Raghu; Liu, Ping; Balasubramanian, Rajasekhar

    2013-05-01

    Aerosol acidity is one of the most important parameters that can influence atmospheric visibility, climate change and human health. Based on continuous field measurements of inorganic aerosol species and their thermodynamic modeling on a time resolution of 1h, this study has investigated the acidic properties of PM2.5 and their relation with the formation of secondary inorganic aerosols (SIA). The study was conducted by taking into account the prevailing ambient temperature (T) and relative humidity (RH) in a tropical urban atmosphere. The in-situ aerosol pH (pH(IS)) on a 12h basis ranged from -0.20 to 1.46 during daytime with an average value of 0.48 and 0.23 to 1.53 during nighttime with an average value of 0.72. These diurnal variations suggest that the daytime aerosol was more acidic than that caused by the nighttime aerosol. The hourly values of pH(IS) showed a reverse trend as compared to that of in-situ aerosol acidity ([H(+)]Ins). The pH(IS) had its maximum values at 3:00 and at 20:00 and its minimum during 11:00 to 12:00. Correlation analyses revealed that the molar concentration ratio of ammonium to sulfate (R(N/S)), equivalent concentration ratio of cations to anions (RC/A), T and RH can be used as independent variables for prediction of pH(IS). A multi-linear regression model consisting of RN/S, RC/A, T and RH was developed to estimate aerosol pH(IS). PMID:23523726

  8. Site-specific functionalization for chemical speciation of Cr(III) and Cr(VI) using polyaniline impregnated nanocellulose composite: equilibrium, kinetic, and thermodynamic modeling

    NASA Astrophysics Data System (ADS)

    Jain, Priyanka; Varshney, Shilpa; Srivastava, Shalini

    2015-10-01

    Site-specific functionalizations are the emergent attention for the enhancement of sorption latent of heavy metals. Limited chemistry has been applied for the fabrication of diafunctionalized materials having potential to tether both environmentally stable oxidation states of chromium (Cr(III) and Cr(VI). Polyaniline impregnated nanocellulose composite (PANI-NCC) has been fabricated using click chemistry and explored for the removal of Cr(III) and Cr(VI) from hydrological environment. The structure, stability, morphology, particle size, surface area, hydrophilicity, and porosity of fabricated PANI-NCC were characterized comprehensively using analytical techniques and mathematical tools. The maximum sorption performance of PANI-NCC was procured for (Cr(III): 47.06 mg g-1; 94.12 %) and (Cr(VI): 48.92 mg g-1; 97.84 %) by equilibrating 0.5 g sorbent dose with 1000 mL of 25 mg L-1 chromium conc. at pH 6.5 and 2.5 for Cr(III) and Cr(VI), respectively. The sorption data showed a best fit to the Langmuir isotherm and pseudo-second-order kinetic model. The negative value of ∆ G° (-8.59 and -11.16 kJ mol-1) and ∆ H° (66.46 × 10-1 and 17.84 × 10-1 kJ mol-1), and positive value of ∆ S° (26.66 and 31.46 J mol-1K-1) for Cr(III) and Cr(VI), respectively, reflect the spontaneous, feasibility, and exothermic nature of the sorption process. The application of fabricated PANI-NCC for removing both the forms of chromium in the presence of other heavy metals was also tested at laboratory and industrial waste water regime. These findings open up new avenues in the row of high performance, scalable, and economic nanobiomaterial for the remediation of both forms of chromium from water streams.

  9. Rate-Controlled Constrained-Equilibrium Theory of Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Keck, James C.

    2008-08-01

    The Rate-Controlled Constrained-Equilibrium (RCCE) method for simplifying the treatment of reactions in complex systems is summarized and the selection of constraints for both close-to and far-from equilibrium systems is discussed. Illustrative examples of RCCE calculations of carbon monoxide concentrations in the exhaust products of an internal combustion engine and ignition delays for methane-oxygen mixtures in a constant volume adiabatic chamber are given and compared with "detailed" calculations. The advantages of RCCE calculations over "detailed" calculations are discussed.

  10. An unstructured shock-fitting solver for hypersonic plasma flows in chemical non-equilibrium

    NASA Astrophysics Data System (ADS)

    Pepe, R.; Bonfiglioli, A.; D'Angola, A.; Colonna, G.; Paciorri, R.

    2015-11-01

    A CFD solver, using Residual Distribution Schemes on unstructured grids, has been extended to deal with inviscid chemical non-equilibrium flows. The conservative equations have been coupled with a kinetic model for argon plasma which includes the argon metastable state as independent species, taking into account electron-atom and atom-atom processes. Results in the case of an hypersonic flow around an infinite cylinder, obtained by using both shock-capturing and shock-fitting approaches, show higher accuracy of the shock-fitting approach.

  11. A rapid method for the computation of equilibrium chemical composition of air to 15000 K

    NASA Technical Reports Server (NTRS)

    Prabhu, Ramadas K.; Erickson, Wayne D.

    1988-01-01

    A rapid computational method has been developed to determine the chemical composition of equilibrium air to 15000 K. Eleven chemically reacting species, i.e., O2, N2, O, NO, N, NO+, e-, N+, O+, Ar, and Ar+ are included. The method involves combining algebraically seven nonlinear equilibrium equations and four linear elemental mass balance and charge neutrality equations. Computational speeds for determining the equilibrium chemical composition are significantly faster than the often used free energy minimization procedure. Data are also included from which the thermodynamic properties of air can be computed. A listing of the computer program together with a set of sample results are included.

  12. Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

    USGS Publications Warehouse

    Balistrieri, L.S.; Blank, R.G.

    2008-01-01

    In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models. ?? 2008 Elsevier Ltd.

  13. Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

    2016-02-01

    We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

  14. A Hybrid Method for Flows in Local Chemical Equilibrium and Nonequilibrium

    NASA Astrophysics Data System (ADS)

    Currier, Nicholas G.

    The primary objective of this work is to develop a more efficient chemically active compressible Euler equation solver. Currently, a choice between the physical accuracy of a finite-rate solver or the computational efficiency of an equilibrium flow solver must be made. The number of species modeled continues to increase with available computational resources. A method of further leveraging the increase in computational power is desired. The hybrid chemistry scheme proposed here attempts to maintain the accuracy of finite-rate schemes while retaining some of the cost savings associated with equilibrium chemistry solvers. The method given uses a full finite-rate flux in regions where chemistry is slow compared to the advection rate and an equilibrium chemistry scheme in regions where the chemistry outpaces the fluid transport. Control volume switching is based on a locally defined Damkohler number. This method could be extremely useful for full reaction path modeling or the tracking of a very large number of species. The cost of symmetric Gauss-Seidel iterations grows like the number of species plus four, quantity squared. Thus, eliminating the increased cost of solving for a large number of unknowns in regions where it is unjustified can be very useful. Tenasi, a University of Tennessee SimCenter research code, is used as a base for the new solver. The hybrid method is implemented and tested with an explicit solution technique in one dimension. In combination with a five species air chemistry model, a high-temperature shock tube is used as a verification test case. Results are compared with those from pure equilibrium, full finite-rate, perfect gas Euler, and exact perfect gas Riemann solvers. Timings are also given, suggesting the cost savings that would be possible should the hybrid method be extended using implicit algorithms.

  15. Effect of a Perturbation on the Chemical Equilibrium: Comparison with Le Chatelier's Principle

    ERIC Educational Resources Information Center

    Torres, Emilio Martinez

    2007-01-01

    This article develops a general thermodynamic treatment to predict the direction of shift in a chemical equilibrium when it is subjected to a stress. This treatment gives an inequality that relates the change in the perturbed variable and the change that the equilibrium shift produces in the conjugated variable. To illustrate the generality of…

  16. A two-dimensional, TVD numerical scheme for inviscid, high Mach number flows in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Eberhardt, S.; Palmer, G.

    1986-01-01

    A new algorithm has been developed for hypervelocity flows in chemical equilibrium. Solutions have been achieved for Mach numbers up to 15 with no adverse effect on convergence. Two methods of coupling an equilibrium chemistry package have been tested, with the simpler method proving to be more robust. Improvements in boundary conditions are still required for a production-quality code.

  17. Relating Students' Reasoning To the History of Science: The Case of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Van Driel, Jan H.; De Vos, Wobbe; Verloop, Nico

    1998-01-01

    Relates the reasoning of students introduced to the concept of chemical equilibrium to the historical development of the concept. Concludes that the study of authentic historical sources may inspire the design of effective teaching activities. Contains 33 references. (DDR)

  18. Chemical Equilibrium in Supramolecular Systems as Studied by NMR Spectrometry

    ERIC Educational Resources Information Center

    Gonzalez-Gaitano, Gustavo; Tardajos, Gloria

    2004-01-01

    Undergraduate students are required to study the chemical balance in supramolecular assemblies constituting two or more interacting species, by using proton NMR spectrometry. A good knowledge of physical chemistry, fundamentals of chemical balance, and NMR are pre-requisites for conducting this study.

  19. Equilibrium, kinetic, and reactive transport models for plutonium

    NASA Astrophysics Data System (ADS)

    Schwantes, Jon Michael

    Equilibrium, kinetic, and reactive transport models for plutonium (Pu) have been developed to help meet environmental concerns posed by past war-related and present and future peacetime nuclear technologies. A thorough review of the literature identified several hurdles that needed to be overcome in order to develop capable predictive tools for Pu. These hurdles include: (1) missing or ill-defined chemical equilibrium and kinetic constants for environmentally important Pu species; (2) no adequate conceptual model describing the formation of Pu oxy/hydroxide colloids and solids; and (3) an inability of two-phase reactive transport models to adequately simulate Pu behavior in the presence of colloids. A computer program called INVRS K was developed that integrates the geochemical modeling software of PHREEQC with a nonlinear regression routine. This program provides a tool for estimating equilibrium and kinetic constants from experimental data. INVRS K was used to regress on binding constants for Pu sorbing onto various mineral and humic surfaces. These constants enhance the thermodynamic database for Pu and improve the capability of current predictive tools. Time and temperature studies of the Pu intrinsic colloid were also conducted and results of these studies were presented here. Formation constants for the fresh and aged Pu intrinsic colloid were regressed upon using INVRS K. From these results, it was possible to develop a cohesive diagenetic model that describes the formation of Pu oxy/hydroxide colloids and solids. This model provides for the first time a means of deciphering historically unexplained observations with respect to the Pu intrinsic colloid, as well as a basis for simulating the behavior within systems containing these solids. Discussion of the development and application of reactive transport models is also presented and includes: (1) the general application of a 1-D in flow, three-phase (i.e., dissolved, solid, and colloidal), reactive

  20. Rate Constant in Far-from-Equilibrium States of a Replicating System with Mutually Catalyzing Chemicals

    NASA Astrophysics Data System (ADS)

    Kamimura, Atsushi; Yukawa, Satoshi; Ito, Nobuyasu

    2006-02-01

    As a first step to study reaction dynamics in far-from-equilibrium open systems, we propose a stochastic protocell model in which two mutually catalyzing chemicals are replicating depending on the external flow of energy resources J. This model exhibits an Arrhenius type reaction; furthermore, it produces a non-Arrhenius reaction that exhibits a power-law reaction rate with regard to the activation energy. These dependences are explained using the dynamics of J; the asymmetric random walk of J results in the Arrhenius equation and conservation of J results in a power-law dependence. Further, we find that the discreteness of molecules results in the power change. Effects of cell divisions are also discussed in our model.

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

    PubMed

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

    2007-05-01

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

  2. A Unified Graphical Representation of Chemical Thermodynamics and Equilibrium

    ERIC Educational Resources Information Center

    Hanson, Robert M.

    2012-01-01

    During the years 1873-1879, J. Willard Gibbs published his now-famous set of articles that form the basis of the current perspective on chemical thermodynamics. The second article of this series, "A Method of Geometrical Representation of the Thermodynamic Properties of Substances by Means of Surfaces," published in 1873, is particularly notable…

  3. Features of the chemical equilibrium of dimerization in a system of solid spheres

    NASA Astrophysics Data System (ADS)

    Tkachev, N. K.; Zinatullina, A. R.

    2013-09-01

    Statistical and thermodynamic analyses of the equilibrium of dimerization in solid-phase systems is performed for a model of the Van der Waals type and the Perkus-Yevik approximation. For the model of Van der Waals type, the simple equation γ = exp[ p 0(2-λ3)] is obtained for an average activity coefficient ( p 0 is reduced pressure and λ is bond length in dimer) that describes both positive and negative deviations from the ideal, depending on the change in volume after the elementary act of chemical reaction. It is found that the Perkus-Yevik approximation predicts similar results with more pronounced deviations from the ideal, and the activity coefficient depends on the degree of dissociation as well.

  4. Rapid computation of chemical equilibrium composition - An application to hydrocarbon combustion

    NASA Technical Reports Server (NTRS)

    Erickson, W. D.; Prabhu, R. K.

    1986-01-01

    A scheme for rapidly computing the chemical equilibrium composition of hydrocarbon combustion products is derived. A set of ten governing equations is reduced to a single equation that is solved by the Newton iteration method. Computation speeds are approximately 80 times faster than the often used free-energy minimization method. The general approach also has application to many other chemical systems.

  5. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

  6. The assumption of equilibrium in models of migration.

    PubMed

    Schachter, J; Althaus, P G

    1993-02-01

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

  7. A time-accurate algorithm for chemical non-equilibrium viscous flows at all speeds

    NASA Technical Reports Server (NTRS)

    Shuen, J.-S.; Chen, K.-H.; Choi, Y.

    1992-01-01

    A time-accurate, coupled solution procedure is described for the chemical nonequilibrium Navier-Stokes equations over a wide range of Mach numbers. This method employs the strong conservation form of the governing equations, but uses primitive variables as unknowns. Real gas properties and equilibrium chemistry are considered. Numerical tests include steady convergent-divergent nozzle flows with air dissociation/recombination chemistry, dump combustor flows with n-pentane-air chemistry, nonreacting flow in a model double annular combustor, and nonreacting unsteady driven cavity flows. Numerical results for both the steady and unsteady flows demonstrate the efficiency and robustness of the present algorithm for Mach numbers ranging from the incompressible limit to supersonic speeds.

  8. Modeling of bi-equilibrium states in dielectric elastomer

    NASA Astrophysics Data System (ADS)

    Peng, Longgui

    2014-03-01

    Dielectric elastomer is a soft active material, producing fast deformation under voltage-activation. Under a specific boundary condition, trussed dielectric elastomer elongates mimicking the behavior of biological muscle. During this process, dielectric elastomer experiences a snap from one deformation mode to another, though both at the electromechanical equilibrium states. Based on thermodynamics, models are established to investigate electromechanical coupling at the two equilibrium states. Particular emphasis is devoted to establishing the governing equations of the two deformation modes with physical interpretations. The transition of equilibrium state is discussed, to predict the attainable stable state for application.

  9. Alkali metals in circulating fluidized bed combustion of biomass and coal: measurements and chemical equilibrium analysis

    SciTech Connect

    Michal P. Glazer; Nafees A. Khan; Wiebren de Jong; Hartmut Spliethoff; Heiko Schuermann; Penelope Monkhouse

    2005-10-01

    Combustion and co-combustion experiments with four kinds of straw, specially selected for their different alkali, Cl, and Si contents, and Colombian black coal were carried out in a circulating fluidized bed (CFB) reactor at Delft University of Technology. The influence of operating conditions and fuel composition on the release of the alkali compounds to the gas phase was investigated. The amount of the total gas-phase sodium and potassium compounds in the flue gases was measured with excimer laser induced fluorescence (ELIF). The results show that the release of gaseous alkali species depends on fuel composition, in particular the K/Cl and K/Si ratios in the fuel. The fuels with high K and Cl values show higher concentrations of the gaseous alkalis. A synergetic effect of the co-combustion with coal was observed, which led to a strong decrease in gaseous alkali concentrations. Together with experiments, chemical equilibrium modeling was performed to help in interpreting the experimental data. The calculations confirmed that the equilibrium is very strongly influenced by the composition of the fuel blend. Moreover, the simulations provided more information on sequestering of alkali species. 22 refs., 5 figs., 4 tabs.

  10. Turbulence modeling for non-equilibrium flows

    NASA Technical Reports Server (NTRS)

    Durbin, Paul A.

    1993-01-01

    Two projects are reported. The first is the development and testing of an eddy viscosity transport model. This project also is a starting point for our work on developing computational tools for solving turbulence models in complex geometries. The second project is a stochastic analysis of the realizability of Reynolds stress transport models.

  11. Modeling MOSFET surface capacitance behavior under non-equilibrium

    NASA Astrophysics Data System (ADS)

    Kapoor, Abhishek; Jindal, R. P.

    2005-06-01

    A normalized analytical solution for the capacitance associated with a MOSFET surface under non-equilibrium conditions is presented. It is shown that this model can be mapped into an equivalent equilibrium problem with 98% accuracy for near intrinsic samples (UB ≅ 2). The precision becomes even better for highly doped semiconductors. The physics behind this transformation is explained and nomograms generated to present data in a highly normalized form.

  12. 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.

  13. MODELING CHEMICAL INTERACTIONS IN ANAEROBIC BIOFILM SYSTEMS

    EPA Science Inventory

    Rigorous steady-state models of acetate- and methanol-utilizing methanogenic biofilms are developed taking into account the mass transfer of neutral and ionic species, pH changes within the biofilm, pH-dependent Monod kinetics, chemical equilibrium,, electronueutrality, gas produ...

  14. Effects of angular-momentum conservation in unified pre-equilibrium and equilibrium reaction models

    NASA Astrophysics Data System (ADS)

    Shi, Xiangjun; Gruppelaar, H.; Akkermans, J. M.

    1987-05-01

    The master-equation theory of precompound and compound nuclear decay is generalized to the inclusion of the conservation of angular momentum. It is demonstrated that the constructed model contains the Hauser-Feshbach, Weisskopf-Ewing as well as standard exciton models as limiting cases. This unified pre-equilibrium/Hauser-Feshbach model, which may be considered as a practicable version of the quantum-statistical, so-called AWM theory of Agassi et al., has been computationally optimized, such that the related numerical effort has become comparable to or less than that of a standard Hauser-Feshbach calculation. With this unified model the nature and importance of some spin effects in pre-equilibrium reactions has been investigated. The main conclusion from numerical calculations is that the standard precompound-model results are close to those of the angular-momentum conserving model, implying that the popular semi-classical models are quite reliable in this respect from a practical point of view.

  15. Modeling non-equilibrium phase transitions in isentropically compressed Bi

    SciTech Connect

    Kane, J; Smith, R

    2005-09-19

    We report here on modeling of non-equilibrium phase transitions in Bi samples isentropically compressed to 120 GPa by a ramped drive, which is produced using the Janus laser. In the experiments, the Bi samples are attached to windows of LiF or sapphire, and the velocity history of the sample-window interface is recorded with line VISAR. The 1D response of the targets is modeled using a multiphase Bi EOS, the Andrews-Hayes method for non-equilibrium transitions, and a Boettger-Wallace kinetics model. The pressure drive is deduced by back integration of VISAR data from shots performed with Al samples.

  16. Freight Network Equilibrium Model revisited: the Freight Network Modeling System

    SciTech Connect

    Tobin, R.L.

    1984-01-01

    The Freight Network Equilibrium Model (FNEM) was developed to study potential coal transportation impacts that could result from widespread conversion of boilers to use coal for fuel, as mandated under the Powerplant and Industrial Fuel Use Act of 1978. Continued improvement of FNEM and creation of auxiliary software and data during applications of the model in various transportation analyses led to the development of the Freight Network Modeling System, a general and flexible modeling system designed to have wide applicability to a variety of freight transportation analyses. It consists of compatible network data bases, data management software, models of freight transportation, report generators, and graphics output. The network data include US rail, water, highway, and pipeline systems. Data management software automates the task of setting up a study network of appropriate detail in appropriate regions of the country. The major analytical tools in the system are FNEM and Shortest Path Analysis and Display (SPAD); FNEM is predictive and simulates decisions of both shippers and carriers, taking into account the competition for transportation facilities; SPAD is a simpler model that optimizes routings of single shipments. Output for both FNEM and SPAD includes detailed routings, cost and delay estimates for all shipments, and data on total traffic levels. SPAD can be used interactively with routes displayed graphically. 13 references, 10 figures, 2 tables.

  17. A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

    NASA Technical Reports Server (NTRS)

    Gokoglu, S. A.; Kuczmarski, M. A.

    1993-01-01

    Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

  18. Modelling spectral properties of non-equilibrium atomic hydrogen plasma

    NASA Astrophysics Data System (ADS)

    D'Ammando, G.; Pietanza, L. D.; Colonna, G.; Longo, S.; Capitelli, M.

    2010-02-01

    A model to predict the emissivity and absorption coefficient of atomic hydrogen plasma is presented in detail. Non-equilibrium plasma is studied through coupling of the model with a collisional-radiative code for the excited states population as well as with the Boltzmann equation for the electron energy distribution function.

  19. Heavy ion collisions and the pre-equilibrium exciton model

    SciTech Connect

    Betak, E.

    2012-10-20

    We present a feasible way to apply the pre-equilibrium exciton model in its masterequation formulation to heavy-ion induced reactions including spin variables. Emission of nucleons, {gamma}'s and also light clusters is included in our model.

  20. A novel local equilibrium model for shaped tokamak plasmas

    SciTech Connect

    Yu Weihong; Zhou Deng; Xiang Nong

    2012-07-15

    A model is proposed for a local up-down symmetric equilibrium in the vicinity of a specified magnetic surface with given elongation and triangularity. Different from the Miller's model [R. L. Miller et al., Phys. Plasmas 5, 973 (1998)], the derivative of the Shafranov shift in the present model is self-consistently determined. The equilibrium accounts for all the essential features, like the elongation, the triangularity, and the Shafranov shift etc., of a shaped cross section. Hence, it can be used for investigation of radially localized plasma modes, like reversed shear Alfvenic eigenmodes and ballooning mode, etc., and it is also suitable for local equilibrium construction used for flux tube plasma simulations.

  1. Argumentation Practices in Classroom: Pre-Service Teachers' Conceptual Understanding of Chemical Equilibrium

    ERIC Educational Resources Information Center

    Kaya, Ebru

    2013-01-01

    This study examines the impact of argumentation practices on pre-service teachers' understanding of chemical equilibrium. The sample consisted of 100 pre-service teachers in two classes of a public university. One of these classes was assigned as experimental and the other as control group, randomly. In the experimental group, the subject of…

  2. Strategies Reported Used by Instructors to Address Student Alternate Conceptions in Chemical Equilibrium

    ERIC Educational Resources Information Center

    Piquette, Jeff S.; Heikkinen, Henry W.

    2005-01-01

    This study explores general-chemistry instructors' awareness of and ability to identify and address common student learning obstacles in chemical equilibrium. Reported instructor strategies directed at remediating student alternate conceptions were investigated and compared with successful, literature-based conceptual change methods. Fifty-two…

  3. Control of Chemical Equilibrium by Solvent: A Basis for Teaching Physical Chemistry of Solutions

    ERIC Educational Resources Information Center

    Prezhdo, Oleg V.; Craig, Colleen F.; Fialkov, Yuriy; Prezhdo, Victor V.

    2007-01-01

    The study demonstrates that the solvent present in a system can highly alter and control the chemical equilibrium of a system. The results show that the dipole moment and polarizibility of a system can be highly altered by using different mixed solvents.

  4. The Effectiveness of Conceptual Change Texts in Remediating High School Students' Alternative Conceptions Concerning Chemical Equilibrium

    ERIC Educational Resources Information Center

    Ozmen, Haluk

    2007-01-01

    This study investigated the effectiveness of conceptual change texts in remediating high school students' alternative conceptions concerning chemical equilibrium. A quasi-experimental design was used in this study. The subjects for this study consisted of a total 78 tenth-grade students, 38 of them in the experimental group and 40 of them in the…

  5. Analogies in the Teaching of Chemical Equilibrium: A Synthesis/Analysis of the Literature

    ERIC Educational Resources Information Center

    Raviolo, Andres; Garritz, Andoni

    2009-01-01

    This paper presents a thorough literature review of the analogies used to teach chemical equilibrium. The main objective is to compile all the analogies that have been found to be of service to the teacher and the student. Additionally, we categorize and analyze analogies in relation to the following aspects: representation of the dynamic nature…

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

    ERIC Educational Resources Information Center

    Cheung, Derek

    2009-01-01

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

  7. A time-accurate implicit method for chemical non-equilibrium flows at all speeds

    NASA Technical Reports Server (NTRS)

    Shuen, Jian-Shun

    1992-01-01

    A new time accurate coupled solution procedure for solving the chemical non-equilibrium Navier-Stokes equations over a wide range of Mach numbers is described. The scheme is shown to be very efficient and robust for flows with velocities ranging from M less than or equal to 10(exp -10) to supersonic speeds.

  8. Exploring the Impact of Argumentation on Pre-Service Science Teachers' Conceptual Understanding of Chemical Equilibrium

    ERIC Educational Resources Information Center

    Aydeniz, Mehmet; Dogan, Alev

    2016-01-01

    This study examines the impact of argumentation on pre-service science teachers' (PST) conceptual understanding of chemical equilibrium. The sample consisted of 57 first-year PSTs enrolled in a teacher education program in Turkey. Thirty two of the 57 PSTs who participated in this study were in the experimental group and 25 in the control group.…

  9. The Effect of a Conceptual Change Approach on Understanding of Students' Chemical Equilibrium Concepts

    ERIC Educational Resources Information Center

    Atasoy, Basri; Akkus, Huseyin; Kadayifci, Hakki

    2009-01-01

    The purpose of this study was to compare the effects of a conceptual change approach over traditional instruction on tenth-grade students' conceptual achievement in understanding chemical equilibrium. The study was conducted in two classes of the same teacher with participation of a total of 44 tenth-grade students. In this study, a…

  10. A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

    ERIC Educational Resources Information Center

    Vargas, Francisco M.

    2014-01-01

    The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

  11. Systematic Approach to Calculate the Concentration of Chemical Species in Multi-Equilibrium Problems

    ERIC Educational Resources Information Center

    Baeza-Baeza, Juan Jose; Garcia-Alvarez-Coque, Maria Celia

    2011-01-01

    A general systematic approach is proposed for the numerical calculation of multi-equilibrium problems. The approach involves several steps: (i) the establishment of balances involving the chemical species in solution (e.g., mass balances, charge balance, and stoichiometric balance for the reaction products), (ii) the selection of the unknowns (the…

  12. A Teaching Sequence for Learning the Concept of Chemical Equilibrium in Secondary School Education

    ERIC Educational Resources Information Center

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

    2014-01-01

    A novel didactic sequence is proposed for the teaching of chemical equilibrium. This teaching sequence takes into account the historical and epistemological evolution of the concept, the alternative conceptions and learning difficulties highlighted by teaching science and research in education, and the need to focus on both the students'…

  13. Investigation of Mixing and Chemical Reaction Interactions Using Rate-Controlled Constrained-Equilibrium

    NASA Astrophysics Data System (ADS)

    Hadi, Fatemeh; Janbozorgi, Mohammad; Sheikhi, Reza H.; Metghalchi, Hameed

    2014-11-01

    The Rate-Controlled Constrained-Equilibrium (RCCE) method is applied to study the interaction between mixing and chemical reaction in a constant pressure Partially-Stirred Reactor (PaSR). The objective is to understand the influence of mixing on RCCE predictions. The RCCE is a computationally efficient method based on thermodynamics to implement the combustion chemistry. In the RCCE the dynamics of reacting systems is described by a small number of rate-controlling reactions and slowly-varying constraints. The method is applied to study methane combustion via 12 constraints and 133 reaction steps. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The RCCE predictions are assessed by comparing with those of detailed kinetics model, in which the same kinetics, involving 29 species and 133 reaction steps, is integrated directly. Chemical kinetics and mixing interactions are studied for different residence and mixing time scales. Results show that the RCCE accurately represents the effect of mixing with different mixing strengths. An assessment of numerical performance of the RCCE is also performed. It is shown that the method is effective to reduce the stiffness of the kinetics and thus allows simulations with much lower computation costs.

  14. A numerical model of non-equilibrium thermal plasmas. II. Governing equations

    SciTech Connect

    Li HePing; Zhang XiaoNing; Xia Weidong

    2013-03-15

    Governing equations and the corresponding physical properties of the plasmas are both prerequisites for studying the fundamental processes in a non-equilibrium thermal plasma system numerically. In this paper, a kinetic derivation of the governing equations used for describing the complicated thermo-electro-magneto-hydrodynamic-chemical coupling effects in non-equilibrium thermal plasmas is presented. This derivation, which is achieved using the Chapman-Enskog method, is completely consistent with the theory of the transport properties reported in the previous paper by the same authors. It is shown, based on this self-consistent theory, that the definitions of the specific heat at constant pressure and the reactive thermal conductivity of two-temperature plasmas are not necessary. The governing equations can be reduced to their counterparts under local thermodynamic equilibrium (LTE) and local chemical equilibrium (LCE) conditions. The general method for the determination of the boundary conditions of the solved variables is also discussed briefly. The two papers establish a self-consistent physical-mathematical model that describes the complicated physical and chemical processes in a thermal plasma system for the cases both in LTE or LCE conditions and under non-equilibrium conditions.

  15. Evaluation of the Diffusive Equilibrium Models by the IMAGE RPI

    NASA Astrophysics Data System (ADS)

    Ozhogin, Pavel; Reinisch, Bodo W.; Song, Paul; Tu, Jiannan

    2013-04-01

    Using measured field-aligned electron density profiles, this study investigates the validity of the diffusive equilibrium model in Earth's plasmasphere. This model which describes the electron and ion densities along a magnetic field line in the plasmasphere has been widely used for ray tracing and pitch-angle scattering calculations. It is based on the hydrostatic equilibrium with the electrostatic force that acts on ions and electrons along geomagnetic field lines while actually there is no motion or diffusion of the plasma involved. The model requires multiple input parameters: electron density and ion composition (H+, He+, O+) at a base level for a magnetic field line in the ionosphere, and the (electron or ion) temperature in the plasmasphere. It has been recognized that these input parameters have to be flexible from one field line to another so that the model output does not contradict some known observed relationships. However, while the flexibility provides the possibility to fit any individual observed density distribution which is measured across many different field lines, the model prediction becomes questionable along a single field line. Before the launch of the IMAGE satellite in 2000 no plasma density measurements along a single field line were available, and therefore the validity of the diffusive equilibrium models had not been independently verified. Our qualitative and quantitative analysis shows that the fundamental functional form of the diffusive equilibrium model is inconsistent with the large database of field-aligned electron density distributions obtained by the radio plasma imager (RPI) instrument onboard the IMAGE satellite. Review of the procedures used in the derivation of the original diffusive equilibrium model suggests that the physical processes described by the mathematical procedures are fundamentally incorrect.

  16. Derivation of the chemical-equilibrium rate coefficient using scattering theory

    NASA Technical Reports Server (NTRS)

    Mickens, R. E.

    1977-01-01

    Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.

  17. An implicit flux-split algorithm to calculate hypersonic flowfields in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Palmer, Grant

    1987-01-01

    An implicit, finite-difference, shock-capturing algorithm that calculates inviscid, hypersonic flows in chemical equilibrium is presented. The flux vectors and flux Jacobians are differenced using a first-order, flux-split technique. The equilibrium composition of the gas is determined by minimizing the Gibbs free energy at every node point. The code is validated by comparing results over an axisymmetric hemisphere against previously published results. The algorithm is also applied to more practical configurations. The accuracy, stability, and versatility of the algorithm have been promising.

  18. The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the NaKCaMgClSO 4H 2O system at temperatures below 25°C

    NASA Astrophysics Data System (ADS)

    Spencer, Ronald J.; Møller, Nancy; Weare, John H.

    1990-03-01

    A low temperature thermochemical model for the system NaKCaMgClSO 4H 2O is presented. Aqueous species and standard chemical potentials of solid-solution reactions are modeled from published data for binary and ternary solutions. The temperature range below 25°C (to near -60°C) is emphasized, although the model parameters are fitted to merge smoothly with those of higher temperature models at temperatures between 25 and 100°C. Binary and ternary specific ion interaction terms vary independently with temperature and are modeled using freezing point depression and mineral solubility measurements. The standard chemical potential of the ice-water reaction is fitted independent of the model (from vapor pressure and free energy data). Remaining standard chemical potentials of solidsolution reactions are fitted along with the specific ion interaction terms. Model predictions are tested against published data for minerals formed and brine compositions obtained by chilling seawater to the eutectic (about -54°C). The model predicts the sequence of solid phases observed to precipitate from chilled seawater (mice-mirabilite-hydrohalite-sylvite-MgCl 2 · 12H 2Oantarcticite). For all but mirabilite model temperatures are within the uncertainty of the measured temperature. The compositions of brines predicted by the model also closely follow the observed compositions. The model allows accurate predictions of the freezing points of simple and complex solutions in the system. Low temperature phase equilibria and mineral solubilities may also be predicted. The model may be used to determine the composition of brines in fluid inclusions in the multicomponent system based on low temperature phase equilibria.

  19. Thermal And Chemical Non-Equilibrium Effects In The Wake Of A Boundary-Layer Sized Object In Hypersonic Flows

    NASA Astrophysics Data System (ADS)

    Birrer, Marcel; Stemmer, Christian; Adams, Nikolaus N.

    2011-05-01

    Investigations of hypersonic boundary-layer flows around a cubical obstacle with a height in the order of half the boundary layer thickness were carried out in this work. Special interest was laid on the influence of chemical non-equilibrium effects on the wake flow of the obstacle. Direct numerical simulations were conducted using three different gas models, a caloric perfect, an equilibrium and a chemical non-equilibrium gas model. The geometry was chosen as a wedge with a six degree half angle, according to the aborted NASA HyBoLT free flight experiment. At 0.5 m downstream of the leading edge, a surface trip was positioned. The free-stream flow was set to Mach 8.5 with air conditions taken from the 1976 standard atmosphere at an altitude of 42 km according to the predicted flight path. The simulations were done in three steps for all models. First, two-dimensional calculations of the whole configuration including the leading edge and the obstacle were conducted. These provide constant span-wise profiles for detailed, steady three-dimensional simulations around the close vicinity of the obstacle. A free-stream Mach number of about 6.3 occurs behind the shock. A cross-section in the wake of the object then delivers the steady inflow for detailed unsteady simulations of the wake. Perturbations at unstable frequencies, obtained from a bi-global secondary stability analysis, were added to these profiles. The solutions are time-Fourier transformed to investigate the unsteady downstream development of the different modes due to the interaction with the base-flow containing two counter-rotating vortices. Results will be presented that show the influence of the presence of chemical non-equilibrium on the instability in the wake of the object leading to a laminar or a turbulent wake.

  20. IDES: an integrated demand and energy supply equilibrium model. [IDES

    SciTech Connect

    Macal, C.M.

    1985-01-01

    The IDES (Integrated Demand and Energy Supply) Model is a price-quantity equilibrium model similar to the Long-Term Energy Analysis Package (LEAP) for projecting energy quantities and prices over a 30-year time horizon. The model integrates resource production activities, petroleum refining, electricity generation, fuel processing, and demand modules. The design objectives, mathematical formulation, iterative solution algorithm, and computer implementation are described in this paper.

  1. GROUNDWATER MASS TRANSPORT AND EQUILIBRIUM CHEMISTRY MODEL FOR MULTICOMPONENT SYSTEMS

    EPA Science Inventory

    A mass transport model, TRANQL, for a multicomponent solution system has been developed. The equilibrium interaction chemistry is posed independently of the mass transport equations which leads to a set of algebraic equations for the chemistry coupled to a set of differential equ...

  2. Approach to equilibrium in accelerated global oceanic models

    SciTech Connect

    Danabasoglu, G.; McWilliams, J.C.; Large, W.G.

    1996-05-01

    The approach to equilibrium of a coarse-resolution, seasonally forced, global oceanic general circulation model is investigated, considering the effects of a widely used acceleration technique that distorts the dynamics by using unequal time steps in the governing equations. A measure of the equilibration time for any solution property is defined as the time it takes to go 90% of the way from its present value to its equilibrium value. This measure becomes approximately time invariant only after sufficiently long integration. It indicates that the total kinetic energy and most mass transport rates attain equilibrium within about 90 and 40 calendar years, respectively. The upper-ocean potential temperature and salinity equilibrium times are about 480 and 380 calender years, following 150- and 20-year initial adjustments, respectively. In the abyssal ocean, potential temperature and salinity equilibration take about 4500 and 3900 calender years, respectively. These longer equilibration times are due to the slow diffusion of tracers both along and across the isopycnal surfaces in stably stratified regions, and these times vary with the associated diffusivities. An analysis of synchronous (i.e., not accelerated) integrations shows that there is a complex interplay between convective, advective, and diffusive timescales. Because of the distortion by acceleration of the seasonal cycle, the solutions display some significant adjustments upon switching to synchronous integration. However, the proper seasonal cycle is recovered within five years. Provided that a sufficient equilibrium state has been achieved with acceleration, the model must be integrated synchronously for only about 15 years thereafter to closely approach synchronous equilibrium. 16 refs., 11 figs., 1 tab.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  4. 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.

  5. Radiative-convective equilibrium models of Jupiter and Saturn

    NASA Astrophysics Data System (ADS)

    Appleby, J. F.; Hogan, J. S.

    1984-09-01

    Radiative-convective equilibrium models for Jupiter and Saturn have been produced in a study concentrating on the stratospheric energy balance and the possible role of aerosol heating. These models are compared directly with the thermal structure profiles obtained from Voyager radio occultation measurements. The method is based on a straightforward flux divergence formulation derived from earlier work. The balance between absorbed and emitted energies is computed iteratively at each level in the atmosphere, assuming local thermodynamic equilibrium and employing a standard treatment of opacities. Results for Jupiter indicate that a dust-free model furnishes a good mean thermal profile for the stratosphere when compared with the Voyager 1 radio occultation measurements. Observations of the equatorial region exhibit periodic vertical structure. The Saturn models are relatively simple and in good agreement with the Voyager 2 radio occultation temperature profiles at all levels. Aerosol heating played a minor role in Saturn's midlatitude stratospheric energy balance at the time of the Voyager 2 encounter.

  6. Equilibrium and Disequilibrium Dynamics in Cobweb Models with Time Delays

    NASA Astrophysics Data System (ADS)

    Gori, Luca; Guerrini, Luca; Sodini, Mauro

    2015-06-01

    This paper aims to study price dynamics in two different continuous time cobweb models with delays close to [Hommes, 1994]. In both cases, the stationary equilibrium may be not representative of the long-term dynamics of the model, since it is possible to observe endogenous and persistent fluctuations (supercritical Hopf bifurcations) even if a deterministic context without external shocks is considered. In the model in which markets are in equilibrium every time, we show that the existence of time delays in the expectations formation mechanism may cause chaotic dynamics similar to those obtained in [Hommes, 1994] in a discrete time context. From a mathematical point of view, we apply the Poincaré-Lindstedt perturbation method to study the local dynamic properties of the models. In addition, several numerical experiments are used to investigate global properties of the systems.

  7. Development of Accurate Chemical Equilibrium Models for the Hanford Waste Tanks: The System Na-Ca-Sr-OH-CO3-NO3-EDTA-HEDTA-H2O from 25 to 75°C

    SciTech Connect

    Felmy, Andrew R.; Mason, Marvin J.; Qafoku, Odeta; Dixon, David A.

    2005-04-19

    This symposium manuscript describes the development of an accurate aqueous thermodynamic model for predicting the speciation of Sr in the waste tanks at the Hanford site. A systematic approach is described that details the studies performed to define the most important inorganic and organic complexation reactions as well as the effects of other important metal ions that compete with Sr for complexation reactions with the chelates. By using this approach we were able to define a reduced set of inorganic complexation, organic complexation, and competing metal reactions that best represent the much more complex waste tank chemical system. A summary is presented of the final thermodynamic model for the system Na-Ca-Sr-OH-CO3-NO3-EDTA-HEDTA-H2O from 25 to 75 ºC that was previously published in a variety of sources. Previously unpublished experimental data are also given for the competing metal Ni as well for certain chemical systems, Na-Sr-CO3-PO4-H2O, and for the solubility of amorphous iron hydroxide in the presence of several organic chelating agents. These data were not used in model development but were key to the final selection of the specific chemical systems prioritized for detailed study.

