Stepwise kinetic equilibrium models of quantitative polymerase chain reaction
Cobbs Gary
2012-08-01
Full Text Available Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Results Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the
An Equilibrium-Based Model of Gas Reaction and Detonation
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.
Response reactions: equilibrium coupling.
Hoffmann, Eufrozina A; Nagypal, Istvan
2006-06-01
It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle.
Zhang, Fan [ORNL; Yeh, Gour-Tsyh [University of Central Florida, Orlando; Parker, Jack C [ORNL; Brooks, Scott C [ORNL; Pace, Molly [ORNL; Kim, Young Jin [ORNL; Jardine, Philip M [ORNL; Watson, David B [ORNL
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.
Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C.; Pace, Molly N.; Kim, Young-Jin; Jardine, Philip M.; Watson, David B.
2007-06-01
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.
Quantifying mixing using equilibrium reactions
Wheat, Philip M.; Posner, Jonathan D.
2009-03-01
A method of quantifying equilibrium reactions in a microchannel using a fluorometric reaction of Fluo-4 and Ca2+ ions is presented. Under the proper conditions, equilibrium reactions can be used to quantify fluid mixing without the challenges associated with constituent mixing measures such as limited imaging spatial resolution and viewing angle coupled with three-dimensional structure. Quantitative measurements of CaCl and calcium-indicating fluorescent dye Fluo-4 mixing are measured in Y-shaped microchannels. Reactant and product concentration distributions are modeled using Green's function solutions and a numerical solution to the advection-diffusion equation. Equilibrium reactions provide for an unambiguous, quantitative measure of mixing when the reactant concentrations are greater than 100 times their dissociation constant and the diffusivities are equal. At lower concentrations and for dissimilar diffusivities, the area averaged fluorescence signal reaches a maximum before the species have interdiffused, suggesting that reactant concentrations and diffusivities must be carefully selected to provide unambiguous, quantitative mixing measures. Fluorometric equilibrium reactions work over a wide range of pH and background concentrations such that they can be used for a wide variety of fluid mixing measures including industrial or microscale flows.
Luigi, A.; Saputelli, B.; Carlas, M.; Canache, P.; Lopez, E. [DPVS Exploracion y Produccion (Venezuela)
1998-12-31
This study was designed to determine the activation energy ranges and frequency factor ranges in chemical reactions in heavy oils of the Orinoco Belt in Venezuela, in order to account for the kinetics of physical changes that occur in the morphology of gas-oil dispersion. A non-equilibrium reaction model was used to model foamy oil behaviour observed at SDZ-182 horizontal well in the Zuata field. Results showed that activation energy for the first reaction ranged from 0 to 0.01 BTU/lb-mol and frequency factor from 0.001 to 1000 l/day. For the second reaction the activation energy was 50x10{sub 3} BTU/lb-mol and the frequency factor 2.75x10{sub 1}2 l/day. The second reaction was highly sensitive to the modifications in activation energy and frequency factor. However, both the activation energy and frequency factor were independent of variations for the first reaction. In the case of the activation energy, the results showed that the high sensitivity of this parameter reflected the impact that temperature has on the representation of foamy oil behaviour. 8 refs., 2 tabs., 6 figs.
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.
Van Ende, Marie-Aline; Jung, In-Ho
2017-02-01
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.
Westerterp, K.R.; Kuczynski, M.
1987-01-01
The theoretical background for a novel, countercurrent gas—solid—solid trickle flow reactor for equilibrium gas reactions is presented. A one-dimensional, steady-state reactor model is developed. The influence of the various process parameters on the reactor performance is discussed. The physical
On the overlap of the pre-equilibrium and direct reaction models
Avrigeanu, M.; Bucurescu, D.; Ivascu, M.; Semenescu, G.; Avrigeanu, V. (Institute for Physics and Nuclear Engineering, Bucharest (Romania))
1989-11-01
An analysis of neutron inelastic scattering on {sup 56}Fe proves that the phenomenological pre-equilibrium emission geometry-dependent hybrid model is able to describe direct inelastic scattering in the continuum. A method is given for incorporating consistently the distorted-wave Born approximation method to characterise this process on discrete excited nuclear states and the generalised version of the GDH model for the higher excitation energies. (author).
Yeh, G.T.; Salvage, K.M. [Pennsylvania State Univ., University Park, PA (United States). Dept. of Civil and Environmental Engineering; Gwo, J.P. [Oak Ridge National Lab., TN (United States); Zachara, J.M.; Szecsody, J.E. [Pacific Northwest National Lab., Richland, WA (United States)
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.
Characteristics of equilibrium reaction of zolazepam.