  8. Viscous-shock-layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Anderson, E. C.; Moss, J. N.

    1975-01-01

    The viscous-shock-layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially-symmetric flow fields. Solutions were obtained using an implicit finite-difference scheme and results are presented for hypersonic flow over spherically-blunted cone configurations at freestream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

  9. Viscous shock layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Anderson, E. C.; Moss, J. N.

    1975-01-01

    The viscous shock layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially symmetric flow fields. Solutions are obtained using an implicit finite difference scheme and results are presented for hypersonic flow over spherically blunted cone configurations at free stream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

  10. Equilibrium and stability properties of detonation waves in the hydrodynamic limit of a kinetic model

    NASA Astrophysics Data System (ADS)

    Marques, Wilson, Jr.; Jacinta Soares, Ana; Pandolfi Bianchi, Miriam; Kremer, Gilberto M.

    2015-06-01

    A shock wave structure problem, like the one which can be formulated for the planar detonation wave, is analyzed here for a binary mixture of ideal gases undergoing the symmetric reaction {{A}1}+{{A}1}\\rightleftharpoons {{A}2}+{{A}2}. The problem is studied at the hydrodynamic Euler limit of a kinetic model of the reactive Boltzmann equation. The chemical rate law is deduced in this frame with a second-order reaction rate, in a chemical regime such that the gas flow is not far away from the chemical equilibrium. The caloric and the thermal equations of state for the specific internal energy and temperature are employed to close the system of balance laws. With respect to other approaches known in the kinetic literature for detonation problems with a reversible reaction, this paper aims to improve some aspects of the wave solution. Within the mathematical analysis of the detonation model, the equation of the equilibrium Hugoniot curve of the final states is explicitly derived for the first time and used to define the correct location of the equilibrium Chapman-Jouguet point in the Hugoniot diagram. The parametric space is widened to investigate the response of the detonation solution to the activation energy of the chemical reaction. Finally, the mathematical formulation of the linear stability problem is given for the wave detonation structure via a normal-mode approach, when bidimensional disturbances perturb the steady solution. The stability equations with their boundary conditions and the radiation condition of the considered model are explicitly derived for small transversal deviations of the shock wave location. The paper shows how a second-order chemical kinetics description, derived at the microscopic level, and an analytic deduction of the equilibrium Hugoniot curve, lead to an accurate picture of the steady detonation with reversible reaction, as well as to a proper bidimensional linear stability analysis.

  11. Mixing and non-equilibrium chemical reaction in a compressible mixing layer. M.S. Thesis Final Report

    NASA Technical Reports Server (NTRS)

    Steinberger, Craig J.

    1991-01-01

    The effects of compressibility, chemical reaction exothermicity, and non-equilibrium chemical modeling in a reacting plane mixing layer were investigated by means of two dimensional direct numerical simulations. The chemical reaction was irreversible and second order of the type A + B yields Products + Heat. The general governing fluid equations of a compressible reacting flow field were solved by means of high order finite difference methods. Physical effects were then determined by examining the response of the mixing layer to variation of the relevant non-dimensionalized parameters. The simulations show that increased compressibility generally results in a suppressed mixing, and consequently a reduced chemical reaction conversion rate. Reaction heat release was found to enhance mixing at the initial stages of the layer growth, but had a stabilizing effect at later times. The increased stability manifested itself in the suppression or delay of the formation of large coherent structures within the flow. Calculations were performed for a constant rate chemical kinetics model and an Arrhenius type kinetic prototype. The choice of the model was shown to have an effect on the development of the flow. The Arrhenius model caused a greater temperature increase due to reaction than the constant kinetic model. This had the same effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.

  12. Non-Equilibrium Turbulence and Two-Equation Modeling

    NASA Technical Reports Server (NTRS)

    Rubinstein, Robert

    2011-01-01

    Two-equation turbulence models are analyzed from the perspective of spectral closure theories. Kolmogorov theory provides useful information for models, but it is limited to equilibrium conditions in which the energy spectrum has relaxed to a steady state consistent with the forcing at large scales; it does not describe transient evolution between such states. Transient evolution is necessarily through nonequilibrium states, which can only be found from a theory of turbulence evolution, such as one provided by a spectral closure. When the departure from equilibrium is small, perturbation theory can be used to approximate the evolution by a two-equation model. The perturbation theory also gives explicit conditions under which this model can be valid, and when it will fail. Implications of the non-equilibrium corrections for the classic Tennekes-Lumley balance in the dissipation rate equation are drawn: it is possible to establish both the cancellation of the leading order Re1/2 divergent contributions to vortex stretching and enstrophy destruction, and the existence of a nonzero difference which is finite in the limit of infinite Reynolds number.

  13. Development and application of a numerical model of kinetic and equilibrium microbiological and geochemical reactions (BIOKEMOD)

    NASA Astrophysics Data System (ADS)

    Salvage, Karen M.; Yeh, Gour-Tsyh

    1998-08-01

    This paper presents the conceptual and mathematical development of the numerical model titled BIOKEMOD, and verification simulations performed using the model. BIOKEMOD is a general computer model for simulation of geochemical and microbiological reactions in batch aqueous solutions. BIOKEMOD may be coupled with hydrologic transport codes for simulation of chemically and biologically reactive transport. The chemical systems simulated may include any mixture of kinetic and equilibrium reactions. The pH, pe, and ionic strength may be specified or simulated. Chemical processes included are aqueous complexation, adsorption, ion-exchange and precipitation/dissolution. Microbiological reactions address growth of biomass and degradation of chemicals by microbial metabolism of substrates, nutrients, and electron acceptors. Inhibition or facilitation of growth due to the presence of specific chemicals and a lag period for microbial acclimation to new substrates may be simulated if significant in the system of interest. Chemical reactions controlled by equilibrium are solved using the law of mass action relating the thermodynamic equilibrium constant to the activities of the products and reactants. Kinetic chemical reactions are solved using reaction rate equations based on collision theory. Microbiologically mediated reactions for substrate removal and biomass growth are assumed to follow Monod kinetics modified for the potentially limiting effects of substrate, nutrient, and electron acceptor availability. BIOKEMOD solves the ordinary differential and algebraic equations of mixed geochemical and biogeochemical reactions using the Newton-Raphson method with full matrix pivoting. Simulations may be either steady state or transient. Input to the program includes the stoichiometry and parameters describing the relevant chemical and microbiological reactions, initial conditions, and sources/sinks for each chemical species. Output includes the chemical and biomass concentrations

  14. Rates of coalescence for common epidemiological models at equilibrium

    PubMed Central

    Koelle, Katia; Rasmussen, David A.

    2012-01-01

    Coalescent theory provides a mathematical framework for quantitatively interpreting gene genealogies. With the increased availability of molecular sequence data, disease ecologists now regularly apply this body of theory to viral phylogenies, most commonly in attempts to reconstruct demographic histories of infected individuals and to estimate parameters such as the basic reproduction number. However, with few exceptions, the mathematical expressions at the core of coalescent theory have not been explicitly linked to the structure of epidemiological models, which are commonly used to mathematically describe the transmission dynamics of a pathogen. Here, we aim to make progress towards establishing this link by presenting a general approach for deriving a model's rate of coalescence under the assumption that the disease dynamics are at their endemic equilibrium. We apply this approach to four common families of epidemiological models: standard susceptible-infected-susceptible/susceptible-infected-recovered/susceptible-infected-recovered-susceptible models, models with individual heterogeneity in infectivity, models with an exposed but not yet infectious class and models with variable distributions of the infectious period. These results improve our understanding of how epidemiological processes shape viral genealogies, as well as how these processes affect levels of viral diversity and rates of genetic drift. Finally, we discuss how a subset of these coalescent rate expressions can be used for phylodynamic inference in non-equilibrium settings. For the ones that are limited to equilibrium conditions, we also discuss why this is the case. These results, therefore, point towards necessary future work while providing intuition on how epidemiological characteristics of the infection process impact gene genealogies. PMID:21920961

  15. 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.

  16. Understanding Chemical Equilibrium Using Entropy Analysis: The Relationship between [delta]S[subscript tot](sys[superscript o]) and the Equilibrium Constant

    ERIC Educational Resources Information Center

    Bindel, Thomas H.

    2010-01-01

    Entropy analyses as a function of the extent of reaction are presented for a number of physicochemical processes, including vaporization of a liquid, dimerization of nitrogen dioxide, and the autoionization of water. Graphs of the total entropy change versus the extent of reaction give a visual representation of chemical equilibrium and the second…

  17. Equilibrium slab models of Lyman-alpha clouds

    NASA Technical Reports Server (NTRS)

    Charlton, Jane C.; Salpeter, Edwin E.; Hogan, Craig J.

    1993-01-01

    Solutions for the equilibrium configuration of a slab with ionizing radiation incident equally from both sides are explored. Radiation effects (photoionization, Ly-alpha photon trapping, and mock gravity) as well as external pressure and self gravity (with and without dark matter) are included. The general formalism is applied to structure growth on small scales at very high z due to mock gravity on dust. Emphasis is placed on the application of slab models at z of less than 5, particularly those that may correspond to Ly-alpha forest, Lyman limit, and damped Ly-alpha systems. The regime with a dominant outward force contributed by trapping of Ly-alpha photons is discussed. General expressions are given for the equilibrium, including dark matter, assuming various relationships between the density of the dark matter halo and the total gas column density.

  18. Facilitated Oriented Spin Models: Some Non Equilibrium Results

    NASA Astrophysics Data System (ADS)

    Cancrini, N.; Martinelli, F.; Schonmann, R.; Toninelli, C.

    2010-03-01

    We perform the rigorous analysis of the relaxation to equilibrium for some facilitated or kinetically constrained spin models (KCSM) when the initial distribution ν is different from the reversible one, μ. This setting has been intensively studied in the physics literature to analyze the slow dynamics which follows a sudden quench from the liquid to the glass phase. We concentrate on two basic oriented KCSM: the East model on ℤ, for which the constraint requires that the East neighbor of the to-be-update vertex is vacant and the AD model on the binary tree introduced in Aldous and Diaconis (J. Stat. Phys. 107(5-6):945-975, 2002), for which the constraint requires the two children to be vacant. It is important to observe that, while the former model is ergodic at any p≠1, the latter displays an ergodicity breaking transition at p c =1/2. For the East we prove exponential convergence to equilibrium with rate depending on the spectral gap if ν is concentrated on any configuration which does not contain a forever blocked site or if ν is a Bernoulli( p') product measure for any p'≠1. For the model on the binary tree we prove similar results in the regime p, p'< p c and under the (plausible) assumption that the spectral gap is positive for p< p c . By constructing a proper test function, we also prove that if p'> p c and p≤ p c convergence to equilibrium cannot occur for all local functions. Finally, in a short appendix, we present a very simple argument, different from the one given in Aldous and Diaconis (J. Stat. Phys. 107(5-6):945-975, 2002), based on a combination of some combinatorial results together with "energy barrier" considerations, which yields the sharp upper bound for the spectral gap of East when p↑1.

  19. Chemical kinetics and relaxation of non-equilibrium air plasma generated by energetic photon and electron beams

    NASA Astrophysics Data System (ADS)

    Maulois, Melissa; Ribière, Maxime; Eichwald, Olivier; Yousfi, Mohammed; Azaïs, Bruno

    2016-04-01

    The comprehension of electromagnetic perturbations of electronic devices, due to air plasma-induced electromagnetic field, requires a thorough study on air plasma. In the aim to understand the phenomena at the origin of the formation of non-equilibrium air plasma, we simulate, using a volume average chemical kinetics model (0D model), the time evolution of a non-equilibrium air plasma generated by an energetic X-ray flash. The simulation is undertaken in synthetic air (80% N2 and 20% O2) at ambient temperature and atmospheric pressure. When the X-ray flash crosses the gas, non-relativistic Compton electrons (low energy) and a relativistic Compton electron beam (high energy) are simultaneously generated and interact with the gas. The considered chemical kinetics scheme involves 26 influent species (electrons, positive ions, negative ions, and neutral atoms and molecules in their ground or metastable excited states) reacting following 164 selected reactions. The kinetics model describing the plasma chemistry was coupled to the conservation equation of the electron mean energy, in order to calculate at each time step of the non-equilibrium plasma evolution, the coefficients of reactions involving electrons while the energy of the heavy species (positive and negative ions and neutral atoms and molecules) is assumed remaining close to ambient temperature. It has been shown that it is the relativistic Compton electron beam directly created by the X-ray flash which is mainly responsible for the non-equilibrium plasma formation. Indeed, the low energy electrons (i.e., the non-relativistic ones) directly ejected from molecules by Compton collisions contribute to less than 1% on the creation of electrons in the plasma. In our simulation conditions, a non-equilibrium plasma with a low electron mean energy close to 1 eV and a concentration of charged species close to 1013 cm-3 is formed a few nanoseconds after the peak of X-ray flash intensity. 200 ns after the flash

  20. Pharmaceutical Industry and Trade Liberalization Using Computable General Equilibrium Model

    PubMed Central

    Barouni, M; Ghaderi, H; Banouei, AA

    2012-01-01

    Background Computable general equilibrium models are known as a powerful instrument in economic analyses and widely have been used in order to evaluate trade liberalization effects. The purpose of this study was to provide the impacts of trade openness on pharmaceutical industry using CGE model. Methods: Using a computable general equilibrium model in this study, the effects of decrease in tariffs as a symbol of trade liberalization on key variables of Iranian pharmaceutical products were studied. Simulation was performed via two scenarios in this study. The first scenario was the effect of decrease in tariffs of pharmaceutical products as 10, 30, 50, and 100 on key drug variables, and the second was the effect of decrease in other sectors except pharmaceutical products on vital and economic variables of pharmaceutical products. The required data were obtained and the model parameters were calibrated according to the social accounting matrix of Iran in 2006. Results: The results associated with simulation demonstrated that the first scenario has increased import, export, drug supply to markets and household consumption, while import, export, supply of product to market, and household consumption of pharmaceutical products would averagely decrease in the second scenario. Ultimately, society welfare would improve in all scenarios. Conclusion: We presents and synthesizes the CGE model which could be used to analyze trade liberalization policy issue in developing countries (like Iran), and thus provides information that policymakers can use to improve the pharmacy economics. PMID:23641393

  1. Model fitting and inference under Latent Equilibrium Processes

    PubMed Central

    Bhattacharya, Sourabh; Gelfand, Alan E.; Holsinger, Kent E.

    2008-01-01

    This paper presents a methodology for model fitting and inference in the context of Bayesian models of the type f(Y | X, θ)f(X | θ)f(θ), where Y is the (set of) observed data, θ is a set of model parameters and X is an unobserved (latent) stationary stochastic process induced by the first order transition model f(X(t+1) | X(t), θ), where X(t) denotes the state of the process at time (or generation) t. The crucial feature of the above type of model is that, given θ, the transition model f(X(t+1) | X(t), θ) is known but the distribution of the stochastic process in equilibrium, that is f(X | θ), is, except in very special cases, intractable, hence unknown. A further point to note is that the data Y has been assumed to be observed when the underlying process is in equilibrium. In other words, the data is not collected dynamically over time. We refer to such specification as a latent equilibrium process (LEP) model. It is motivated by problems in population genetics (though other applications are discussed), where it is of interest to learn about parameters such as mutation and migration rates and population sizes, given a sample of allele frequencies at one or more loci. In such problems it is natural to assume that the distribution of the observed allele frequencies depends on the true (unobserved) population allele frequencies, whereas the distribution of the true allele frequencies is only indirectly specified through a transition model. As a hierarchical specification, it is natural to fit the LEP within a Bayesian framework. Fitting such models is usually done via Markov chain Monte Carlo (MCMC). However, we demonstrate that, in the case of LEP models, implementation of MCMC is far from straightforward. The main contribution of this paper is to provide a methodology to implement MCMC for LEP models. We demonstrate our approach in population genetics problems with both simulated and real data sets. The resultant model fitting is computationally intensive

  2. LLNL Chemical Kinetics Modeling Group

    SciTech Connect

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  3. Formation of copper porous structures under near-equilibrium chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Kornyushchenko, A. S.; Natalich, V. V.; Perekrestov, V. I.

    2016-05-01

    The mechanism of copper structure formation under near-equilibrium conditions in a chemically-active medium-condensate system has been investigated. The desired conditions have been implemented using CVD system. Copper chloride CuCl2 was used as a source material, and mixture of hydrogen with nitrogen served as a working gas. The influence of the evaporation temperature, condensation temperature and state of the growth surface on the porous structures formation has been investigated. It has been established, that the structure formation mechanism is determined by layer-by-layer or normal crystal growth, nucleation and growth of whiskers, and also by partial intergrowth of structural elements.

  4. One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

    USGS Publications Warehouse

    Runkel, Robert L.

    2010-01-01

    OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, 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 (waterborne) 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. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

  5. Chemical kinetics modeling

    SciTech Connect

    Westbrook, C.K.; Pitz, W.J.

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  6. Modeling Inflation Using a Non-Equilibrium Equation of Exchange

    NASA Technical Reports Server (NTRS)

    Chamberlain, Robert G.

    2013-01-01

    Inflation is a change in the prices of goods that takes place without changes in the actual values of those goods. The Equation of Exchange, formulated clearly in a seminal paper by Irving Fisher in 1911, establishes an equilibrium relationship between the price index P (also known as "inflation"), the economy's aggregate output Q (also known as "the real gross domestic product"), the amount of money available for spending M (also known as "the money supply"), and the rate at which money is reused V (also known as "the velocity of circulation of money"). This paper offers first a qualitative discussion of what can cause these factors to change and how those causes might be controlled, then develops a quantitative model of inflation based on a non-equilibrium version of the Equation of Exchange. Causal relationships are different from equations in that the effects of changes in the causal variables take time to play out-often significant amounts of time. In the model described here, wages track prices, but only after a distributed lag. Prices change whenever the money supply, aggregate output, or the velocity of circulation of money change, but only after a distributed lag. Similarly, the money supply depends on the supplies of domestic and foreign money, which depend on the monetary base and a variety of foreign transactions, respectively. The spreading of delays mitigates the shocks of sudden changes to important inputs, but the most important aspect of this model is that delays, which often have dramatic consequences in dynamic systems, are explicitly incorporated.macroeconomics, inflation, equation of exchange, non-equilibrium, Athena Project

  7. Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

    NASA Technical Reports Server (NTRS)

    Gokoglu, Suleyman A.

    1988-01-01

    This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

  8. A tightly coupled non-equilibrium model for inductively coupled radio-frequency plasmas

    SciTech Connect

    Munafò, A. Alfuhaid, S. A. Panesi, M.; Cambier, J.-L.

    2015-10-07

    The objective of the present work is the development of a tightly coupled magneto-hydrodynamic model for inductively coupled radio-frequency plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State approach. A multi-temperature formulation is used to account for thermal non-equilibrium between translation of heavy-particles and vibration of molecules. Excited electronic states of atoms are instead treated as separate pseudo-species, allowing for non-Boltzmann distributions of their populations. Free-electrons are assumed Maxwellian at their own temperature. The governing equations for the electro-magnetic field and the gas properties (e.g., chemical composition and temperatures) are written as a coupled system of time-dependent conservation laws. Steady-state solutions are obtained by means of an implicit Finite Volume method. The results obtained in both LTE and NLTE conditions over a broad spectrum of operating conditions demonstrate the robustness of the proposed coupled numerical method. The analysis of chemical composition and temperature distributions along the torch radius shows that: (i) the use of the LTE assumption may lead to an inaccurate prediction of the thermo-chemical state of the gas, and (ii) non-equilibrium phenomena play a significant role close the walls, due to the combined effects of Ohmic heating and macroscopic gradients.

  9. A tightly coupled non-equilibrium model for inductively coupled radio-frequency plasmas

    NASA Astrophysics Data System (ADS)

    Munafò, A.; Alfuhaid, S. A.; Cambier, J.-L.; Panesi, M.

    2015-10-01

    The objective of the present work is the development of a tightly coupled magneto-hydrodynamic model for inductively coupled radio-frequency plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State approach. A multi-temperature formulation is used to account for thermal non-equilibrium between translation of heavy-particles and vibration of molecules. Excited electronic states of atoms are instead treated as separate pseudo-species, allowing for non-Boltzmann distributions of their populations. Free-electrons are assumed Maxwellian at their own temperature. The governing equations for the electro-magnetic field and the gas properties (e.g., chemical composition and temperatures) are written as a coupled system of time-dependent conservation laws. Steady-state solutions are obtained by means of an implicit Finite Volume method. The results obtained in both LTE and NLTE conditions over a broad spectrum of operating conditions demonstrate the robustness of the proposed coupled numerical method. The analysis of chemical composition and temperature distributions along the torch radius shows that: (i) the use of the LTE assumption may lead to an inaccurate prediction of the thermo-chemical state of the gas, and (ii) non-equilibrium phenomena play a significant role close the walls, due to the combined effects of Ohmic heating and macroscopic gradients.

  10. Model of opacity and emissivity of non-equilibrium plasma

    NASA Astrophysics Data System (ADS)

    Politov, V. Y.

    2008-05-01

    In this work the model describing absorption and emission properties of the non-equilibrium plasma is presented. It is based on the kinetics equations for populations of the ground, singly and doubly excited states of multi-charged ions. After solving these equations, the states populations together with the spectroscopic data, supplied in the special database for a lot ionization stages, are used for building the spectral distributions of plasma opacity and emissivity in STA approximation. Results of kinetics simulation are performed for such important X-ray converter as gold, which is investigated intensively in ICF-experiments.

  11. On equilibrium parameters of a radiation-compression model pinch

    SciTech Connect

    Afonin, V.I.

    1994-12-31

    Up to date, the micropinch effect in high-current axially symmetric electric discharges was the subject of extensive theoretical and experimental research. The radiation compression mechanism proved to fit the experimental data better than any other model. It assumes the pinch equilibrium to occur when the surface radiation emission replaces the surface emission mode. The aim of the present work is to show that a quasi-stationary pinch state can exist in the case of an optically thin plasma as well. 8 figs.

  12. A Quasi-Equilibrium Tropical Circulation Model--Formulation*.

    NASA Astrophysics Data System (ADS)

    Neelin, J. David; Zeng, Ning

    2000-06-01

    A class of model for simulation and theory of the tropical atmospheric component of climate variations is introduced. These models are referred to as quasi-equilibrium tropical circulation models, or QTCMs, because they make use of approximations associated with quasi-equilibrium (QE) convective parameterizations. Quasi-equilibrium convective closures tend to constrain the vertical temperature profile in convecting regions. This can be used to generate analytical solutions for the large-scale flow under certain approximations. A tropical atmospheric model of intermediate complexity is constructed by using the analytical solutions as the first basis function in a Galerkin representation of vertical structure. This retains much of the simplicity of the analytical solutions, while retaining full nonlinearity, vertical momentum transport, departures from QE, and a transition between convective and nonconvective zones based on convective available potential energy. The atmospheric model is coupled to a one-layer land surface model with interactive soil moisture and simulates its own tropical climatology. In the QTCM version presented here, the vertical structure of temperature variations is truncated to a single profile associated with deep convection. Though designed to be accurate in and near regions dominated by deep convection, the model simulates the tropical and subtropical climatology reasonably well, and even has a qualitative representation of midlatitude storm tracks.The model is computationally economical, since part of the solution has been carried out analytically, but the main advantage is relative simplicity of analysis under certain conditions. The formulation suggests a slightly different way of looking at the tropical atmosphere than has been traditional in tropical meteorology. While convective scales are unstable, the large-scale motions evolve with a positive effective stratification that takes into account the partial cancellation of adiabatic

  13. How is PCK embodied in the instructional decisions teachers make while teaching chemical equilibrium?

    NASA Astrophysics Data System (ADS)

    Shannon, Joseph Charles

    Much of the research concerning pedagogical content knowledge (PCK) in science education has been focused on its nature and development rather than how it is dynamically employed in the classroom with respect to specific topics. Research on how PCK is linked with actual classroom decisions has been limited since its tacit nature makes it challenging to identify what dimensions of PCK a teacher employs in various aspects of their practice. This study, using a multi-method case study design, examined four chemistry teachers' (two 1 st year and two 3rd year) decision-making during the planning, teaching, and reflection stages of their practice to determine PCK's influence for the topic of chemical equilibrium. The research occurred in undergraduate chemistry classrooms and special emphasis was placed on examining discourse to illuminate the relationships between how a teacher recognizes the need for a decision, what pedagogical 'moves' were chosen for implementation, and how talk was utilized to execute it. Findings indicated there were distinct differences between 1st and 3rd year teachers' PCK and how they employed it in their practice. The various types of knowledge and beliefs supporting the teachers' model of PCK such as subject matter knowledge, knowledge of student understanding, knowledge of instructional strategies as well as knowledge and beliefs about teaching and their learners influenced their decision-making ability during pre-lesson planning which subsequently influenced their communicative approach in the classroom. Two patterns were observed. Teachers with less teaching experience displayed a model of PCK characterized by an underdeveloped and sometimes fragmented understanding of the topic as well as a fragile knowledge of student understanding. As a result of having limited resources to draw on in the classroom they relied on a controlling communicative approach, thereby inhibiting the elicitation and incorporation of student thinking and

  14. 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.

  15. Equilibrium model constraints on baryon cycling across cosmic time

    NASA Astrophysics Data System (ADS)

    Mitra, Sourav; Davé, Romeel; Finlator, Kristian

    2015-09-01

    Galaxies strongly self-regulate their growth via energetic feedback from stars, supernovae, and black holes, but these processes are among the least understood aspects of galaxy formation theory. We present an analytic galaxy evolution model that directly constrains such feedback processes from observed galaxy scaling relations. The equilibrium model, which is broadly valid for star-forming central galaxies that dominate cosmic star formation, is based on the ansatz that galaxies live in a slowly evolving equilibrium between inflows, outflows, and star formation. Using a Bayesian Monte Carlo Markov chain approach, we constrain our model to match observed galaxy scaling relations between stellar mass and halo mass, star formation rate, and metallicity from 0 < z < 2. A good fit (χ2 ≈ 1.6) is achieved with eight free parameters. We further show that constraining our model to any two of the three data sets also produces a fit to the third that is within reasonable systematic uncertainties. The resulting best-fitting parameters that describe baryon cycling suggest galactic outflow scalings intermediate between energy and momentum-driven winds, a weak dependence of wind recycling time on mass, and a quenching mass scale that evolves modestly upwards with redshift. This model further predicts a stellar mass-star formation rate relation that is in good agreement with observations to z ˜ 6. Our results suggest that this simple analytic framework captures the basic physical processes required to model the mean evolution of stars and metals in galaxies, despite not incorporating many canonical ingredients of galaxy formation models such as merging or disc formation.

  16. Dimension reduction of non-equilibrium plasma kinetic models using principal component analysis

    NASA Astrophysics Data System (ADS)

    Peerenboom, Kim; Parente, Alessandro; Kozák, Tomáš; Bogaerts, Annemie; Degrez, Gérard

    2015-04-01

    The chemical complexity of non-equilibrium plasmas poses a challenge for plasma modeling because of the computational load. This paper presents a dimension reduction method for such chemically complex plasmas based on principal component analysis (PCA). PCA is used to identify a low-dimensional manifold in chemical state space that is described by a small number of parameters: the principal components. Reduction is obtained since continuity equations only need to be solved for these principal components and not for all the species. Application of the presented method to a CO2 plasma model including state-to-state vibrational kinetics of CO2 and CO demonstrates the potential of the PCA method for dimension reduction. A manifold described by only two principal components is able to predict the CO2 to CO conversion at varying ionization degrees very accurately.

  17. A Metastable Equilibrium Model for the Relative Abundances of Microbial Phyla in a Hot Spring

    PubMed Central

    Dick, Jeffrey M.; Shock, Everett L.

    2013-01-01

    Many studies link the compositions of microbial communities to their environments, but the energetics of organism-specific biomass synthesis as a function of geochemical variables have rarely been assessed. We describe a thermodynamic model that integrates geochemical and metagenomic data for biofilms sampled at five sites along a thermal and chemical gradient in the outflow channel of the hot spring known as “Bison Pool” in Yellowstone National Park. The relative abundances of major phyla in individual communities sampled along the outflow channel are modeled by computing metastable equilibrium among model proteins with amino acid compositions derived from metagenomic sequences. Geochemical conditions are represented by temperature and activities of basis species, including pH and oxidation-reduction potential quantified as the activity of dissolved hydrogen. By adjusting the activity of hydrogen, the model can be tuned to closely approximate the relative abundances of the phyla observed in the community profiles generated from BLAST assignments. The findings reveal an inverse relationship between the energy demand to form the proteins at equal thermodynamic activities and the abundance of phyla in the community. The distance from metastable equilibrium of the communities, assessed using an equation derived from energetic considerations that is also consistent with the information-theoretic entropy change, decreases along the outflow channel. Specific divergences from metastable equilibrium, such as an underprediction of the relative abundances of phototrophic organisms at lower temperatures, can be explained by considering additional sources of energy and/or differences in growth efficiency. Although the metabolisms used by many members of these communities are driven by chemical disequilibria, the results support the possibility that higher-level patterns of chemotrophic microbial ecosystems are shaped by metastable equilibrium states that depend on both the

  18. A metastable equilibrium model for the relative abundances of microbial phyla in a hot spring.

    PubMed

    Dick, Jeffrey M; Shock, Everett L

    2013-01-01

    Many studies link the compositions of microbial communities to their environments, but the energetics of organism-specific biomass synthesis as a function of geochemical variables have rarely been assessed. We describe a thermodynamic model that integrates geochemical and metagenomic data for biofilms sampled at five sites along a thermal and chemical gradient in the outflow channel of the hot spring known as "Bison Pool" in Yellowstone National Park. The relative abundances of major phyla in individual communities sampled along the outflow channel are modeled by computing metastable equilibrium among model proteins with amino acid compositions derived from metagenomic sequences. Geochemical conditions are represented by temperature and activities of basis species, including pH and oxidation-reduction potential quantified as the activity of dissolved hydrogen. By adjusting the activity of hydrogen, the model can be tuned to closely approximate the relative abundances of the phyla observed in the community profiles generated from BLAST assignments. The findings reveal an inverse relationship between the energy demand to form the proteins at equal thermodynamic activities and the abundance of phyla in the community. The distance from metastable equilibrium of the communities, assessed using an equation derived from energetic considerations that is also consistent with the information-theoretic entropy change, decreases along the outflow channel. Specific divergences from metastable equilibrium, such as an underprediction of the relative abundances of phototrophic organisms at lower temperatures, can be explained by considering additional sources of energy and/or differences in growth efficiency. Although the metabolisms used by many members of these communities are driven by chemical disequilibria, the results support the possibility that higher-level patterns of chemotrophic microbial ecosystems are shaped by metastable equilibrium states that depend on both the

  19. Modeling dune response using measured and equilibrium bathymetric profiles

    USGS Publications Warehouse

    Fauver, Laura A.; Thompson, David M.; Sallenger, Asbury H.

    2007-01-01

    Coastal engineers typically use numerical models such as SBEACH to predict coastal change due to extreme storms. SBEACH model inputs include pre-storm profiles, wave heights and periods, and water levels. This study focuses on the sensitivity of SBEACH to the details of pre-storm bathymetry. The SBEACH model is tested with two initial conditions for bathymetry, including (1) measured bathymetry from lidar, and (2) calculated equilibrium profiles. Results show that longshore variability in the predicted erosion signal is greater over measured bathymetric profiles, due to longshore variations in initial surf zone bathymetry. Additionally, patterns in predicted erosion can be partially explained by the configuration of the inner surf zone from the shoreline to the trough, with surf zone slope accounting for 67% of the variability in predicted erosion volumes.

  20. Equilibrium Analysis of a Yellow Fever Dynamical Model with Vaccination

    PubMed Central

    Martorano Raimundo, Silvia

    2015-01-01

    We propose an equilibrium analysis of a dynamical model of yellow fever transmission in the presence of a vaccine. The model considers both human and vector populations. We found thresholds parameters that affect the development of the disease and the infectious status of the human population in the presence of a vaccine whose protection may wane over time. In particular, we derived a threshold vaccination rate, above which the disease would be eradicated from the human population. We show that if the mortality rate of the mosquitoes is greater than a given threshold, then the disease is naturally (without intervention) eradicated from the population. In contrast, if the mortality rate of the mosquitoes is less than that threshold, then the disease is eradicated from the populations only when the growing rate of humans is less than another threshold; otherwise, the disease is eradicated only if the reproduction number of the infection after vaccination is less than 1. When this reproduction number is greater than 1, the disease will be eradicated from the human population if the vaccination rate is greater than a given threshold; otherwise, the disease will establish itself among humans, reaching a stable endemic equilibrium. The analysis presented in this paper can be useful, both to the better understanding of the disease dynamics and also for the planning of vaccination strategies. PMID:25834634

  1. Tropospheric chemical models

    NASA Technical Reports Server (NTRS)

    Prinn, R. G.

    1992-01-01

    The differences in atmospheric composition over the globe and the short- and long-term variations in this composition are the net effect of several atmospheric and biospheric processes: biospheric emissions, atmospheric circulation, atmospheric chemical transformations and finally deposition back to the surface. Accurate and realistic atmospheric chemistry and circulation models are essential to interpret the observed global distributions and trends of atmospheric species in terms of these underlying processes. Comparisons between model predictions and observations test current understanding of these processes and models used in conjunction with inverse methods allow deductions of the rates of these processes from the observations. With the planned inclusion of at least CO and CH4 observations on the Earth Observing System (EOS) satellites, together with the large global data set expected from in situ observations under the International Global Atmospheric Chemistry (IGAC) Project, the further development of global three-dimensional high-resolution atmospheric chemistry and circulation models in order to interpret this new data is a high-priority endeavor.

  2. Non-Equilibrium Zeldovich-Von Neumann-Doring Theory and Reactive Flow Modeling of Detonation

    SciTech Connect

    Tarver, C M; Forbes, J W; Urtiew, P A

    2002-05-02

    This paper discusses the Non-Equilibrium Zeldovich - von Neumann - Doring (NEZND) theory of self-sustaining detonation waves and the Ignition and Growth reactive flow model of shock initiation and detonation wave propagation in solid explosives. The NEZND theory identified the non-equilibrium excitation processes that precede and follow the exothermic decomposition of a large high explosive molecule into several small reaction product molecules. The thermal energy deposited by the leading shock wave must be distributed to the vibrational modes of the explosive molecule before chemical reactions can occur. The induction time for the onset of the initial endothermic reactions can be calculated using high pressure, high temperature transition state theory. Since the chemical energy is released well behind the leading shock front of a detonation wave, a physical mechanism is required for this chemical energy to reinforce the leading shock front and maintain its overall constant velocity. This mechanism is the amplification of pressure wavelets in the reaction zone by the process of de-excitation of the initially highly vibrationally excited reaction product molecules. This process leads to the development of the three-dimensional structure of detonation waves observed for all explosives. For practical predictions of shock initiation and detonation in hydrodynamic codes, phenomenological reactive flow models have been developed. The Ignition and Growth reactive flow model of shock initiation and detonation in solid explosives has been very successful in describing the overall flow measured by embedded gauges and laser interferometry. This reactive flow model uses pressure and compression dependent reaction rates, because time resolved experimental temperature data is not yet available. Since all chemical reaction rates are ultimately controlled by temperature, the next generation of reactive flow models will use temperature dependent reaction rates. Progress on a

  3. A radial non-uniform helicon equilibrium discharge model

    NASA Astrophysics Data System (ADS)

    Cheng, Yu-Guo; Cheng, Mou-Sen; Wang, Mo-Ge; Li, Xiao-Kang

    2014-10-01

    Helicon discharges have attracted great attention in the electric propulsion community in recent years. To acquire the equilibrium properties, a self-consistent model is developed, which combines the helicon/Trivelpiece—Gould (TG) waves-plasma interaction mechanism and the plasma flow theory under the confinement of the magnetic field. The calculations reproduce the central peak density phenomenon observed in the experiments. The results show that when operating in the wave coupling mode, high magnetic field strength B0 results in the deviation of the central density versus B0 from the linear relationship, while the density rise becomes flatter as the radiofrequency (rf) input power Prf grows, and the electron temperature Te radial profile is mainly determined by the characteristic of the rf energy deposition. The model could provide suggestions in choosing the B0 and Prf for medium power helicon thrusters.

  4. Local Thermal Equilibrium for Certain Stochastic Models of Heat Transport

    NASA Astrophysics Data System (ADS)

    Li, Yao; Nándori, Péter; Young, Lai-Sang

    2016-04-01

    This paper is about nonequilibrium steady states (NESS) of a class of stochastic models in which particles exchange energy with their "local environments" rather than directly with one another. The physical domain of the system can be a bounded region of R^d for any d ge 1. We assume that the temperature at the boundary of the domain is prescribed and is nonconstant, so that the system is forced out of equilibrium. Our main result is local thermal equilibrium in the infinite volume limit. In the Hamiltonian context, this would mean that at any location x in the domain, local marginal distributions of NESS tend to a probability with density 1/Z e^{-β (x) H}, permitting one to define the local temperature at x to be β (x)^{-1}. We prove also that in the infinite volume limit, the mean energy profile of NESS satisfies Laplace's equation for the prescribed boundary condition. Our method of proof is duality: by reversing the sample paths of particle movements, we convert the problem of studying local marginal energy distributions at x to that of joint hitting distributions of certain random walks starting from x, and prove that the walks in question become increasingly independent as system size tends to infinity.

  5. Stellar and gaseous disc structures in cosmological galaxy equilibrium models

    NASA Astrophysics Data System (ADS)

    Rathaus, Ben; Sternberg, Amiel

    2016-05-01

    We present `radially resolved equilibrium models' for the growth of stellar and gaseous discs in cosmologically accreting massive haloes. Our focus is on objects that evolve to redshifts z ˜ 2. We solve the time-dependent equations that govern the radially dependent star formation rates, inflows and outflows from and to the inter- and circumgalactic medium, and inward radial gas flows within the discs. The stellar and gaseous discs reach equilibrium configurations on dynamical time-scales much shorter than variations in the cosmological dark matter halo growth and baryonic accretions rates. We show analytically that mass and global angular momentum conservation naturally give rise to exponential gas and stellar discs over many radial length-scales. As expected, the gaseous discs are more extended as set by the condition Toomre Q < 1 for star formation. The discs rapidly become baryon dominated. For massive, 5 × 1012 M⊙ haloes at redshift z = 2, we reproduced the typical observed star formation rates of ˜100 M⊙ yr-1, stellar masses ˜9 × 1010 M⊙, gas contents ˜1011 M⊙, half-mass sizes of 4.5 and 5.8 kpc for the stars and gas, and characteristic surface densities of 500 and 400 M⊙ pc-2 for the stars and gas.

  6. CHEMICAL REACTIONS SIMULATED BY GROUND-WATER-QUALITY MODELS.

    USGS Publications Warehouse

    Grove, David B.; Stollenwerk, Kenneth G.

    1987-01-01

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

  7. Radiative-convective equilibrium models of Uranus and Neptune

    SciTech Connect

    Appleby, J.F.

    1986-03-01

    The present study of Uranus and Neptune radiative-convective equilibrium models gives emphasis to such aspects of the stratospheric energy balance as the influence of aerosol heating and convective penetration. The results obtained for Uranus imply that a continuum absorber may be a significant factor in the stratosphere despite the great distance from the sun. The results obtained for Neptune show that such a continuum absorber could significantly contribute to the energy balance within a localized stratospheric region, although it probably cannot furnish sufficient power to account for the observed IR spectrum irrespective of its vertical distribution. Attention is accordingly given to the convective penetration that could arise under such rapid vertical mixing that CH4's condensation cannot occur before the gas is carried above the condensation region. 64 references.