Hong, W H; Szulczewski, D H
1981-06-01
The equilibrium reaction of zolazepam, a pyrazolodiazepinone, was studied and analyzed using the approach used previously for other pyrazolodiazepinone derivatives. The intrinsic ring closure equilibrium constant for this reaction was approximately 100 times larger than that observed for pyrazolodiazepinones studied previously. This study illustrates that the diazepinone ring can dominate in equilibrium mixtures formed at pH values far below the pKa of the corresponding form.
Tufvesson, Pär; Bach, Christian; Woodley, John
2014-01-01
removal was then coupled to a simple model for biocatalyst kinetics and also for loss of substrate ketone by evaporation. The three models were used to simulate the effects of varying the critical process parameters and reaction equilibrium constants (K eq) as well as different substrate ketone...
Calculation of individual isotope equilibrium constants for geochemical reactions
Thorstenson, D.C.; Parkhurst, D.L.
2004-01-01
Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) 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 ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation
Equilibrium and pre-equilibrium emissions in proton-induced reactions on 203,205Tl
A Kaplan; A Aydin; E Tel; B Şarer
2009-02-01
In this study, the excitation functions for the reactions 203Tl(, )203Pb, 203Tl(, 3)203Pb, 203Tl(, 2)202Pb, 205Tl(, 4)202Pb, 203Tl(, 3)201Pb, 205Tl(, 5)201Pb, 203Tl(, 4)200Pb and 205Tl(, 6)200Pb have been calculated using pre-equilibrium and equilibrium reaction mechanisms. Calculated results based on hybrid model, geometry-dependent hybrid model and cascade-exciton model have been compared with the experimental data.
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.
Non-equilibrium effects in high temperature chemical reactions
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.
Equilibrium models and variational inequalities
Konnov, Igor
2007-01-01
The concept of equilibrium plays a central role in various applied sciences, such as physics (especially, mechanics), economics, engineering, transportation, sociology, chemistry, biology and other fields. If one can formulate the equilibrium problem in the form of a mathematical model, solutions of the corresponding problem can be used for forecasting the future behavior of very complex systems and, also, for correcting the the current state of the system under control. This book presents a unifying look on different equilibrium concepts in economics, including several models from related sciences.- Presents a unifying look on different equilibrium concepts and also the present state of investigations in this field- Describes static and dynamic input-output models, Walras, Cassel-Wald, spatial price, auction market, oligopolistic equilibrium models, transportation and migration equilibrium models- Covers the basics of theory and solution methods both for the complementarity and variational inequality probl...
A Multiperiod Equilibrium Pricing Model
Minsuk Kwak
2014-01-01
Full Text Available We propose an equilibrium pricing model in a dynamic multiperiod stochastic framework with uncertain income. There are one tradable risky asset (stock/commodity, one nontradable underlying (temperature, and also a contingent claim (weather derivative written on the tradable risky asset and the nontradable underlying in the market. The price of the contingent claim is priced in equilibrium by optimal strategies of representative agent and market clearing condition. The risk preferences are of exponential type with a stochastic coefficient of risk aversion. Both subgame perfect strategy and naive strategy are considered and the corresponding equilibrium prices are derived. From the numerical result we examine how the equilibrium prices vary in response to changes in model parameters and highlight the importance of our equilibrium pricing principle.
Glowacki, David R., E-mail: drglowacki@gmail.com [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Department of Computer Science, University of Bristol, Bristol BS8 1UB (United Kingdom); PULSE Institute and Department of Chemistry, Stanford University, Stanford, California 94305 (United States); SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States); Orr-Ewing, Andrew J. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Harvey, Jeremy N. [Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Heverlee (Belgium)
2015-07-28
We describe a parallelized linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM and TINKER. Forces are obtained using the Hellmann-Feynman relationship, giving continuous gradients, and good energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to explicitly correlated coupled cluster theory, we built a 64-state MS-EVB model designed to study the F + CD{sub 3}CN → DF + CD{sub 2}CN reaction in CD{sub 3}CN solvent (recently reported in Dunning et al. [Science 347(6221), 530 (2015)]). This approach allows us to build a reactive potential energy surface whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We ran molecular dynamics simulations to examine a range of observables which follow in the wake of the reactive event: energy deposition in the nascent reaction products, vibrational relaxation rates of excited DF in CD{sub 3}CN solvent, equilibrium power spectra of DF in CD{sub 3}CN, and time dependent spectral shifts associated with relaxation of the nascent DF. Many of our results are in good agreement with time-resolved experimental observations, providing evidence for the accuracy of our MS-EVB framework in treating both the solute and solute/solvent interactions. The simulations provide additional insight into the dynamics at sub-picosecond time scales that are difficult to resolve experimentally. In particular, the simulations show that (immediately following deuterium abstraction) the nascent DF finds itself in a non-equilibrium regime in two different respects: (1) it is highly vibrationally excited, with ∼23 kcal mol{sup −1} localized in the stretch and (2) its post-reaction solvation environment, in which it is not yet hydrogen-bonded to CD{sub 3}CN solvent molecules, is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational
Research on the Quantum Multistep Theory for Pre-equilibrium Nuclear Reaction
2001-01-01
The Feshbach-Kerman-Koonin (FKK) quantum multistep theory of the pre-equilibrium reaction is further improved and perfected, A unified description for the multistep compound (MSC) process of the pre-equilibrium reaction and the compound nucleus (CN) process of full equilibrium reaction can be presented. This formula can integrate MSC and CN theories with the optical model and Hauser-Feshbach formula, and can get self-consistent expression. In multistep direct (MSB) process of the pre-equilibrium reaction, the μ-step cross section can be expressed by the convolution of μ
Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks
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…
Hydration of saccharides: estimation of reaction properties and equilibrium conversion
Lobanova, O.; Mueller, K.; Mokrushina, L.; Arlt, W. [Friedrich-Alexander-University of Erlangen-Nuremberg, Chair of Separation Science and Technology, Erlangen (Germany)
2012-04-15
Biomass holds great promise as a renewable source of hydrogen and thus as a zero-emission, carbon-neutral, and nearly inexhaustible energy resource. Thermodynamic analysis of biomass hydration is carried out to study the reaction properties considering a series of saccharides as a model. Equilibrium constants and composition are estimated in dependence on the saccharide chain length and temperature. The latter is also studied as a function of the reactant ratios and in the presence of nonreacting additives. Being highly endothermic, the reaction is thermodynamically favorable due to a high entropic contribution. Increase in the saccharide chain length affects the conversion only slightly, so the results for low-molecular-weight saccharides can be transferred to long-chain ones. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
Chemical Reactions Using a Non-Equilibrium Wigner Function Approach
Ramón F. Álvarez-Estrada
2016-10-01
Full Text Available A three-dimensional model of binary chemical reactions is studied. We consider an ab initio quantum two-particle system subjected to an attractive interaction potential and to a heat bath at thermal equilibrium at absolute temperature T > 0 . Under the sole action of the attraction potential, the two particles can either be bound or unbound to each other. While at T = 0 , there is no transition between both states, such a transition is possible when T > 0 (due to the heat bath and plays a key role as k B T approaches the magnitude of the attractive potential. We focus on a quantum regime, typical of chemical reactions, such that: (a the thermal wavelength is shorter than the range of the attractive potential (lower limit on T and (b ( 3 / 2 k B T does not exceed the magnitude of the attractive potential (upper limit on T. In this regime, we extend several methods previously applied to analyze the time duration of DNA thermal denaturation. The two-particle system is then described by a non-equilibrium Wigner function. Under Assumptions (a and (b, and for sufficiently long times, defined by a characteristic time scale D that is subsequently estimated, the general dissipationless non-equilibrium equation for the Wigner function is approximated by a Smoluchowski-like equation displaying dissipation and quantum effects. A comparison with the standard chemical kinetic equations is made. The time τ required for the two particles to transition from the bound state to unbound configurations is studied by means of the mean first passage time formalism. An approximate formula for τ, in terms of D and exhibiting the Arrhenius exponential factor, is obtained. Recombination processes are also briefly studied within our framework and compared with previous well-known methods.
Determining Equilibrium Constants for Dimerization Reactions from Molecular Dynamics Simulations
De Jong, Djurre H.; Schafer, Lars V.; De Vries, Alex H.; Marrink, Siewert J.; Berendsen, Herman J. C.; Grubmueller, Helmut
2011-01-01
With today's available computer power, free energy calculations from equilibrium molecular dynamics simulations "via counting" become feasible for an increasing number of reactions. An example is the dimerization reaction of transmembrane alpha-helices. If an extended simulation of the two helices c
Self-organization in precipitation reactions far from the equilibrium.
Nakouzi, Elias; Steinbock, Oliver
2016-08-01
Far from the thermodynamic equilibrium, many precipitation reactions create complex product structures with fascinating features caused by their unusual origins. Unlike the dissipative patterns in other self-organizing reactions, these features can be permanent, suggesting potential applications in materials science and engineering. We review four distinct classes of precipitation reactions, describe similarities and differences, and discuss related challenges for theoretical studies. These classes are hollow micro- and macrotubes in chemical gardens, polycrystalline silica carbonate aggregates (biomorphs), Liesegang bands, and propagating precipitation-dissolution fronts. In many cases, these systems show intricate structural hierarchies that span from the nanometer scale into the macroscopic world. We summarize recent experimental progress that often involves growth under tightly regulated conditions by means of wet stamping, holographic heating, and controlled electric, magnetic, or pH perturbations. In this research field, progress requires mechanistic insights that cannot be derived from experiments alone. We discuss how mesoscopic aspects of the product structures can be modeled by reaction-transport equations and suggest important targets for future studies that should also include materials features at the nanoscale.