  8. Equilibrium Slab Models of Lyman-Alpha Clouds

    NASA Technical Reports Server (NTRS)

    Charlton, Jane C.; Salpeter, Edwin E.; Hogan, Craig J.

    1993-01-01

    We model the L(sub y(alpha)) clouds as slabs of hydrogen with an ionizing extragalactic radiation field incident from both sides. In general, the equilibrium configuration of a slab at redshift z approx. less than 5 is determined by a balance of the gas pressure, gravity (including the effects of a dark matter halo), and the pressure exerted by the inter-galactic medium, P(sub ext). These models have been used to make predictions of the number of slabs as a function of the neutral hydrogen column density, N(sub H). A break in the curve is predicted at the transition between regimes where gravity and pressure are the dominant confining forces, with a less rapid decrease at larger N(sub H). The transition from optically thin to optically thick slabs leads to a gap in the distribution, whose location is governed largely by the spectrum of ionizing radiation. There are certain parallels between lines of sight through the outer HI disk of spiral galaxy with increasing radius, and the progression from damped, to Lyman limit, to forest clouds. We discuss briefly the possibility that at least some of the observed low z forest clouds may be a separate population, associated with galaxies, as suggested by the observations of Bahcall et al. This population could dominate the forest at present if the dark matter attached to galaxies should lead to gravity confinement for this disk population, while the isolated clouds remain pressure confined. The formalism developed in this paper will allow a more detailed study. We also discuss a more general parameter study of the equilibrium configuration of slabs, including mock gravity and L(sub y(alpha)) photon trapping.

  9. Estimated Performance of Radial-Flow Exit Nozzles for Air in Chemical Equilibrium

    NASA Technical Reports Server (NTRS)

    Englert, Gerald W.; Kochendorfer, Fred D.

    1959-01-01

    The thrust, boundary-layer, and heat-transfer characteristics were computed for nozzles having radial flow in the divergent part. The working medium was air in chemical equilibrium, and the boundary layer was assumed to be all turbulent. Stagnation pressure was varied from 1 to 32 atmospheres, stagnation temperature from 1000 to 6000 R, and wall temperature from 1000 to 3000 R. Design pressure ratio was varied from 5 to 320, and operating pressure ratio was varied from 0.25 to 8 times the design pressure ratio. Results were generalized independent of divergence angle and were also generalized independent of stagnation pressure in the temperature range of 1000 to 3000 R. A means of determining the aerodynamically optimum wall angle is provided.

  10. Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions

    NASA Technical Reports Server (NTRS)

    Johnson, R. E.

    1986-01-01

    Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

  11. An Analytical Investigation of Three General Methods of Calculating Chemical-Equilibrium Compositions

    NASA Technical Reports Server (NTRS)

    Zeleznik, Frank J.; Gordon, Sanford

    1960-01-01

    The Brinkley, Huff, and White methods for chemical-equilibrium calculations were modified and extended in order to permit an analytical comparison. The extended forms of these methods permit condensed species as reaction products, include temperature as a variable in the iteration, and permit arbitrary estimates for the variables. It is analytically shown that the three extended methods can be placed in a form that is independent of components. In this form the Brinkley iteration is identical computationally to the White method, while the modified Huff method differs only'slightly from these two. The convergence rates of the modified Brinkley and White methods are identical; and, further, all three methods are guaranteed to converge and will ultimately converge quadratically. It is concluded that no one of the three methods offers any significant computational advantages over the other two.

  12. An improved flux-split algorithm applied to hypersonic flows in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Palmer, Grant

    1988-01-01

    An explicit, finite-difference, shock-capturing numerical algorithm is presented and applied to hypersonic flows assumed to be in thermochemical equilibrium. Real-gas chemistry is either loosely coupled to the gasdynamics by way of a Gibbs free energy minimization package or fully coupled using species mass conservation equations with finite-rate chemical reactions. A scheme is developed that maintains stability in the explicit, finite-rate formulation while allowing relatively high time steps. The codes use flux vector splitting to difference the inviscid fluxes and employ real-gas corrections to viscosity and thermal conductivity. Numerical results are compared against existing ballistic range and flight data. Flows about complex geometries are also computed.

  13. Coupling of an average-atom model with a collisional-radiative equilibrium model

    SciTech Connect

    Faussurier, G. Blancard, C.; Cossé, P.

    2014-11-15

    We present a method to combine a collisional-radiative equilibrium model and an average-atom model to calculate bound and free electron wavefunctions in hot dense plasmas by taking into account screening. This approach allows us to calculate electrical resistivity and thermal conductivity as well as pressure in non local thermodynamic equilibrium plasmas. Illustrations of the method are presented for dilute titanium plasma.

  14. LIFE Chamber Chemical Equilibrium Simulations with Additive Hydrogen, Oxygen, and Nitrogen

    SciTech Connect

    DeMuth, J A; Simon, A J

    2009-09-03

    In order to enable continuous operation of a Laser Inertial confinement Fusion Energy (LIFE) engine, the material (fill-gas and debris) in the fusion chamber must be carefully managed. The chamber chemical equilibrium compositions for post-shot mixtures are evaluated to determine what compounds will be formed at temperatures 300-5000K. It is desired to know if carbon and or lead will deposit on the walls of the chamber, and if so: at what temperature, and what elements can be added to prevent this from happening. The simulation was conducted using the chemical equilibrium solver Cantera with a Matlab front-end. Solutions were obtained by running equilibrations at constant temperature and constant specific volume over the specified range of temperatures. It was found that if nothing is done, carbon will deposit on the walls once it cools to below 2138K, and lead below 838K. Three solutions to capture the carbon were found: adding pure oxygen, hydrogen/nitrogen combo, and adding pure nitrogen. The best of these was the addition of oxygen which would readily form CO at around 4000K. To determine the temperature at which carbon would deposit on the walls, temperature solutions to evaporation rate equations needed to be found. To determine how much carbon or any species was in the chamber at a given time, chamber flushing equations needed to be developed. Major concerns are deposition of carbon and/or oxygen on the tungsten walls forming tungsten oxides or tungsten carbide which could cause embrittlement and cause failure of the first wall. Further research is needed.

  15. Equilibrium and Kinetic Models for Colloid Release Under Transient Solution Chemistry Conditions

    NASA Astrophysics Data System (ADS)

    Bradford, S. A.; Torkzaban, S.; Leij, F. J.; Simunek, J.

    2014-12-01

    Colloid retention and release is well known to depend on a wide variety of physical, chemical, and microbiological factors that may vary temporally in the subsurface environment. We present equilibrium, kinetic, combined equilibrium and kinetic, and two-site kinetic models of colloid release during transient physicochemical conditions. Our mathematical modeling approach relates colloid release under transient conditions to changes in the fraction of the solid surface area that contributes to retention. The developed models were subsequently applied to experimental colloid release datasets to investigate the influence of variations in ionic strength (IS), pH, cation exchange, colloid size, and water velocity on release. Various combinations of equilibrium and/or kinetic release models were needed to describe the experimental data depending on the transient conditions and colloid type. Release of E. coli D21g was promoted by a decrease in solution IS and an increase in pH, similar to expected trends for a reduction in the secondary minimum and nanoscale chemical heterogeneity, respectively. The retention and release of 20 nm carboxyl modified latex nanoparticles (NPs) were demonstrated to be more sensitive to the presence of Ca2+ than D21g. Specifically, retention of NPs was greater than D21g in the presence of 2 mM CaCl2 solution, and release of NPs only occurred after exchange of Ca2+ by Na+ and then a reduction in the solution IS. These findings highlight the limitations of conventional interaction energy calculations to describe colloid retention and release, and point to the need to consider Born repulsion and nanoscale heterogeneity. Temporal changes in the water velocity did not have a large influence on the release of D21g. This insensitivity was likely due to factors that reduce the applied hydrodynamic torque and/or increase the resisting adhesive torque. Collectively, experimental and modeling results indicate that episodic colloid transport in the

  16. Simplified Thermo-Chemical Modelling For Hypersonic Flow

    NASA Astrophysics Data System (ADS)

    Sancho, Jorge; Alvarez, Paula; Gonzalez, Ezequiel; Rodriguez, Manuel

    2011-05-01

    Hypersonic flows are connected with high temperatures, generally associated with strong shock waves that appear in such flows. At high temperatures vibrational degrees of freedom of the molecules may become excited, the molecules may dissociate into atoms, the molecules or free atoms may ionize, and molecular or ionic species, unimportant at lower temperatures, may be formed. In order to take into account these effects, a chemical model is needed, but this model should be simplified in order to be handled by a CFD code, but with a sufficient precision to take into account the physics more important. This work is related to a chemical non-equilibrium model validation, implemented into a commercial CFD code, in order to obtain the flow field around bodies in hypersonic flow. The selected non-equilibrium model is composed of seven species and six direct reactions together with their inverse. The commercial CFD code where the non- equilibrium model has been implemented is FLUENT. For the validation, the X38/Sphynx Mach 20 case is rebuilt on a reduced geometry, including the 1/3 Lref forebody. This case has been run in laminar regime, non catalytic wall and with radiative equilibrium wall temperature. The validated non-equilibrium model is applied to the EXPERT (European Experimental Re-entry Test-bed) vehicle at a specified trajectory point (Mach number 14). This case has been run also in laminar regime, non catalytic wall and with radiative equilibrium wall temperature.

  17. 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.

  18. Ising Model Reprogramming of a Repeat Protein's Equilibrium Unfolding Pathway.

    PubMed

    Millership, C; Phillips, J J; Main, E R G

    2016-05-01

    Repeat proteins are formed from units of 20-40 aa that stack together into quasi one-dimensional non-globular structures. This modular repetitive construction means that, unlike globular proteins, a repeat protein's equilibrium folding and thus thermodynamic stability can be analysed using linear Ising models. Typically, homozipper Ising models have been used. These treat the repeat protein as a series of identical interacting subunits (the repeated motifs) that couple together to form the folded protein. However, they cannot describe subunits of differing stabilities. Here we show that a more sophisticated heteropolymer Ising model can be constructed and fitted to two new helix deletion series of consensus tetratricopeptide repeat proteins (CTPRs). This analysis, showing an asymmetric spread of stability between helices within CTPR ensembles, coupled with the Ising model's predictive qualities was then used to guide reprogramming of the unfolding pathway of a variant CTPR protein. The designed behaviour was engineered by introducing destabilising mutations that increased the thermodynamic asymmetry within a CTPR ensemble. The asymmetry caused the terminal α-helix to thermodynamically uncouple from the rest of the protein and preferentially unfold. This produced a specific, highly populated stable intermediate with a putative dimerisation interface. As such it is the first step in designing repeat proteins with function regulated by a conformational switch. PMID:26947150

  19. Multiscale stochastic simulation algorithm with stochastic partial equilibrium assumption for chemically reacting systems

    SciTech Connect

    Cao Yang . E-mail: ycao@cs.ucsb.edu; Gillespie, Dan . E-mail: GillespieDT@mailaps.org; Petzold, Linda . E-mail: petzold@engineering.ucsb.edu

    2005-07-01

    In this paper, we introduce a multiscale stochastic simulation algorithm (MSSA) which makes use of Gillespie's stochastic simulation algorithm (SSA) together with a new stochastic formulation of the partial equilibrium assumption (PEA). This method is much more efficient than SSA alone. It works even with a very small population of fast species. Implementation details are discussed, and an application to the modeling of the heat shock response of E. Coli is presented which demonstrates the excellent efficiency and accuracy obtained with the new method.

  20. Reduction of chemical reaction models

    NASA Technical Reports Server (NTRS)

    Frenklach, Michael

    1991-01-01

    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  1. VHTR Prismatic Super Lattice Model for Equilibrium Fuel Cycle Analysis

    SciTech Connect

    G. S. Chang

    2006-09-01

    The advanced Very High Temperature gas-cooled Reactor (VHTR), which is currently being developed, achieves simplification of safety through reliance on innovative features and passive systems. One of the VHTRs innovative features is the reliance on ceramic-coated fuel particles to retain the fission products under extreme accident conditions. The effect of the random fuel kernel distribution in the fuel prismatic block is addressed through the use of the Dancoff correction factor in the resonance treatment. However, if the fuel kernels are not perfect black absorbers, the Dancoff correction factor is a function of burnup and fuel kernel packing factor, which requires that the Dancoff correction factor be updated during Equilibrium Fuel Cycle (EqFC) analysis. An advanced Kernel-by-Kernel (K-b-K) hexagonal super lattice model can be used to address and update the burnup dependent Dancoff effect during the EqFC analysis. The developed Prismatic Super Homogeneous Lattice Model (PSHLM) is verified by comparing the calculated burnup characteristics of the double-heterogeneous Prismatic Super Kernel-by-Kernel Lattice Model (PSK-b-KLM). This paper summarizes and compares the PSHLM and PSK-b-KLM burnup analysis study and results. This paper also discusses the coupling of a Monte-Carlo code with fuel depletion and buildup code, which provides the fuel burnup analysis tool used to produce the results of the VHTR EqFC burnup analysis.

  2. Languages and Societies: The "Punctuated Equilibrium" Model of Language Development.

    ERIC Educational Resources Information Center

    Kuteva, Tania

    1999-01-01

    The goal of this article is twofold: (1) on the basis of non-conjectural, concrete cases, to establish the linguistic situations that are characteristic of the socio-historical states of equilibrium and punctuation; and (2) to show that neither the equilibrium nor punctuation can be uniquely defined by a particular linguistic situation specific to…

  3. A Synthesis of Equilibrium and Historical Models of Landform Development.

    ERIC Educational Resources Information Center

    Renwick, William H.

    1985-01-01

    The synthesis of two approaches that can be used in teaching geomorphology is described. The equilibrium approach explains landforms and landform change in terms of equilibrium between landforms and controlling processes. The historical approach draws on climatic geomorphology to describe the effects of Quaternary climatic and tectonic events on…

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

    ERIC Educational Resources Information Center

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

    2007-01-01

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

  5. Reaction ensemble molecular dynamics: Direct simulation of the dynamic equilibrium properties of chemically reacting mixtures

    NASA Astrophysics Data System (ADS)

    Brennan, John K.; Lísal, Martin; Gubbins, Keith E.; Rice, Betsy M.

    2004-12-01

    A molecular simulation method to study the dynamics of chemically reacting mixtures is presented. The method uses a combination of stochastic and dynamic simulation steps, allowing for the simulation of both thermodynamic and transport properties. The method couples a molecular dynamics simulation cell (termed dynamic cell) to a reaction mixture simulation cell (termed control cell) that is formulated upon the reaction ensemble Monte Carlo (RxMC) method, hence the term reaction ensemble molecular dynamics. Thermodynamic and transport properties are calculated in the dynamic cell by using a constant-temperature molecular dynamics simulation method. RxMC forward and reverse reaction steps are performed in the control cell only, while molecular dynamics steps are performed in both the dynamic cell and the control cell. The control cell, which acts as a sink and source reservoir, is maintained at reaction equilibrium conditions via the RxMC algorithm. The reaction ensemble molecular dynamics method is analogous to the grand canonical ensemble molecular dynamics technique, while using some elements of the osmotic molecular dynamics method, and so simulates conditions that directly relate to real, open systems. The accuracy and stability of the method is assessed by considering the ammonia synthesis reaction N2+3H2⇔2NH3 . It is shown to be a viable method for predicting the effects of nonideal environments on the dynamic properties (particularly diffusion) as well as reaction equilibria for chemically reacting mixtures.

  6. A non-equilibrium neutral model for analysing cultural change.

    PubMed

    Kandler, Anne; Shennan, Stephen

    2013-08-01

    Neutral evolution is a frequently used model to analyse changes in frequencies of cultural variants over time. Variants are chosen to be copied according to their relative frequency and new variants are introduced by a process of random mutation. Here we present a non-equilibrium neutral model which accounts for temporally varying population sizes and mutation rates and makes it possible to analyse the cultural system under consideration at any point in time. This framework gives an indication whether observed changes in the frequency distributions of a set of cultural variants between two time points are consistent with the random copying hypothesis. We find that the likelihood of the existence of the observed assemblage at the end of the considered time period (expressed by the probability of the observed number of cultural variants present in the population during the whole period under neutral evolution) is a powerful indicator of departures from neutrality. Further, we study the effects of frequency-dependent selection on the evolutionary trajectories and present a case study of change in the decoration of pottery in early Neolithic Central Europe. Based on the framework developed we show that neutral evolution is not an adequate description of the observed changes in frequency. PMID:23538207

  7. Calculation of individual isotope equilibrium constants for implementation in geochemical models

    USGS Publications Warehouse

    Thorstenson, Donald C.; Parkhurst, David L.

    2002-01-01

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

  8. Model atmospheres for cool stars. [varying chemical composition

    NASA Technical Reports Server (NTRS)

    Johnson, H. R.

    1974-01-01

    This report contains an extensive series of model atmospheres for cool stars having a wide range in chemical composition. Model atmospheres (temperature, pressure, density, etc.) are tabulated, along with emergent energy flux distributions, limb darkening, and information on convection for selected models. The models are calculated under the usual assumptions of hydrostatic equilibrium, constancy of total energy flux (including transport both by radiation and convection) and local thermodynamic equilibrium. Some molecular and atomic line opacity is accounted for as a straight mean. While cool star atmospheres are regimes of complicated physical conditions, and these atmospheres are necessarily approximate, they should be useful for a number of kinds of spectral and atmospheric analysis.

  9. Modeling of electrochemical double layers in thermodynamic non-equilibrium.

    PubMed

    Dreyer, Wolfgang; Guhlke, Clemens; Müller, Rüdiger

    2015-10-28

    We consider the contact between an electrolyte and a solid electrode. At first we formulate a thermodynamic consistent model that resolves boundary layers at interfaces. The model includes charge transport, diffusion, chemical reactions, viscosity, elasticity and polarization under isothermal conditions. There is a coupling between these phenomena that particularly involves the local pressure in the electrolyte. Therefore the momentum balance is of major importance for the correct description of the boundary layers. The width of the boundary layers is typically very small compared to the macroscopic dimensions of the system. In the second step we thus apply the method of asymptotic analysis to derive a simpler reduced bulk model that already incorporates the electrochemical properties of the double layers into a set of new boundary conditions. With the reduced model, we analyze the double layer capacitance for a metal-electrolyte interface. PMID:26415592

  10. Development of Accurate Chemical Equilibrium Models for Oxalate Species to High Ionic Strength in the System: Na-Ba-Ca-Mn-Sr-Cl-NO3-PO4-SO4-H2O at 25°C

    SciTech Connect

    Qafoku, Odeta; Felmy, Andrew R.

    2007-01-01

    The development of an accurate aqueous thermodynamic model is described for oxalate species in the Na-Ba-Ca-Mn-Sr-Cl-NO3-PO4-SO4-H2O system at 25°C. The model is valid to high ionic strength (as high as 10m) and from very acid (10m H2SO4) to neutral and basic conditions. The model is based upon the equations of Pitzer and co-workers. The necessary ion-interaction parameters are determined by comparison with experimental data taken from the literature or determined in this study. The proposed aqueous activity and solubility model is valid for a range of applications from interpretation of studies on mineral dissolution at circumneutral pH to the dissolution of high-level waste tank sludges under acidic conditions.

  11. Equilibrium Models of Coronal Loops That Involve Curvature and Buoyancy

    NASA Astrophysics Data System (ADS)

    Hindman, Bradley W.; Jain, Rekha

    2013-12-01

    We construct magnetostatic models of coronal loops in which the thermodynamics of the loop is fully consistent with the shape and geometry of the loop. This is achieved by treating the loop as a thin, compact, magnetic fibril that is a small departure from a force-free state. The density along the loop is related to the loop's curvature by requiring that the Lorentz force arising from this deviation is balanced by buoyancy. This equilibrium, coupled with hydrostatic balance and the ideal gas law, then connects the temperature of the loop with the curvature of the loop without resorting to a detailed treatment of heating and cooling. We present two example solutions: one with a spatially invariant magnetic Bond number (the dimensionless ratio of buoyancy to Lorentz forces) and the other with a constant radius of the curvature of the loop's axis. We find that the density and temperature profiles are quite sensitive to curvature variations along the loop, even for loops with similar aspect ratios.

  12. Equilibrium models of coronal loops that involve curvature and buoyancy

    SciTech Connect

    Hindman, Bradley W.; Jain, Rekha

    2013-12-01

    We construct magnetostatic models of coronal loops in which the thermodynamics of the loop is fully consistent with the shape and geometry of the loop. This is achieved by treating the loop as a thin, compact, magnetic fibril that is a small departure from a force-free state. The density along the loop is related to the loop's curvature by requiring that the Lorentz force arising from this deviation is balanced by buoyancy. This equilibrium, coupled with hydrostatic balance and the ideal gas law, then connects the temperature of the loop with the curvature of the loop without resorting to a detailed treatment of heating and cooling. We present two example solutions: one with a spatially invariant magnetic Bond number (the dimensionless ratio of buoyancy to Lorentz forces) and the other with a constant radius of the curvature of the loop's axis. We find that the density and temperature profiles are quite sensitive to curvature variations along the loop, even for loops with similar aspect ratios.

  13. Non-equilibrium Ionization Modeling of Simulated Pseudostreamers in a Solar Corona Model

    NASA Astrophysics Data System (ADS)

    Shen, Chengcai; Raymond, John C.; Mikić, Zoran; Linker, Jon; Reeves, Katharine K.; Murphy, Nicholas A.

    2015-04-01

    Time-dependent ionization is important for diagnostics of coronal streamers, where the thermodynamic time scale could be shorter than the ionization or recombination time scales, and ions are therefor in non-equilibrium ionization states. In this work, we perform post-processing time-dependent ionization calculations for a three dimensional solar corona and inner heliosphere model from Predictive Sciences Inc. (Mikić & Linker 1999) to analyze the influence of non-equilibrium ionization on emission from coronal streamers. Using the plasma temperature, density, velocity and magnetic field distributions provided by the 3D MHD simulation covering the Whole Sun Month (Carrington rotation CR1913, 1996 August 22 to September 18), we calculate non-equilibrium ionization states in the region around a pseudostreamer. We then obtain the synthetic emissivities with the non-equilibrium ion populations. Under the assumption that the corona is optically thin, we also obtain intensity profiles of several emission lines. We compare our calculations with intensities of Lyman-alpha lines and OVI lines from SOHO/Ultraviolet Coronagraph Spectrometer (UVCS) observations at 14 different heights. The results show that intensity profiles of both Lyman-alpha and OVI lines match well UVCS observations at low heights. At large heights, OVI intensites are higher for non-equilibrium ionization than equilibrium ionization inside this pseudostreamer. The assumption of ionization equilibrium would lead to a underestimate of the OVI intensity by about ten percent at a height of 2 solar radii, and the difference between these two ionization cases increases with height. The intensity ratio of OVI 1032 line to OVI 1037 lines is also obtained for non-equilibrium ionization modeling.

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

    ERIC Educational Resources Information Center

    Nikolaychuk, Pavel Anatolyevich; Kuvaeva, Alyona Olegovna

    2016-01-01

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

  15. 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…

  16. Determination of Students' Alternative Conceptions about Chemical Equilibrium: A Review of Research and the Case of Turkey

    ERIC Educational Resources Information Center

    Ozmen, Haluk

    2008-01-01

    This study aims to determine prospective science student teachers' alternative conceptions of the chemical equilibrium concept. A 13-item pencil and paper, two-tier multiple choice diagnostic instrument, the Test to Identify Students' Alternative Conceptions (TISAC), was developed and administered to 90 second-semester science student teachers…

  17. Functional Fixedness and Functional Reduction as Common Sense Reasonings in Chemical Equilibrium and in Geometry and Polarity of Molecules.

    ERIC Educational Resources Information Center

    Furio, C.; Calatayud, M. L.; Barcenas, S. L.; Padilla, O. M.

    2000-01-01

    Focuses on learning difficulties in procedural knowledge, and assesses the procedural difficulties of grade 12 and first- and third-year university students based on common sense reasoning in two areas of chemistry--chemical equilibrium and geometry, and polarity of molecules. (Contains 55 references.) (Author/YDS)

  18. Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

    NASA Astrophysics Data System (ADS)

    Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

    2014-05-01

    The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

  19. Reviewing Some Crucial Concepts of Gibbs Energy in Chemical Equilibrium Using a Computer-Assisted, Guided-Problem-Solving Approach

    ERIC Educational Resources Information Center

    Borge, Javier

    2015-01-01

    G, G°, ?rG, ?rG°, ?G, and ?G° are essential quantities to master the chemical equilibrium. Although the number of publications devoted to explaining these items is extremely high, it seems that they do not produce the desired effect because some articles and textbooks are still being written with some of these quantities that appear to be…

  20. The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation

    SciTech Connect

    Oliveira, Luciana Renata de; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C.

    2014-08-14

    We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their “far from equilibrium behavior,” hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative “external vector field” whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the “plasticity property” of biological systems

  1. Silicon Oxysulfide, OSiS: Rotational Spectrum, Quantum-Chemical Calculations, and Equilibrium Structure.

    PubMed

    Thorwirth, Sven; Mück, Leonie Anna; Gauss, Jürgen; Tamassia, Filippo; Lattanzi, Valerio; McCarthy, Michael C

    2011-06-01

    Silicon oxysulfide, OSiS, and seven of its minor isotopic species have been characterized for the first time in the gas phase at high spectral resolution by means of Fourier transform microwave spectroscopy. The equilibrium structure of OSiS has been determined from the experimental data using calculated vibration-rotation interaction constants. The structural parameters (rO-Si = 1.5064 Å and rSi-S = 1.9133 Å) are in very good agreement with values from high-level quantum chemical calculations using coupled-cluster techniques together with sophisticated additivity and extrapolation schemes. The bond distances in OSiS are very short in comparison with those in SiO and SiS. This unexpected finding is explained by the partial charges calculated for OSiS via a natural population analysis. The results suggest that electrostatic effects rather than multiple bonding are the key factors in determining bonding in this triatomic molecule. The data presented provide the spectroscopic information needed for radio astronomical searches for OSiS. PMID:26295414

  2. Modeling of Non-equilibrium Processes in Oil Trunk Pipeline Using Godunov Type Method

    NASA Astrophysics Data System (ADS)

    Sumskoi, S. I.; Sverchkov, A. M.

    The Article presents the numerical method of solving the system of one-dimensional non-stationary equations describing oil movement in the oil pipeline. The method is aimed at modeling the non-equilibrium and transitional processes in the oil pipelines in the normal and emergency modes. This new developed method can be applied for relaxation non-equilibrium flow case, that can't be modeling using another methods. Also this method is aimed at modeling the non-equilibrium and transitional processes in the liquefied hydrocarbon pipelines in the normal and emergency modes. Phase non-equilibrium flow is considered for boiling liquids transporting pipeline.

  3. Analysis of the explosion of gas mixtures with a shift in the chemical equilibrium of the products taken into account

    SciTech Connect

    Zhdan, S.A.

    1983-07-01

    Starting from a representation of the detonation products as a reacting medium with an equilibrium chemical composition at each point, a generalized formulation of the problem on the explosion of a reacting gas mixture in air is given. Methaneoxygen and hydrogen-oxygen systems are considered. It is seen that almost half the energy is in the chemical component of the total internal energy behind the detonation wave front. The results of computations by the mathematical model yield greater values of the excess pressures on the shock front. Experimental data and numerical solutions are compared for the dependence of the excess pressures on the shock front radius, and are found to be in good agreement for the hydrogen-oxygen system. The methane-oxygen system shows a systematic excess in the experimental data which is apparently associated with non-one-dimensional effects in formulation of the experiment. The magnitude of the efficiency of an explosion, defined as the energy transferred to the wave during maximal detonation product expansion and the total energy initially included in the mixture, is of interest. For oxygen mixtures, only a third of the total explosion energy performs work on the surrounding air.

  4. Use of the augmented Young-Laplace equation to model equilibrium and evaporating extended menisci

    SciTech Connect

    DasGupta, S.; Schonberg, J.A.; Kim, I.Y.; Wayner, P.C.Jr. )

    1993-05-01

    The generic importance of fluid flow and change-of-phase heat transfer in the contact line region of an extended meniscus has led to theoretical and experimental research on the details of these transport processes. Numerical solutions of equilibrium and nonequilibrium models based on the augmented Young-Laplace equation were successfully used to evaluate experimental data for an extended meniscus. The data for the equilibrium and nonequilibrium meniscus profiles were obtained optically using ellipsometry and image processing interferometry. A Taylor series expansion of the fourth-order nonlinear transport model was used to obtain the extremely sensitive initial conditions at the interline. The solid-liquid-vapor Hamaker constants for the systems were obtained from the experimental data. The consistency of the data was demonstrated by using the combining rules to calculate the unknown value of the Hamaker constant for the experimental substrate. The sensitivity of the meniscus profile to small changes in the environment was demonstrated. Both temperature and intermolecular forces need to be included in modeling transport processes in the contact line region because the chemical potential is a function of both temperature and pressure.

  5. Modelling of Equilibrium Between Mantle and Core: Refractory, Volatile, and Highly Siderophile Elements

    NASA Technical Reports Server (NTRS)

    Righter, K.; Danielson, L.; Pando, K.; Shofner, G.; Lee, C. -T.

    2013-01-01

    Siderophile elements have been used to constrain conditions of core formation and differentiation for the Earth, Mars and other differentiated bodies [1]. Recent models for the Earth have concluded that the mantle and core did not fully equilibrate and the siderophile element contents of the mantle can only be explained under conditions where the oxygen fugacity changes from low to high during accretion and the mantle and core do not fully equilibrate [2,3]. However these conclusions go against several physical and chemical constraints. First, calculations suggest that even with the composition of accreting material changing from reduced to oxidized over time, the fO2 defined by metal-silicate equilibrium does not change substantially, only by approximately 1 logfO2 unit [4]. An increase of more than 2 logfO2 units in mantle oxidation are required in models of [2,3]. Secondly, calculations also show that metallic impacting material will become deformed and sheared during accretion to a large body, such that it becomes emulsified to a fine scale that allows equilibrium at nearly all conditions except for possibly the length scale for giant impacts [5] (contrary to conclusions of [6]). Using new data for D(Mo) metal/silicate at high pressures, together with updated partitioning expressions for many other elements, we will show that metal-silicate equilibrium across a long span of Earth s accretion history may explain the concentrations of many siderophile elements in Earth's mantle. The modeling includes refractory elements Ni, Co, Mo, and W, as well as highly siderophile elements Au, Pd and Pt, and volatile elements Cd, In, Bi, Sb, Ge and As.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  7. New non-equilibrium matrix imbibition equation for double porosity model

    NASA Astrophysics Data System (ADS)

    Konyukhov, Andrey; Pankratov, Leonid

    2016-07-01

    The paper deals with the global Kondaurov double porosity model describing a non-equilibrium two-phase immiscible flow in fractured-porous reservoirs when non-equilibrium phenomena occur in the matrix blocks, only. In a mathematically rigorous way, we show that the homogenized model can be represented by usual equations of two-phase incompressible immiscible flow, except for the addition of two source terms calculated by a solution to a local problem being a boundary value problem for a non-equilibrium imbibition equation given in terms of the real saturation and a non-equilibrium parameter.

  8. The lagRST Model: A Turbulence Model for Non-Equilibrium Flows

    NASA Technical Reports Server (NTRS)

    Lillard, Randolph P.; Oliver, A. Brandon; Olsen, Michael E.; Blaisdell, Gregory A.; Lyrintzis, Anastasios S.

    2011-01-01

    This study presents a new class of turbulence model designed for wall bounded, high Reynolds number flows with separation. The model addresses deficiencies seen in the modeling of nonequilibrium turbulent flows. These flows generally have variable adverse pressure gradients which cause the turbulent quantities to react at a finite rate to changes in the mean flow quantities. This "lag" in the response of the turbulent quantities can t be modeled by most standard turbulence models, which are designed to model equilibrium turbulent boundary layers. The model presented uses a standard 2-equation model as the baseline for turbulent equilibrium calculations, but adds transport equations to account directly for non-equilibrium effects in the Reynolds Stress Tensor (RST) that are seen in large pressure gradients involving shock waves and separation. Comparisons are made to several standard turbulence modeling validation cases, including an incompressible boundary layer (both neutral and adverse pressure gradients), an incompressible mixing layer and a transonic bump flow. In addition, a hypersonic Shock Wave Turbulent Boundary Layer Interaction with separation is assessed along with a transonic capsule flow. Results show a substantial improvement over the baseline models for transonic separated flows. The results are mixed for the SWTBLI flows assessed. Separation predictions are not as good as the baseline models, but the over prediction of the peak heat flux downstream of the reattachment shock that plagues many models is reduced.

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

    NASA Astrophysics Data System (ADS)

    Kawai, Soshi; Larsson, Johan

    2013-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

  11. Non-equilibrium Steady States in Kac's Model Coupled to a Thermostat

    NASA Astrophysics Data System (ADS)

    Evans, Josephine

    2016-09-01

    This paper studies the existence, uniqueness and convergence to non-equilibrium steady states in Kac's model with an external coupling. We work in both Fourier distances and Wasserstein distances. Our methods work in the case where the external coupling is not a Maxwellian equilibrium. This provides an example of a non-equilibrium steady state. We also study the behaviour as the number of particles goes to infinity and show quantitative estimates on the convergence rate of the first marginal.

  12. The earth's core: Speculations on its chemical equilibrium with the mantle

    USGS Publications Warehouse

    Brett, R.

    1971-01-01

    A review of the literature indicates that a reasonable estimate of the composition of the earth's core is iron with Ni0-5, Si10-25 (wt.%). Thermodynamic calculations and comparison of chondritic with terrestrial abundances indicate that 1 wt.% each of Mn, P, and Cr might also be present. A core of this composition was probably in chemical equilibrium with the mantle at the time of core formation because: 1. (1) The reactions 2Fe + SiO2 = 2FeO + Si and Fe2SiO4 + 2Ni = Ni2SiO4 + 2Fe proceed further to the right at the T and P values prevailing at the core-mantle boundary than at lower temperatures, thus supporting the presence of Si in the core and the relatively high Ni concentration of the mantle; 2. (2) the Fe3+ Fe2+ ratios in mantle materials indicate oxygen fugacity values close to that of the Fe-Fe1-xO buffer; and 3. (3) the apparent partitioning of Au and similar elements between the core and the mantle is close to that of pallasites. The anomalously high abundance of Cu in the upper mantle can be explained by enrichment through partial melting. Volcanic gases are not likely to represent the composition of volatile elements at the core-mantle boundary, and hence cannot be regarded as valid criteria of disequilibrium at the boundary. Available data on reaction kinetics suggest that a disequilibrium state would be unlikely during core formation. ?? 1971.

  13. Numerical study on the spontaneous condensation flow in an air cryogenic turbo-expander using equilibrium and non-equilibrium models

    NASA Astrophysics Data System (ADS)

    Sun, Wan; Niu, Lu; Chen, Liang; Chen, Shuangtao; Zhang, Xingqun; Hou, Yu

    2016-01-01

    The difficulty of data measurement in cryogenic environments and the complicated mechanism of nucleation process have restricted the design of wet type turbo-expander for cryogenic liquid plants. In this paper, equilibrium and non-equilibrium models are used to model the spontaneous condensation flow in a cryogenic turbo-expander along the main stream passage including nozzle, impeller and diffuser. The comparison shows a distinct difference of the predicted wetness fraction distribution along the streamline between the equilibrium model and the non-equilibrium model. In non-equilibrium model, the distributions of supercooling and nucleation rate along the length of turbo-expander are given for the analysis of flow characteristics. The comparison of outlet wetness fraction with the experimental data is also provided for verification and discussion. Both the effects of the rotation on nucleation and the effects of the nucleation on flow along suction side of the impeller are investigated.

  14. Local Equilibrium in Inhomogeneous Stochastic Models of Heat Transport

    NASA Astrophysics Data System (ADS)

    Nándori, Péter

    2016-07-01

    We extend the duality of Kipnis et al. (J Stat Phys 27:65-74, 1982) to inhomogeneous lattice gas systems where either the components have different degrees of freedom or the rate of interaction depends on the spatial location. Then the dual process is applied to prove local equilibrium in the hydrodynamic limit for some inhomogeneous high dimensional systems and in the nonequilibrium steady state for one dimensional systems with arbitrary inhomogeneity.

  15. Constant Entropy Properties for an Approximate Model of Equilibrium Air

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick; Hodge, Marion E.

    1961-01-01

    Approximate analytic solutions for properties of equilibrium air up to 15,000 K have been programmed for machine computation. Temperature, compressibility, enthalpy, specific heats, and speed of sound are tabulated as constant entropy functions of temperature. The reciprocal of acoustic impedance and its integral with respect to pressure are also given for the purpose of evaluating the Riemann constants for one-dimensional, isentropic flow.

  16. Equilibrium and volumetric data and model development of coal fluids

    SciTech Connect

    Robinson, R.L. Jr.; Gasem, K.A.M.; Park, J.

    1992-04-28

    The long term goal of our efforts is to develop accurate predictive methods for description of equilibrium phase properties for a variety of types of mixtures and operating conditions. The specific objectives of the work specified herein include: (1) development of an experimental facility having the capability to provide data on equilibrium phase compositions (solubilities) and liquid densities, and doing so with greater accuracy and speed than our previous facility, (2) measurement of equilibrium phase properties for systematically-selected mixtures-specifically those containing important solute gases (such as hydrogen, carbon monoxide, methane, ethane, carbonyl sulfide, ammonia) in a series of heavy paraffinic, naphthenic and aromatic solvents (e.g., n-decane, n-eicosane, n-octacosane, n-hexatriacontane, cyclohexane, Decalin, perhydrophenanthrene, perhydropyrene, benzene, naphthalene, phenanthrene, pyrene), (3) testing/development of correlation frameworks for representing the phase behavior of fluids of the type encountered in coal conversion processes, and (4) generalization of parameters in the correlation frameworks to enable accurate predictions for systems of the type studied, permitting predictions to be made for systems and conditions other than those for which experimental data are available.

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

    NASA Astrophysics Data System (ADS)

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

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

  18. Criticality and punctuated equilibrium in a spin system model of a financial market

    NASA Astrophysics Data System (ADS)

    Ponzi, A.; Aizawa, Y.

    2000-09-01

    We describe a financial market model which shows a non-equilibrium phase transition. Near the transition punctuated equilibrium behaviour is seen, with avalanches occuring on all scales. This scaling is described by an exponent very near 1. This system shows intermittent time development with bursts of global synchronization reminiscent of a market rollercoaster.

  19. Spectral Modeling in Astrophysics - The Physics of Non-equilibrium Clouds

    NASA Astrophysics Data System (ADS)

    Ferland, Gary; Williams, Robin

    2016-02-01

    Collisional-radiative spectral modeling plays a central role in astrophysics, probing phenomena ranging from the chemical evolution of the Universe to the energy production near supermassive black holes in distant quasars. The observed emission lines form in non-equilibrium clouds that have very low densities by laboratory standards, and are powered by energy sources which themselves are not in equilibrium. The spectrum is the result of a large number of microphysical processes, thermal statistics often do not apply, and analytical theory cannot be used. Numerical simulations are used to understand the physical state and the resulting spectrum. The greatest distinction between astrophysical modeling and conventional plasma simulations lies in the range of phenomena that must be considered. A single astronomical object will often have gas with kinetic temperatures of T˜10^6 K, 10^4 K, and T≤ 10^3 K, with the physical state ranging from molecular to fully ionized, and emitting over all wavelengths between the radio and x-ray. Besides atomic, plasma, and chemical physics, condensed matter physics is important because of the presence of small solid `grains' which affect the gas through catalytic reactions and the infrared emission they produce. The ionization, level populations, chemistry, and grain properties must be determined self-consistently, along with the radiation transport, to predict the observed spectrum. Although the challenge is great, so are the rewards. Numerical spectral simulations allow us to read the message contained in the spectrum emitted by objects far from the Earth that existed long ago.