Elucidation of Reaction Mechanisms Far from Thermodynamic Equilibrium.
Nagao, Raphael
2016-04-01
Far from equilibrium: This thesis provides a deep mechanistic analysis of the electrooxidation of methanol when the system is kept far from the thermodynamic equilibrium. Under an oscillatory regime, interesting characteristics between the elementary reaction steps were observed. We were able to elucidate the effect of the intrinsic drift in a potential time-series responsible for spontaneous transition of temporal patterns and the carbon dioxide decoupling from direct and indirect pathways.
Equilibrium composition for the reaction of plutonium hydride with air
无
2002-01-01
There are six independent constituents with 4 chemical elements, i.e. PuH2.7(s), PuN(s), Pu2O3(s), N2, O2 and H2, therefore , the system described involves of 2 independent reactions ,both those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The present paper has briefly discussed the simultaneous reactions and its thermodynamic coupling effect.
Pre-equilibrium effects in (n,2n) reactions at 14. 2 meV/sup +/
Lakshmana Das, N.; Thirumala Rao, B.V. (Andhra Univ., Visakhapatnam (India). Labs. for Nuclear Research); Srinivasa Rao, C.V. (Indian Inst. of Tech., Kanpur. Dept. of Physics); Rama Rao, J. (Banaras Hindu Univ., Varanasi (India). Dept. of Physics)
1981-07-01
With a view to study the pre-equilibrium effects in neutron-induced reactions, the activation cross-sections for (n,2n) reactions at 14.2 +- 0.2 MeV in the heavy mass region have been measured using the versatile mixed powder technique and high resolution Ge(Li) detection. The experimental cross-sections are found to be consistently smaller than the predictions based on the statistical theory and this is attributed to the effect of pre-equilibrium decay in these reactions. The cross-sections due to pre-equilibrium decay were estimated using exciton, hybrid and unified models. When this cross-section was included in comparing the experimental cross-sections with theory, better agreement has been obtained within the limitations of the present-day pre-equilibrium theories.
Voituriez, R.; Moreau, M.; Oshanin, G.
2004-01-01
The validity of two fundamental concepts of classical chemical kinetics - the notion of "Chemical Equilibrium" and the "Law of Mass Action" - are re-examined for reversible \\textit{diffusion-limited} reactions (DLR), as exemplified here by association/dissociation $A+A \\rightleftharpoons B$ reactions. We consider a general model of long-ranged reactions, such that any pair of $A$ particles, separated by distance $\\mu$, may react with probability $\\omega_+(\\mu)$, and any $B$ may dissociate wit...
Lyapunov Functions, Stationary Distributions, and Non-equilibrium Potential for Reaction Networks
Anderson, David F; Craciun, Gheorghe; Gopalkrishnan, Manoj;
2015-01-01
We consider the relationship between stationary distributions for stochastic models of reaction systems and Lyapunov functions for their deterministic counterparts. Specifically, we derive the well-known Lyapunov function of reaction network theory as a scaling limit of the non-equilibrium potent......We consider the relationship between stationary distributions for stochastic models of reaction systems and Lyapunov functions for their deterministic counterparts. Specifically, we derive the well-known Lyapunov function of reaction network theory as a scaling limit of the non......-equilibrium potential of the stationary distribution of stochastically modeled complex balanced systems. We extend this result to general birth-death models and demonstrate via example that similar scaling limits can yield Lyapunov functions even for models that are not complex or detailed balanced, and may even have...
Non-equilibrium modelling of distillation
Wesselingh, JA; Darton, R
1997-01-01
There are nasty conceptual problems in the classical way of describing distillation columns via equilibrium stages, and efficiencies or HETP's. We can nowadays avoid these problems by simulating the behaviour of a complete column in one go using a non-equilibrium model. Such a model has phase
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.
A Multi Period Equilibrium Pricing Model
Pirvu, Traian A
2012-01-01
In this paper, we propose an equilibrium pricing model in a dynamic multi-period stochastic framework with uncertain income streams. In an incomplete market, there exist two traded risky assets (e.g. stock/commodity and weather derivative) and a non-traded underlying (e.g. temperature). The risk preferences are of exponential (CARA) type with a stochastic coefficient of risk aversion. Both time consistent and time inconsistent trading strategies are considered. We obtain the equilibriums prices of a contingent claim written on the risky asset and non-traded underlying. By running numerical experiments we examine how the equilibriums prices vary in response to changes in model parameters.
An analytical model of crater count equilibrium
Hirabayashi, Masatoshi; Minton, David A.; Fassett, Caleb I.
2017-06-01
Crater count equilibrium occurs when new craters form at the same rate that old craters are erased, such that the total number of observable impacts remains constant. Despite substantial efforts to understand this process, there remain many unsolved problems. Here, we propose an analytical model that describes how a heavily cratered surface reaches a state of crater count equilibrium. The proposed model formulates three physical processes contributing to crater count equilibrium: cookie-cutting (simple, geometric overlap), ejecta-blanketing, and sandblasting (diffusive erosion). These three processes are modeled using a degradation parameter that describes the efficiency for a new crater to erase old craters. The flexibility of our newly developed model allows us to represent the processes that underlie crater count equilibrium problems. The results show that when the slope of the production function is steeper than that of the equilibrium state, the power law of the equilibrium slope is independent of that of the production function slope. We apply our model to the cratering conditions in the Sinus Medii region and at the Apollo 15 landing site on the Moon and demonstrate that a consistent degradation parameterization can successfully be determined based on the empirical results of these regions. Further developments of this model will enable us to better understand the surface evolution of airless bodies due to impact bombardment.
Pre-equilibrium emission in neutron induced reactions on /sup 54,56/Fe
Avrigeanu, M.; Ivascu, M.; Avrigeanu, V.
1988-02-01
The experimentally well known (n,p), (n,..cap alpha..) and (n,2n) reaction excitation functions, from threshold to 20 MeV incident energy, and neutron and proton emission spectra at 14.8 MeV from /sup 54,56/Fe targets are calculated in the frame of the geometry-dependent hybrid pre-equilibrium emission model, including angular momentum and parity conservation, and the Hauser-Feshbach statistical model. Use of a consistent statistical model parameter set enables the validation of the pre-equilibrium emission model. Moreover, an enhanced pre-equilibrium emission from higher spin composite system states, associated with higher incoming orbital momenta, has been evidenced. Higher orbital momenta involved also in the emergent channels of the process are suggested by calculations of the residual nuclei level populations.
Lyapunov Functions, Stationary Distributions, and Non-equilibrium Potential for Reaction Networks.
Anderson, David F; Craciun, Gheorghe; Gopalkrishnan, Manoj; Wiuf, Carsten
2015-09-01
We consider the relationship between stationary distributions for stochastic models of reaction systems and Lyapunov functions for their deterministic counterparts. Specifically, we derive the well-known Lyapunov function of reaction network theory as a scaling limit of the non-equilibrium potential of the stationary distribution of stochastically modeled complex balanced systems. We extend this result to general birth-death models and demonstrate via example that similar scaling limits can yield Lyapunov functions even for models that are not complex or detailed balanced, and may even have multiple equilibria.
Rumor Propagation Model: An Equilibrium Study
José Roberto C. Piqueira
2010-01-01
information is analogous phenomena. Here, in an analogy with the SIR (Susceptible-Infected-Removed epidemiological model, the ISS (Ignorant-Spreader-Stifler rumor spreading model is studied. By using concepts from the Dynamical Systems Theory, stability of equilibrium points is established, according to propagation parameters and initial conditions. Some numerical experiments are conducted in order to validate the model.
Pre-Equilibrium Effects in the Secondary Particle Spectra in the Reactions with Heavy Ions
Fotina, O. V.; Eremenko, D. O.; Parfenova, Yu. L.; Platonov, S. Yu.; Yuminov, O. A.; Kravchuk, V. L.; Gramegna, F.; Barlini, S.; Casini, G.; Bruno, M.; D'Agostino, M.; Wieland, O.; Bracco, A.; Camera, F.
Theoretical description of the experimentally obtained spectra for protons and α-particles and model calculations for the neutron spectra in the reactions with heavy ions has been presented. The hybrid model of non-equilibrium processes was used. Equilibrium evaporation process was analyzed in the framework of the statistical theory of nuclear reactions with Monte-Carlo simulation including certain dynamical and kinematical characteristics. This approach was included in PACE code, which permits to simulate Monte-Carlo de-excitation nuclear process. The Fermi-gas model and level-density phenomenological model for the variation of the nuclear level density parameters was used. In this approach data on 16O+116Sn reaction with Ebeam = 130, 250 MeV were analyzed. Double-differential light charged particle spectra for this reaction were measured using the GARFIELD apparatus in coincidence with evaporation residues. The experimental data were collected in four angular ranges from 29 to 41, 41 to 53, 53 to 67 and 67 to 82 degrees in the laboratory system. The results of the calculations are shown and discussed for these four angular ranges. The contributions from the evaporative and pre-equilibrium processes were analyzed in connection with different nucleus equilibration mechanisms.
Vibrational non-equilibrium in the hydrogen-oxygen reaction. Comparison with experiment
Skrebkov, Oleg V.