  20. Modeling of methane and ethane hydrate formation kinetics based on non-equilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Mottahedin, Mona; Varaminian, Farshad; Mafakheri, Kaveh

    2011-05-01

    In this study, experimental data of the kinetics of methane and ethane hydrate formation at constant volume were collected. The experiments were carried out in a batch reactor at different temperatures and pressures. The property of chemical affinity was used in the modeling of hydrate formation rate in a constant volume process. In this model a macroscopic driving force was defined which only needed the initial (experimental condition, temperature, and pressure) and final conditions (equilibrium conditions); thus, this model did not have the limitations of microscopic models, such as heat and mass transfer coefficients or population of particles, which may differ for each experiment. The experiments were carried out at temperatures 273, 274, 275.5, and 276 K for methane and 272, 273, 274, and 275 K for ethane with different initial pressures. The parameters of the model, Ar and tK , were obtained for each experiment, and the results show that the parameter of for each gas has a constant value. Subsequently, parameters of the model were used to predict experimental data and the variation of pressures with time. The results indicated that this model can well predict constant volume experimental data for crystals I hydrate former.

  1. Novel non-equilibrium modelling of a DC electric arc in argon

    NASA Astrophysics Data System (ADS)

    Baeva, M.; Benilov, M. S.; Almeida, N. A.; Uhrlandt, D.

    2016-06-01

    A novel non-equilibrium model has been developed to describe the interplay of heat and mass transfer and electric and magnetic fields in a DC electric arc. A complete diffusion treatment of particle fluxes, a generalized form of Ohm’s law, and numerical matching of the arc plasma with the space-charge sheaths adjacent to the electrodes are applied to analyze in detail the plasma parameters and the phenomena occurring in the plasma column and the near-electrode regions of a DC arc generated in atmospheric pressure argon for current levels from 20 A up to 200 A. Results comprising electric field and potential, current density, heating of the electrodes, and effects of thermal and chemical non-equilibrium are presented and discussed. The current–voltage characteristic obtained is in fair agreement with known experimental data. It indicates a minimum for arc current of about 80 A. For all current levels, a field reversal in front of the anode accompanied by a voltage drop of (0.7–2.6) V is observed. Another field reversal is observed near the cathode for arc currents below 80 A.

  2. Disequilibrium Textures vs Equilibrium Modelling: Geochronology at the Crossroads

    NASA Astrophysics Data System (ADS)

    Villa, I. M.

    2007-12-01

    Observations made by electron microscopy show the processes affecting minerals at the atomic scale. The majority of reported analyses demonstrate chemical disequilibrium. A classic example are overgrowths of one mineral generation by a secondary one, which may be recognized on textural grounds. Disequilibrium recrystallization is promoted by water, which is everywhere on this planet (granites, contact aureoles, regional metamorphism, faults). It is mostly easier and energetically less costly to recrystallize a mineral at any temperature than to induce genuine volume diffusion in it. However, these observations are only relevant to geochronologists if chemical disequilibria are also accompanied by isotopic disequilibria. If a mineral mixture gives a mixed isotope record, then the interpretation of ages does not come cheap. If, on the contrary, diffusive reequilibration of the isotopic record is faster than that of chemical heterogeneities, then the petrology and microchemistry of a mineral could be ignored and its apparent age termed a "cooling age". First principle arguments and experimental data of the last decade concordantly show that the diffusivity of radiogenic isotopes is never higher than that of major elements forming the mineral structure. And indeed, end- member ages of mineral mixtures can be unravelled if the petrogenesis is understood. This was first shown by CL images of zircon grains (Gebauer et al, Schweiz Min Pet Mitt 68 (1988) 485-490). Similar progress was reported on monazite (Williams et al, Ann Rev Earth Planet Sci 35 (2007) 137-175), amphibole (Belluso et al, Eur J Mineral 12 (2000) 45-62), K-feldspar (Nyfeler et al, Schweiz Min Pet Mitt 78 (1998) 11-21), biotite (Villa et al, Water Rock Interaction 10 (2001) 1589-92). The mechanism for resetting the isotope record in nature thus seems more dependent on the availability of water to enhance disequilibrium recrystallization than on reaching a preset temperature. Intercomparison of laboratory

  3. Chemical equilibrium and mass balance relationships associated with the Long Valley hydrothermal system, California, U.S.A.

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1991-01-01

    Recent drilling and sampling of hydrothermal fluids from Long Valley permit an accurate characterization of chemical concentrations and equilibrium conditions in the hydrothermal reservoir. Hydrothermal fluids are thermodynamically saturated with secondary quartz, calcite, and pyrite but are in disequilibrium with respect to aqueous sulfide-sulfate speciation. Hydrothermal fluids are enriched in 18O by approximately 1??? relative to recharge waters. 18O and Cl concentrations in well cuttings and core from high-temperature zones of the reservoir are extensively depleted relative to fresh rhyolitic tuff compositions. Approximately 80% of the Li and 50% of the B are retained in the altered reservoir rock. Cl mass balance and open-system 18O fractionation models produce similar water-rock ratios of between 1.0 and 2.5 kg kg-1. These water-rock ratios coupled with estimates of reservoir porosity and density produce a minimum fluid residence time of 1.3 ka. The low fluid Cl concentrations in Long Valley correlate with corresponding low rock concentrations. Mass balance calculations indicate that leaching of these reservoir rocks accounts for Cl losses during hydrothermal activity over the last 40 ka. ?? 1991.

  4. Information performances and illative sequences: Sequential organization of explanations of chemical phase equilibrium

    NASA Astrophysics Data System (ADS)

    Brown, Nathaniel James Swanton

    While there is consensus that conceptual change is surprisingly difficult, many competing theories of conceptual change co-exist in the literature. This dissertation argues that this discord is partly the result of an inadequate account of the unwritten rules of human social interaction that underlie the field's preferred methodology---semi-structured interviewing. To better understand the contributions of interaction during explanations, I analyze eight undergraduate general chemistry students as they attempt to explain to various people, for various reasons, why phenomena involving chemical phase equilibrium occur. Using the methods of interaction analysis, I characterize the unwritten, but systematic, rules that these participants follow as they explain. The result is a description of the contributions of interaction to explaining. Each step in each explanation is a jointly performed expression of a subject-predicate relation, an interactive accomplishment I call an information performance (in-form, for short). Unlike clauses, in-forms need not have a coherent grammatical structure. Unlike speaker turns, in-forms have the clear function of expressing information. Unlike both clauses and speaker turns, in-forms are a co-construction, jointly performed by both the primary speaker and the other interlocutor. The other interlocutor strongly affects the form and content of each explanation by giving or withholding feedback at the end of each in-form, moments I call feedback-relevant places. While in-forms are the bricks out of which the explanation is constructed, they are secured by a series of inferential links I call an illative sequence. Illative sequences are forward-searching, starting with a remembered fact or observation and following a chain of inferences in the hope it leads to the target phenomenon. The participants treat an explanation as a success if the illative sequence generates an in-form that describes the phenomenon. If the illative sequence does

  5. Chemical Equilibrium of the Dissolved Uranium in Groundwaters From a Spanish Uranium-Ore Deposit

    SciTech Connect

    Garralon, Antonio; Gomez, Paloma; Turrero, Maria Jesus; Buil, Belen; Sanchez, Lorenzo

    2007-07-01

    The main objectives of this work are to determine the hydrogeochemical evolution of an uranium ore and identify the main water/rock interaction processes that control the dissolved uranium content. The Mina Fe uranium-ore deposit is the most important and biggest mine worked in Spain. Sageras area is located at the north part of the Mina Fe, over the same ore deposit. The uranium deposit was not mined in Sageras and was only perturbed by the exploration activities performed 20 years ago. The studied area is located 10 Km northeast of Ciudad Rodrigo (Salamanca) at an altitude over 650 m.a.s.l. The uranium mineralization is related to faults affecting the metasediments of the Upper Proterozoic to Lower Cambrian schist-graywacke complex (CEG), located in the Centro-Iberian Zone of the Hesperian Massif . The primary uranium minerals are uraninite and coffinite but numerous secondary uranium minerals have been formed as a result of the weathering processes: yellow gummite, autunite, meta-autunite, torbernite, saleeite, uranotile, ianthinite and uranopilite. The water flow at regional scale is controlled by the topography. Recharge takes place mainly in the surrounding mountains (Sierra Pena de Francia) and discharge at fluvial courses, mainly Agueda and Yeltes rivers, boundaries S-NW and NE of the area, respectively. Deep flows (lower than 100 m depth) should be upwards due to the river vicinity, with flow directions towards the W, NW or N. In Sageras-Mina Fe there are more than 100 boreholes drilled to investigate the mineral resources of the deposit. 35 boreholes were selected in order to analyze the chemical composition of groundwaters based on their depth and situation around the uranium ore. Groundwater samples come from 50 to 150 m depth. The waters are classified as calcium-bicarbonate type waters, with a redox potential that indicates they are slightly reduced (values vary between 50 to -350 mV). The TOC varies between <0.1 and 4.0 mgC/L and the dissolved

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

    PubMed

    Bradford, Scott A; Torkzaban, Saeed; Leij, Feike; Simunek, Jiri

    2015-10-01

    We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and kinetic, and two-site kinetic models were developed to describe various rates of colloid release. These models were subsequently applied to experimental colloid release datasets to investigate the influence of variations in ionic strength (IS), pH, cation exchange, colloid size, and water velocity on release. Various combinations of equilibrium and/or kinetic release models were needed to describe the experimental data depending on the transient conditions and colloid type. Release of Escherichia coli D21g was promoted by a decrease in solution IS and an increase in pH, similar to expected trends for a reduction in the secondary minimum and nanoscale chemical heterogeneity. The retention and release of 20nm carboxyl modified latex nanoparticles (NPs) were demonstrated to be more sensitive to the presence of Ca(2+) than D21g. Specifically, retention of NPs was greater than D21g in the presence of 2mM CaCl2 solution, and release of NPs only occurred after exchange of Ca(2+) by Na(+) and then a reduction in the solution IS. These findings highlight the limitations of conventional interaction energy calculations to describe colloid retention and release, and point to the need to consider other interactions (e.g., Born, steric, and/or hydration forces) and/or nanoscale heterogeneity. Temporal changes in the water velocity did not have a large influence on the release of D21g for the examined conditions. This insensitivity was likely due to factors that reduce the applied hydrodynamic torque and/or increase the resisting adhesive torque; e.g., macroscopic roughness and grain-grain contacts. Our analysis and models improve our understanding and ability to describe the amounts

  7. Computer model of one-dimensional equilibrium controlled sorption processes

    USGS Publications Warehouse

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

    1984-01-01

    A numerical solution to the one-dimensional solute-transport equation with equilibrium-controlled sorption and a first-order irreversible-rate reaction is presented. The computer code is written in FORTRAN language, with a variety of options for input and output for user ease. Sorption reactions include Langmuir, Freundlich, and ion-exchange, with or without equal valance. General equations describing transport and reaction processes are solved by finite-difference methods, with nonlinearities accounted for by iteration. Complete documentation of the code, with examples, is included. (USGS)

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

    NASA Astrophysics Data System (ADS)

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

    2007-01-01

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

  9. Internal Thermodynamical Equilibrium And Consequences For Rate Law Expressions For Elementary Chemical And Physical Reactions

    NASA Astrophysics Data System (ADS)

    Jesudason, Christopher G.

    2009-07-01

    By viewing reactant species to be in a state of thermodynamical equilibrium with its various members which constitutes a set within a set of topological parameters various states of internal equilibrium within the same species would exist subject to the Gibbs thermodynamical criteria. Some examples from actual ab initio computer simulations show that there exists an empirical relationship between the activity coefficient ratio and the so-called reactivity coefficients, defined as a measure of departure of the rate constant with varying concentration of reactants in a system at equilibrium, where forward and backward rates can still be measured. These ideas are applied to charged reaction dynamics where a generalization of the Brönsted and Bjerrum rate expression is obtained.

  10. TICKET-UWM: a coupled kinetic, equilibrium, and transport screening model for metals in lakes.

    PubMed

    Farley, Kevin J; Carbonaro, Richard F; Fanelli, Christopher J; Costanzo, Robert; Rader, Kevin J; Di Toro, Dominic M

    2011-06-01

    The tableau input coupled kinetic equilibrium transport-unit world model (TICKET-UWM) has been developed as a screening model for assessing potential environmental risks associated with the release of metals into lakes. The model is based on a fully implicit, one-step solution algorithm that allows for simultaneous consideration of dissolved and particulate phase transport; metal complexation to organic matter and inorganic ligands; precipitation of metal hydroxides, carbonates, and sulfides; competitive interactions of metals and major cations with biotic ligands; a simplified description of biogeochemical cycling of organic carbon and sulfur; and dissolution kinetics for metal powders, massives, and other solid forms. Application of TICKET-UWM to a generalized lake in the Sudbury area of the Canadian Shield is presented to demonstrate the overall cycling of metals in lakes and the nonlinear effects of chemical speciation on metal responses. In addition, the model is used to calculate critical loads for metals, with acute toxicity of Daphnia magna as the final endpoint. Model results show that the critical loads for Cu, Ni, Pb, and Zn varied from 2.5 to 39.0 g metal/m(2) -year and were found to be one or more orders of magnitude higher than comparable loads for pesticides (lindane, 4,4'-DDT) and several polyaromatic hydrocarbon (PAH) compounds. In sensitivity calculations, critical metal-loading rates were found to vary significantly as a function of the hydraulic detention time, water hardness, and metal dissolution kinetic rates. PMID:21381089

  11. Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

    NASA Technical Reports Server (NTRS)

    Thompson, W. R.; Zollweg, John A.; Gabis, David H.

    1992-01-01

    A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

  12. HYDROBIOGEOCHEM: A coupled model of HYDROlogic transport and mixed BIOGEOCHEMical kinetic/equilibrium reactions in saturated-unsaturated media

    SciTech Connect

    Yeh, G.T.; Salvage, K.M.; Gwo, J.P.; Zachara, J.M.; Szecsody, J.E.

    1998-07-01

    The computer program HYDROBIOGEOCHEM is a coupled model of HYDROlogic transport and BIOGEOCHEMical kinetic and/or equilibrium reactions in saturated/unsaturated media. HYDROBIOGEOCHEM iteratively solves the two-dimensional transport equations and the ordinary differential and algebraic equations of mixed biogeochemical reactions. The transport equations are solved for all aqueous chemical components and kinetically controlled aqueous species. HYDROBIOGEOCHEM is designed for generic application to reactive transport problems affected by both microbiological and geochemical reactions in subsurface media. Input to the program includes the geometry of the system, the spatial distribution of finite elements and nodes, the properties of the media, the potential chemical and microbial reactions, and the initial and boundary conditions. Output includes the spatial distribution of chemical and microbial concentrations as a function of time and space, and the chemical speciation at user-specified nodes.

  13. 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.

  14. Does the Addition of Inert Gases at Constant Volume and Temperature Affect Chemical Equilibrium?

    ERIC Educational Resources Information Center

    Paiva, Joao C. M.; Goncalves, Jorge; Fonseca, Susana

    2008-01-01

    In this article we examine three approaches, leading to different conclusions, for answering the question "Does the addition of inert gases at constant volume and temperature modify the state of equilibrium?" In the first approach, the answer is yes as a result of a common students' alternative conception; the second approach, valid only for ideal…

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

    ERIC Educational Resources Information Center

    Cwikel, Dori; And Others

    1986-01-01

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

  16. Equilibrium chemical reaction of supersonic hydrogen-air jets (the ALMA computer program)

    NASA Technical Reports Server (NTRS)

    Elghobashi, S.

    1977-01-01

    The ALMA (axi-symmetrical lateral momentum analyzer) program is concerned with the computation of two dimensional coaxial jets with large lateral pressure gradients. The jets may be free or confined, laminar or turbulent, reacting or non-reacting. Reaction chemistry is equilibrium.

  17. Quantum chemical calculation of the equilibrium structures of small metal atom clusters

    NASA Technical Reports Server (NTRS)

    Kahn, L. R.

    1981-01-01

    A decomposition of the molecular energy is presented that is motivated by the atom superposition and electron delocalization physical model of chemical binding. The energy appears in physically transparent form consisting of a classical electrostatic interaction, a zero order two electron exchange interaction, a relaxation energy, and the atomic energies. Detailed formulae are derived in zero and first order of approximation. The formulation extends beyond first order to any chosen level of approximation leading, in principle, to the exact energy. The structure of this energy decomposition lends itself to the fullest utilization of the solutions to the atomic sub problems to simplify the calculation of the molecular energy. If nonlinear relaxation effects remain minor, the molecular energy calculation requires at most the calculation of two center, two electron integrals. This scheme thus affords the prospects of substantially reducing the computational effort required for the calculation of molecular energies.

  18. NNEPEQ - Chemical equilibrium version of the Navy/NASA Engine Program

    NASA Technical Reports Server (NTRS)

    Fishbach, L. H.; Gordon, S.

    1989-01-01

    The Navy NASA Engine Program, NNEP, currently is in use at a large number of government agencies, commercial companies and universities. This computer code has been used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, there has been increased interest in applications for which NNEP was not capable of simulating, namely, high Mach applications, alternate fuels including cryogenics, and cycles such as the gas generator air-turbo-rocker (ATR). In addition, there is interest in cycles employing ejectors such as for military fighters. New engine component models had to be created for incorporation into NNEP, and it was found necessary to include chemical dissociation effects of high temperature gases. The incorporation of these extended capabilities into NNEP is discussed and some of the effects of these changes are illustrated.

  19. NNEPEQ: Chemical equilibrium version of the Navy/NASA Engine Program

    NASA Technical Reports Server (NTRS)

    Fishbach, Laurence H.; Gordon, Sanford

    1988-01-01

    The Navy NASA Engine Program, NNEP, currently is in use at a large number of government agencies, commercial companies and universities. This computer code has bee used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, there has been increased interest in applications for which NNEP was not capable of simulating, namely, high Mach applications, alternate fuels including cryogenics, and cycles such as the gas generator air-turbo-rocker (ATR). In addition, there is interest in cycles employing ejectors such as for military fighters. New engine component models had to be created for incorporation into NNEP, and it was found necessary to include chemical dissociation effects of high temperature gases. The incorporation of these extended capabilities into NNEP is discussed and some of the effects of these changes are illustrated.

  20. Models of supply function equilibrium with applications to the electricity industry

    NASA Astrophysics Data System (ADS)

    Aromi, J. Daniel

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

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  2. Modeling Mathematical Programs with Equilibrium Constraints in Pyomo

    SciTech Connect

    Hart, William E.; Siirola, John Daniel

    2015-07-01

    We describe new capabilities for modeling MPEC problems within the Pyomo modeling software. These capabilities include new modeling components that represent complementar- ity conditions, modeling transformations for re-expressing models with complementarity con- ditions in other forms, and meta-solvers that apply transformations and numeric optimization solvers to optimize MPEC problems. We illustrate the breadth of Pyomo's modeling capabil- ities for MPEC problems, and we describe how Pyomo's meta-solvers can perform local and global optimization of MPEC problems.

  3. A two-phase restricted equilibrium model for combustion of metalized solid propellants

    NASA Technical Reports Server (NTRS)

    Sabnis, J. S.; Dejong, F. J.; Gibeling, H. J.

    1992-01-01

    An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

  4. Addition to the Lewis Chemical Equilibrium Program to allow computation from coal composition data

    NASA Technical Reports Server (NTRS)

    Sevigny, R.

    1980-01-01

    Changes made to the Coal Gasification Project are reported. The program was developed by equilibrium combustion in rocket engines. It can be applied directly to the entrained flow coal gasification process. The particular problem addressed is the reduction of the coal data into a form suitable to the program, since the manual process is involved and error prone. A similar problem in relating the normal output of the program to parameters meaningful to the coal gasification process is also addressed.

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

    SciTech Connect

    Thornton, Peter E; Wang, Weile; Law, Beverly E.; Nemani, Ramakrishna R

    2009-01-01

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

  6. Chemical modeling of irreversible reactions in nuclear waste-water-rock systems

    SciTech Connect

    Wolery, T.J.

    1981-02-01

    Chemical models of aqueous geochemical systems are usually built on the concept of thermodynamic equilibrium. Though many elementary reactions in a geochemical system may be close to equilibrium, others may not be. Chemical models of aqueous fluids should take into account that many aqueous redox reactions are among the latter. The behavior of redox reactions may critically affect migration of certain radionuclides, especially the actinides. In addition, the progress of reaction in geochemical systems requires thermodynamic driving forces associated with elementary reactions not at equilibrium, which are termed irreversible reactions. Both static chemical models of fluids and dynamic models of reacting systems have been applied to a wide spectrum of problems in water-rock interactions. Potential applications in nuclear waste disposal range from problems in geochemical aspects of site evaluation to those of waste-water-rock interactions. However, much further work in the laboratory and the field will be required to develop and verify such applications of chemical modeling.

  7. An approximate single fluid 3-dimensional magnetohydrodynamic equilibrium model with toroidal flow

    NASA Astrophysics Data System (ADS)

    Cooper, W. A.; Hirshman, S. P.; Chapman, I. T.; Brunetti, D.; Faustin, J. M.; Graves, J. P.; Pfefferlé, D.; Raghunathan, M.; Sauter, O.; Tran, T. M.; Aiba, N.

    2014-09-01

    An approximate model for a single fluid three-dimensional (3D) magnetohydrodynamic (MHD) equilibrium with pure isothermal toroidal flow with imposed nested magnetic flux surfaces is proposed. It recovers the rigorous toroidal rotation equilibrium description in the axisymmetric limit. The approximation is valid under conditions of nearly rigid or vanishing toroidal rotation in regions with significant 3D deformation of the equilibrium flux surfaces. Bifurcated helical core equilibrium simulations of long-lived modes in the MAST device demonstrate that the magnetic structure is only weakly affected by the flow but that the 3D pressure distortion is important. The pressure is displaced away from the major axis and therefore is not as noticeably helically deformed as the toroidal magnetic flux under the subsonic flow conditions measured in the experiment. The model invoked fails to predict any significant screening by toroidal plasma rotation of resonant magnetic perturbations in MAST free boundary computations.

  8. METAL SPECIATION EQUILIBRIUM MODEL FOR SURFACE AND GROUND WATER (MINTEQA2), AND PROBLEM DEFINITION PROGRAM FOR MINTEQA2 (PRODEF)

    EPA Science Inventory

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

  9. Estimation of Equilibrium Liquid from the Pyroxene Chemical Compositions of Monomict and Polymict Cumulate Eucrites

    NASA Astrophysics Data System (ADS)

    Saiki, K.; Takeda, H.

    1993-07-01

    Cumulate eucrites have bulk compositions between diogenites and ordinary (noncumulate) eucrites (OE). The study of polymict eucrite Y791439 shows that ordinary to cumulate eucrites are located adjacent to each other in the parent body crust, and shows that there are four stages in the crystallization sequence of pyroxene, including two types of cumulate eucrite [1]. In this study we calculate the activities of some elements in the liquid equilibrated with pyroxenes in Y791439 and some cumulate eucrites by single element partition coefficients for the better understanding of the liquid evolution on the HED parent body's crust. Polished thin sections (PTS) of Y791439,51 and Y791195,92-1 were supplied from the National Institute of Polar Research (NIPR) in Japan. Medanitos was supplied from the British Museum of Natural History. A PTS of ALH85001 was made from a chip supplied from Meteorite Working Group (MWG) in the U.S. These PTSs were investigated by SEM (JEOL840A) equipped with a chemical mapping system (PXQUAD system) originally constructed by us and the chemical compositions of pyroxenes were obtained by EPMA (JEOL 733 mark II). Y791439 is composed of four types of pyroxene; JV (Juvinas), MC (Moore County), BD (Binda), and D (Diogenite)-type in order from Fe-rich to Mg-rich. The activities of some network-modifier elements (e.g., Fe, Mg, and Ca) in the liquid equilibrated with the pyroxenes in Y791439 are calculated and plotted in the Ca/Fe vs. Mg/Fe (atomic ratio) diagram. For the calculation we adopted the modified Bottinga-Weill two-lattice melt model [2] and single "M"-site pyroxene model and applied Nielsen-Drake partition coefficients [3]. The bulk chemical composition of Y7308 is taken from Ikeda and Takeda (1985) and those of the other meteorites are taken from BVSP (1981). The bulk of Y7308 is one of the probable candidates for the parental liquid that crystallized diogenites and eucrites and the bulks of OE are candidates for the most evolved liquid

  10. Self-consistent chemical model of partially ionized plasmas

    SciTech Connect

    Arkhipov, Yu. V.; Baimbetov, F. B.; Davletov, A. E.

    2011-01-15

    A simple renormalization theory of plasma particle interactions is proposed. It primarily stems from generic properties of equilibrium distribution functions and allows one to obtain the so-called generalized Poisson-Boltzmann equation for an effective interaction potential of two chosen particles in the presence of a third one. The same equation is then strictly derived from the Bogolyubov-Born-Green-Kirkwood-Yvon (BBGKY) hierarchy for equilibrium distribution functions in the pair correlation approximation. This enables one to construct a self-consistent chemical model of partially ionized plasmas, correctly accounting for the close interrelation of charged and neutral components thereof. Minimization of the system free energy provides ionization equilibrium and, thus, permits one to study the plasma composition in a wide range of its parameters. Unlike standard chemical models, the proposed one allows one to study the system correlation functions and thereby to obtain an equation of state which agrees well with exact results of quantum-mechanical activity expansions. It is shown that the plasma and neutral components are strongly interrelated, which results in the short-range order formation in the corresponding subsystem. The mathematical form of the results obtained enables one to both firmly establish this fact and to determine a characteristic length of the structure formation. Since the cornerstone of the proposed self-consistent chemical model of partially ionized plasmas is an effective pairwise interaction potential, it immediately provides quite an efficient calculation scheme not only for thermodynamical functions but for transport coefficients as well.

  11. Investigation of the production of (68)Ga using pre-equilibrium models.

    PubMed

    Baldik, Rıdvan; Dombayci, Ayten

    2016-07-01

    In this study, some nuclear reactions for the production of (68)Ga radioisotope are investigated using pre-equilibrium nuclear reaction models. For this aim, by the pre-equilibrium reaction mechanisms, the excitation functions and emission spectra of some nuclear reactions for the production of (68)Ga radioisotope are calculated. These calculations are performed in the ALICE/ASH and the TALYS 1.6 codes. The obtained results have been discussed and compared with the available experimental results. PMID:27108069

  12. Combustion of hydrogen-air jets in local chemical equilibrium: A guide to the CHARNAL computer program

    NASA Technical Reports Server (NTRS)

    Spalding, D. B.; Launder, B. E.; Morse, A. P.; Maples, G.

    1974-01-01

    A guide to a computer program, written in FORTRAN 4, for predicting the flow properties of turbulent mixing with combustion of a circular jet of hydrogen into a co-flowing stream of air is presented. The program, which is based upon the Imperial College group's PASSA series, solves differential equations for diffusion and dissipation of turbulent kinetic energy and also of the R.M.S. fluctuation of hydrogen concentration. The effective turbulent viscosity for use in the shear stress equation is computed. Chemical equilibrium is assumed throughout the flow.

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

    PubMed

    Shen, Lu; Decker, Caitlin G; Maynard, Heather D; Levine, Alex J

    2016-09-01

    We present here the calculation of the mean time to capture of a tethered ligand to the receptor. This calculation is then used to determine the shift in the partitioning between (1) free, (2) singly bound, and (3) doubly bound ligands in chemical equilibrium as a function of the length of the tether. These calculations are used in the research article Fibroblast Growth Factor 2 Dimer with Superagonist in vitro Activity Improves Granulation Tissue Formation During Wound Healing (Decker et al., in press [1]) to explain quantitatively how changes in polymeric linker length in the ligand dimers modifies the efficacy of these molecules relative to that of free ligands. PMID:27408925

  14. Chemical kinetics and combustion modeling

    SciTech Connect

    Miller, J.A.

    1993-12-01

    The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.

  15. Chemical Models of Star-Forming Cores

    NASA Astrophysics Data System (ADS)

    Aikawa, Y.

    2013-10-01

    We review chemical models of low-mass star forming cores including our own work. Chemistry in molecular clouds are not in equilibrium. Molecular abundances in star forming cores change not only with physical conditions in cores but also with time. In prestellar cores, temperature stays almost constant ˜ 10 K, while the gas density increases as the core collapses. Three chemical phenomena are observed in this cold phase: molecular depletion, chemical fractionation, and deuterium enrichment. They are reproduced by chemical models combined with isothermal gravitational collapse. The collapse timescale of prestellar cores depends on the initial ratios of thermal, turbulent and magnetic pressure to gravitational energy. Since the chemical timescales, such as adsorption timescale of gas particle onto grains, are comparable to the collapse timescale, molecular abundances in cores should vary depending on the collapse timescale. Observations found that molecular abundances in some cores deviate from those in other cores, in spite of their similar central densities; it could originate in the pressure to gravity ratio in the cores. As the core contraction proceeds, compressional heating eventually overwhelms radiative cooling, and the core starts to warm up. Temperature of the infalling gas rises, as it approaches the central region. Grain-surface reactions of adsorbed molecules occur in this warm-up phase, as well as in prestellar phase. Hydrogenation is efficient at T ≤ 20 K, whereas radicals can migrate on grain surface and react with each other to form complex organic molecules (COMs) at T ≥ 30 K. Grain-surface species are sublimated to the gas phase and re-start gas-phase reactions; e.g. unsaturated carbon chains are formed from sublimated methane. Our model calculation predicts that COMs increases as the warm region extends outwards and the abundances of unsaturated carbon chains depend on the gas density in the CH4 sublimation zone. Recent detection of COMs in

  16. The Entropy Criterion for Chemical Equilibrium: An Exercise in the Second Law.

    ERIC Educational Resources Information Center

    Smith, Norman O.

    1985-01-01

    Describes an exercise in which the entropy maximum is illustrated with a chemical example. The exercise allows students to work with an isolated, chemically reactive system and shows that the entropy of a nonisolated system can pass through a maximum but does so at a nonequilibrium point. (JN)

  17. The Sulfur-Iodine Cycle: Process Analysis and Design Using Comprehensive Phase Equilibrium Measurements and Modeling

    SciTech Connect

    Thies, Mark C.; O'Connell, J. P.; Gorensek, Maximilian B.

    2010-01-10

    Of the 100+ thermochemical hydrogen cycles that have been proposed, the Sulfur-Iodine (S-I) Cycle is a primary target of international interest for the centralized production of hydrogen from nuclear power. However, the cycle involves complex and highly nonideal phase behavior at extreme conditions that is only beginning to be understood and modeled for process simulation. The consequence is that current designs and efficiency projections have large uncertainties, as they are based on incomplete data that must be extrapolated from property models. This situation prevents reliable assessment of the potential viability of the system and, even more, a basis for efficient process design. The goal of this NERI award (05-006) was to generate phase-equilibrium data, property models, and comprehensive process simulations so that an accurate evaluation of the S-I Cycle could be made. Our focus was on Section III of the Cycle, where the hydrogen is produced by decomposition of hydroiodic acid (HI) in the presence of water and iodine (I2) in a reactive distillation (RD) column. The results of this project were to be transferred to the nuclear hydrogen community in the form of reliable flowsheet models for the S-I process. Many of the project objectives were achieved. At Clemson University, a unique, tantalum-based, phase-equilibrium apparatus incorporating a view cell was designed and constructed for measuring fluid-phase equilibria for mixtures of iodine, HI, and water (known as HIx) at temperatures to 350 °C and pressures to 100 bar. Such measurements were of particular interest for developing a working understanding of the expected operation of the RD column in Section III. The view cell allowed for the IR observation and discernment of vapor-liquid (VL), liquid-liquid, and liquid-liquid-vapor (LLVE) equilibria for HIx systems. For the I2-H2O system, liquid-liquid equilibrium (LLE) was discovered to exist at temperatures up to 310-315 °C, in contrast to the models and

  18. Passive equilibrium sampler for in situ measurements of freely dissolved concentrations of hydrophobic organic chemicals in sediments.

    PubMed

    Witt, Gesine; Lang, Susann-Cathrin; Ullmann, Dagny; Schaffrath, Gotja; Schulz-Bull, Detlef; Mayer, Philipp

    2013-07-16

    In this study, an equilibrium passive sampling device is introduced that facilitates the in situ measurement of hydrophobic organic chemicals bioavailability in sediments in terms of freely dissolved concentrations. The new field sampler allows SPME fibers and silicone hollow fibers to be immersed and equilibrated in situ, whereas an automated liner exchanger (ALEX) facilitates the quantitative transfer of analytes to the GC without the use of extraction solvents. The sampler was developed for environmental monitoring as follows: (1) It is of very solid construction and can be reused practically ad infinitum. (2) Fibers with varying surface to volume ratios can be exposed in parallel in order to confirm that equilibrium was reached between sampler and sediment. (3) The equilibrium times allow a temporal resolution that is suited for monitoring of both long-term trends and seasonal effects. The automated thermal desorption reduced sample treatment to a minimum and ensured cost- and time-efficient measurements while minimizing potential error sources after the sampling. The sampler is applicable in a multitude of aquatic environments, especially where currents are low and sediments are muddy and well-mixed, e.g. by bioturbation. Examples for such environments are mud flats, harbor basins, river banks, and lakes. PMID:23819657

  19. General and Partial Equilibrium Modeling of Sectoral Policies to Address Climate Change in the United States

    SciTech Connect

    Pizer, William; Burtraw, Dallas; Harrington, Winston; Newell, Richard; Sanchirico, James; Toman, Michael

    2003-03-31

    This document provides technical documentation for work using detailed sectoral models to calibrate a general equilibrium analysis of market and non-market sectoral policies to address climate change. Results of this work can be found in the companion paper, "Modeling Costs of Economy-wide versus Sectoral Climate Policies Using Combined Aggregate-Sectoral Model".

  20. Temporal cross-correlation asymmetry and departure from equilibrium in a bistable chemical system

    NASA Astrophysics Data System (ADS)

    Bianca, C.; Lemarchand, A.

    2014-06-01

    This paper aims at determining sustained reaction fluxes in a nonlinear chemical system driven in a nonequilibrium steady state. The method relies on the computation of cross-correlation functions for the internal fluctuations of chemical species concentrations. By employing Langevin-type equations, we derive approximate analytical formulas for the cross-correlation functions associated with nonlinear dynamics. Kinetic Monte Carlo simulations of the chemical master equation are performed in order to check the validity of the Langevin equations for a bistable chemical system. The two approaches are found in excellent agreement, except for critical parameter values where the bifurcation between monostability and bistability occurs. From the theoretical point of view, the results imply that the behavior of cross-correlation functions cannot be exploited to measure sustained reaction fluxes in a specific nonlinear system without the prior knowledge of the associated chemical mechanism and the rate constants.

  1. Collective Flocking Dynamics: Long Rang Order in a Non-Equilibrium 2D XY Model

    NASA Astrophysics Data System (ADS)

    Tu, Yuhai

    1996-03-01

    We propose and study a non-equilibrium continuum dynamical model for the collective motion of large groups of biological organisms (e.g., flocks of birds, slime molds, schools of fishs, etc.) (J. Toner and Y. Tu, Phys. Rev. Lett.), 75(23), 4326(1995) Our model becomes highly non-trivial, and different from the equilibrium model, for dequilibrium systems, our model exhibits a broken continuous symmetry even in d=2. Our model describes a large universality class of microscopic rules, including those recently simulated by Vicsek et. al.( T. Vicsek et. al. , Phys. Rev. Lett.) 75, 1226(95).

  2. An interactive computer code for calculation of gas-phase chemical equilibrium (EQLBRM)

    NASA Technical Reports Server (NTRS)

    Pratt, B. S.; Pratt, D. T.

    1984-01-01

    A user friendly, menu driven, interactive computer program known as EQLBRM which calculates the adiabatic equilibrium temperature and product composition resulting from the combustion of hydrocarbon fuels with air, at specified constant pressure and enthalpy is discussed. The program is developed primarily as an instructional tool to be run on small computers to allow the user to economically and efficiency explore the effects of varying fuel type, air/fuel ratio, inlet air and/or fuel temperature, and operating pressure on the performance of continuous combustion devices such as gas turbine combustors, Stirling engine burners, and power generation furnaces.

  3. Politics, Organizations, and Choice: Applications of an Equilibrium Model

    ERIC Educational Resources Information Center

    Roos, Leslie L., Jr.

    1972-01-01

    An economic model of consumer choice is used to link the separate theories that have dealt with comparative politics, job satisfaction, and organizational mobility. The model is used to structure data taken from studies of Turkish and French elites on environmental change, organizational mobility, and satisfaction. (Author/DN)

  4. Chemical vapor deposition modeling for high temperature materials

    NASA Technical Reports Server (NTRS)

    Gokoglu, Suleyman A.

    1992-01-01

    The formalism for the accurate modeling of chemical vapor deposition (CVD) processes has matured based on the well established principles of transport phenomena and chemical kinetics in the gas phase and on surfaces. The utility and limitations of such models are discussed in practical applications for high temperature structural materials. Attention is drawn to the complexities and uncertainties in chemical kinetics. Traditional approaches based on only equilibrium thermochemistry and/or transport phenomena are defended as useful tools, within their validity, for engineering purposes. The role of modeling is discussed within the context of establishing the link between CVD process parameters and material microstructures/properties. It is argued that CVD modeling is an essential part of designing CVD equipment and controlling/optimizing CVD processes for the production and/or coating of high performance structural materials.

  5. Simulating adsorption of U(VI) under transient groundwater flow and hydrochemistry – Physical versus non-equilibrium model

    SciTech Connect

    Greskowiak, Janek; Hay, Michael B.; Prommer, Henning; Liu, Chongxuan; Post, Vincent; Ma, Rui; Davis, James A.; Zheng, Chunmiao; Zachara, John M.

    2011-08-03

    Coupled intra-grain diffusional mass-transfer and non-linear surface complexation processes play an important role for the transport behaviour of U(VI) in contaminated aquifers. Two alternative model approaches for simulating these coupled processes have been analysed and compared: (i) the physical non-equilibrium approach that explicitly accounts for aqueous speciation and instantaneous surface complexation reactions in the intra-grain regions and approximates the diffusive mass exchange between the immobile intra-grain pore water and the advective pore water as multi-rate 1st-order mass transfer and (ii) the chemical non-equilibrium approach that approximates the diffusion-limited intra-grain surface complexation reactions by a set of multiple 1st-order surface complexation reaction kinetics, thereby eliminating the explicit treatment of aqueous speciation in the intra grain pore water. Model comparison has been carried out for column and field scale scenarios, representing the highly transient hydrological and geochemical conditions in the U(VI)-contaminated aquifer at the Hanford 300A site, Washington, USA. It was found that the response of apparent U(VI) adsorption/desorption kinetic behaviour to hydrogeochemically induced changes in U(VI) sorption strength is more pronounced in the physical than in the chemical non-equilibrium model. The magnitude of the differences in model behaviour depends particularly on the degree of disequilibrium between the advective and immobile phase U(VI) concentrations. While a clear difference in U(VI) transport behaviour between the two models was noticeable for the column-scale scenarios, only minor differences were found for the Hanford 300A field scale scenarios, where the model-generated disequilibrium conditions were less pronounced as a result of high frequent groundwater flow reversals.

  6. Chemical modeling of waste sludges

    SciTech Connect

    Weber, C.F.; Beahm, E.C.

    1996-10-01

    The processing of waste from underground storage tanks at the Oak Ridge National Laboratory (ORNL) and other facilities will require an understanding of the chemical interactions of the waste with process chemicals. Two aspects of sludge treatment should be well delineated and predictable: (1) the distribution of chemical species between aqueous solutions and solids, and (2) potential problems due to chemical interactions that could result in process difficulties or safety concerns. It is likely that the treatment of waste tank sludge will begin with washing, followed by basic or acidic leaching. The dissolved materials will be in a solution that has a high ionic strength where activity coefficients are far from unity. Activity coefficients are needed in order to calculate solubilities. Several techniques are available for calculating these values, and each technique has its advantages and disadvantages. The techniques adopted and described here is the Pitzer method. Like any of the methods, prudent use of this approach requires that it be applied within concentration ranges where the experimental data were fit, and its use in large systems should be preceded by evaluating subsystems. While much attention must be given to the development of activity coefficients, other factors such as coprecipitation of species and Ostwald ripening must also be considered when one aims to interpret results of sludge tests or to predict results of treatment strategies. An understanding of sludge treatment processes begins with the sludge tests themselves and proceeds to a general interpretation with the aid of modeling. One could stop with only data from the sludge tests, in which case the table of data would become an implicit model. However, this would be a perilous approach in situations where processing difficulties could be costly or result in concerns for the environment or health and safety.

  7. The Navy/NASA Engine Program (NNEP89): Interfacing the program for the calculation of complex Chemical Equilibrium Compositions (CEC)

    NASA Technical Reports Server (NTRS)

    Gordon, Sanford

    1991-01-01

    The NNEP is a general computer program for calculating aircraft engine performance. NNEP has been used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, however, there has been increased interest in applications for which NNEP is not capable of simulating, such as the use of alternate fuels including cryogenic fuels and the inclusion of chemical dissociation effects at high temperatures. To overcome these limitations, NNEP was extended by including a general chemical equilibrium method. This permits consideration of any propellant system and the calculation of performance with dissociation effects. The new extended program is referred to as NNEP89.

  8. Characterization of sodium carboxymethylcellulose-gelatin complex coacervation by chemical analysis of the coacervate and equilibrium fluid phases.

    PubMed

    Koh, G L; Tucker, I G

    1988-05-01

    The complex coacervation of sodium carboxymethylcellulose (SCMC) and gelatin has been characterized by chemical analyses of the coacervate and equilibrium fluid phases. The phenol-sulphuric acid (for SCMC) and Lowry (for gelatin) assays were used. Chemically analysed coacervate yield was used to predict optimum coacervation conditions, which occurred at a SCMC-gelatin mixing ratio of 3:7 at pH 3.5. The effects of pH, colloid mixing ratio and total colloid concentration on coacervate yield and composition were studied. The colloid mixing ratio, at which the peak coacervate yields occurred varied with coacervation pH. Increase in the total colloid concentration suppressed coacervation, resulting in a coacervate of higher water content. A similar coacervation mechanism was seen for two viscosity grades SCMC. However, because of the different degree of substitution of these two grades the SCMC-gelatin coacervates had different SCMC contents. PMID:2899623

  9. Non-equilibrium STLS approach to transport properties of single impurity Anderson model

    NASA Astrophysics Data System (ADS)

    Rezai, Raheleh; Ebrahimi, Farshad

    2014-04-01

    In this work, using the non-equilibrium Keldysh formalism, we study the effects of the electron-electron interaction and the electron-spin correlation on the non-equilibrium Kondo effect and the transport properties of the symmetric single impurity Anderson model (SIAM) at zero temperature by generalizing the self-consistent method of Singwi, Tosi, Land, and Sjolander (STLS) for a single-band tight-binding model with Hubbard type interaction to out of equilibrium steady-states. We at first determine in a self-consistent manner the non-equilibrium spin correlation function, the effective Hubbard interaction, and the double-occupancy at the impurity site. Then, using the non-equilibrium STLS spin polarization function in the non-equilibrium formalism of the iterative perturbation theory (IPT) of Yosida and Yamada, and Horvatic and Zlatic, we compute the spectral density, the current-voltage characteristics and the differential conductance as functions of the applied bias and the strength of on-site Hubbard interaction. We compare our spectral densities at zero bias with the results of numerical renormalization group (NRG) and depict the effects of the electron-electron interaction and electron-spin correlation at the impurity site on the aforementioned properties by comparing our numerical result with the order U2 IPT. Finally, we show that the obtained numerical results on the differential conductance have a quadratic universal scaling behavior and the resulting Kondo temperature shows an exponential behavior.

  10. Gibbs free energy and integrability of continuum models for granular media at equilibrium

    NASA Astrophysics Data System (ADS)

    Varsakelis, C.

    2015-05-01

    In this letter, we address the problem of the integrability of a continuum model for granular media at equilibrium. By the means of a formal integrability analysis, we show that the equilibrium limit of such models can be cast into a gradient equation with zero right-hand side. In turn, this implies that the model of interest is inherently Frobenius integrable, in the absence of additional compatibility conditions. Moreover, the quantity inside the gradient is identified with the granular material's Gibbs free energy. Consequently, the integrability for the model at hand is equivalent to setting the Gibbs free energy of the granular material constant throughout the domain. In other words, integrability is equivalent to the definition of equilibrium employed in statistical physics.

  11. 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.

  12. Equilibrium modeling of trace metal transport from Duluth complex rockpile

    SciTech Connect

    Kelsey, P.D.; Klusman, R.W.; Lapakko, K.

    1996-12-31

    Geochemical modeling was used to predict weathering processes and the formation of trace metal-adsorbing secondary phases in a waste rock stockpile containing Cu-Ni ore mined from the Duluth Complex, MN. Amorphous ferric hydroxide was identified as a secondary phase within the pile, from observation and geochemical modeling of the weathering process. Due to the high content of cobalt, copper, nickel, and zinc in the primary minerals of the waste rock and in the effluent, it was hypothesized that the predicted and observed precipitant ferric hydroxide would adsorb small quantities of these trace metals. This was verified using sequential extractions and simulated using adsorption geochemical modeling. It was concluded that the trace metals were adsorbed in small quantities, and adsorption onto the amorphous ferric hydroxide was in decreasing order of Cu > Ni > Zn > Co. The low degree of adsorption was due to low pH water and competition for adsorption sites with other ions in solution.

  13. Non-Equilibrium Turbulence Modeling for High Lift Aerodynamics

    NASA Technical Reports Server (NTRS)

    Durbin, P. A.

    1998-01-01

    This phase is discussed in ('Non linear kappa - epsilon - upsilon(sup 2) modeling with application to high lift', Application of the kappa - epsilon -upsilon(sup 2) model to multi-component airfoils'). Further results are presented in 'Non-linear upsilon(sup 2) - f modeling with application to high-lift' The ADI solution method in the initial implementation was very slow to converge on multi-zone chimera meshes. I modified the INS implementation to use GMRES. This provided improved convergence and less need for user intervention in the solution process. There were some difficulties with implementation into the NASA compressible codes, due to their use of approximate factorization. The Helmholtz equation for f is not an evolution equation, so it is not of the form assumed by the approximate factorization method. Although The Kalitzin implementation involved a new solution algorithm ('An implementation of the upsilon(sup 2) - f model with application to transonic flows'). The algorithm involves introducing a relaxation term in the f-equation so that it can be factored. The factorization can be into a plane and a line, with GMRES used in the plane. The NASA code already evaluated coefficients in planes, so no additional memory is required except that associated the the GMRES algorithm. So the scope of this project has expanded via these interactions. . The high-lift work has dovetailed into turbine applications.

  14. Non-equilibrium Dynamics of an Optomechanical Dicke Model

    NASA Astrophysics Data System (ADS)

    Kamanasish, Debnath; Aranya, B. Bhattacherjee

    2015-07-01

    Motivated by the experimental realization of Dicke model in optical cavities, we model an optomechanical system consisting of two-level BEC atoms with transverse pumping. We investigate the transition from normal and inverted state to the superradiant phase through a detailed study of the phase portraits of the system. The rich phase portraits generated by analytical arguments display two types of superradiant phases, regions of coexistence and some portion determining the persistent oscillations. We study the time evolution of the system from any phase and discuss the role of mirror frequency in reaching their attractors. Further, we add an external mechanical pump to the mirror which is capable of changing the mirror frequency through radiation pressure and study the impact of the pump on the phase portraits and the dynamics of the system. We find the external mirror frequency changing the phase portraits and even shifting the critical transition point, thereby predicting a system with controllable phase transition.

  15. Mathematical model for liquid-gas equilibrium in acetic acid fermentations

    PubMed

    Romero; Cantero

    1998-08-01

    An experimental study was conducted to propose an adequate mathematical model for liquid-gas equilibrium in acetic acid fermentations. Three operation scales (laboratory, pilot plant, and industrial plant) were employed to obtain the sets of experimental data. The proposed model, based in the UNIFAC method for the estimation of activity coefficients of a solution consisting of several components, takes into account the effect of temperature. However, in the set of equations, it has been necessary to put in the degree of equilibrium (epsilon). This coefficient adequately reflects the physical conditions of fermentation equipment. The experimental and numerical results help to define the fundamental mechanisms for liquid-gas equilibrium in these systems and demonstrate the model validity in the three tested scales. It was also found that in an industrial setting, closed systems are those with lowest evaporation losses. Copyright 1998 John Wiley & Sons, Inc. PMID:10099342

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

    The objective of this paper is to define empirical parameters (or closwre models) for an initial thermai non-equilibrium porous-media model for use in Computational Fluid Dynamics (CFD) codes for simulation of Stirling regenerators. The two CFD codes currently being used at Glenn Research Center (GRC) for Stirling engine modeling are Fluent and CFD-ACE. The porous-media models available in each of these codes are equilibrium models, which assmne that the solid matrix and the fluid are in thermal equilibrium at each spatial location within the porous medium. This is believed to be a poor assumption for the oscillating-flow environment within Stirling regenerators; Stirling 1-D regenerator models, used in Stirling design, we non-equilibrium regenerator models and suggest regenerator matrix and gas average temperatures can differ by several degrees at a given axial location end time during the cycle. A NASA regenerator research grant has been providing experimental and computational results to support definition of various empirical coefficients needed in defining a noa-equilibrium, macroscopic, porous-media model (i.e., to define "closure" relations). The grant effort is being led by Cleveland State University, with subcontractor assistance from the University of Minnesota, Gedeon Associates, and Sunpower, Inc. Friction-factor and heat-transfer correlations based on data taken with the NASAlSunpower oscillating-flow test rig also provide experimentally based correlations that are useful in defining parameters for the porous-media model; these correlations are documented in Gedeon Associates' Sage Stirling-Code Manuals. These sources of experimentally based information were used to define the following terms and parameters needed in the non-equilibrium porous-media model: hydrodynamic dispersion, permeability, inertial coefficient, fluid effective thermal conductivity (including themal dispersion and estimate of tortuosity effects}, and fluid-solid heat transfer

  17. SPECIES - EVALUATING THERMODYNAMIC PROPERTIES, TRANSPORT PROPERTIES & EQUILIBRIUM CONSTANTS OF AN 11-SPECIES AIR MODEL

    NASA Technical Reports Server (NTRS)

    Thompson, R. A.

    1994-01-01

    Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the

  18. Effects of chemical equilibrium on turbine engine performance for various fuels and combustor temperatures

    NASA Technical Reports Server (NTRS)

    Tran, Donald H.; Snyder, Christopher A.

    1992-01-01

    A study was performed to quantify the differences in turbine engine performance with and without the chemical dissociation effects for various fuel types over a range of combustor temperatures. Both turbojet and turbofan engines were studied with hydrocarbon fuels and cryogenic, nonhydrocarbon fuels. Results of the study indicate that accuracy of engine performance decreases when nonhydrocarbon fuels are used, especially at high temperatures where chemical dissociation becomes more significant. For instance, the deviation in net thrust for liquid hydrogen fuel can become as high as 20 percent at 4160 R. This study reveals that computer central processing unit (CPU) time increases significantly when dissociation effects are included in the cycle analysis.

  19. Laminar or turbulent boundary-layer flows of perfect gases or reacting gas mixtures in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Anderson, E. C.; Lewis, C. H.

    1971-01-01

    Turbulent boundary layer flows of non-reacting gases are predicted for both interal (nozzle) and external flows. Effects of favorable pressure gradients on two eddy viscosity models were studied in rocket and hypervelocity wind tunnel flows. Nozzle flows of equilibrium air with stagnation temperatures up to 10,000 K were computed. Predictions of equilibrium nitrogen flows through hypervelocity nozzles were compared with experimental data. A slender spherically blunted cone was studied at 70,000 ft altitude and 19,000 ft/sec. in the earth's atmosphere. Comparisons with available experimental data showed good agreement. A computer program was developed and fully documented during this investigation for use by interested individuals.

  20. Atomistic modeling of thermodynamic equilibrium and polymorphism of iron

    NASA Astrophysics Data System (ADS)

    Lee, Tongsik; Baskes, Michael I.; Valone, Steven M.; Doll, J. D.

    2012-06-01

    We develop two new modified embedded-atom method (MEAM) potentials for elemental iron, intended to reproduce the experimental phase stability with respect to both temperature and pressure. These simple interatomic potentials are fitted to a wide variety of material properties of bcc iron in close agreement with experiments. Numerous defect properties of bcc iron and bulk properties of the two close-packed structures calculated with these models are in reasonable agreement with the available first-principles calculations and experiments. Performance at finite temperatures of these models has also been examined using Monte Carlo simulations. We attempt to reproduce the experimental iron polymorphism at finite temperature by means of free energy computations, similar to the procedure previously pursued by Müller et al (2007 J. Phys.: Condens. Matter 19 326220), and re-examine the adequacy of the conclusion drawn in the study by addressing two critical aspects missing in their analysis: (i) the stability of the hcp structure relative to the bcc and fcc structures and (ii) the compatibility between the temperature and pressure dependences of the phase stability. Using two MEAM potentials, we are able to represent all of the observed structural phase transitions in iron. We discuss that the correct reproductions of the phase stability among three crystal structures of iron with respect to both temperature and pressure are incompatible with each other due to the lack of magnetic effects in this class of empirical interatomic potential models. The MEAM potentials developed in this study correctly predict, in the bcc structure, the self-interstitial in the <110> orientation to be the most stable configuration, and the screw dislocation to have a non-degenerate core structure, in contrast to many embedded-atom method potentials for bcc iron in the literature.

  1. Chemical modeling of exoplanet atmospheres

    NASA Astrophysics Data System (ADS)

    Venot, O.; Agúndez, M.

    2015-12-01

    The past twenty years have revealed the diversity of planets that exist in the Universe. It turned out that most of exoplanets are different from the planets of our Solar System and thus, everything about them needs to be explored. Thanks to current observational technologies, we are able to determine some information about the atmospheric composition the thermal structure and the dynamics of these exoplanets, but many questions remain still unanswered. To improve our knowledge about exoplanetary systems, more accurate observations are needed and that is why the Exoplanet Characterisation Observatory (EChO) is an essential space mission. Thanks to its large spectral coverage and high spectral resolution, EChO will provide exoplanetary spectra with an unprecedented accuracy, allowing to improve our understanding of exoplanets. In this work, we review what has been done to date concerning the chemical modeling of exoplanet atmospheres and what are the main characteristics of warm exoplanet atmospheres, which are one of the main targets of EChO. Finally we will present the ongoing developments that are necessary for the chemical modeling of exoplanet atmospheres.

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

    NASA Astrophysics Data System (ADS)

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

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

  3. MODELING MULTICOMPONENT ORGANIC CHEMICAL TRANSPORT IN THREE-FLUID-PHASE POROUS MEDIA

    EPA Science Inventory

    A two dimensional finite-element model was developed to predict coupled transient flow and multicomponent transport of organic chemicals which can partition between NAPL, water, gas and solid phases in porous media under the assumption of local chemical equilibrium. as-phase pres...

  4. Equilibrium and thermodynamic studies of Cd (II) biosorption by chemically modified orange peel.

    PubMed

    Kumar, Arbind; Kumar, Vipin

    2016-03-01

    Agricultural wastes have great potential of removing heavy metal ions from aqueous solution. Removal of Cd (II) from aqueous solutions onto chemically modified orange peel was studied at different pH, contact time, initial metal concentrations, adsorbent doses and temperature. Batch experiments were carried out under optimized conditions to evaluate the adsorption capacity of orange peel chemically modified with NaOH. The results showed that maximum adsorption capacity of modified orange peel, approximately 97.0%, was observed 3 mg 1⁻¹ of initial Cd(II) concentration pH 6 for 4 g 1⁻¹ adsorbent dosage, 200 min contact time and 298 K temperature. Adsorption efficiency of modified orange peel decreased with increase in temperature indicated exothermic nature of adsorption. A negative value of ΔG⁰(-8.59 kJ mol⁻¹) confirmed the feasibility of adsorption process and spontaneous nature of adsorption. A negative value of ΔH⁰ (-28.08 kJ mol⁻¹) indicated exothermic nature while a negative ΔS⁰ (-66.86 J K⁻¹ mol⁻¹) value suggested decrease in degree of freedom of the adsorbed species. The results showed that biosorption process of Cd(II) ions by chemically modified orange peel is feasible, spontaneous and exothermic under studied conditions. Chemically by modified orange peel investigated in the present study showed good potential for the removal of cadmium from aqueous solutions. PMID:27097438

  5. Modelling Coral Biomineralization: Mixed Kinetic/Equilibrium Trace Element Coprecipitation Models Reveal new Complexity

    NASA Astrophysics Data System (ADS)

    Sinclair, D. J.; Risk, M.

    2004-12-01

    A mixed kinetic/equilibrium steady state model of trace-element co-precipitation in coral skeleton is presented, and tested against high spatial resolution observations of coral trace-element composition made previously by LA-ICP-MS. The model is implemented in PHREEQC, and simulates physicochemical precipitation from a small pocket of seawater which is isolated by the coral, and modified by enzyme exchange of 2 H+ for Ca2+. The model assumes that all aqueous trace-element species in the calcifying fluid are in full equilibrium and that selected trace element species compete kinetically for precipitation with the major aqueous species (Ca2+ for cation substituents and CO32- for anion substituents). No equilibrium is assumed for the CaCO3 skeleton. Carbon is supplied to the system by diffusion of CO2 into the high-pH calcifying fluid, and trace elements are continuously replenished through the addition of fresh seawater. The rate at which the coral operates the enzyme pump, and the rate at which it replenishes the seawater component are independent variables, and the steady state trace-element composition of the skeleton/calcifying fluid are evaluated over a 2D grid of variables spanning realistic rates of pumping and seawater influx. It is assumed that variations in the trace element composition of the coral skeleton are the result of shifts in the steady-state caused by changes to these variables. The results indicate an unexpected complexity in the response of the trace elements. First order predictions suggest that increasing the rate of calcification by increasing the enzyme pumping should result in a mutual dilution of most trace element species by pumped Ca2+ and diffused CO2. However, for high rates of pumping and low seawater replenishment, the model predicts a change in the trace-element response of the system as high CO32- concentrations drive calcification and deplete Ca2+. This added complexity makes rationalizing observations with models more difficult.

  6. Kinetic model of continuous-wave flow chemical lasers

    NASA Astrophysics Data System (ADS)

    Gao, Z.; X., E.

    1982-02-01

    A kinetic approach to modeling the gain in a chemical wave continuous laser when the lasing frequency is coincident with the center of the line shape is presented. Governing equations are defined for the relaxing behavior of an initially nonequilibrium distribution toward the local equilibrium Boltzmann-Maxwellian distribution. A new gain is introduced which is related to the thermal motion of the molecules and cold-reaction and premixed CW models are discussed. Coincidence of the lasing frequency with the line shape is demonstrated to result in a radiative intensity within the homogeneous broadening limit. The rate model predictions are compared with those of the kinetic model. It is found that when the broadening parameter is less than 0.2 the kinetic model more accurately describes the behavior of the CW chemical laser.

  7. Diffusive equilibrium models for the height region above the F2 peak

    NASA Astrophysics Data System (ADS)

    Leitinger, R.; Radicella, S.; Hochegger, G.; Nava, B.

    The International Reference Ionosphere (IRI, see, e.g., Bilitza et al., 1993) does not take full advantage of (geo)physical relations in modelling the topside F region. This approach corresponds to the original IRI concept to provide a purely empirical model. Since O +H + diffusive equilibrium is a very good approximation for the upper F region above about 600 km, we should make use of this geophysical relation to model the topside of the ionosphere. This was done for the "family" of "profiler" models developed at Graz and Trieste. Cost prof uses height aligned O +H + diffusive equilibrium with 3 modeled parameters: the O + plasma scale height at the F2 peak, its height gradient, and the O +H + transition height. A peak is forced by using a Chapman layer formulation. NeUoG—plas uses a magnetic field aligned continuation of H + diffusive equilibrium above a plasmasphere foot height of 2000 km. NeQuick applies the diffusive equilibrium concept in a simplified way by using an Epstein layer formulation, with a height dependence for the thickness parameter. The parameters that are used to calculate the topside in the three profilers are modeled from observed data.

  8. Field-aligned Electron Density Measurements and Comparison with Diffusive Equilibrium Models

    NASA Astrophysics Data System (ADS)

    Ozhogin, P.; Song, P.; Tu, J.; Reinisch, B. W.

    2012-12-01

    The diffusive equilibrium model describes the electron and ion densities along the magnetic field line in the plasmasphere and has been widely used in, for example, ray tracing and pitch-angle scattering calculations. It is based on the hydrostatic equilibrium with the electrostatic force that acts on ions and electrons along geomagnetic field lines while there is actually no motion or diffusion of the plasma involved. The model requires multiple input parameters: electron density and ion composition (H+, He+, O+) at a base level for a magnetic field line in the ionosphere, and the (electron or ion) temperature in the plasmasphere. It has been recognized that these input parameters have to be flexible from one field line to another so that the model output does not contradict some known observed relationship. However, while the flexibility provides the possibility to fit any individual observed density distribution which is measured across many different field lines, the model prediction becomes questionable along a single field line. Since the plasma density measurements along a single field line were not available until recently, the validity of the diffusive equilibrium models has not been verified independently. This study is to investigate both qualitatively and quantitatively whether the fundamental functional form of the diffusive equilibrium model can be useful and consistent with a large database of field-aligned electron density distributions from the radio plasma imager (RPI) instrument onboard the IMAGE satellite.

  9. A general equilibrium model of a production economy with asset markets

    NASA Astrophysics Data System (ADS)

    Raberto, Marco; Teglio, Andrea; Cincotti, Silvano

    2006-10-01

    In this paper, a general equilibrium model of a monetary production economy is presented. The model is characterized by three classes of agents: a representative firm, heterogeneous households, and the government. Two markets (i.e., a labour market and a goods market, are considered) and two assets are traded in exchange of money, namely, government bonds and equities. Households provide the labour force and decide on consumption and savings, whereas the firm provides consumption goods and demands labour. The government receives taxes from households and pays interests on debt. The Walrasian equilibrium is derived analytically. The dynamics through quantity constrained equilibria out from the Walrasian equilibrium is also studied by means of computer simulations.

  10. Investigating the Chemical Evolution of the Universe via Numerical Simulations: Supernova Dust Destruction and Non-Equilibrium Ionization Chemistry

    NASA Astrophysics Data System (ADS)

    Silvia, Devin W.

    2013-12-01

    The chemical evolution of the Universe is a complicated process with countless facets that define its properties over the course of time. In the early Universe, the metal-free first stars were responsible for originally introducing metals into the pristine gas left over from the Big Bang. Once these metals became prevalent, they forever altered the thermodynamics of the Universe. Understanding precisely where these metals originated, where they end up, and the conditions they experience along the way is of great interest in the astrophysical community. In this work, I have used numerical simulations as a means of understanding two separate phenomena related to the chemical evolution the Universe. The first topic focuses on the question as to whether or not core-collapse supernovae in the high-redshift universe are capable of being "dust factories" for the production of galactic dust. To achieve this, I carried out idealized simulations of supernova ejecta clouds being impacted by reverse-shock blast waves. By post-processing the results of these simulations, I was able to estimate the amount of dust destruction that would occur due to thermal sputtering. In the most extreme scenarios, simulated with high relative velocities between the shock and the ejecta cloud and high gas metallicities, I find complete destruction for some grains species and only 44% dust mass survival for even the most robust species. This raises the question as to whether or not high-redshift supernova can produce dust masses in sufficient excess of the ˜1 Msun per event required to match observations of high-z galaxies. The second investigation was driven by the desire to find an answer to the missing baryon problem and a curiosity as to the impact that including a full non-equilibrium treatment of ionization chemistry has on simulations of the intergalactic medium. To address these questions, I have helped to develop Dengo, a new software package for solving complex chemical networks. Once

  11. Towards a Global Model of Equilibrium Solar Behavior: the Tachocline as a trans-Alfenic Feature

    NASA Astrophysics Data System (ADS)

    Gunderson, L.

    2015-12-01

    Observations and simulations suggest that thermal wind balance holds to lowest order in the solar convection zone (SCZ), and an analytic model of solar rotation has been developed by further assuming a functional relationship between the entropy and rotation. Below the SCZ, analytic arguments and simulations have implicated the necessity of a large poloidal field in the deep solar interior for the thin structure of the tachocline. We seek to unify these pictures and find a global equilibrium base state of solar behavior by starting from the exact solution to axisymmetric ideal MHD, the generalized Grad-Shafranov equation, thereby including magnetic field and poloidal flow from the onset. We find that a tachocline-like structure naturally arises as an equilibrium feature if the poloidal Alfvénic Mach number approaches unity near the bottom of the SCZ. FLOW, a code developed to analyze tokamak equilibrium with arbitrary flow, has been adapted for use in the solar regime and used to examine effects of magnetic field and meridional flow. The next steps include constructing a global equilibrium and establishing linear stability. Considering slow perturbations to equilibrium by transport and dissipation provides connections to global solar cycle models (e.g. Babcock-Leighton dynamos).

  12. A coupled implicit method for chemical non-equilibrium flows at all speeds

    NASA Technical Reports Server (NTRS)

    Shuen, Jian-Shun; Chen, Kuo-Huey; Choi, Yunho

    1993-01-01

    The present time-accurate coupled-solution procedure addresses the chemical nonequilibrium Navier-Stokes equations over a wide Mach-number range uses, in conjunction with the strong conservation form of the governing equations, five unknown primitive variables. The numerical tests undertaken address steady convergent-divergent nozzle flows with air dissociation/recombination, dump combustor flows with n-pentane/air chemistry, and unsteady nonreacting cavity flows.

  13. Non-equilibrium STLS approach to transport properties of single impurity Anderson model

    SciTech Connect

    Rezai, Raheleh Ebrahimi, Farshad

    2014-04-15

    In this work, using the non-equilibrium Keldysh formalism, we study the effects of the electron–electron interaction and the electron-spin correlation on the non-equilibrium Kondo effect and the transport properties of the symmetric single impurity Anderson model (SIAM) at zero temperature by generalizing the self-consistent method of Singwi, Tosi, Land, and Sjolander (STLS) for a single-band tight-binding model with Hubbard type interaction to out of equilibrium steady-states. We at first determine in a self-consistent manner the non-equilibrium spin correlation function, the effective Hubbard interaction, and the double-occupancy at the impurity site. Then, using the non-equilibrium STLS spin polarization function in the non-equilibrium formalism of the iterative perturbation theory (IPT) of Yosida and Yamada, and Horvatic and Zlatic, we compute the spectral density, the current–voltage characteristics and the differential conductance as functions of the applied bias and the strength of on-site Hubbard interaction. We compare our spectral densities at zero bias with the results of numerical renormalization group (NRG) and depict the effects of the electron–electron interaction and electron-spin correlation at the impurity site on the aforementioned properties by comparing our numerical result with the order U{sup 2} IPT. Finally, we show that the obtained numerical results on the differential conductance have a quadratic universal scaling behavior and the resulting Kondo temperature shows an exponential behavior. -- Highlights: •We introduce for the first time the non-equilibrium method of STLS for Hubbard type models. •We determine the transport properties of SIAM using the non-equilibrium STLS method. •We compare our results with order-U2 IPT and NRG. •We show that non-equilibrium STLS, contrary to the GW and self-consistent RPA, produces the two Hubbard peaks in DOS. •We show that the method keeps the universal scaling behavior and correct

  14. A new model of equilibrium subsurface hydration on Mars

    NASA Astrophysics Data System (ADS)

    Hecht, M. H.

    2011-12-01

    One of the surprises of the Odyssey mission was the discovery by the Gamma Ray Spectrometer (GRS) suite of large concentrations of water-equivalent hydrogen (WEH) in the shallow subsurface at low latitudes, consistent with 5-7% regolith water content by weight (Mitrofanov et al. Science 297, p. 78, 2002; Feldman et al. Science 297, p. 75, 2002). Water at low latitudes on Mars is generally believed to be sequestered in the form of hydrated minerals. Numerous attempts have been made to relate the global map of WEH to specific mineralogy. For example Feldman et al. (Geophys. Res. Lett., 31, L16702, 2004) associated an estimated 10% sulfate content of the soil with epsomite (51% water), hexahydrite (46% water) and kieserite (13% water). In such studies, stability maps have been created by assuming equilibration of the subsurface water vapor density with a global mean annual column mass vapor density. Here it is argued that this value significantly understates the subsurface humidity. Results from the Phoenix mission are used to suggest that the midday vapor pressure measured just above the surface is a better proxy for the saturation vapor pressure of subsurface hydrous minerals. The measured frostpoint at the Phoenix site was found to be equal to the surface temperature by night and the modeled temperature at the top of the ice table by day (Zent et al. J. Geophys. Res., 115, E00E14, 2010). It was proposed by Hecht (41st LPSC abstract #1533, 2010) that this phenomenon results from water vapor trapping at the coldest nearby surface. At night, the surface is colder than the surface of the ice table; by day it is warmer. Thus, at night, the subsurface is bounded by a fully saturated layer of cold water frost or adsorbed water at the surface, not by the dry boundary layer itself. This argument is not strongly dependent on the particular saturation vapor pressure (SVP) of ice or other subsurface material, only on the thickness of the dry layer. Specifically, the diurnal

  15. Evaluating the diffusive equilibrium models: Comparison with the IMAGE RPI field-aligned electron density measurements

    NASA Astrophysics Data System (ADS)

    Ozhogin, P.; Song, P.; Tu, J.; Reinisch, B. W.

    2014-06-01

    The diffusive equilibrium models that are widely used by the space physics community to describe the plasma densities in the plasmasphere are evaluated with field-aligned electron density measurements from the radio plasma imager (RPI) instrument onboard the IMAGE satellite. The original mathematical form of the diffusive equilibrium model was based on the hydrostatic equilibrium along the magnetic field line with the centrifugal force and the field-aligned electrostatic force as well as a large number of simplifying approximations. Six free parameters in the mathematical form have been conventionally determined from observations. We evaluate four sets of the parameters that have been reported in the literature. The evaluation is made according to the equatorial radial distance dependence, latitudinal dependence at a given radial distance, and the combined radial and latitudinal dependences. We find that the mathematical form given in the diffusive equilibrium model is intrinsically incompatible with the measurements unless another large number of free parameters are artificially introduced, which essentially changes the nature of a theoretical model to an empirical model.

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

    PubMed

    Lehnert, A L; Kearfott, K J

    2010-08-01

    Radon in indoor air is often measured using canisters of activated charcoal that function by adsorbing radon gas. The use of a diffusion barrier charcoal canister (DBCC) minimizes the effects of environmental humidity and extends the useful exposure time by several days. Many DBCC protocols model charcoal canisters as simple integrating detectors, which introduces errors due to the fact that radon uptake changes over the exposure period. Errors are compensated for by calculating a calibration factor that is nonlinear with respect to exposure time. This study involves the development and testing of an equilibrium-based model and corresponding measurement protocol that treats the charcoal canisters as a system coming into equilibrium with the surrounding radon environment. This model applies to both constant and temporally varying radon concentration situations, which was essential, as efforts are currently underway using a temporally varying radon chamber. It was found that the DBCCs equilibrate following the relationship E = (1 - e) where E is a measure of how close the DBCC is to equilibrium, t is exposure time, and q is the equilibration constant. This equilibration constant was empirically determined to be 0.019 h. The proposed model was tested in a blind test as well as compared with the currently accepted U.S. Environmental Protection Agency (U.S. EPA) model. Comparisons between the two methods showed a slight decrease in measurement error when using the equilibrium-based method as compared to the U.S. EPA method. PMID:20622564

  17. A chemical model for the interstellar medium in galaxies

    NASA Astrophysics Data System (ADS)

    Bovino, S.; Grassi, T.; Capelo, Pedro R.; Schleicher, D. R. G.; Banerjee, R.

    2016-05-01

    Aims: We present and test chemical models for three-dimensional hydrodynamical simulations of galaxies. We explore the effect of changing key parameters such as metallicity, radiation, and non-equilibrium versus equilibrium metal cooling approximations on the transition between the gas phases in the interstellar medium. Methods: The microphysics was modelled by employing the public chemistry package KROME, and the chemical networks were tested to work in a wide range of densities and temperatures. We describe a simple H/He network following the formation of H2 and a more sophisticated network that includes metals. Photochemistry, thermal processes, and different prescriptions for the H2 catalysis on dust are presented and tested within a one-zone framework. The resulting network is made publicly available on the KROME webpage. Results: We find that employing an accurate treatment of the dust-related processes induces a faster HI-H2 transition. In addition, we show when the equilibrium assumption for metal cooling holds and how a non-equilibrium approach affects the thermal evolution of the gas and the HII-HI transition. Conclusions: These models can be employed in any hydrodynamical code via an interface to KROME and can be applied to different problems including isolated galaxies, cosmological simulations of galaxy formation and evolution, supernova explosions in molecular clouds, and the modelling of star-forming regions. The metal network can be used for a comparison with observational data of CII 158 μm emission both for high-redshift and for local galaxies.

  18. Upwind differencing and LU factorization for chemical non-equilibrium Navier-Stokes equations

    NASA Technical Reports Server (NTRS)

    Shuen, Jian-Shun

    1992-01-01

    By means of either the Roe or the Van Leer flux-splittings for inviscid terms, in conjunction with central differencing for viscous terms in the explicit operator and the Steger-Warming splitting and lower-upper approximate factorization for the implicit operator, the present, robust upwind method for solving the chemical nonequilibrium Navier-Stokes equations yields formulas for finite-volume discretization in general coordinates. Numerical tests in the illustrative cases of a hypersonic blunt body, a ramped duct, divergent nozzle flows, and shock wave/boundary layer interactions, establish the method's efficiency.

  19. Detection of interstellar DNC - Difficulties of chemical equilibrium hypothesis for enrichment

    NASA Technical Reports Server (NTRS)

    Godfrey, P. D.; Brown, R. D.; Gunn, H. I.; Blackman, G. L.; Storey, J. W. V.

    1977-01-01

    The J = 1-0 transition of DNC at 76.3058 GHz has been observed in emission in NGC 2264. Comparison with previous observations of HN(C-13) indicates that deuterium is enriched in DNC similarly to the enrichment reported for DCO(+) in this source. The DNC/HNC ratio is estimated to be about 1/24. The results cannot readily be interpreted in terms of chemical equilibria relating to the formation of DNC. It is suggested that the explanation must be sought in isotope effects on rates of formation of interstellar molecules.

  20. Modeling the hot-dense plasma of the solar interior in and out of thermal equilibrium

    NASA Astrophysics Data System (ADS)

    Lin, Hsiao-Hsuan

    The developments in helioseismology ensure a wealth of studies in solar physics. In particular, with the high precision of the observations of helioseismology, a high-quality solar model is mandated, since even the tiny deviations between a model and the real Sun can be detected. One crucial ingredient of any solar model is the thermodynamics of hot-dense plasmas, in particular the equation of state. This has motivated efforts to develop sophisticated theoretical equations of state (EOS). It is important to realize that for the conditions of solar-interior plasmas, there are no terrestrial laboratory experiments; the only observational constraints come from helioseismology. Among the most successful EOS is so called OPAL EOS, which is part of the Opacity Project at Livermore. It is based on an activity expansion of the quantum plasma, and realized in the so-called "physical picture". One of its main competitor is the so called MHD EOS, which is part of the international Opacity Project (OP), a non-classified multi-country consortium. The approach of MHD is via the so-called "chemical picture". Since OPAL is the most accurate equation of state so far, there has been a call for a public-domain version of it. However, the OPAL code remains proprietary, and its "emulation" makes sense. An additional reason for such a project is that the results form OPAL can only be accessed via tables generated by the OPAL team. Their users do not have the flexibility to change the chemical composition from their end. The earlier MHD-based OPAL emulator worked well with its modifications of the MHD equation of state, which is the Planck-Larkin partition function and its corresponding scattering terms. With this modification, MHD can serve as a OPAL emulator with all the flexibility and accessibility. However, to build a really user-friendly OPAL emulator one should consider CEFF-based OPAL emulator. CEFF itself is already widely used practical EOS which can be easily implemented

  1. A grain scale non-equilibrium sediment transport model for unsteady flow

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A one dimensional (1-D) finite-volume model was developed for simulating non-equilibrium sediment transport in unsteady flow. The governing equations are the 1-D St. Venant equations for sediment-laden flow and the Exner equation including both bed load and suspended-load transport. The Rouse profil...

  2. Development and validation of an equilibrium model for struvite formation with calcium co-precipitation

    NASA Astrophysics Data System (ADS)

    Lee, Sang-Hun; Yoo, Byeoung-Hak; Lim, Seung Joo; Kim, Tak-Hyun; Kim, Sun-Kyoung; Kim, Jun Young

    2013-06-01

    This study developed an equilibrium model to predict the P recovery and struvite amounts by newly incorporating two separate equilibrium constants on the struvite formation with HPO42- and PO43-, as well as free ammonium (NH4+), phosphate (PO4), magnesium (Mg2+), and calcium (Ca2+) ion species. The equilibrium struvite reaction and its solubility constant with HPO42- species was verified by deriving a reasonable correlation between solution pH and the conditional solubility products that were obtained from the equilibrium reaction. Also, based on the Visual MINTEQ software program, the potentially precipitated Ca phosphates and struvite precipitates were selected, and these compounds were utilized as target precipitants for the modeling to simulate P recovery and struvite formation under the competitive inhibition of Ca ions. The resultant simulated P recovery data were validated by experimental data with synthetic wastewater. The model data showed good agreement with the experimental results (R2>95%). The model also confirmed that the purity of struvite in the precipitate and the pH that maximizes the struvite fraction are dependent on the initial concentrations of NH4+, Mg2+, and PO4. Because only PO43-, not HPO42-, was regarded in Ca precipitation, Ca phosphate precipitation was underestimated as compared with the experimental results.

  3. Hydrodynamic Models of Line-Driven Accretion Disk Winds III: Local Ionization Equilibrium

    NASA Technical Reports Server (NTRS)

    Pereyra, Nicolas Antonio; Kallman, Timothy R.; White, Nicholas E. (Technical Monitor)

    2002-01-01

    We present time-dependent numerical hydrodynamic models of line-driven accretion disk winds in cataclysmic variable systems and calculate wind mass-loss rates and terminal velocities. The models are 2.5-dimensional, include an energy balance condition with radiative heating and cooling processes, and includes local ionization equilibrium introducing time dependence and spatial dependence on the line radiation force parameters. The radiation field is assumed to originate in an optically thick accretion disk. Wind ion populations are calculated under the assumption that local ionization equilibrium is determined by photoionization and radiative recombination, similar to a photoionized nebula. We find a steady wind flowing from the accretion disk. Radiative heating tends to maintain the temperature in the higher density wind regions near the disk surface, rather than cooling adiabatically. For a disk luminosity L (sub disk) = solar luminosity, white dwarf mass M(sub wd) = 0.6 solar mass, and white dwarf radii R(sub wd) = 0.01 solar radius, we obtain a wind mass-loss rate of M(sub wind) = 4 x 10(exp -12) solar mass yr(exp -1) and a terminal velocity of approximately 3000 km per second. These results confirm the general velocity and density structures found in our earlier constant ionization equilibrium adiabatic CV wind models. Further we establish here 2.5D numerical models that can be extended to QSO/AGN winds where the local ionization equilibrium will play a crucial role in the overall dynamics.

  4. Exact results for spatiotemporal correlations in a self-organized critical model of punctuated equilibrium

    SciTech Connect

    Boettcher, S.; Paczuski, M.

    1996-01-01

    We introduce a self-organized critical model of punctuated equilibrium with many internal degrees of freedom ({ital M}) per site. We find exact solutions for {ital M}{r_arrow}{infinity} of cascade equations describing avalanche dynamics in the steady state. This proves the existence of simple power laws with critical exponents that verify general scaling relations for nonequilibrium phenomena. Punctuated equilibrium is described by a devil{close_quote}s staircase with a characteristic exponent {tau}{sub first}=2{minus}{ital d}/4 where {ital d} is the spatial dimension. {copyright} {ital 1996 The American Physical Society.}

  5. Equilibrium microphase separation in the two-leaflet model of lipid membranes

    NASA Astrophysics Data System (ADS)

    Reigada, Ramon; Mikhailov, Alexander S.