2015-03-01
A theoretical model is proposed for the chemical and vibrational kinetics of hydrogen oxidation based on consistent accounting of the vibrational non-equilibrium of the HO2 radical that forms as a result of the bimolecular recombination H+O2 → HO2. In the proposed model, the chain branching H+O2 = O+OH and inhibiting H+O2+M = HO2+M formal reactions are treated (in the terms of elementary processes) as a single multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and unimolecular decay of the comparatively long-lived vibrationally excited HO2 radical, which is able to react and exchange energy with the other components of the mixture. The model takes into account the vibrational non-equilibrium of the starting (primary) H2 and O2 molecules, as well as the most important molecular intermediates HO2, OH, O2(1Δ), and the main reaction product H2O. It is shown that the hydrogen-oxygen reaction proceeds in the absence of vibrational equilibrium, and the vibrationally excited HO2(v) radical acts as a key intermediate in a fundamentally important chain branching process and in the generation of electronically excited species O2(1Δ), O(1D), and OH(2Σ+). The calculated results are compared with the shock tube experimental data for strongly diluted H2-O2 mixtures at 1000 reaction is especially non-equilibrium, and the vibrational non-equilibrium of the HO2 radical is the essence of this process. The quantitative estimation of the vibrational relaxation characteristic time of the HO2 radical in its collisions with H2 molecules has been obtained as a result of the comparison of different experimental data on induction time measurements with the relevant calculations.
Micro Data and General Equilibrium Models
Browning, Martin; Hansen, Lars Peter; Heckman, James J.
1999-01-01
Dynamic general equilibrium models are required to evaluate policies applied at the national level. To use these models to make quantitative forecasts requires knowledge of an extensive array of parameter values for the economy at large. This essay describes the parameters required for different ...
Determining equilibrium constants for dimerization reactions from molecular dynamics simulations.
De Jong, Djurre H; Schäfer, Lars V; De Vries, Alex H; Marrink, Siewert J; Berendsen, Herman J C; Grubmüller, Helmut
2011-07-15
With today's available computer power, free energy calculations from equilibrium molecular dynamics simulations "via counting" become feasible for an increasing number of reactions. An example is the dimerization reaction of transmembrane alpha-helices. If an extended simulation of the two helices covers sufficiently many dimerization and dissociation events, their binding free energy is readily derived from the fraction of time during which the two helices are observed in dimeric form. Exactly how the correct value for the free energy is to be calculated, however, is unclear, and indeed several different and contradictory approaches have been used. In particular, results obtained via Boltzmann statistics differ from those determined via the law of mass action. Here, we develop a theory that resolves this discrepancy. We show that for simulation systems containing two molecules, the dimerization free energy is given by a formula of the form ΔG ∝ ln(P(1) /P(0) ). Our theory is also applicable to high concentrations that typically have to be used in molecular dynamics simulations to keep the simulation system small, where the textbook dilute approximations fail. It also covers simulations with an arbitrary number of monomers and dimers and provides rigorous error estimates. Comparison with test simulations of a simple Lennard Jones system with various particle numbers as well as with reference free energy values obtained from radial distribution functions show full agreement for both binding free energies and dimerization statistics.
Return to equilibrium in the XY model
Hume, L.; Robinson, D.W.
1986-09-01
We prove that the locally perturbed XY model returns to equilibrium under the unperturbed evolution but the unperturbed model does not necessarily approach equilibrium under the perturbed evolution. In fact this latter property is false for perturbation by a local magnetization. The failure is directly attributable to the formation of bound states. If the perturbation is quadratic these problems are reduced to spectral analysis of the one-particle Hamiltonian. We demonstrate that the perturbed Hamiltonian has a finite set of eigenvalues of finite multiplicity together with some absolutely continuous spectrum. Eigenvalues can occur in the continuum if, and only if, the perturbation dislocates the system. Singular continuous spectrum cannot occur.
Non-equilibrium model for catalytic distillation process
Feng WANG; Ning ZHAO; Junping LI; Fukui XIAO; Wei WEI; Yuhan SUN
2008-01-01
A new improved tri-diagonal method was developed for the non-equilibrium stage model of the catalytic distillation by coupling consumptive reaction coefficient. The reactions in the distillation column were divided into generative reaction and consumptive reac-tion. The non-equilibrium stage model was introduced for the catalytic distillation process of the dimethyl car-bonate (DMC) synthesis by urea methanolysis over solid based catalyst, and the improved tri-diagonal method was used to solve the model equations. Comparison of pre-dicted results with experiment data shows that the mean relative error of the yield of DMC was 3.78% under dif-ferent conditions such as different operating pressures and reaction temperatures. The improved tri-diagonal matrix method could avoid the negative values of the liquid com-positions during the calculations and restrain the fluc-tuation of compositions by slowing down the variations of the values in the iteration. The modeling results show that the improved tri-diagonal method was appropriate for system containing a wide range of boiling point com-ponents and a different rate of reactions.