    2016-01-01

    Because of the coupling between local lipid composition and the thickness of the membrane, microphase separation in two-component lipid membranes can take place; such effects may underlie the formation of equilibrium nanoscale rafts. Using a kinetic description, this phenomenon is analytically and numerically investigated. The phase diagram is constructed through the stability analysis for linearized kinetic equations, and conditions for microphase separation are discussed. Simulations of the full kinetic model reveal the development of equilibrium membrane nanostructures with various morphologies from the initial uniform state.

  6. Relevant Models of Equilibrium Structures in One-Phase Regimes of Microemulsions.

    NASA Astrophysics Data System (ADS)

    Edwards, M. E.

    2000-11-01

    Although several studies have focused on equilibrium structures--domains--in one-phase regimes of dilutive microemulsions, the structures have not been completely determined. Here, we review the relevant continuum-statistical and continuum-mechanical models with the ultimate objective of their extension or modification. Presently, the models describe single droplet domains, two interacting droplets or dimer constructions, and thermal fluctuation description. Also, we present the rudiments of an interaction model which considers the undulations of two ellipsoidal droplets. A satisfactory model of equilibrium structures is essential if we are to further elucidate the behavior of microemulsions in various environments, such as, the case of microemulsions being located in a pulsed, external electric field: the phenomenon of static electro-optical Kerr effect. Currently, variations exist between relevant models and experimental results.

  7. Development of a bi-equilibrium model for biomass gasification in a downdraft bed reactor.

    PubMed

    Biagini, Enrico; Barontini, Federica; Tognotti, Leonardo

    2016-02-01

    This work proposes a simple and accurate tool for predicting the main parameters of biomass gasification (syngas composition, heating value, flow rate), suitable for process study and system analysis. A multizonal model based on non-stoichiometric equilibrium models and a repartition factor, simulating the bypass of pyrolysis products through the oxidant zone, was developed. The results of tests with different feedstocks (corn cobs, wood pellets, rice husks and vine pruning) in a demonstrative downdraft gasifier (350kW) were used for validation. The average discrepancy between model and experimental results was up to 8 times less than the one with the simple equilibrium model. The repartition factor was successfully related to the operating conditions and characteristics of the biomass to simulate different conditions of the gasifier (variation in potentiality, densification and mixing of feedstock) and analyze the model sensitivity. PMID:26642221

  8. An Equilibrium Model for the Combined Effect of Macromolecular Crowding and Surface Adsorption on the Formation of Linear Protein Fibrils

    PubMed Central

    Hoppe, Travis; Minton, Allen P.

    2015-01-01

    The formation of linear protein fibrils has previously been shown to be enhanced by volume exclusion or crowding in the presence of a high concentration of chemically inert protein or polymer, and by adsorption to membrane surfaces. An equilibrium mesoscopic model for the combined effect of both crowding and adsorption upon the fibrillation of a dilute tracer protein is presented. The model exhibits behavior that differs qualitatively from that observed in the presence of crowding or adsorption alone. The model predicts that in a crowded solution, at critical values of the volume fraction of crowder or intrinsic energy of the tracer-wall interaction, the tracer protein will undergo an extremely cooperative transition—approaching a step function—from existence as a slightly self-associated species in solution to existence as a highly self-associated and completely adsorbed species. Criteria for a valid experimental test of these predictions are presented. PMID:25692600

  9. Chemical Modeling of Cometary Anions

    NASA Astrophysics Data System (ADS)

    Cordiner, Martin; Charnley, S. B.

    2009-09-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of 1P/Halley. The anions O-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not previously been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydrodynamical model of Rodgers & Charnley (2002), we investigate the role of the hydrocarbon and nitrile anions Cn-, CnH- and CnN- in the coma. We calculate the effects of these anions on the charge balance and examine their impact on cometary coma chemistry. References: Chaizy, P. et al. 1991, Nature, 349, 393 Rodgers, S.D. & Charnley, S.B. 2002, MNRAS, 330, 660

  10. General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions

    NASA Technical Reports Server (NTRS)

    Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

    1951-01-01

    A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

  11. CHEMICAL AND PHYSICAL PROCESS AND MECHANISM MODELING

    EPA Science Inventory

    The goal of this task is to develop and test chemical and physical mechanisms for use in the chemical transport models of EPA's Models-3. The target model for this research is the Community Multiscale Air Quality (CMAQ) model. These mechanisms include gas and aqueous phase ph...

  12. Adaptive behaviour and multiple equilibrium states in a predator-prey model.

    PubMed

    Pimenov, Alexander; Kelly, Thomas C; Korobeinikov, Andrei; O'Callaghan, Michael J A; Rachinskii, Dmitrii

    2015-05-01

    There is evidence that multiple stable equilibrium states are possible in real-life ecological systems. Phenomenological mathematical models which exhibit such properties can be constructed rather straightforwardly. For instance, for a predator-prey system this result can be achieved through the use of non-monotonic functional response for the predator. However, while formal formulation of such a model is not a problem, the biological justification for such functional responses and models is usually inconclusive. In this note, we explore a conjecture that a multitude of equilibrium states can be caused by an adaptation of animal behaviour to changes of environmental conditions. In order to verify this hypothesis, we consider a simple predator-prey model, which is a straightforward extension of the classic Lotka-Volterra predator-prey model. In this model, we made an intuitively transparent assumption that the prey can change a mode of behaviour in response to the pressure of predation, choosing either "safe" of "risky" (or "business as usual") behaviour. In order to avoid a situation where one of the modes gives an absolute advantage, we introduce the concept of the "cost of a policy" into the model. A simple conceptual two-dimensional predator-prey model, which is minimal with this property, and is not relying on odd functional responses, higher dimensionality or behaviour change for the predator, exhibits two stable co-existing equilibrium states with basins of attraction separated by a separatrix of a saddle point. PMID:25732186

  13. An equilibrium model for chloride removal from recycled cooling water using the ultra-high lime with aluminum process.

    PubMed

    Abdel-Wahab, Ahmed; Batchelor, Bill; Schwantes, Jon

    2005-01-01

    Removal of chloride from recycled cooling water is needed to reduce corrosion and prolong equipment life. Laboratory experiments have demonstrated that the ultra-high lime with aluminum (UHLA) process has the ability to achieve high chloride removal efficiency from recycled cooling water. In an effort to further understand the behavior of chloride in the UHLA process, a fundamental model of the chemical processes was developed. The purpose of this paper is to describe this equilibrium model and present values for solubility products of precipitated solids that have not been investigated previously. The model was based on PHREEQC and a new program called INVRS K was integrated with PHREEQC to calculate values of unknown or poorly defined equilibrium or kinetic constants using a Gauss-Newton nonlinear regression routine. Model predictions indicated that the results could be best described by assuming the formation of a solid solution of calcium chloroaluminate (Ca4Al2Cl2OH12), tricalcium hydroxyaluminate (Ca3Al2OH12), and tetracalcium hydroxyaluminate (Ca4Al2OH14). PMID:16381154

  14. Punctuated-equilibrium model of biological evolution is also a self-organized-criticality model of earthquakes

    NASA Astrophysics Data System (ADS)

    Ito, Keisuke

    1995-09-01

    Bak and Sneppen proposed a self-organized-criticality model to explain the punctuated equilibrium of biological evolution. The model, as it is, is a good self-organized-criticality model of earthquakes. Real earthquakes satisfy the required conditions of criticality; that is, power laws in (1) the size distribution of earthquakes, and (2) both the spatial and the temporal correlation functions.

  15. 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.

  16. Econometrics and data of the 9 sector Dynamic General Equilibrium Model. Volume III. Final report

    SciTech Connect

    Berndt, E.R.; Fraumeni, B.M.; Hudson, E.A.; Jorgenson, D.W.; Stoker, T.M.

    1981-03-01

    This report presents the econometrics and data of the 9 sector Dynamic General Equilibrium Model. There are two key components of 9DGEM - the model of household behavior and the model of produconcrneer behavior. The household model is concerned with decisions on consumption, saving, labor supply and the composition of consumption. The producer model is concerned with output price formation and determination of input patterns and purchases for each of the nine producing sectors. These components form the behavioral basis of DGEM. The remaining components are concerned with constraints, balance conditions, accounting, and government revenues and expenditures (these elements are developed in the report on the model specification).

  17. PACKAGE (Plasma Analysis, Chemical Kinetics and Generator Efficiency): a computer program for the calculation of partial chemical equilibrium/partial chemical rate controlled composition of multiphased mixtures under one dimensional steady flow

    SciTech Connect

    Yousefian, V.; Weinberg, M.H.; Haimes, R.

    1980-02-01

    The NASA CEC Code was the starting point for PACKAGE, whose function is to evaluate the composition of a multiphase combustion product mixture under the following chemical conditions: (1) total equilibrium with pure condensed species; (2) total equilibrium with ideal liquid solution; (3) partial equilibrium/partial finite rate chemistry; and (4) fully finite rate chemistry. The last three conditions were developed to treat the evolution of complex mixtures such as coal combustion products. The thermodynamic variable pairs considered are either pressure (P) and enthalpy, P and entropy, at P and temperature. Minimization of Gibbs free energy is used. This report gives detailed discussions of formulation and input/output information used in the code. Sample problems are given. The code development, description, and current programming constraints are discussed. (DLC)

  18. A local noncircular equilibrium model and its application to residual zonal flow calculations

    SciTech Connect

    Zhou Deng; Yu Weihong

    2011-05-15

    A local up-down symmetric tokamak equilibrium model is proposed. The model, with constant plasma shape parameters, is a special case of the more general Miller's local model [R. L. Miller et al., Phys. Plasmas 5, 973 (1998)]. Correspondingly, the equilibrium is determined only by a given reference flux surface, the local safety factor, the local pressure profile, and the profile of local toroidal field function. Although it is not complete, the model is particularly suitable for analytically investigating the effect of plasma shape factors on the radially localized plasma modes, like reversed shear Alfvenic eigenmodes, ballooning mode, etc. As an example of the application, the residual zonal flow in a shaped plasma is evaluated, and the result is in qualitative agreement with the previous investigations.

  19. Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations. Interim Revision, March 1976

    NASA Technical Reports Server (NTRS)

    Gordon, S.; Mcbride, B. J.

    1976-01-01

    A detailed description of the equations and computer program for computations involving chemical equilibria in complex systems is given. A free-energy minimization technique is used. The program permits calculations such as (1) chemical equilibrium for assigned thermodynamic states (T,P), (H,P), (S,P), (T,V), (U,V), or (S,V), (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. The program considers condensed species as well as gaseous species.

  20. Equilibrium Statistical Mechanics and Energy Partition for the Shallow Water Model

    NASA Astrophysics Data System (ADS)

    Renaud, A.; Venaille, A.; Bouchet, F.

    2016-05-01

    The aim of this paper is to use large deviation theory in order to compute the entropy of macrostates for the microcanonical measure of the shallow water system. The main prediction of this full statistical mechanics computation is the energy partition between a large scale vortical flow and small scale fluctuations related to inertia-gravity waves. We introduce for that purpose a semi-Lagrangian discrete model of the continuous shallow water system, and compute the corresponding statistical equilibria. We argue that microcanonical equilibrium states of the discrete model in the continuous limit are equilibrium states of the actual shallow water system. We show that the presence of small scale fluctuations selects a subclass of equilibria among the states that were previously computed by phenomenological approaches that were neglecting such fluctuations. In the limit of weak height fluctuations, the equilibrium state can be interpreted as two subsystems in thermal contact: one subsystem corresponds to the large scale vortical flow, the other subsystem corresponds to small scale height and velocity fluctuations. It is shown that either a non-zero circulation or rotation and bottom topography are required to sustain a non-zero large scale flow at equilibrium. Explicit computation of the equilibria and their energy partition is presented in the quasi-geostrophic limit for the energy-enstrophy ensemble. The possible role of small scale dissipation and shocks is discussed. A geophysical application to the Zapiola anticyclone is presented.

  1. ASHEE-1.0: a compressible, equilibrium-Eulerian model for volcanic ash plumes

    NASA Astrophysics Data System (ADS)

    Cerminara, M.; Esposti Ongaro, T.; Berselli, L. C.

    2016-02-01

    A new fluid-dynamic model is developed to numerically simulate the non-equilibrium dynamics of polydisperse gas-particle mixtures forming volcanic plumes. Starting from the three-dimensional N-phase Eulerian transport equations for a mixture of gases and solid dispersed particles, we adopt an asymptotic expansion strategy to derive a compressible version of the first-order non-equilibrium model, valid for low-concentration regimes (particle volume fraction less than 10-3) and particle Stokes number (St - i.e., the ratio between relaxation time and flow characteristic time) not exceeding about 0.2. The new model, which is called ASHEE (ASH Equilibrium Eulerian), is significantly faster than the N-phase Eulerian model while retaining the capability to describe gas-particle non-equilibrium effects. Direct Numerical Simulation accurately reproduces the dynamics of isotropic, compressible turbulence in subsonic regimes. For gas-particle mixtures, it describes the main features of density fluctuations and the preferential concentration and clustering of particles by turbulence, thus verifying the model reliability and suitability for the numerical simulation of high-Reynolds number and high-temperature regimes in the presence of a dispersed phase. On the other hand, Large-Eddy Numerical Simulations of forced plumes are able to reproduce the averaged and instantaneous flow properties. In particular, the self-similar Gaussian radial profile and the development of large-scale coherent structures are reproduced, including the rate of turbulent mixing and entrainment of atmospheric air. Application to the Large-Eddy Simulation of the injection of the eruptive mixture in a stratified atmosphere describes some of the important features of turbulent volcanic plumes, including air entrainment, buoyancy reversal and maximum plume height. For very fine particles (St → 0, when non-equilibrium effects are negligible) the model reduces to the so-called dusty-gas model. However

  2. Monte Carlo computer simulations of Venus equilibrium and global resurfacing models

    NASA Technical Reports Server (NTRS)

    Dawson, D. D.; Strom, R. G.; Schaber, G. G.

    1992-01-01

    Two models have been proposed for the resurfacing history of Venus: (1) equilibrium resurfacing and (2) global resurfacing. The equilibrium model consists of two cases: in case 1, areas less than or equal to 0.03 percent of the planet are spatially randomly resurfaced at intervals of less than or greater than 150,000 yr to produce the observed spatially random distribution of impact craters and average surface age of about 500 m.y.; and in case 2, areas greater than or equal to 10 percent of the planet are resurfaced at intervals of greater than or equal to 50 m.y. The global resurfacing model proposes that the entire planet was resurfaced about 500 m.y. ago, destroying the preexisting crater population and followed by significantly reduced volcanism and tectonism. The present crater population has accumulated since then with only 4 percent of the observed craters having been embayed by more recent lavas. To test the equilibrium resurfacing model we have run several Monte Carlo computer simulations for the two proposed cases. It is shown that the equilibrium resurfacing model is not a valid model for an explanation of the observed crater population characteristics or Venus' resurfacing history. The global resurfacing model is the most likely explanation for the characteristics of Venus' cratering record. The amount of resurfacing since that event, some 500 m.y. ago, can be estimated by a different type of Monte Carolo simulation. To date, our initial simulation has only considered the easiest case to implement. In this case, the volcanic events are randomly distributed across the entire planet and, therefore, contrary to observation, the flooded craters are also randomly distributed across the planet.

  3. Mathematical Modeling of Chemical Stoichiometry

    ERIC Educational Resources Information Center

    Croteau, Joshua; Fox, William P.; Varazo, Kristofoland

    2007-01-01

    In beginning chemistry classes, students are taught a variety of techniques for balancing chemical equations. The most common method is inspection. This paper addresses using a system of linear mathematical equations to solve for the stoichiometric coefficients. Many linear algebra books carry the standard balancing of chemical equations as an…

  4. Modeling the Spin Equilibrium of Neutron Stars in LMXBs Without Gravitational Radiation

    NASA Technical Reports Server (NTRS)

    Andersson, N.; Glampedakis, K.; Haskell, B.; Watts, A. L.

    2004-01-01

    In this paper we discuss the spin-equilibrium of accreting neutron stars in LMXBs. We demonstrate that, when combined with a naive spin-up torque, the observed data leads to inferred magnetic fields which are at variance with those of galactic millisecond radiopulsars. This indicates the need for either additional spin-down torques (eg. gravitational radiation) or an improved accretion model. We show that a simple consistent accretion model can be arrived at by accounting for radiation pressure in rapidly accreting systems (above a few percent of the Eddington accretion rate). In our model the inner disk region is thick and significantly sub-Keplerian, and the estimated equilibrium periods are such that the LMXB neutron stars have properties that accord well with the galactic millisecond radiopulsar sample. The implications for future gravitational-wave observations are also discussed briefly.

  5. Chiral ligand exchange countercurrent chromatography: Equilibrium model study on enantioseparation of mandelic acid.

    PubMed

    Tong, Shengqiang; Shen, Mangmang; Xiong, Qing; Wang, Xiaoping; Lu, Mengxia; Yan, Jizhong

    2016-05-20

    The equilibrium model in enantioseparation of mandelic acid by chiral ligand exchange countercurrent chromatography was investigated using N-n-dodecyl-l-proline as chiral ligand and cupric ion as central metal. Important parameters, including physical partition coefficient and formation constants of binary and ternary coordination complexes in the two-phase solvent system, were determined. This equilibrium model could give an excellent prediction of distribution ratio and enantioseparation factor of the analyte in the biphasic solvent system, which was further verified by experiments. All the average relative deviations were less than 12%, indicating that the established model could provide a simple computational approach for optimization of enantioseparation conditions in chiral ligand exchange countercurrent chromatography. PMID:27102304

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  7. Thermodynamic parameters for mixtures of quartz under shock wave loading in views of the equilibrium model

    SciTech Connect

    Maevskii, K. K. Kinelovskii, S. A.

    2015-10-27

    The numerical results of modeling of shock wave loading of mixtures with the SiO{sub 2} component are presented. The TEC (thermodynamic equilibrium component) model is employed to describe the behavior of solid and porous multicomponent mixtures and alloys under shock wave loading. State equations of a Mie–Grüneisen type are used to describe the behavior of condensed phases, taking into account the temperature dependence of the Grüneisen coefficient, gas in pores is one of the components of the environment. The model is based on the assumption that all components of the mixture under shock-wave loading are in thermodynamic equilibrium. The calculation results are compared with the experimental data derived by various authors. The behavior of the mixture containing components with a phase transition under high dynamic loads is described.

  8. A radiative-convective equilibrium model for young giant exoplanets: Application to GPI commissioning data

    NASA Astrophysics Data System (ADS)

    Baudino, J.-L.; Bézard, B.; Boccaletti, A.; Lagrange, A.-M.; Bonnefoy, M.; Galicher, R.

    2014-12-01

    We developed a radiative-convective equilibrium model for young giant exoplanets, in the context of direct imaging. Input parameters are the planet's surface gravity (g), effective temperature ({T_{eff}}) and elemental composition. Under the additional assumption of thermochemical equilibrium, the model predicts the equilibrium temperature profile and mixing ratio profiles of the most important gases. Opacity sources include the H_2-He collision-induced absorption and molecular lines from H_2O, CO, CH_4, NH_3, VO, TiO, Na and K. Line opacity is modeled using k-correlated coefficients pre-calculated over a fixed pressure-temperature grid. Absorption by iron and silicate cloud particles is added above the expected condensation levels with a fixed scale height and a given optical depth at some reference wavelength. Model predictions are compared with the existing photometric and spectroscopic measurements of β Pictoris b and photometric data of HD95086 b recorded during GPI commissioning. This model was developed to interpret data of the instrument SPHERE at the VLT.

  9. Modeling the economic costs of disasters and recovery: analysis using a dynamic computable general equilibrium model

    NASA Astrophysics Data System (ADS)

    Xie, W.; Li, N.; Wu, J.-D.; Hao, X.-L.

    2014-04-01

    Disaster damages have negative effects on the economy, whereas reconstruction investment has positive effects. The aim of this study is to model economic causes of disasters and recovery involving the positive effects of reconstruction activities. Computable general equilibrium (CGE) model is a promising approach because it can incorporate these two kinds of shocks into a unified framework and furthermore avoid the double-counting problem. In order to factor both shocks into the CGE model, direct loss is set as the amount of capital stock reduced on the supply side of the economy; a portion of investments restores the capital stock in an existing period; an investment-driven dynamic model is formulated according to available reconstruction data, and the rest of a given country's saving is set as an endogenous variable to balance the fixed investment. The 2008 Wenchuan Earthquake is selected as a case study to illustrate the model, and three scenarios are constructed: S0 (no disaster occurs), S1 (disaster occurs with reconstruction investment) and S2 (disaster occurs without reconstruction investment). S0 is taken as business as usual, and the differences between S1 and S0 and that between S2 and S0 can be interpreted as economic losses including reconstruction and excluding reconstruction, respectively. The study showed that output from S1 is found to be closer to real data than that from S2. Economic loss under S2 is roughly 1.5 times that under S1. The gap in the economic aggregate between S1 and S0 is reduced to 3% at the end of government-led reconstruction activity, a level that should take another four years to achieve under S2.

  10. Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

    NASA Astrophysics Data System (ADS)

    Lasheen, Mohamed R.; Ammar, Nabila S.; Ibrahim, Hanan S.

    2012-02-01

    Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd 2+, Cu 2+ and Pb 2+, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm -1 after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.

  11. Collisional radiative model for heavy atoms in hot non-local-thermodynamical-equilibrium plasmas

    NASA Astrophysics Data System (ADS)

    Bar-Shalom, A.; Oreg, J.; Klapisch, M.

    1997-07-01

    A collisional radiative model for calculating non-local-thermodynamical-equilibrium (non-LTE) spectra of heavy atoms in hot plasmas has been developed, taking into account the numerous excited and autoionizing states. This model uses superconfigurations as effective levels with an iterative procedure which converges to the detailed configuration spectrum. The non-LTE opacities and emissivities may serve as a reliable benchmark for simpler on-line models in hydrodynamic code simulations. The model is tested against detailed configuration calculations of selenium and is applied to non-LTE optically thin plasma of lutetium.

  12. Comparison of transition densities in the DDHMS model of pre-equilibrium emission

    SciTech Connect

    Brito, L.; Carlson, B. V.

    2014-11-11

    The DDHMS (double differential hybrid Monte Carlo simulation) model treats nucleon-induced pre-equilibrium reactions as a series of particle-particle and particle-hole interactions in the space of energy and angle. This work compares spectra obtained within the model using diferent approximations to the density of accessible states. The calculations are performed with the EMPIRE reaction model code, a modular system containing several nuclear reaction models that permits a fairly complete descritpion of the reaction, from elastic scattering and absorption through the pre-equilbrium stage to the final decay by statistical emission.

  13. Comparison of transition densities in the DDHMS model of pre-equilibrium emission

    NASA Astrophysics Data System (ADS)

    Brito, L.; Carlson, B. V.

    2014-11-01

    The DDHMS (double differential hybrid Monte Carlo simulation) model treats nucleon-induced pre-equilibrium reactions as a series of particle-particle and particle-hole interactions in the space of energy and angle. This work compares spectra obtained within the model using diferent approximations to the density of accessible states. The calculations are performed with the EMPIRE reaction model code, a modular system containing several nuclear reaction models that permits a fairly complete descritpion of the reaction, from elastic scattering and absorption through the pre-equilbrium stage to the final decay by statistical emission.

  14. Analytical model for thermal boundary conductance and equilibrium thermal accommodation coefficient at solid/gas interfaces.

    PubMed

    Giri, Ashutosh; Hopkins, Patrick E

    2016-02-28

    We develop an analytical model for the thermal boundary conductance between a solid and a gas. By considering the thermal fluxes in the solid and the gas, we describe the transmission of energy across the solid/gas interface with diffuse mismatch theory. From the predicted thermal boundary conductances across solid/gas interfaces, the equilibrium thermal accommodation coefficient is determined and compared to predictions from molecular dynamics simulations on the model solid-gas systems. We show that our model is applicable for modeling the thermal accommodation of gases on solid surfaces at non-cryogenic temperatures and relatively strong solid-gas interactions (εsf ≳ kBT). PMID:26931716

  15. Equilibrium speciation dynamics in a model adaptive radiation of island lizards

    PubMed Central

    Rabosky, Daniel L.; Glor, Richard E.

    2010-01-01

    The relative importance of equilibrium and nonequilibrium processes in shaping patterns of species richness is one of the most fundamental questions in biodiversity studies. If equilibrium processes predominate, then ecological interactions presumably limit species diversity, potentially through diversity dependence of immigration, speciation, and extinction rates. Alternatively, species richness may be limited by the rate at which diversity arises or by the amount of time available for diversification. These latter explanations constitute nonequilibrium processes and can apply only to biotas that are unsaturated or far from diversity equilibria. Recent studies have challenged whether equilibrium models apply to biotas assembled through in situ speciation, as this process may be too slow to achieve steady-state diversities. Here we demonstrate that speciation rates in replicate Caribbean lizard radiations have undergone parallel declines to equilibrium conditions on three of four major islands. Our results suggest that feedback between total island diversity and per-capita speciation rates scales inversely with island area, with proportionately greater declines occurring on smaller islands. These results are consistent with strong ecological controls on species richness and suggest that the iconic adaptive radiation of Caribbean anoles may have reached an endpoint. PMID:21135239

  16. Modeling of Spacecraft Advanced Chemical Propulsion Systems

    NASA Technical Reports Server (NTRS)

    Benfield, Michael P. J.; Belcher, Jeremy A.

    2004-01-01

    This paper outlines the development of the Advanced Chemical Propulsion System (ACPS) model for Earth and Space Storable propellants. This model was developed by the System Technology Operation of SAIC-Huntsville for the NASA MSFC In-Space Propulsion Project Office. Each subsystem of the model is described. Selected model results will also be shown to demonstrate the model's ability to evaluate technology changes in chemical propulsion systems.

  17. Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical stochastic perturbations method and application to a solution between (120) gypsum faces

    NASA Astrophysics Data System (ADS)

    Pedesseau, Laurent; Jouanna, Paul

    2004-12-01

    The SASP (semianalytical stochastic perturbations) method is an original mixed macro-nano-approach dedicated to the mass equilibrium of multispecies phases, periphases, and interphases. This general method, applied here to the reflexive relation Ck⇔μk between the concentrations Ck and the chemical potentials μk of k species within a fluid in equilibrium, leads to the distribution of the particles at the atomic scale. The macroaspects of the method, based on analytical Taylor's developments of chemical potentials, are intimately mixed with the nanoaspects of molecular mechanics computations on stochastically perturbed states. This numerical approach, directly linked to definitions, is universal by comparison with current approaches, DLVO Derjaguin-Landau-Verwey-Overbeek, grand canonical Monte Carlo, etc., without any restriction on the number of species, concentrations, or boundary conditions. The determination of the relation Ck⇔μk implies in fact two problems: a direct problem Ck⇒μk and an inverse problem μk⇒Ck. Validation of the method is demonstrated in case studies A and B which treat, respectively, a direct problem and an inverse problem within a free saturated gypsum solution. The flexibility of the method is illustrated in case study C dealing with an inverse problem within a solution interphase, confined between two (120) gypsum faces, remaining in connection with a reference solution. This last inverse problem leads to the mass equilibrium of ions and water molecules within a 3 Å thick gypsum interface. The major unexpected observation is the repulsion of SO42- ions towards the reference solution and the attraction of Ca2+ ions from the reference solution, the concentration being 50 times higher within the interphase as compared to the free solution. The SASP method is today the unique approach able to tackle the simulation of the number and distribution of ions plus water molecules in such extreme confined conditions. This result is of prime

  18. Comparison of different models for non-equilibrium CO2 flows in a shock layer near a blunt body

    NASA Astrophysics Data System (ADS)

    Kustova, E. V.; Nagnibeda, E. A.; Shevelev, Yu. D.; Syzranova, N. G.

    2011-06-01

    The paper presents results of a numerical simulation of a supersonic two-dimensional (2D) viscous flow containing CO2 molecules near a spacecraft entering the Mars atmosphere. The gas-dynamic equations in the shock layer are coupled to the equations of non-equilibrium vibrational and chemical kinetics in the five-component mixture CO2/CO/O2/C/O. Transport and relaxation processes in the flow are studied on the basis of the rigorous kinetic theory methods; the developed transport algorithms are incorporated in the numerical scheme. The influence of the vibrational excitation of CO2 and chemical reactions on the gas flow parameters and heat transfer is analyzed. The obtained results are compared with those found using two simplified models based on the two-temperature and one-temperature vibrational distributions in CO2. The accuracy of the simplified models and the limits of their validity within the shock layer are evaluated. The effect of bulk viscosity in a flow near a re-entry body is discussed. The role of different diffusion processes, chemical reactions, and surface catalytic properties in a flow of the considered mixture in the shock layer is estimated.

  19. Equilibrium Phase Behavior of the Square-Well Linear Microphase-Forming Model.

    PubMed

    Zhuang, Yuan; Charbonneau, Patrick

    2016-07-01

    We have recently developed a simulation approach to calculate the equilibrium phase diagram of particle-based microphase formers. Here, this approach is used to calculate the phase behavior of the square-well linear model for different strengths and ranges of the linear long-range repulsive component. The results are compared with various theoretical predictions for microphase formation. The analysis further allows us to better understand the mechanism for microphase formation in colloidal suspensions. PMID:27117230

  20. A non-equilibrium model for soil heating and moisture transport during extreme surface heating

    NASA Astrophysics Data System (ADS)

    Massman, W. J.

    2015-03-01

    With increasing use of prescribed fire by land managers and increasing likelihood of wildfires due to climate change comes the need to improve modeling capability of extreme heating of soils during fires. This issue is addressed here by developing a one-dimensional non-equilibrium model of soil evaporation and transport of heat, soil moisture, and water vapor, for use with surface forcing ranging from daily solar cycles to extreme conditions encountered during fires. The model employs a linearized Crank-Nicolson scheme for the conservation equations of energy and mass and its performance is evaluated against dynamic soil temperature and moisture observations obtained during laboratory experiments on soil samples exposed to surface heat fluxes ranging between 10 000 and 50 000 W m-2. The Hertz-Knudsen equation is the basis for constructing the model's non-equilibrium evaporative source term. The model includes a dynamic residual soil moisture as a function of temperature and soil water potential, which allows the model to capture some of the dynamic aspects of the strongly bound soil moisture that seems to require temperatures well beyond 150 °C to fully evaporate. Furthermore, the model emulates the observed increase in soil moisture ahead of the drying front and the hiatus in the soil temperature rise during the strongly evaporative stage of drying. It also captures the observed rapid evaporation of soil moisture that occurs at relatively low temperatures (50-90 °C). Sensitivity analyses indicate that the model's success results primarily from the use of a temperature and moisture potential dependent condensation coefficient in the evaporative source term. The model's solution for water vapor density (and vapor pressure), which can exceed one standard atmosphere, cannot be experimentally verified, but they are supported by results from (earlier and very different) models developed for somewhat different purposes and for different porous media. Overall, this non-equilibrium

  1. Thermodynamic Phase And Chemical Equilibrium At 0-110 C For The H+-K+-Na+-Cl--H2O System Up To 16 Molal And The HNO3-H2O System Up To 20 Molal Using An Association-Based Pitzer Model Compatible With ASPEN Plus

    SciTech Connect

    Nichols,T.T.; Taylor,D.D.

    2003-09-26

    A status is presented of the parameterization during FY2003 of an association-based Pitzer model to simulate chemical and phase equilibria of acid-chloride-nitrate-mercury aqueous electrolyte systems at 0-100 C within the industry-standard process simulator, ASPEN Plus. Compatibility with ASPEN Plus requires that the Pitzer model used be limited to the third virial coefficient and have the values of b and a1 as originally proposed by Pitzer. Two aqueous models for 0-110 C at atmospheric pressure were parameterized in FY03. The model for the aqueous H+-K+-Na+-Cl- system is applicable for 0-16 molal, and the HNO3-H2O for 0-20 molal. An association-based Pitzer activity coefficient model is combined with Henry's law to predict activity/osmotic coefficient and VLE. The chloride model also predicts KCl and NaCl solubility, while the nitric acid model has the unique capability of predicting extent of dissociation with an average absolute deviation of 1.43%. The association-based approach presented here extends the utility of the molality-based Pitzer model past 6 molal to predict activity/osmotic coefficients up to 16-20 molal. The association-based approach offers the additional benefits of predicting extent of dissociation and of allowing the Pitzer model to be fully utilized in commercial simulators, such as ASPEN Plus, that require accounting for association to implement Henry's law. The Pitzer models presented here provide the chemical process simulation engineer with a superior alternative to the Electrolyte NRTL model that can easily be used in ASPEN Plus.

  2. Verify Super Double-Heterogeneous Spherical Lattice Model for Equilibrium Fuel Cycle Analysis AND HTR Spherical Super Lattice Model for Equilibrium Fuel Cycle Analysis

    SciTech Connect

    Gray S. Chang

    2005-11-01

    The currently being developed advanced High Temperature gas-cooled Reactors (HTR) is able to achieve a simplification of safety through reliance on innovative features and passive systems. One of the innovative features in these HTRs is reliance on ceramic-coated fuel particles to retain the fission products even under extreme accident conditions. Traditionally, the effect of the random fuel kernel distribution in the fuel pebble / block is addressed through the use of the Dancoff correction factor in the resonance treatment. However, the Dancoff correction factor is a function of burnup and fuel kernel packing factor, which requires that the Dancoff correction factor be updated during Equilibrium Fuel Cycle (EqFC) analysis. An advanced KbK-sph model and whole pebble super lattice model (PSLM), which can address and update the burnup dependent Dancoff effect during the EqFC analysis. The pebble homogeneous lattice model (HLM) is verified by the burnup characteristics with the double-heterogeneous KbK-sph lattice model results. This study summarizes and compares the KbK-sph lattice model and HLM burnup analyzed results. Finally, we discuss the Monte-Carlo coupling with a fuel depletion and buildup code - ORIGEN-2 as a fuel burnup analysis tool and its PSLM calculated results for the HTR EqFC burnup analysis.

  3. Assimilating chemical compound with a regional chemical model

    NASA Astrophysics Data System (ADS)

    Chang, C.; Yang, S.; Liang, M.; Hsu, S.; Tseng, Y.

    2012-12-01

    To constrain the source and sink of the chemical compounds at surface during model simulation, chemical compound assimilation with Local Ensemble Transform Kalman Filter (LETKF) has been implemented for the WRF-ChemT model. In this study, a two-tier system is applied to assimilating the meteorological and chemical variables in an OSSE framework. The unobserved surface flux is estimated according to the observations in the chemical component. A long-term nature run with total constant emission of 5.3×108 g/s is assumed to be the truth state in the OSSE. The simulated observations are obtained from the truth state by adding random errors. In order to generate the initial CO2 ensembles with similar spatial distribution as truth state without other prior information, the initial perturbation fields of CO2 are randomly chosen from three long-term runs with different emissions. The results indicate that in the constant emission case, the system can successfully estimate the unobserved chemical forcing and improve the distribution of the chemical compound. Under the scenario of diurnal forcing induced by human activities, the problem in estimating surface flux becomes more complex and difficult. A set of experiments with different initial chemical states suggest that the estimation of flux is sensitive to the quality of initial CO2 and CO2 surface flux. Strategies are designed to retrieve the time-varying information. The results show that with time-varying information and reliable initial ensembles, the estimation of surface flux have been significantly improved. Couple assimilation with meteorological and chemical components Surface flux estimation

  4. Hydrostatic equilibrium of causally consistent and dynamically stable neutron star models

    NASA Astrophysics Data System (ADS)

    Negi, P. S.

    2008-08-01

    We show that the mass-radius (M-R) relation corresponding to the stiffest equation of state (EOS) does not provide the necessary and sufficient condition of dynamical stability for equilibrium configurations, because such configurations cannot satisfy the `compatibility criterion'. In this regard, we construct sequences composed of core-envelope models such that, like the central condition belonging to the stiffest EOS, each member of these sequences satisfies the extreme case of the causality condition, v = c = 1, at the centre. We thereafter show that the M-R relation corresponding to the said core-envelope model sequences can provide the necessary and sufficient condition of dynamical stability only when the `compatibility criterion' for these sequences is `appropriately' satisfied. However, the `compatibility criterion' can remain satisfied even when the M-R relation does not provide the necessary and sufficient condition of dynamical stability for the equilibrium configurations. In continuation of the results of a previous study, these results explicitly show that the `compatibility criterion' independently provides, in general, the necessary and sufficient condition of hydrostatic equilibrium for any regular sequence. In addition to its fundamental result, this study can explain simultaneously the higher and the lower values of the glitch healing parameter observed for the Crab-like and Vela-like pulsars respectively, on the basis of the starquake model of glitch generation.

  5. Exoplanet Equilibrium Chemistry Calculations

    NASA Astrophysics Data System (ADS)

    Blumenthal, Sarah; Harrington, J.; Bowman, M.; Blecic, J.

    2013-10-01

    Recently, Agundez et al. (2012, A&A 548, A73) used a chemical kinetics code to study a model HD 209458b (equilibrium temperature of 1450 K, assuming full redistribution and 0 albedo). They found that thermochemistry dominates most of the dayside, but that significant compositional gradients may exist across the dayside. We calculate equilibrium-chemistry molecular abundances for several model exoplanets, using NASA's open-source Chemical Equilibrium Abundances code (McBride and Gordon 1996). We vary the degree of radiation redistribution to the dark side, ranging from total redistribution to instantaneous reradiation. Atomically, both the solar abundance multiple and the carbon fraction vary. Planet substellar temperatures range from just above 1200 K, where photochemistry should no longer be important, to those of hot planets (3000 K). We present synthetic abundance images for the key spectroscopic molecules CO, CH4, and H2O for several hot-Jupiter model planets. This work was supported by the NASA Planetary Atmospheres grant NNX12AI69G.

  6. Frontiers of chemical bioaccumulation modeling with fish

    EPA Science Inventory

    Predictive models for chemical accumulation in fish have been provided by numerous authors. Historically, these models were developed to describe the accumulation of neutral hydrophobic compounds which undergo little or no biotransformation. In such cases, accumulation can be p...

  7. A long-term macroeconomic equilibrium model for the European Community

    NASA Astrophysics Data System (ADS)

    Rogner, H. H.

    1982-04-01

    A version of MACRO, a highly aggregated, long-term, two-sector general equilibrium model, developed to examine energy-economy linkage, calibrated for the European community, is presented. Based on a range of energy supply scenarios, the impact of rising energy costs on economic activity, the feasibility of common assumptions about price-induced conservation, and the impact of continued high energy levels of energy imports on trade balance were examined, in order to assess model performance. Results suggest that the model meets the requirements for a consistency check of member country energy strategies.

  8. Modeling of gamma/gamma-prime phase equilibrium in the nickel-aluminum system

    NASA Technical Reports Server (NTRS)

    Sanchez, J. M.; Barefoot, J. R.; Jarrett, R. N.; Tien, J. K.

    1984-01-01

    A theoretical model is proposed for the determination of phase equilibrium in alloys, taking into consideration dissimilar lattice parameters. Volume-dependent pair interactions are introduced by means of phenomenological Lennard-Jones potentials and the configurational entropy of the system is treated in the tetrahedron approximation of the cluster variation method. The model is applied to the superalloy-relevant, nickel-rich, gamma/gamma-prime phase region of the Ni-Al phase diagram. The model predicts reasonable values for the lattice parameters and the enthalpy of formation as a function of composition, and the calculated phase diagram closely approximates the experimental diagram.

  9. Equilibrium structure and relative stability of glyceraldehyde conformers: Gas-phase electron diffraction (GED) and quantum-chemical studies

    NASA Astrophysics Data System (ADS)

    Vogt, Natalja; Atavin, Evgenii G.; Rykov, Anatolii N.; Popov, Evgenii V.; Vilkov, Lev V.

    2009-11-01

    For the first time, the five dimensional (5-D) analysis of potential energy surface (PES) from quantum-chemical calculations was carried out to predict reliably the various glyceraldehyde (GLA) conformers. 36 conformers with relative stabilities up to 38 kJ/mol were found in the B3LYP approximation. According to results of MP2/cc-pVQZ calculations, the molecule exists at the experimental temperature of 388 K as a mixture of five conformers in the ratio I:II:III:IV:V = 63:18:4:10:5. Contrary to the theoretical conclusion of Lovas et al., the conformer IV is predicted to be more stable than the conformer III. Our result can explain why the conformer IV could be detected in the microwave (MW) spectroscopic experiment by Lovas et al., whereas the conformer III could not. For the first time, thermal-average and equilibrium structural parameters of GLA (main conformer) have been determined from gas-phase electron diffraction (GED) data. Vibrational corrections to the experimental bond lengths were determined using quadratic and cubic force constants from high-level ab initio calculations (MP2/cc-pVTZ). It was shown that the experimental intensities are sensitive to the contribution of the second conformer (27(15)%). Rotational constants calculated from MP2/cc-pVQZ geometries were found to be in excellent agreement with the experimental rotational constants corrected for anharmonic effects.

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

    PubMed

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

    2016-01-21

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

  11. NON-EQUILIBRIUM CHEMISTRY OF DYNAMICALLY EVOLVING PRESTELLAR CORES. I. BASIC MAGNETIC AND NON-MAGNETIC MODELS AND PARAMETER STUDIES

    SciTech Connect

    Tassis, Konstantinos; Willacy, Karen; Yorke, Harold W.; Turner, Neal J.

    2012-07-01

    We combine dynamical and non-equilibrium chemical modeling of evolving prestellar molecular cloud cores and investigate the evolution of molecular abundances in the contracting core. We model both magnetic cores, with varying degrees of initial magnetic support, and non-magnetic cores, with varying collapse delay times. We explore, through a parameter study, the competing effects of various model parameters in the evolving molecular abundances, including the elemental C/O ratio, the temperature, and the cosmic-ray ionization rate. We find that different models show their largest quantitative differences at the center of the core, whereas the outer layers, which evolve slower, have abundances which are severely degenerate among different dynamical models. There is a large range of possible abundance values for different models at a fixed evolutionary stage (central density), which demonstrates the large potential of chemical differentiation in prestellar cores. However, degeneracies among different models, compounded with uncertainties induced by other model parameters, make it difficult to discriminate among dynamical models. To address these difficulties, we identify abundance ratios between particular molecules, the measurement of which would have maximal potential for discrimination among the different models examined here. In particular, we find that the ratios between NH{sub 3} and CO, NH{sub 2} and CO, and NH{sub 3} and HCO{sup +} are sensitive to the evolutionary timescale, and that the ratio between HCN and OH is sensitive to the C/O ratio. Finally, we demonstrate that measurements of the central deviation (central depletion or enhancement) of abundances of certain molecules are good indicators of the dynamics of the core.

  12. 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…

  13. Non-equilibrium model of two-phase porous media flow with phase change

    NASA Astrophysics Data System (ADS)

    Cueto-Felgueroso, L.; Fu, X.; Juanes, R.

    2014-12-01

    The efficient simulation of multi-phase multi-component flow through geologic porous media is challenging and computationally intensive, yet quantitative modeling of these processes is essential in engineering and the geosciences. Multiphase flow with phase change and complex phase behavior arises in numerous applications, including enhanced oil recovery, steam injection in groundwater remediation, geologic CO2 storage and enhanced geothermal energy systems. A challenge of multiphase compositional simulation is that the number of existing phases varies with position and time, and thus the number of state variables in the saturation-based conservation laws is a function of space and time. The tasks of phase-state identification and determination of the composition of the different phases are performed assuming local thermodynamic equilibrium. Here we investigate a thermodynamically consistent formulation for non-isothermal two-phase flow, in systems where the hypothesis of instantaneous local equilibrium does not hold. Non-equilibrium effects are important in coarse-scale simulations where the assumption of complete mixing in each gridblock is not realistic. We apply our model to steam injection in water-saturated porous media.

  14. An improved dynamic non-equilibrium wall-model for large eddy simulation

    NASA Astrophysics Data System (ADS)

    Park, George Ilhwan; Moin, Parviz

    2014-01-01

    A non-equilibrium wall-model based on unsteady 3D Reynolds-averaged Navier-Stokes (RANS) equations has been implemented in an unstructured mesh environment. The method is similar to that of the wall-model for structured mesh described by Wang and Moin [Phys. Fluids 14, 2043-2051 (2002)], but is supplemented by a new dynamic eddy viscosity/conductivity model that corrects the effect of the resolved Reynolds stress (resolved turbulent heat flux) on the skin friction (wall heat flux). This correction is crucial in predicting the correct level of the skin friction. Unlike earlier models, this eddy viscosity/conductivity model does not have a stress-matching procedure or a tunable free parameter, and it shows consistent performance over a wide range of Reynolds numbers. The wall-model is validated against canonical (attached) transitional and fully turbulent flows at moderate to very high Reynolds numbers: a turbulent channel flow at Reτ = 2000, an H-type transitional boundary layer up to Reθ = 3300, and a high Reynolds number boundary layer at Reθ = 31 000. Application to a separated flow over a NACA4412 airfoil operating close to maximum lift is also considered to test the performance of the wall-model in complex non-equilibrium flows.

  15. Turbulence Modeling of Non-equilibrium Flows Using Turbulent Body Force Potentials

    NASA Astrophysics Data System (ADS)

    Wang, Hudong; Perot, Blair

    1998-11-01

    Results of a new turbulence model for non-equilibrium flow which is based on turbulent body force potentials are presented. Initial predictions of the model for basic turbulent flows produced promising results. This work concentrates on predicting more complex and realistic turbulent flows that are similar to the problems in design and manufacturing process. Three major cases are presented and the computational results are compared with existing experimental data and DNS data whenever possible. First, backwards-facing step flows at both high and low Reynolds numbers are investigated in order to evaluate the model's ability for correctly predicting separation and reattachment. Second, two adverse pressure gradient flows are analyzed, namely, the classic Samuel & Joubert flow and more severe case documented by Schubauer & Spangenberg. Finally, the performance of the model in predicting stagnation flows is evaluated by investigating planar and axisymmetric impinging jets. Comparisons show that model predictions match well with experimental data and DNS data. It is demonstrated that by introducing turbulent body force potentials this new non-equilibrium turbulence model is able to predict complex turbulent flows as well as Reynolds stress transport models with significant less computational cost and complexity.

  16. Coupled equilibrium model of hybridization error for the DNA microarray and tag-antitag systems.

    PubMed

    Rose, John A; Deaton, Russell J; Hagiya, Masami; Suyama, Akira

    2007-03-01

    In this work, a detailed coupled equilibrium model is presented for predicting the ensemble average probability of hybridization error per chip-hybridized input strand, providing the first ensemble average method for estimating postannealing microarray/TAT system error rates. Following a detailed presentation of the model and implementation via the software package NucleicPark, under a mismatched statistical zipper model of duplex formation, error response is simulated for both mean-energy and randomly encoded TAT systems versus temperature and input concentration. Limiting expressions and simulated model behavior indicate the occurrence of a transition in hybridization error response, from a logarithmically convex function of temperature for excess inputs (high-error behavior), to a monotonic, log-linear function of temperature for dilute inputs (low-error behavior), a novel result unpredicted by uncoupled equilibrium models. Model scaling behavior for random encodings is investigated versus system size and strand-length. Application of the model to TAT system design is also undertaken, via the in silico evolution of a high-fidelity 100-strand TAT system, with an error response improved by nine standard deviations over the performance of the mean random encoding. PMID:17393846

  17. Integrated tokamak modelling taskforce: Validation of the equilibrium reconstruction from experimental data

    SciTech Connect

    Zwingmann, W.; Airaj, M.; Eriksson, L.-G.; Guillerminet, B.; Huysmans, G. T. A.; Imbeaux, F.; Moreau, Ph.; McCarthy, P.; Strand, P.

    2008-03-19

    The Integrated tokamak modelling taskforce was set up to provide the European scientific community with simulation tools for preparing and analysing discharges of fusion experiments. We will report on recent progress made on the taskforce project on equilibrium and linear stability. A generic data structure has been devised to describe the geometry of a machine and physical processes in the discharge. This data structure is used to interface all individual analysis program within the taskforce. One of the analysis tools, the equilibrium code EFIT-ITM, based on the EFIT code written by L. L. Lao, has been completely rewritten in order to make it suitable for the ITM. It has algorithm enhancements to increase execution speed, and the ability to treat anisotropic pressure and deviation from axisymmetry. The reconstruction code is now completely independent of the machine description. First results on veriflcation and validation of the new tool are presented.

  18. Non-equilibrium steady states in two-temperature Ising models with Kawasaki dynamics

    NASA Astrophysics Data System (ADS)

    Borchers, Nick; Pleimling, Michel; Zia, R. K. P.

    2013-03-01

    From complex biological systems to a simple simmering pot, thermodynamic systems held out of equilibrium are exceedingly common in nature. Despite this, a general theory to describe these types of phenomena remains elusive. In this talk, we explore a simple modification of the venerable Ising model in hopes of shedding some light on these issues. In both one and two dimensions, systems attached to two distinct heat reservoirs exhibit many of the hallmarks of phase transition. When such systems settle into a non-equilibrium steady-state they exhibit numerous interesting phenomena, including an unexpected ``freezing by heating.'' There are striking and surprising similarities between the behavior of these systems in one and two dimensions, but also intriguing differences. These phenomena will be explored and possible approaches to understanding the behavior will be suggested. Supported by the US National Science Foundation through Grants DMR-0904999, DMR-1205309, and DMR-1244666

  19. Coulombic Models in Chemical Bonding.

    ERIC Educational Resources Information Center

    Sacks, Lawrence J.

    1986-01-01

    Compares the coulumbic point charge model for hydrogen chloride with the valence bond model. It is not possible to assign either a nonpolar or ionic canonical form of the valence bond model, while the covalent-ionic bond distribution does conform to the point charge model. (JM)

  20. An equilibrium double-twist model for the radial structure of collagen fibrils.

    PubMed

    Brown, Aidan I; Kreplak, Laurent; Rutenberg, Andrew D

    2014-11-14

    Mammalian tissues contain networks and ordered arrays of collagen fibrils originating from the periodic self-assembly of helical 300 nm long tropocollagen complexes. The fibril radius is typically between 25 to 250 nm, and tropocollagen at the surface appears to exhibit a characteristic twist-angle with respect to the fibril axis. Similar fibril radii and twist-angles at the surface are observed in vitro, suggesting that these features are controlled by a similar self-assembly process. In this work, we propose a physical mechanism of equilibrium radius control for collagen fibrils based on a radially varying double-twist alignment of tropocollagen within a collagen fibril. The free-energy of alignment is similar to that of liquid crystalline blue phases, and we employ an analytic Euler-Lagrange and numerical free energy minimization to determine the twist-angle between the molecular axis and the fibril axis along the radial direction. Competition between the different elastic energy components, together with a surface energy, determines the equilibrium radius and twist-angle at the fibril surface. A simplified model with a twist-angle that is linear with radius is a reasonable approximation in some parameter regimes, and explains a power-law dependence of radius and twist-angle at the surface as parameters are varied. Fibril radius and twist-angle at the surface corresponding to an equilibrium free-energy minimum are consistent with existing experimental measurements of collagen fibrils. Remarkably, in the experimental regime, all of our model parameters are important for controlling equilibrium structural parameters of collagen fibrils. PMID:25238208

  1. Dynamical coupling between magnetic equilibrium and transport in tokamak scenario modelling, with application to current ramps

    NASA Astrophysics Data System (ADS)

    Fable, E.; Angioni, C.; Ivanov, A. A.; Lackner, K.; Maj, O.; Medvedev, S. Yu; Pautasso, G.; Pereverzev, G. V.; Treutterer, W.; the ASDEX Upgrade Team

    2013-07-01

    The modelling of tokamak scenarios requires the simultaneous solution of both the time evolution of the plasma kinetic profiles and of the magnetic equilibrium. Their dynamical coupling involves additional complications, which are not present when the two physical problems are solved separately. Difficulties arise in maintaining consistency in the time evolution among quantities which appear in both the transport and the Grad-Shafranov equations, specifically the poloidal and toroidal magnetic fluxes as a function of each other and of the geometry. The required consistency can be obtained by means of iteration cycles, which are performed outside the equilibrium code and which can have different convergence properties depending on the chosen numerical scheme. When these external iterations are performed, the stability of the coupled system becomes a concern. In contrast, if these iterations are not performed, the coupled system is numerically stable, but can become physically inconsistent. By employing a novel scheme (Fable E et al 2012 Nucl. Fusion submitted), which ensures stability and physical consistency among the same quantities that appear in both the transport and magnetic equilibrium equations, a newly developed version of the ASTRA transport code (Pereverzev G V et al 1991 IPP Report 5/42), which is coupled to the SPIDER equilibrium code (Ivanov A A et al 2005 32nd EPS Conf. on Plasma Physics (Tarragona, 27 June-1 July) vol 29C (ECA) P-5.063), in both prescribed- and free-boundary modes is presented here for the first time. The ASTRA-SPIDER coupled system is then applied to the specific study of the modelling of controlled current ramp-up in ASDEX Upgrade discharges.

  2. A numerical code for a three-dimensional magnetospheric MHD equilibrium model

    NASA Technical Reports Server (NTRS)

    Voigt, G.-H.

    1992-01-01

    Two dimensional and three dimensional MHD equilibrium models were begun for Earth's magnetosphere. The original proposal was motivated by realizing that global, purely data based models of Earth's magnetosphere are inadequate for studying the underlying plasma physical principles according to which the magnetosphere evolves on the quasi-static convection time scale. Complex numerical grid generation schemes were established for a 3-D Poisson solver, and a robust Grad-Shafranov solver was coded for high beta MHD equilibria. Thus, the effects were calculated of both the magnetopause geometry and boundary conditions on the magnetotail current distribution.

  3. Electron-Impact Excitation Cross Sections for Modeling Non-Equilibrium Gas

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Liu, Yen; Panesi, Marco; Munafo, Alessandro; Wray, Alan; Carbon, Duane F.

    2015-01-01

    In order to provide a database for modeling hypersonic entry in a partially ionized gas under non-equilibrium, the electron-impact excitation cross sections of atoms have been calculated using perturbation theory. The energy levels covered in the calculation are retrieved from the level list in the HyperRad code. The downstream flow-field is determined by solving a set of continuity equations for each component. The individual structure of each energy level is included. These equations are then complemented by the Euler system of equations. Finally, the radiation field is modeled by solving the radiative transfer equation.

  4. Cap-and-Trade Modeling and Analysis: Congested Electricity Market Equilibrium

    NASA Astrophysics Data System (ADS)

    Limpaitoon, Tanachai

    This dissertation presents an equilibrium framework for analyzing the impact of cap-and-trade regulation on transmission-constrained electricity market. The cap-and-trade regulation of greenhouse gas emissions has gained momentum in the past decade. The impact of the regulation and its efficacy in the electric power industry depend on interactions of demand elasticity, transmission network, market structure, and strategic behavior of firms. I develop an equilibrium model of an oligopoly electricity market in conjunction with a market for tradable emissions permits to study the implications of such interactions. My goal is to identify inefficiencies that may arise from policy design elements and to avoid any unintended adverse consequences on the electric power sector. I demonstrate this modeling framework with three case studies examining the impact of carbon cap-and-trade regulation. In the first case study, I study equilibrium results under various scenarios of resource ownership and emission targets using a 24-bus IEEE electric transmission system. The second and third case studies apply the equilibrium model to a realistic electricity market, Western Electricity Coordinating Council (WECC) 225-bus system with a detailed representation of the California market. In the first and second case studies, I examine oligopoly in electricity with perfect competition in the permit market. I find that under a stringent emission cap and a high degree of concentration of non-polluting firms, the electricity market is subject to potential abuses of market power. Also, market power can occur in the procurement of non-polluting energy through the permit market when non-polluting resources are geographically concentrated in a transmission-constrained market. In the third case study, I relax the competitive market structure assumption of the permit market by allowing oligopolistic competition in the market through a conjectural variation approach. A short-term equilibrium

  5. Kinetic Monte Carlo models for the study of chemical reactions in the Earth's upper atmosphere

    NASA Astrophysics Data System (ADS)

    Turchak, L. I.; Shematovich, V. I.

    2016-06-01

    A stochastic approach to study the non-equilibrium chemistry in the Earth's upper atmosphere is presented, which has been developed over a number of years. Kinetic Monte Carlo models based on this approach are an effective tool for investigating the role of suprathermal particles both in local variations of the atmospheric chemical composition and in the formation of the hot planetary corona.

  6. Chemical kinetics models for semiconductor processing

    SciTech Connect

    Coltrin, M.E.; Creighton, J.R.; Meeks, E.; Grcar, J.F.; Houf, W.G.; Kee, R.J.

    1997-12-31

    Chemical reactions in the gas-phase and on surfaces are important in the deposition and etching of materials for microelectronic applications. A general software framework for describing homogeneous and heterogeneous reaction kinetics utilizing the Chemkin suite of codes is presented. Experimental, theoretical and modeling approaches to developing chemical reaction mechanisms are discussed. A number of TCAD application modules for simulating the chemically reacting flow in deposition and etching reactors have been developed and are also described.

  7. Analytical modeling of equilibrium of strongly anisotropic plasma in tokamaks and stellarators

    SciTech Connect

    Lepikhin, N. D.; Pustovitov, V. D.

    2013-08-15

    Theoretical analysis of equilibrium of anisotropic plasma in tokamaks and stellarators is presented. The anisotropy is assumed strong, which includes the cases with essentially nonuniform distributions of plasma pressure on magnetic surfaces. Such distributions can arise at neutral beam injection or at ion cyclotron resonance heating. Then the known generalizations of the standard theory of plasma equilibrium that treat p{sub ‖} and p{sub ⊥} (parallel and perpendicular plasma pressures) as almost constant on magnetic surfaces are not applicable anymore. Explicit analytical prescriptions of the profiles of p{sub ‖} and p{sub ⊥} are proposed that allow modeling of the anisotropic plasma equilibrium even with large ratios of p{sub ‖}/p{sub ⊥} or p{sub ⊥}/p{sub ‖}. A method for deriving the equation for the Shafranov shift is proposed that does not require introduction of the flux coordinates and calculation of the metric tensor. It is shown that for p{sub ⊥} with nonuniformity described by a single poloidal harmonic, the equation for the Shafranov shift coincides with a known one derived earlier for almost constant p{sub ⊥} on a magnetic surface. This does not happen in the other more complex case.

  8. Towards a global model of equilibrium solar behavior: the tachocline as a trans-Alfvenic feature

    NASA Astrophysics Data System (ADS)

    Gunderson, Lee; Bhattacharjee, Amitava; Guazzotto, Luca

    2015-11-01

    Observations and simulations suggest that thermal wind balance holds to lowest order in the solar convection zone (SCZ), and an analytic model of solar rotation has been developed by further assuming a functional relationship between the entropy and rotation. Below the SCZ, analytic arguments and simulations have implicated the necessity of a large poloidal field in the deep solar interior for the thin structure of the tachocline. We seek to unify these pictures and find a global equilibrium base state of solar behavior by starting from the exact solution to axisymmetric ideal MHD, the generalized Grad-Shafranov equation, thereby including magnetic field and poloidal flow from the onset. We find that a tachocline-like structure naturally arises as an equilibrium feature if the poloidal Alfvénic Mach number approaches unity near the bottom of the SCZ. FLOW, a code developed to analyze tokamak equilibrium with arbitrary flow, has been adapted for use in the solar regime and used to examine effects of magnetic field and poloidal flow on thermal wind balance. The next steps include: including the Alfvénic transition, establishing linear stability, and considering the effects of stresses and dissipation.

  9. Modelling actual, reference and equilibrium evaporation from a temperate wet grassland

    NASA Astrophysics Data System (ADS)

    Gavin, H.; Agnew, C. A.

    2004-02-01

    Actual and reference evaporation from a wet grassland in Southeast England was studied over the spring and summer of 1999 (March to September) through changes in surface wetness. The Penman-Monteith (using resistance values for reference grass surface), equilibrium evaporation and Priestley-Taylor models were compared with output from the Bowen ratio energy balance (BREB) method. On field visits, inundation of the grazing marsh was mapped and surface soil moisture monitored in a regular grid using a capacitance probe. During the study period, the extent of flooding fell from approximately 10% to 0% and the surface soil moisture declined from over 38% to 15%. Daily averaged Bowen ratios displayed large variation but were below unity, indicating that latent energy flux was the dominant energy sink. The Penman-Monteith and equilibrium evaporation models underestimated during periods of surface inundation and overestimated when no surface water was present. Computed values of the Priestley-Taylor parameter showed daily variability, but was predictable with surface wetness such an average value of = 1.25 characterized periods of inundation, and an average values of = 0.80 represented periods of no surface water. The performance of the models in computing actual evaporation was compared with the BREB using the root-mean-square error and index of agreement. The optimal model was the Priestley-Taylor model.

  10. Supercritical CO2 extraction of oilseeds: review of kinetic and equilibrium models.

    PubMed

    del Valle, José M; de la Fuente, Juan C

    2006-01-01

    Mass transfer models on supercritical carbon dioxide (SC-CO2) extraction of vegetable oils are reviewed, that may facilitate the scale-up of laboratory data for industrial design purposes. Reviewed mechanisms of oil transport within the solid matrix include the desorption from the solid, the formation of a shrinking core of condensed oil in a non-adsorbing porous matrix, and diffusion in a homogenous medium. Analyzed simplificat ions of a general mass transfer model include external control of mass transfer rates, internal control of mass transfer rates, consideration of a linear driving force, and steady state approximations, among others. More complex two-stage models, and critical comparisons of some of the proposed models are also included. Trends for the external mass transfer coefficient and effective diffusivity in the solid matrix from studies on SC-CO2 extraction of oil from vegetable substrates are thoroughly discussed and contrasted with those obtained using simpler model systems. The possible effect of the axial dispersion on the rate of extraction is also discussed. Finally, the high-pressure vegetable oil-CO2 phase equilibrium is discussed in connection with its influence on the mass transfer process. Special emphasis is given to the role of the solid matrix on high-pressure phase equilibrium. PMID:16431407

  11. Conservation equations and physical models for hypersonic air flows in thermal and chemical nonequilibrium

    SciTech Connect

    Gnoffo, P.A.; Gupta, R.N.; Shinn, J.L.

    1989-02-01

    The conservation equations for simulating hypersonic flows in thermal and chemical nonequilibrium and details of the associated physical models are presented. These details include the curve fits used for defining thermodynamic properties of the 11 species air model, curve fits for collision cross sections, expressions for transport properties, the chemical kinetics models, and the vibrational and electronic energy relaxation models. The expressions are formulated in the context of either a two or three temperature model. Greater emphasis is placed on the two temperature model in which it is assumed that the translational and rotational energy models are in equilibrium at the translational temperature, T, and the vibrational, electronic, and electron translational energy modes are in equilibrium at the vibrational temperature, T sub v. The eigenvalues and eigenvectors associated with the Jacobian of the flux vector are also presented in order to accommodate the upwind based numerical solutions of the complete equation set.

  12. Conservation equations and physical models for hypersonic air flows in thermal and chemical nonequilibrium

    NASA Technical Reports Server (NTRS)

    Gnoffo, Peter A.; Gupta, Roop N.; Shinn, Judy L.

    1989-01-01

    The conservation equations for simulating hypersonic flows in thermal and chemical nonequilibrium and details of the associated physical models are presented. These details include the curve fits used for defining thermodynamic properties of the 11 species air model, curve fits for collision cross sections, expressions for transport properties, the chemical kinetics models, and the vibrational and electronic energy relaxation models. The expressions are formulated in the context of either a two or three temperature model. Greater emphasis is placed on the two temperature model in which it is assumed that the translational and rotational energy models are in equilibrium at the translational temperature, T, and the vibrational, electronic, and electron translational energy modes are in equilibrium at the vibrational temperature, T sub v. The eigenvalues and eigenvectors associated with the Jacobian of the flux vector are also presented in order to accommodate the upwind based numerical solutions of the complete equation set.

  13. Nonlocal-thermal-equilibrium model of a pulsed capillary discharge waveguide.

    PubMed

    Broks, B H P; Garloff, K; van der Mullen, J J A M

    2005-01-01

    Slow pulsed capillary discharges are under investigation for use as plasma channel waveguides in laser-wakefield acceleration. In this study, we present a non-local thermal equilibrium (non-LTE) plasma model with a model for the wall temperature coupled to it. This model is used to describe an example of a slow pulsed capillary discharge, and the results are compared with experimental results. The agreement is satisfactory, indicating suitability of our model. Significant deviations from LTE are found during the formation of the plasma channel. The model is also used to study the influence of the discharge current on the guiding properties. It was found that this influence is small over most of the current range that was investigated. PMID:15697729

  14. Global stability of equilibrium of multi-species model with cross diffusion

    NASA Astrophysics Data System (ADS)

    Anguelov, R.; Tenkam, H. M. D.

    2015-10-01

    In this work, we study a model of the interaction of N species (N > 2) which involves cross-diffusion. The model generalizes the model introduced in 1979 by Shigesada, Kawasaki and Teramoto for two species (SKT). All species are assumed to exhibit a functional response of the same form similar to SKT model. By constructing a Lyapunov functional of the system, we establish the global stability of the equilibrium, subject to some conditions on the cross-diffusion matrix and the diffusion vector. A sufficient condition is also derived for the coexistence of a large number of interacting species. Particular cases of the model for two species are considered extensively in the literature. Most of these results are shown to follow as consequences of the general theory developed here.

  15. Equilibrium sorption of cobalt, cesium, and strontium on Bandelier Tuff: analysis of alternative mathematical modeling

    SciTech Connect

    Polzer, W.L.; Fuentes, H.R.; Essington, E.H.; Roensch, F.R.

    1985-01-01

    Sorption isotherms are derived from batch equilibrium data for cobalt, cesium and strontium on Bandelier Tuff. Experiments were conducted at an average temperature of 23/sup 0/C and equilibrium was defined at 48 hours. The solute concentrations ranged from 0 to 500 mg/L. The radioactive isotopes /sup 60/Co, /sup 137/Cs, and /sup 85/Sr were used to trace the sorption of the stable solutes. The Linear, Langmuir, Freundlich and a Modified Freundlich isotherm equations are evaluated. The Modified Freundlich isotherm equation is validated as a preferred general mathematical tool for representing the sorption of the three solutes. The empirical constants derived from the Modified Freundlich isotherm equation indicate that under dynamic flow conditions strontium will move most rapidly and cobalt least rapidly. On the other hand, chemical dispersion will be greatest for cesium and least for strontium. Hill Plots of the sorption data suggest that in the region of low saturation sorption of all three solutes is impeded by interactions among sorption sites; cobalt exhibits the greatest effect of interactions and strontium shows only a minimal effect. In the saturation region of 50% or more, sorption of cobalt is enhanced slightly by interactions among sorption sites whereas sorption of cesium and strontium appears to be independent of site interactions. 9 references, 4 figures, 2 tables.

  16. Continental radiative-convective equilibrium experiments in a single column model (LMDZ5B GCM)

    NASA Astrophysics Data System (ADS)

    Rochetin, N.; Gentine, P.; Lintner, B. R.; Sobel, A. H.; Findell, K. L.

    2013-12-01

    The radiative-convective instability results both from (i) the average net cooling experienced by the Earth's atmosphere (~ 110 W/m?) and (ii) from the equivalent warming of the Earth's surface. Ultimately, this drives the Earth atmosphere to a radiative-convective equilibrium (RCE) state, in a sense that, at the global scale, surface fluxes and radiative cooling compensate each other. Since the convection time scale (i.e. some hours) is much shorter than the radiation one (i.e. about 40 days), the resulting global temperature lapse rate is generally closer to the moist adiabat than to the dry adiabat. This is especially true over the tropics, where moist convection is in near-equilibrium. The RCE is then often used as a common approximation of the tropical mean state. It has been extensively used over oceans in SCMs (Single Column Models), as well as in CRMs (Cloud Resolving Models), to investigate the tropical moist convection sensitivity (i) to boundary conditions (e.g. SST, surface wind, drag coefficient, etc...) and (ii) to atmospheric conditions (e.g. radiative cooling, wind shear, tropospheric humidity, etc...). Nevertheless, to our knowledge the present study is the first one investigating the RCE over a continental surface. Indeed, in the present study, the single column version of the LMDZ GCM (LMDZ5B, from the Laboratoire de Meteorologie Dynamique) is ran to RCE, with a coupled land surface both in terms of temperature and moisture. This continental RCE demonstrates very different sensitivity compared to its oceanic counterpart in particular because of the large- amplitude heat flux diurnal cycle, which is shown to strongly impact the equilibrium state. Sensitivity studies (i) to solar forcing (latitude) (ii) to total water content, and (iii) to the initial conditions are performed to study the different equilibrium states, with a particular focus on the role of clouds. We also performed a bifurcation diagram. Low-level clouds and fog are shown to be key

  17. The equilibrium state in the Si-O-C ternary system during SiC growth by chemical substitution of atoms

    NASA Astrophysics Data System (ADS)

    Kukushkin, S. A.; Osipov, A. V.

    2015-03-01

    The equilibrium state in the silicon-carbon-oxygen (Si-O-C) ternary system has been calculated in the framework of the thermodynamics of chemical reactions. It is established that, in the practically important temperature interval of 1000°C < T < 1400°C, the system initially consisting of crystalline Si and gaseous CO tends toward an equilibrium state comprising a mixture of four solid phases (Si, C, SiC, and SiO2) and vapor mixture (predominantly of SiO, CO, Si, and CO2). Equilibrium partial pressures of all gases in the mixture have been calculated. An optimum regime of SiC film growth from Si by the method of atomic substitution is proposed, whereby only SiC phase is growing while SiO2 and C phases are not formed.

  18. PHASE-OTI: A pre-equilibrium model code for nuclear reactions calculations

    NASA Astrophysics Data System (ADS)

    Elmaghraby, Elsayed K.

    2009-09-01

    The present work focuses on a pre-equilibrium nuclear reaction code (based on the one, two and infinity hypothesis of pre-equilibrium nuclear reactions). In the PHASE-OTI code, pre-equilibrium decays are assumed to be single nucleon emissions, and the statistical probabilities come from the independence of nuclei decay. The code has proved to be a good tool to provide predictions of energy-differential cross sections. The probability of emission was calculated statistically using bases of hybrid model and exciton model. However, more precise depletion factors were used in the calculations. The present calculations were restricted to nucleon-nucleon interactions and one nucleon emission. Program summaryProgram title: PHASE-OTI Catalogue identifier: AEDN_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEDN_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 5858 No. of bytes in distributed program, including test data, etc.: 149 405 Distribution format: tar.gz Programming language: Fortran 77 Computer: Pentium 4 and Centrino Duo Operating system: MS Windows RAM: 128 MB Classification: 17.12 Nature of problem: Calculation of the differential cross section for nucleon induced nuclear reaction in the framework of pre-equilibrium emission model. Solution method: Single neutron emission was treated by assuming occurrence of the reaction in successive steps. Each step is called phase because of the phase transition nature of the theory. The probability of emission was calculated statistically using bases of hybrid model [1] and exciton model [2]. However, more precise depletion factor was used in the calculations. Exciton configuration used in the code is that described in earlier work [3]. Restrictions: The program is restricted to single nucleon emission and nucleon

  19. Laser induced plasma on copper target, a non-equilibrium model

    SciTech Connect

    Oumeziane, Amina Ait Liani, Bachir; Parisse, Jean-Denis

    2014-02-15

    The aim of this work is to present a comprehensive numerical model for the UV laser ablation of metal targets, it focuses mainly on the prediction of laser induced plasma thresholds, the effect of the laser-plasma interaction, and the importance of the electronic non-equilibrium in the laser induced plume and its expansion in the background gas. This paper describes a set of numerical models for laser-matter interaction between 193-248 and 355 nm lasers and a copper target. Along with the thermal effects inside the material resulting from the irradiation of the latter with the pulsed laser, the laser-evaporated matter interaction and the plasma formation are thoroughly modelled. In the laser induced plume, the electronic nonequilibrium and the laser beam absorption have been investigated. Our calculations of the plasmas ignition thresholds on copper targets have been validated and compared to experimental as well as theoretical results. Comparison with experiment data indicates that our results are in good agreement with those reported in the literature. Furthermore, the inclusion of electronic non-equilibrium in our work indicated that this important process must be included in models of laser ablation and plasma plume formation.

  20. Liquid-Vapor Equilibrium Isotopic Fractionation of Water. How well can classical water models predict it?

    SciTech Connect

    Chialvo, Ariel A; Horita, Juske

    2009-01-01

    The liquid-vapor equilibrium isotopic fractionation of water is determined by molecular-based simulation, via Gibbs Ensemble Monte Carlo and isothermal-isochoric molecular dynamics involving two radically different but realistic models, the extended simple point charge (SPC/E) and the Gaussian charge polarizable (GCP) models. The predicted temperature dependence of the liquid-vapor equilibrium isotopic fractionation factors for H 2 18O / H 2 16O, H 2 17O / H 2 16O, and 2H 1H 16O / 1H 2 16O are compared against the most accurate experimental datasets to assess the ability of these intermolecular potential models to describe quantum effects according to the Kirkwood-Wigner free energy perturbation ! 2 !expansion. Predictions of the vapor pressure isotopic effect for the H 2 18O / H 2 16O and H 2 17O / H 2 16O pairs are also presented in comparison with experimental data and two recently proposed thermodynamic modeling approaches. Finally, the simulation results are used to discuss some approximations behind the microscopic interpretation of isotopic fractionation based on the underlying roto-translational coupling.

  1. Chemical Equilibrium of Aluminate in Hanford Tank Waste Originating from Tanks 241-AN-105 and 241-AP-108

    SciTech Connect

    McCoskey, Jacob K.; Cooke, Gary A.; Herting, Daniel L.

    2015-09-23

    The purposes of the study described in this document follow; Determine or estimate the thermodynamic equilibrium of gibbsite in contact with two real tank waste supernatant liquids through both dissolution of gibbsite (bottom-up approach) and precipitation of aluminum-bearing solids (top-down approach); determine or estimate the thermodynamic equilibrium of a mixture of gibbsite and real tank waste saltcake in contact with real tank waste supernatant liquid through both dissolution of gibbsite and precipitation of aluminum-bearing solids; and characterize the solids present after equilibrium and precipitation of aluminum-bearing solids.

  2. Econometrically calibrated computable general equilibrium models: Applications to the analysis of energy and climate politics

    NASA Astrophysics Data System (ADS)

    Schu, Kathryn L.

    Economy-energy-environment models are the mainstay of economic assessments of policies to reduce carbon dioxide (CO2) emissions, yet their empirical basis is often criticized as being weak. This thesis addresses these limitations by constructing econometrically calibrated models in two policy areas. The first is a 35-sector computable general equilibrium (CGE) model of the U.S. economy which analyzes the uncertain impacts of CO2 emission abatement. Econometric modeling of sectors' nested constant elasticity of substitution (CES) cost functions based on a 45-year price-quantity dataset yields estimates of capital-labor-energy-material input substitution elasticities and biases of technical change that are incorporated into the CGE model. I use the estimated standard errors and variance-covariance matrices to construct the joint distribution of the parameters of the economy's supply side, which I sample to perform Monte Carlo baseline and counterfactual runs of the model. The resulting probabilistic abatement cost estimates highlight the importance of the uncertainty in baseline emissions growth. The second model is an equilibrium simulation of the market for new vehicles which I use to assess the response of vehicle prices, sales and mileage to CO2 taxes and increased corporate average fuel economy (CAFE) standards. I specify an econometric model of a representative consumer's vehicle preferences using a nested CES expenditure function which incorporates mileage and other characteristics in addition to prices, and develop a novel calibration algorithm to link this structure to vehicle model supplies by manufacturers engaged in Bertrand competition. CO2 taxes' effects on gasoline prices reduce vehicle sales and manufacturers' profits if vehicles' mileage is fixed, but these losses shrink once mileage can be adjusted. Accelerated CAFE standards induce manufacturers to pay fines for noncompliance rather than incur the higher costs of radical mileage improvements

  3. Modeling the dynamic equilibrium of objects weakened by thin low-strength inclusions

    SciTech Connect

    Skopetskii, V.V.; Deineka, V.S.; Marchenko, O.A.

    1995-11-01

    Successful development of hydroelectric power as well as the use and protection of the resources of the Azov/Black Sea basin require formulation and solution of design and control problems for hydroengineering and coastal constructions. The authors have developed two-dimensional mathematical models of dynamic equilibrium of various hydroengineering and coastal constructions with weak thin sections of natural or artificial origin (low-strength inclusions, cracks, technological seams), where shearing strength conditions must be considered. These models are applicable to objects whose dynamic characteristics can be fully described by considering their profile cross-sections (dams, coastal slopes, wave breakers). The weak thin sections are modeled by cuts with appropriate contact conditions. Finite-element algorithms have been developed for solving the corresponding initial-boundary-value problems, and a model example has been solved.

  4. Analysis of a decision model in the context of equilibrium pricing and order book pricing

    NASA Astrophysics Data System (ADS)

    Wagner, D. C.; Schmitt, T. A.; Schäfer, R.; Guhr, T.; Wolf, D. E.

    2014-12-01

    An agent-based model for financial markets has to incorporate two aspects: decision making and price formation. We introduce a simple decision model and consider its implications in two different pricing schemes. First, we study its parameter dependence within a supply-demand balance setting. We find realistic behavior in a wide parameter range. Second, we embed our decision model in an order book setting. Here, we observe interesting features which are not present in the equilibrium pricing scheme. In particular, we find a nontrivial behavior of the order book volumes which reminds of a trend switching phenomenon. Thus, the decision making model alone does not realistically represent the trading and the stylized facts. The order book mechanism is crucial.

  5. Surface structures of equilibrium restricted curvature model on two fractal substrates

    NASA Astrophysics Data System (ADS)

    Song, Li-Jian; Tang, Gang; Zhang, Yong-Wei; Han, Kui; Xun, Zhi-Peng; Xia, Hui; Hao, Da-Peng; Li, Yan

    2014-01-01

    With the aim to probe the effects of the microscopic details of fractal substrates on the scaling of discrete growth models, the surface structures of the equilibrium restricted curvature (ERC) model on Sierpinski arrowhead and crab substrates are analyzed by means of Monte Carlo simulations. These two fractal substrates have the same fractal dimension df, but possess different dynamic exponents of random walk zrw. The results show that the surface structure of the ERC model on fractal substrates are related to not only the fractal dimension df, but also to the microscopic structures of the substrates expressed by the dynamic exponent of random walk zrw. The ERC model growing on the two substrates follows the well-known Family—Vicsek scaling law and satisfies the scaling relations 2α + df asymp z asymp 2zrw. In addition, the values of the scaling exponents are in good agreement with the analytical prediction of the fractional Mullins—Herring equation.

  6. Mapping Nonequilibrium onto Equilibrium: The Macroscopic Fluctuations of Simple Transport Models

    NASA Astrophysics Data System (ADS)

    Tailleur, Julien; Kurchan, Jorge; Lecomte, Vivien

    2007-10-01

    We study a simple transport model driven out of equilibrium by reservoirs at the boundaries, corresponding to the hydrodynamic limit of the symmetric simple exclusion process. We show that a nonlocal transformation of densities and currents maps the large deviations of the model into those of an open, isolated chain satisfying detailed balance, where rare fluctuations are the time reversals of relaxations. We argue that the existence of such a mapping is the immediate reason why it is possible for this model to obtain an explicit solution for the large-deviation function of densities through elementary changes of variables. This approach can be generalized to the other models previously treated with the macroscopic fluctuation theory.