A General Thermal Equilibrium Discharge Flow Model
ZHAO; Min-fu; ZHANG; Dong-xu; LV; Yu-feng
2015-01-01
In isentropic and thermal equilibrium assumptions,a discharge flow model was derived,which unified the rules of normal temperature water discharge,high temperature and high pressure water discharge,two-phase critical flow,saturated steam and superheated steam critical
General Equilibrium Models: Improving the Microeconomics Classroom
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…
Modeling market equilibrium for transboundary environmental problem
Kryazhimskii, A.; Nentjes, A.; Shybaiev, S; Tarasyev, A.
2001-01-01
We model the international negotiations on acid deposition reduction in Europe as a multiplayer non-cooperative normal form game. The equilibrium combining the properties of Nash equilibria and Pareto-optimal outcomes, is studied. We prove its existence and investigate a dynamic combined best reply-
A Monetary Equilibrium Model with Transactions Costs
Julio J. Rotemberg
1982-01-01
This paper presents the competitive equilibrium of an economy in which people hold money for transactions purposes. It studies both the steady states which result from different rates of monetary expansion and the effects of such non-steady state events as an open market operation. Even though the model features no uncertainty and perfect foresight, open market operations affect aggregate output. In particular, a simultaneous increase in money and governmental holdings of capital temporarily ...
A Monetary Equilibrium Model with Transactions Costs
Julio J. Rotemberg
1982-01-01
This paper presents the competitive equilibrium of an economy in which people hold money for transactions purposes. It studies both the steady states which result from different rates of monetary expansion and the effects of such non-steady state events as an open market operation. Even though the model features no uncertainty and perfect foresight, open market operations affect aggregate output. In particular, a simultaneous increase in money and governmental holdings of capital temporarily ...
The canonical equilibrium of constrained molecular models
Echenique, Pablo; García-Risueño, Pablo
2011-01-01
In order to increase the efficiency of the computer simulation of biological molecules, it is very common to impose holonomic constraints on the fastest degrees of freedom; normally bond lengths, but also possibly bond angles. However, as any other element that affects the physical model, the imposition of constraints must be assessed from the point of view of accuracy: both the dynamics and the equilibrium statistical mechanics are model-dependent, and they will be changed if constraints are used. In this review, we investigate the accuracy of constrained models at the level of the equilibrium statistical mechanics distributions produced by the different dynamics. We carefully derive the canonical equilibrium distributions of both the constrained and unconstrained dynamics, comparing the two of them by means of a "stiff" approximation to the latter. We do so both in the case of flexible and hard constraints, i.e., when the value of the constrained coordinates depends on the conformation and when it is a cons...
Bygrave, Peter J; Case, David H; Day, Graeme M
2014-01-01
The ability of computational methods to predict the structures and energetics that determine the equilibrium of solid state mechanochemical reactions has been assessed. Two previously characterised base-catalysed metathesis reactions between aromatic disulfides are studied using crystal structure prediction methods and lattice energy calculations that combine molecular electronic structure methods with anisotropic atom-atom potentials. We find that lattice energy searches locate three of the six crystal structures as global minima on their respective crystal energy landscapes. The remaining structures are less successfully predicted, due to problems modelling relative conformational energies due to limitations of the density functional theory method for calculating intramolecular energies. Prediction of the overall reaction energies proves challenging for current methods, but the results show promise as a base on which to build more accurate and reliable approaches.
Multicomponent Equilibrium Models for Testing Geothermometry Approaches
Carl D. Palmer; Robert W. Smith; Travis L. McLing
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.
Kustova, Elena V., E-mail: e.kustova@spbu.ru [Department of Mathematics and Mechanics, Saint Petersburg State University, 198504 Universitetskiy pr. 28, Saint Petersburg (Russian Federation); Kremer, Gilberto M., E-mail: kremer@fisica.ufpr.br [Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, 81531-980 Curitiba (Brazil)
2014-12-05
Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman–Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N{sub 2} flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.
Equilibrium statistical mechanics of lattice models
Lavis, David A
2015-01-01
Most interesting and difficult problems in equilibrium statistical mechanics concern models which exhibit phase transitions. For graduate students and more experienced researchers this book provides an invaluable reference source of approximate and exact solutions for a comprehensive range of such models. Part I contains background material on classical thermodynamics and statistical mechanics, together with a classification and survey of lattice models. The geometry of phase transitions is described and scaling theory is used to introduce critical exponents and scaling laws. An introduction is given to finite-size scaling, conformal invariance and Schramm—Loewner evolution. Part II contains accounts of classical mean-field methods. The parallels between Landau expansions and catastrophe theory are discussed and Ginzburg—Landau theory is introduced. The extension of mean-field theory to higher-orders is explored using the Kikuchi—Hijmans—De Boer hierarchy of approximations. In Part III the use of alge...