  7. Chemical Kinetic Modeling of Advanced Transportation Fuels

    SciTech Connect

    PItz, W J; Westbrook, C K; Herbinet, O

    2009-01-20

    Development of detailed chemical kinetic models for advanced petroleum-based and nonpetroleum based fuels is a difficult challenge because of the hundreds to thousands of different components in these fuels and because some of these fuels contain components that have not been considered in the past. It is important to develop detailed chemical kinetic models for these fuels since the models can be put into engine simulation codes used for optimizing engine design for maximum efficiency and minimal pollutant emissions. For example, these chemistry-enabled engine codes can be used to optimize combustion chamber shape and fuel injection timing. They also allow insight into how the composition of advanced petroleum-based and non-petroleum based fuels affect engine performance characteristics. Additionally, chemical kinetic models can be used separately to interpret important in-cylinder experimental data and gain insight into advanced engine combustion processes such as HCCI and lean burn engines. The objectives are: (1) Develop detailed chemical kinetic reaction models for components of advanced petroleum-based and non-petroleum based fuels. These fuels models include components from vegetable-oil-derived biodiesel, oil-sand derived fuel, alcohol fuels and other advanced bio-based and alternative fuels. (2) Develop detailed chemical kinetic reaction models for mixtures of non-petroleum and petroleum-based components to represent real fuels and lead to efficient reduced combustion models needed for engine modeling codes. (3) Characterize the role of fuel composition on efficiency and pollutant emissions from practical automotive engines.

  8. A game-theoretic model for punctuated equilibrium: species invasion and stasis through coevolution.

    PubMed

    Cressman, Ross; Garay, József

    2006-04-01

    A general theory of coevolution is developed that combines the ecological effects of species' densities with the evolutionary effects of changing phenotypes. Our approach also treats the evolutionary changes between coevolving species with discreet traits after the appearance of a new species. We apply this approach to habitat selection models where new species first emerge through competitive selection in an isolated habitat. This successful invasion is quickly followed by evolutionary changes in behavior when this species discovers the other habitat, leading to punctuated equilibrium as the final outcome. PMID:16513251

  9. Equilibrium-restricted solid-on-solid growth model on fractal substrates.

    PubMed

    Lee, Sang Bub; Kim, Jin Min

    2009-08-01

    The equilibrium-restricted solid-on-solid growth model on fractal substrates is studied by introducing a fractional Langevin equation. The growth exponent beta and the roughness exponent alpha defined, respectively, by the surface width via W approximately t(beta) and the saturated width via W(sat) approximately L(alpha), L being the system size, were obtained by a power-counting analysis, and the scaling relation 2alpha+d(f)=z(RW) was found to hold. The numerical simulation data on Sierpinski gasket, checkerboard fractal, and critical percolation cluster were found to agree well with the analytical predictions of the fractional Langevin equation. PMID:19792071

  10. Regional disaster impact analysis: comparing Input-Output and Computable General Equilibrium models

    NASA Astrophysics Data System (ADS)

    Koks, E. E.; Carrera, L.; Jonkeren, O.; Aerts, J. C. J. H.; Husby, T. G.; Thissen, M.; Standardi, G.; Mysiak, J.

    2015-11-01

    A large variety of models has been developed to assess the economic losses of disasters, of which the most common ones are Input-Output (IO) and Computable General Equilibrium (CGE) models. In addition, an increasing numbers of scholars has developed hybrid approaches; one that combines both or either of them in combination with non-economic methods. While both IO and CGE models are widely used, they are mainly compared on theoretical grounds. Few studies have compared disaster impacts of different model types in a systematic way and for the same geographical area, using similar input data. Such a comparison is valuable from both a scientific and policy perspective as the magnitude and the spatial distribution of the estimated losses are likely to vary with the chosen modelling approach (IO, CGE, or hybrid). Hence, regional disaster impact loss estimates resulting from a range of models facilitates better decisions and policy making. Therefore, in this study we analyze one specific case study, using three regional models: two hybrid IO models and a regionally calibrated version of a global CGE model. The case study concerns two flood scenarios in the Po-river basin in Italy. Modelling results indicate that the difference in estimated total (national) economic losses and the regional distribution of those losses may vary by up to a factor of seven between the three models, depending on the type of recovery path. Total economic impact, comprising all Italian regions, is negative in all models though.

  11. Numerical modeling tools for chemical vapor deposition

    NASA Technical Reports Server (NTRS)

    Jasinski, Thomas J.; Childs, Edward P.

    1992-01-01

    Development of general numerical simulation tools for chemical vapor deposition (CVD) was the objective of this study. Physical models of important CVD phenomena were developed and implemented into the commercial computational fluid dynamics software FLUENT. The resulting software can address general geometries as well as the most important phenomena occurring with CVD reactors: fluid flow patterns, temperature and chemical species distribution, gas phase and surface deposition. The physical models are documented which are available and examples are provided of CVD simulation capabilities.

  12. A stochastic equilibrium model for the North American natural gas market

    NASA Astrophysics Data System (ADS)

    Zhuang, Jifang

    This dissertation is an endeavor in the field of energy modeling for the North American natural gas market using a mixed complementarity formulation combined with the stochastic programming. The genesis of the stochastic equilibrium model presented in this dissertation is the deterministic market equilibrium model developed in [Gabriel, Kiet and Zhuang, 2005]. Based on some improvements that we made to this model, including proving new existence and uniqueness results, we present a multistage stochastic equilibrium model with uncertain demand for the deregulated North American natural gas market using the recourse method of the stochastic programming. The market participants considered by the model are pipeline operators, producers, storage operators, peak gas operators, marketers and consumers. Pipeline operators are described with regulated tariffs but also involve "congestion pricing" as a mechanism to allocate scarce pipeline capacity. Marketers are modeled as Nash-Cournot players in sales to the residential and commercial sectors but price-takers in all other aspects. Consumers are represented by demand functions in the marketers' problem. Producers, storage operators and peak gas operators are price-takers consistent with perfect competition. Also, two types of the natural gas markets are included: the long-term and spot markets. Market participants make both high-level planning decisions (first-stage decisions) in the long-term market and daily operational decisions (recourse decisions) in the spot market subject to their engineering, resource and political constraints, resource constraints as well as market constraints on both the demand and the supply side, so as to simultaneously maximize their expected profits given others' decisions. The model is shown to be an instance of a mixed complementarity problem (MiCP) under minor conditions. The MiCP formulation is derived from applying the Karush-Kuhn-Tucker optimality conditions of the optimization problems

  13. Transport Sector Marginal Abatement Cost Curves in Computable General Equilibrium Model

    NASA Astrophysics Data System (ADS)

    Tippichai, Atit; Fukuda, Atsushi; Morisugi, Hisayoshi

    In the last decade, computable general equilibrium (CGE) models have emerged a standard tool for climate policy evaluation due to their abilities to prospectively elucidate the character and magnitude of the economic impacts of energy and environmental policies. Furthermore, marginal abatement cost (MAC) curves which represent GHG emissions reduction potentials and costs can be derived from these top-down economic models. However, most studies have never address MAC curves for a specific sector that have a large coverage of countries which are needed for allocation of optimal emission reductions. This paper aims to explicitly describe the meaning and character of MAC curves for transport sector in a CGE context through using the AIM/CGE Model developed by Toshihiko Masui. It found that the MAC curves derived in this study are the inverse of the general equilibrium reduction function for CO2 emissions. Moreover, the transport sector MAC curves for six regions including USA, EU-15, Japan, China, India, and Brazil, derived from this study are compared to the reduction potentials under 100 USD/tCO2 in 2020 from a bottom-up study. The results showed that the ranking of the regional reduction potentials in transport sector from this study are almost same with the bottom-up study except the ranks of the EU-15 and China. In addition, the range of the reduction potentials from this study is wider and only the USA has higher potentials than those derived from the bottom-up study.

  14. Application of Equilibrium Models of Solution Hybridization to Microarray Design and Analysis

    PubMed Central

    Gharaibeh, Raad Z.; Newton, Joshua M.; Weller, Jennifer W.; Gibas, Cynthia J.

    2010-01-01

    Background The probe percent bound value, calculated using multi-state equilibrium models of solution hybridization, is shown to be useful in understanding the hybridization behavior of microarray probes having 50 nucleotides, with and without mismatches. These longer oligonucleotides are in widespread use on microarrays, but there are few controlled studies of their interactions with mismatched targets compared to 25-mer based platforms. Principal Findings 50-mer oligonucleotides with centrally placed single, double and triple mismatches were spotted on an array. Over a range of target concentrations it was possible to discriminate binding to perfect matches and mismatches, and the type of mismatch could be predicted accurately in the concentration midrange (100 pM to 200 pM) using solution hybridization modeling methods. These results have implications for microarray design, optimization and analysis methods. Conclusions Our results highlight the importance of incorporating biophysical factors in both the design and the analysis of microarrays. Use of the probe “percent bound” value predicted by equilibrium models of hybridization is confirmed to be important for predicting and interpreting the behavior of long oligonucleotide arrays, as has been shown for short oligonucleotide arrays. PMID:20548788

  15. Non equilibrium dynamics of mixing, oscillations, and equilibration: A model study

    SciTech Connect

    Ho, Chiu Man; Boyanovsky, D.; Ho, C. M.

    2006-12-22

    The non-equilibrium dynamics of mixing, oscillations and equilibration is studied in a field theory of flavored neutral mesons that effectively models two flavors of mixed neutrinos, in interaction with other mesons that represent a thermal bath of hadrons or quarks and charged leptons. This model describes the general features of neutrino mixing and relaxation via charged currents in a medium. The reduced density matrix and the non-equilibrium effective action that describes the propagation of neutrinos is obtained by integrating out the bath degrees of freedom. We obtain the dispersion relations, mixing angles and relaxation rates of ``neutrino'' quasiparticles. The dispersion relations and mixing angles are of the same form as those of neutrinos in the medium, and the relaxation rates are given by $\\Gamma_1(k) = \\Gamma_{ee}(k) \\cos^2\\theta_m(k)+\\Gamma_{\\mu\\mu}(k)\\sin^2\\theta_m(k); \\Gamma_2(k)= \\Gamma_{\\mu\\mu}(k) \\cos^2\\theta_m(k)+\\Gamma_{ee}(k)\\sin^2\\theta_m(k) $ where $\\Gamma_{\\alpha\\alpha}(k)$ are the relaxation rates of the flavor fields in \\emph{absence} of mixing, and $\\theta_m(k)$ is the mixing angle in the medium. A Weisskopf-Wigner approximation that describes the asymptotic time evolution in terms of a non-hermitian Hamiltonian is derived. At long time $>>\\Gamma^{-1}_{1,2}$ ``neutrinos'' equilibrate with the bath. The equilibrium density matrix is nearly diagonal in the basis of eigenstates of an \\emph{effective Hamiltonian that includes self-energy corrections in the medium}. The equilibration of ``sterile neutrinos'' via active-sterile mixing is discussed.

  16. A computer program for two-dimensional and axisymmetric nonreacting perfect gas and equilibrium chemically reacting laminar, transitional and-or turbulent boundary layer flows

    NASA Technical Reports Server (NTRS)

    Miner, E. W.; Anderson, E. C.; Lewis, C. H.

    1971-01-01

    A computer program is described in detail for laminar, transitional, and/or turbulent boundary-layer flows of non-reacting (perfect gas) and reacting gas mixtures in chemical equilibrium. An implicit finite difference scheme was developed for both two dimensional and axisymmetric flows over bodies, and in rocket nozzles and hypervelocity wind tunnel nozzles. The program, program subroutines, variables, and input and output data are described. Also included is the output from a sample calculation of fully developed turbulent, perfect gas flow over a flat plate. Input data coding forms and a FORTRAN source listing of the program are included. A method is discussed for obtaining thermodynamic and transport property data which are required to perform boundary-layer calculations for reacting gases in chemical equilibrium.

  17. Systematic validation of non-equilibrium thermochemical models using Bayesian inference

    SciTech Connect

    Miki, Kenji; Panesi, Marco; Prudhomme, Serge

    2015-10-01

    The validation process proposed by Babuška et al. [1] is applied to thermochemical models describing post-shock flow conditions. In this validation approach, experimental data is involved only in the calibration of the models, and the decision process is based on quantities of interest (QoIs) predicted on scenarios that are not necessarily amenable experimentally. Moreover, uncertainties present in the experimental data, as well as those resulting from an incomplete physical model description, are propagated to the QoIs. We investigate four commonly used thermochemical models: a one-temperature model (which assumes thermal equilibrium among all inner modes), and two-temperature models developed by Macheret et al. [2], Marrone and Treanor [3], and Park [4]. Up to 16 uncertain parameters are estimated using Bayesian updating based on the latest absolute volumetric radiance data collected at the Electric Arc Shock Tube (EAST) installed inside the NASA Ames Research Center. Following the solution of the inverse problems, the forward problems are solved in order to predict the radiative heat flux, QoI, and examine the validity of these models. Our results show that all four models are invalid, but for different reasons: the one-temperature model simply fails to reproduce the data while the two-temperature models exhibit unacceptably large uncertainties in the QoI predictions.

  18. Initial fluxon models of CME onset: loss-of-equilibrium, breakout, tether-cutting

    NASA Astrophysics Data System (ADS)

    Deforest, C.

    2005-12-01

    I will present results from initial models of CME onset using a new force-free magnetic evolution code, FLUX, that uses the novel fluxon approach to MHD modeling. FLUX is a quasi-Lagrangian solver that is free of numerical reconnection and that I am making available as free software. It is currently suitable for studying evolving force-free equilibria in the presence of only controlled reconnection; development work is ongoing to add plasma static and dynamic forces. I plan to consider three simple configurations typical of three current genres of CME onset model: loss of equilibrium under smooth motion by the photosphere; "tether-cutting" (reconnection of a containment field underneath a twisted prominence field); and "breakout" (reconnection of a containment field above a twisted prominence field). In each case I will estimate the magnetic energy available to accelerate mass, and discuss the resulting shape of the remnant open field regions ("dimming regions") after liftoff.

  19. Equilibrium and nonequilibrium molecular-dynamics simulations of the central force model of water

    NASA Astrophysics Data System (ADS)

    Bresme, Fernando

    2001-10-01

    Equilibrium and nonequilibrium molecular-dynamics simulations of the central force model of water (CFM) [Lemberg and Stillinger, J. Chem. Phys. 62, 1677 (1975)] are presented. We consider a model based on a functional form introduced in theoretical studies of associating systems employing integral equations [F. Bresme, J. Chem. Phys. 108, 4505 (1998)]. Results on thermodynamic, dynamic, dielectric, and coexistence properties are presented. The central force model shows satisfactory agreement with the experimental results in all these cases. In addition, nonequilibrium molecular-dynamics simulations show that the CFM predicts a decrease of the thermal conductivity with temperature, as observed in the experiment, but this dependence is reproduced qualitatively at temperatures characteristic of supercooled states. These results emphasize the need for further studies of the heat conduction and properties of water in these conditions. Overall the present potential should provide a basis for further theoretical and simulation studies of complex systems where water is present.

  20. Evolution and non-equilibrium physics: A study of the Tangled Nature Model

    NASA Astrophysics Data System (ADS)

    Becker, Nikolaj; Sibani, Paolo

    2014-01-01

    We argue that the stochastic dynamics of interacting agents which replicate, mutate and die constitutes a non-equilibrium physical process akin to aging in complex materials. Specifically, our study uses extensive computer simulations of the Tangled Nature Model (TNM) of biological evolution to show that punctuated equilibria successively generated by the model's dynamics have increasing entropy and are separated by increasing entropic barriers. We further show that these states are organized in a hierarchy and that limiting the values of possible interactions to a finite interval leads to stationary fluctuations within a component of the latter. A coarse-grained description based on the temporal statistics of quakes, the events leading from one component of the hierarchy to the next, accounts for the logarithmic growth of the population and the decaying rate of change of macroscopic variables. Finally, we question the role of fitness in large-scale evolution models and speculate on the possible evolutionary role of rejuvenation and memory effects.

  1. On the stability of equilibrium for a reformulated foreign trade model of three countries

    NASA Astrophysics Data System (ADS)

    Dassios, Ioannis K.; Kalogeropoulos, Grigoris

    2014-06-01

    In this paper, we study the stability of equilibrium for a foreign trade model consisting of three countries. As the gravity equation has been proven an excellent tool of analysis and adequately stable over time and space all over the world, we further enhance the problem to three masses. We use the basic Structure of Heckscher-Ohlin-Samuelson model. The national income equals consumption outlays plus investment plus exports minus imports. The proposed reformulation of the problem focus on two basic concepts: (1) the delay inherited in our economic variables and (2) the interaction effect along the three economies involved. Stability and stabilizability conditions are investigated while numerical examples provide further insight and better understanding. Finally, a generalization of the gravity equation is somehow obtained for the model.

  2. Novel chamber to measure equilibrium soil-air partitioning coefficients of low-volatility organic chemicals under conditions of varying temperature and soil moisture.

    PubMed

    Wolters, André; Linnemann, Volker; Smith, Kilian E C; Klingelmann, Eva; Park, Byung-Jun; Vereecken, Harry

    2008-07-01

    The need to determine soil-air partitioning coefficients (K(SA)) of low-volatility organic chemicals as a measure of their distribution in the soil surface after release into the environment resulted in the development of a novel chamber system, which has been filed for patent. A major advantage of this pseudo-static system is that sufficient time can be factored into the experiment to ensure that the system has achieved equilibrium. In a highly precise method, the air is collected in adsorption tubes and subsequently liberated in a thermodesorption system for the quantitation of the adsorbed compound. The precision of the method is great enough that even the effects of temperature and soil moisture on the soil-air partitioning of very low-volatility compounds can be quantified. Because of analytical detection limits, quantitation of these influences has not been possible to date. Functionality of the setup was illustrated by measurements on the fungicide fenpropimorph. K(SA) values of fenpropimorph displayed a negative relationship with temperature and soil moisture. The type of application (spraying or incorporation) and the use of formulated compounds was shown to have a major impact on the measured K(SA) values. Comparison with calculations using an estimation method revealed that the use of experimentally determined K(SA) values will facilitate a more adequate consideration of volatilization in recent model approaches. PMID:18678019

  3. Phase-equilibrium modelling of blueschists from the Vestgötabreen Complex (SW Svalbard)

    NASA Astrophysics Data System (ADS)

    Kośmińska, Karolina; Majka, Jarosław; Manecki, Maciej; Lorenz, Henning; Kozub, Gabriela

    2014-05-01

    In Svalbard Archipelago, blueschists are known from Motalafjella area (Oscar II Land). They belong to the Vestgötabreen Complex, which is divided into a Lower (LU) and Upper Unit (UU). The former is composed of high pressure-low temperature (HP-LT) metasediments. The latter consists mainly of blueschists and eclogites. Various radiometric dating yielded an age of c. 470 Ma for the HP-LT metamorphism in the Motalafjella area. The pressure-temperature (P-T) conditions for carpholite-bearing schists from LU have been estimated to c. 16 kbar and 330-450°C (Agard et al., 2005), whereas eclogites from UU indicate peak conditions of 18-24 kbar and 580-640°C (Hirajima et al., 1988). During the fieldwork in 2011, blueschists were also discovered at the western coast of Nordenskiöld Land. They form isolated bodies enclosed within metasedimentary units, but their tectonic position is still under debate. Preliminary P-T estimates indicate peak pressure conditions of c. 17 kbar and 480°C (Kośmińska et al., in revision). The age of metamorphism is unknown, however P-T conditions as well as metamorphic assemblage suggest that the blueschists from Nordenskiöld Land may be an equivalent of these in the Vestgötabreen Complex. Samples of blueschists from UU have been collected on Skipperryggen. They consist mainly of glaucophane, garnet, white micas (phengite and paragonite), rutile, lawsonite and chlorite. The garnet typically forms euhedral to subhedral porphyroblasts which contain voluminous inclusions. Its composition varies from Alm63Prp13Grs22Sps2 in the cores to Alm60Prp19Grs20Sps1 in the rims. The change in chemical zoning is rather gradual. The garnet shows bowl-shaped pyrope profiles and opposite almandine trends. The P-T conditions were estimated using phase equilibrium modeling. Preliminary modeling in the NCKFMMnASHTO system yields peak pressure conditions at c. 20 kbar and 520°C. The estimated P-T conditions for the blueschists from Skipperryggen are in

  4. Self-consistent Equilibrium Model of Low-aspect-ratio Toroidal Plasma with Energetic Beam Ions

    SciTech Connect

    E.V. Belova; N.N. Gorelenkov; C.Z. Cheng

    2003-04-09

    A theoretical model is developed which allows the self-consistent inclusion of the effects of energetic beam ions in equilibrium calculations of low-aspect-ratio toroidal devices. A two-component plasma is considered, where the energetic ions are treated using a kinetic Vlasov description, while a one-fluid magnetohydrodynamic description is used to represent the thermal plasma. The model allows for an anisotropic distribution function and a large Larmor radius of the beam ions. Numerical results are obtained for neutral-beam-heated plasmas in the National Spherical Torus Experiment (NSTX). Self-consistent equilibria with an anisotropic fast-ion distribution have been calculated for NSTX. It is shown for typical experimental parameters that the contribution of the energetic neutral-beam ions to the total current can be comparable to that of the background plasma, and that the kinetic modifications of the equilibrium can be significant. The range of validity of the finite-Larmor-radius expansion and of the reduced kinetic descriptions for the beam ions in NSTX is discussed. The calculated kinetic equilibria can be used for self-consistent numerical studies of beam-ion-driven instabilities in NSTX.

  5. Capital accumulation, income distribution and endogenous fertility in an overlapping generations general equilibrium model.

    PubMed

    Raut, L K

    1991-01-01

    A study is conducted in attempts to increase the understanding of the links between macroeconomic effects and causes of population growth in formulating policy. An overlapping generations general equilibrium model is employed aggregating household decisions about fertility, savings, and investment in the human capital of children with the objective of studying intertemporal relationships among population growth, income distribution, inter-generation social mobility, skill composition of the labor force, and household income. As a result of endogenous fertility, the equilibrium path attains steady state from the second generation. Income tax transfer, child taxation, and social security taxation policies are also examined in the paper. A structural explanation is given for the inverse household income-child quantity and negative child quality-quantity relationships seen in developing countries. In a Cobb-Douglas economy, these relationships hold in the short-run, potentially working over the long-run in other economies. Overall, the model shows that group interests may hinder emergence of perfect capital markets with private initiatives. Where developing countries are concerned, these results have strong implications for population policy. A policy mix of building good quality schools, or subsidizing rural education, introducing a formal social security program, and providing high-yield, risk-free investments, banking, and insurance services to the poor is recommended. PMID:12284076

  6. Final Technical Report: "Representing Endogenous Technological Change in Climate Policy Models: General Equilibrium Approaches"

    SciTech Connect

    Ian Sue Wing

    2006-04-18

    The research supported by this award pursued three lines of inquiry: (1) The construction of dynamic general equilibrium models to simulate the accumulation and substitution of knowledge, which has resulted in the preparation and submission of several papers: (a) A submitted pedagogic paper which clarifies the structure and operation of computable general equilibrium (CGE) models (C.2), and a review article in press which develops a taxonomy for understanding the representation of technical change in economic and engineering models for climate policy analysis (B.3). (b) A paper which models knowledge directly as a homogeneous factor, and demonstrates that inter-sectoral reallocation of knowledge is the key margin of adjustment which enables induced technical change to lower the costs of climate policy (C.1). (c) An empirical paper which estimates the contribution of embodied knowledge to aggregate energy intensity in the U.S. (C.3), followed by a companion article which embeds these results within a CGE model to understand the degree to which autonomous energy efficiency improvement (AEEI) is attributable to technical change as opposed to sub-sectoral shifts in industrial composition (C.4) (d) Finally, ongoing theoretical work to characterize the precursors and implications of the response of innovation to emission limits (E.2). (2) Data development and simulation modeling to understand how the characteristics of discrete energy supply technologies determine their succession in response to emission limits when they are embedded within a general equilibrium framework. This work has produced two peer-reviewed articles which are currently in press (B.1 and B.2). (3) Empirical investigation of trade as an avenue for the transmission of technological change to developing countries, and its implications for leakage, which has resulted in an econometric study which is being revised for submission to a journal (E.1). As work commenced on this topic, the U.S. withdrawal

  7. An Equilibrium Constitutive Model of Anisotropic Cartilage Damage to Elucidate Mechanisms of Damage Initiation and Progression.

    PubMed

    Stender, Michael E; Regueiro, Richard A; Klisch, Stephen M; Ferguson, Virginia L

    2015-08-01

    Traumatic injuries and gradual wear-and-tear of articular cartilage (AC) that can lead to osteoarthritis (OA) have been hypothesized to result from tissue damage to AC. In this study, a previous equilibrium constitutive model of AC was extended to a constitutive damage articular cartilage (CDAC) model. In particular, anisotropic collagen (COL) fibril damage and isotropic glycosaminoglycan (GAG) damage were considered in a 3D formulation. In the CDAC model, time-dependent effects, such as viscoelasticity and poroelasticity, were neglected, and thus all results represent the equilibrium response after all time-dependent effects have dissipated. The resulting CDAC model was implemented in two different finite-element models. The first simulated uniaxial tensile loading to failure, while the second simulated spherical indentation with a rigid indenter displaced into a bilayer AC sample. Uniaxial tension to failure simulations were performed for three COL fibril Lagrangian failure strain (i.e., the maximum elastic COL fibril strain) values of 15%, 30%, and 45%, while spherical indentation simulations were performed with a COL fibril Lagrangian failure strain of 15%. GAG damage parameters were held constant for all simulations. Our results indicated that the equilibrium postyield tensile response of AC and the macroscopic tissue failure strain are highly dependent on COL fibril Lagrangian failure strain. The uniaxial tensile response consisted of an initial nonlinear ramp region due to the recruitment of intact fibrils followed by a rapid decrease in tissue stress at initial COL fibril failure, as a result of COL fibril damage which continued until ultimate tissue failure. In the spherical indentation simulation, damage to both the COL fibril and GAG constituents was located only in the superficial zone (SZ) and near the articular surface with tissue thickening following unloading. Spherical indentation simulation results are in agreement with published experimental

  8. An effective continuum approach for modeling non-equilibrium structural evolution of protein nanofiber networks.

    PubMed

    Cheng, Liang; Englander, Ongi; Paravastu, Anant; Oates, William S

    2011-08-01

    We quantify the formation and evolution of protein nanofibers using a new phase field modeling framework and compare the results to transmission electron microscopy measurements (TEM) and time-dependent growth measurements given in the literature. The modeling framework employs a set of effective continuum equations combined with underlying nanoscale forces and chemical potential relations governing protein nanofiber formation in solution. Calculations based on the theoretical framework are implemented numerically using a nonlinear finite element phase field modeling approach that couples homogenized protein molecular structure via a vector order parameter with chemical potential relations that describe interactions between the nanofibers and the surrounding solution. Homogenized, anisotropic molecular and chemical flux relations are found to be critical in obtaining nanofiber growth from seed particles or a random monomer bath. In addition, the model predicts both sigmoidal and first-order growth kinetics for protein nanofibers for unseeded and seeded models, respectively. These simulations include quantitative predictions on time scales of typical protein self-assembly behavior which qualitatively match TEM measurements of the RADA16-I protein and growth rate measurements for amyloid nanofibers from the literature. For comparisons with experiments, the numerical model performs multiple nanofiber protein evolution simulations with a characteristic length scale of ∼2.4 nm and characteristic time scale of ∼9.1 h. These results provide a new modeling tool that couples underlying monomer structure with self-assembling nanofiber behavior that is compatible with various external loadings and chemical environments. PMID:21823733

  9. An effective continuum approach for modeling non-equilibrium structural evolution of protein nanofiber networks

    NASA Astrophysics Data System (ADS)

    Cheng, Liang; Englander, Ongi; Paravastu, Anant; Oates, William S.

    2011-08-01

    We quantify the formation and evolution of protein nanofibers using a new phase field modeling framework and compare the results to transmission electron microscopy measurements (TEM) and time-dependent growth measurements given in the literature. The modeling framework employs a set of effective continuum equations combined with underlying nanoscale forces and chemical potential relations governing protein nanofiber formation in solution. Calculations based on the theoretical framework are implemented numerically using a nonlinear finite element phase field modeling approach that couples homogenized protein molecular structure via a vector order parameter with chemical potential relations that describe interactions between the nanofibers and the surrounding solution. Homogenized, anisotropic molecular and chemical flux relations are found to be critical in obtaining nanofiber growth from seed particles or a random monomer bath. In addition, the model predicts both sigmoidal and first-order growth kinetics for protein nanofibers for unseeded and seeded models, respectively. These simulations include quantitative predictions on time scales of typical protein self-assembly behavior which qualitatively match TEM measurements of the RADA16-I protein and growth rate measurements for amyloid nanofibers from the literature. For comparisons with experiments, the numerical model performs multiple nanofiber protein evolution simulations with a characteristic length scale of ˜2.4 nm and characteristic time scale of ˜9.1 h. These results provide a new modeling tool that couples underlying monomer structure with self-assembling nanofiber behavior that is compatible with various external loadings and chemical environments.

  10. Implementation of a vibrationally linked chemical reaction model for DSMC

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  11. An equilibrium model for linear and closed-loop amyloid fibril formation

    PubMed Central

    Yang, Shuo; Griffin, Michael D. W.; Binger, Katrina J.; Schuck, Peter; Howlett, Geoffrey J.

    2014-01-01

    Amyloid fibrils and their soluble oligomeric intermediates are implicated in several age-related diseases including Alzheimer’s and Parkinson’s disease. The distribution of oligomers and fibrils is related to toxicity and is dependent on the pathways for fibril assembly, generally considered to occur via a slow nucleation step that precedes fibril elongation. Human apolipoprotein (apo) C-II forms amyloid fibrils via a reversible self-assembly process accompanied by closed-loop formation and fibril breaking and joining. Our fluorescence quenching and sedimentation velocity experiments with Alexa488-labelled apoC-II indicated a time-dependent sub-unit interchange for both linear and closed-loop fibrils, while dilution experiments using mature fibrils indicated a shift to smaller size distributions consistent with a reversible assembly pathway. To account for this behaviour we developed an equilibrium self-association model that describes the final size distributions of apoC-II fibrils formed at different starting concentrations. The model proposes a reversible isomerisation of apoC-II monomer to form an active conformer that self-assembles into fibrils via an isodesmic self-association pathway coupled to fibril length-dependent closed-loop formation. The model adequately described fibril size distributions and the proportion of closed-loops as a function of total apoC-II concentration over the concentration range 0.1–0.5 mg/ml. Extension of the model to include the rates of isomerisation, self-association and fibril breaking and joining provided satisfactory global fits to kinetic data on fibril formation and changes in average fibril size at different apoC-II starting concentrations. The model provides a simple thermodynamic description of the processes governing the size distribution of apoC-II fibrils at equilibrium and the formation of discrete oligomeric intermediates. PMID:22370559

  12. Non-local thermodynamic equilibrium 1.5D modeling of red giant stars

    SciTech Connect

    Young, Mitchell E.; Short, C. Ian

    2014-05-20

    Spectra for two-dimensional (2D) stars in the 1.5D approximation are created from synthetic spectra of one-dimensional (1D) non-local thermodynamic equilibrium (NLTE) spherical model atmospheres produced by the PHOENIX code. The 1.5D stars have the spatially averaged Rayleigh-Jeans flux of a K3-4 III star while varying the temperature difference between the two 1D component models (ΔT {sub 1.5D}) and the relative surface area covered. Synthetic observable quantities from the 1.5D stars are fitted with quantities from NLTE and local thermodynamic equilibrium (LTE) 1D models to assess the errors in inferred T {sub eff} values from assuming horizontal homogeneity and LTE. Five different quantities are fit to determine the T {sub eff} of the 1.5D stars: UBVRI photometric colors, absolute surface flux spectral energy distributions (SEDs), relative SEDs, continuum normalized spectra, and TiO band profiles. In all cases except the TiO band profiles, the inferred T {sub eff} value increases with increasing ΔT {sub 1.5D}. In all cases, the inferred T {sub eff} value from fitting 1D LTE quantities is higher than from fitting 1D NLTE quantities and is approximately constant as a function of ΔT {sub 1.5D} within each case. The difference between LTE and NLTE for the TiO bands is caused indirectly by the NLTE temperature structure of the upper atmosphere, as the bands are computed in LTE. We conclude that the difference between T {sub eff} values derived from NLTE and LTE modeling is relatively insensitive to the degree of the horizontal inhomogeneity of the star being modeled and largely depends on the observable quantity being fit.

  13. An equilibrium model for linear and closed-loop amyloid fibril formation.

    PubMed

    Yang, Shuo; Griffin, Michael D W; Binger, Katrina J; Schuck, Peter; Howlett, Geoffrey J

    2012-08-10

    Amyloid fibrils and their soluble oligomeric intermediates are implicated in several age-related diseases including Alzheimer's and Parkinson's diseases. The distribution of oligomers and fibrils is related to toxicity and is dependent on the pathways for fibril assembly, generally considered to occur via a slow nucleation step that precedes fibril elongation. Human apolipoprotein (apo) C-II forms amyloid fibrils via a reversible self-assembly process accompanied by closed-loop formation and fibril breaking and joining. Our fluorescence quenching and sedimentation velocity experiments with Alexa488-labeled apoC-II indicated a time-dependent subunit interchange for both linear and closed-loop fibrils, while dilution experiments using mature fibrils indicated a shift to smaller size distributions consistent with a reversible assembly pathway. To account for this behavior, we developed an equilibrium self-association model that describes the final size distributions of apoC-II fibrils formed at different starting concentrations. The model proposes a reversible isomerization of apoC-II monomer to form an active conformer that self-assembles into fibrils via an isodesmic self-association pathway coupled to fibril length-dependent closed-loop formation. The model adequately described fibril size distributions and the proportion of closed loops as a function of total apoC-II concentration over the concentration range 0.1-0.5 mg/ml. Extension of the model to include the rates of isomerization, self-association and fibril breaking and joining provided satisfactory global fits to kinetic data on fibril formation and changes in average fibril size at different apoC-II starting concentrations. The model provides a simple thermodynamic description of the processes governing the size distribution of apoC-II fibrils at equilibrium and the formation of discrete oligomeric intermediates. PMID:22370559

  14. A Kinetic Ladle Furnace Process Simulation Model: Effective Equilibrium Reaction Zone Model Using FactSage Macro Processing

    NASA Astrophysics Data System (ADS)

    Van Ende, Marie-Aline; Jung, In-Ho

    2016-05-01

    The ladle furnace (LF) is widely used in the secondary steelmaking process in particular for the de-sulfurization, alloying, and reheating of liquid steel prior to the casting process. The Effective Equilibrium Reaction Zone model using the FactSage macro processing code was applied to develop a kinetic LF process model. The slag/metal interactions, flux additions to slag, various metallic additions to steel, and arcing in the LF process were taken into account to describe the variations of chemistry and temperature of steel and slag. The LF operation data for several steel grades from different plants were accurately described using the present kinetic model.

  15. Equilibrium and kinetic models on the adsorption of Reactive Black 5 from aqueous solution using Eichhornia crassipes/chitosan composite.

    PubMed

    El-Zawahry, Manal M; Abdelghaffar, Fatma; Abdelghaffar, Rehab A; Hassabo, Ahmed G

    2016-01-20

    New natural biopolymer composite was prepared using extracted cellulose from an environmentally problematic water hyacinth Eichhornia crassipes (EC). The extracted cellulose was functionalized by chitosan and TiO2 nanoparticles to form EC/Chitosan (EC/Cs) composite network. Surface characterization of EC/Cs natural biopolymer composite was examined by spectrum analysis FT-IR, specific surface area, micropore volume, pore width and SEM. Furthermore, the sorption experiments were carried out as a function of pH, various initial dye concentration and contact time. Experiment results showed that the EC/Cs composite have high ability to remove C.I. Reactive Black 5 from its dye-bath effluent. The equilibrium sorption evaluation of RB5 conformed and fitted well to Langmuir adsorption isotherm models and the maximum sorption capacity was 0.606 mg/g. The kinetic adsorption models followed pseudo-second order model and the dye intra-particle diffusion may suggesting a chemical reaction mechanism. Further, it was obvious from the investigation that this composite could be applied as a promising low cost adsorbent for anionic dye removal from aqueous solutions. PMID:26572382

  16. Learners' Mental Models of Chemical Bonding.

    ERIC Educational Resources Information Center

    Coll, Richard K.; Treagust, David F.

    2001-01-01

    Reports on a study involving two each year-12, undergraduate and postgraduate Australian students. Elicits learners' mental models for chemical bonding using semi-structured interviews comprising a three-phase interview protocol. Concludes that learners across all three academic levels preferred simple, realistic mental models for chemical…

  17. Water exchanges versus water works: Insights from a computable general equilibrium model for the Balearic Islands

    NASA Astrophysics Data System (ADS)

    Gómez, Carlos M.; Tirado, Dolores; Rey-Maquieira, Javier

    2004-10-01

    We present a computable general equilibrium model (CGE) for the Balearic Islands, specifically performed to analyze the welfare gains associated with an improvement in the allocation of water rights through voluntary water exchanges (mainly between the agriculture and urban sectors). For the implementation of the empirical model we built the social accounting matrix (SAM) from the last available input-output table of the islands (for the year 1997). Water exchanges provide an important alternative to make the allocation of water flexible enough to cope with the cyclical droughts that characterize the natural water regime on the islands. The main conclusion is that the increased efficiency provided by "water markets" makes this option more advantageous than the popular alternative of building new desalinization plants. Contrary to common opinion, a "water market" can also have positive and significant impacts on the agricultural income.

  18. Water exchanges versus water works: Insights from a computable general equilibrium model for the Balearic Islands

    NASA Astrophysics Data System (ADS)

    Gómez, Carlos M.; Tirado, Dolores; Rey-Maquieira, Javier

    2004-10-01

    We present a computable general equilibrium model (CGE) for the Balearic Islands, specifically performed to analyze the welfare gains associated with an improvement in the allocation of water rights through voluntary water exchanges (mainly between the agriculture and urban sectors). For the implementation of the empirical model we built the social accounting matrix (SAM) from the last available input-output table of the islands (for the year 1997). Water exchanges provide an important alternative to make the allocation of water flexible enough to cope with the cyclical droughts that characterize the natural water regime on the islands. The main conclusion is that the increased efficiency provided by ``water markets'' makes this option more advantageous than the popular alternative of building new desalinization plants. Contrary to common opinion, a ``water market'' can also have positive and significant impacts on the agricultural income.

  19. Equilibrium distributions and relaxation times in gaslike economic models: an analytical derivation.

    PubMed

    Calbet, Xavier; López, José-Luis; López-Ruiz, Ricardo

    2011-03-01

    A step-by-step procedure to derive analytically the exact dynamical evolution equations of the probability density functions (PDFs) of well-known kinetic wealth exchange economic models is shown. This technique gives a dynamical insight into the evolution of the PDF, for example, allowing the calculation of its relaxation times. Their equilibrium PDFs can also be calculated by finding its stationary solutions. This gives as a result an integro-differential equation, which can be solved analytically in some cases and numerically in others. This should provide some guidance into the type of PDFs that can be derived from particular economic agent exchange rules or, for that matter, any other kinetic model of gases with particular collision physics. PMID:21517559

  20. On the possibility of constructing a radiative sunspot model in magnetohydrostatic equilibrium.

    NASA Technical Reports Server (NTRS)

    Mullan, D. J.

    1973-01-01

    It is currently believed that it is impossible to construct a radiative sunspot model in magnetohydrostatic equilibrium unless magnetic fields below the surface are excessively large (greater than 100 kG). This belief is based on results obtained using the mixing length theory of convection. We wish to point out that by using a different theory of convection, due to Opik (1950), it is possible to compute a radiative sunspot model in which the field becomes no greater than 9000 G. By applying two boundary conditions (depth of spot equals depth of convection zone, and magnetic field has zero gradient at the base of the spot) we show that a radiative spot has a unique effective temperature for a given Wilson depression.