Neutron skin effect of some Mo isotopes in pre-equilibrium reactions
M H Bölükdemir; E Tel; S Okuducu; N N Akti
2011-03-01
The neutron skin effect has been investigated for even isotopes of molybdenum at 25.6 MeV 94−100Mo(, ) reaction using the geometry-dependent hybrid model of pre-equilibrium nuclear reactions. Here the initial neutron/proton exciton numbers were calculated from the neutron/proton densities obtained from an effective nucleon–nucleon interaction of the Skyrme type. Initial exciton numbers from different radii of even Mo isotopes were used to obtain the corresponding neutron emission spectra. In this investigation the calculated results are compared with the experimental data as also with each other. The results using central densities in the geometry-dependent hybrid model are in better agreement with the experimental data.
MHD Turbulent Mixing Layers: Equilibrium Cooling Models
Esquivel, A; Cho, J; Lazarian, A; Leitner, S N
2006-01-01
We present models of turbulent mixing at the boundaries between hot (T~10^{6-7} K) and warm material (T~10^4 K) in the interstellar medium, using a three-dimensional magnetohydrodynamical code, with radiative cooling. The source of turbulence in our simulations is a Kelvin-Helmholtz instability, produced by shear between the two media. We found, that because the growth rate of the large scale modes in the instability is rather slow, it takes a significant amount of time (~1 Myr) for turbulence to produce effective mixing. We find that the total column densities of the highly ionized species (C IV, N V, and O VI) per interface (assuming ionization equilibrium) are similar to previous steady-state non-equilibrium ionization models, but grow slowly from log N ~10^{11} to a few 10^{12} cm^{-2} as the interface evolves. However, the column density ratios can differ significantly from previous estimates, with an order of magnitude variation in N(C IV)/N(O VI) as the mixing develops.
Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems
Glynn, P.D.; Reardon, E.J.; Plummer, L.N.; Busenberg, E.
1990-01-01
Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.
R Baldik; H Aytekin; E Tel
2013-02-01
In this study, the pre-equilibrium and equilibrium calculations of cross-sections of 89Y(, ), 90Zr$(p, xn)$ and 94Mo(, ) reactions, which were used for the production of 89Zr, 90Nb and 94Tc positron-emitting radioisotopes, have been investigated. Pre-equilibrium calculations have been performed at different proton incident energies by using the hybrid, geometry-dependent-hybrid and full exciton models. The Weisskopf–Ewing model is used for calculating the equilibrium effects at the same incident energies. The calculated results have been discussed and compared with the experimental results.
Mathematical models and equilibrium in irreversible microeconomics
Anatoly M. Tsirlin
2010-07-01
Full Text Available A set of equilibrium states in a system consisting of economic agents, economic reservoirs, and firms is considered. Methods of irreversible microeconomics are used. We show that direct sale/purchase leads to an equilibrium state which depends upon the coefficients of supply/demand functions. To reach the unique equilibrium state it is necessary to add either monetary exchange or an intermediate firm.
Equilibrium Price Dispersion in a Matching Model with Divisible Money
Kamiya, K.; Sato, T.
2002-01-01
The main purpose of this paper is to show that, for any given parameter values, an equilibrium with dispersed prices (two-price equilibrium) exists in a simple matching model with divisible money presented by Green and Zhou (1998).We also show that our two-price equilibrium is unique in certain envi
Progress in microscopic direct reaction modeling of nucleon induced reactions
Dupuis, M.; Bauge, E.; Hilaire, S.; Lechaftois, F.; Peru, S.; Pillet, N.; Robin, C. [CEA, DAM, DIF, Arpajon (France)
2015-12-15
A microscopic nuclear reaction model is applied to neutron elastic and direct inelastic scatterings, and pre-equilibrium reaction. The JLM folding model is used with nuclear structure information calculated within the quasi-particle random phase approximation implemented with the Gogny D1S interaction. The folding model for direct inelastic scattering is extended to include rearrangement corrections stemming from both isoscalar and isovector density variations occurring during a transition. The quality of the predicted (n,n), (n,n{sup '}), (n,xn) and (n,n{sup '}γ) cross sections, as well as the generality of the present microscopic approach, shows that it is a powerful tool that can help improving nuclear reactions data quality. Short- and long-term perspectives are drawn to extend the present approach to more systems, to include missing reactions mechanisms, and to consistently treat both structure and reaction problems. (orig.)
Investigation of the production of (68)Ga using pre-equilibrium models.
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. Copyright © 2016 Elsevier Ltd. All rights reserved.
2012-01-01
This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equil...
Fan Zhang
2012-01-01
Full Text Available This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equilibrium reactions to decouple equilibrium and kinetic reactions. This approach minimizes the number of partial differential advective-dispersive transport equations and enables robust numerical integration. Complete matrix decomposition by further pivoting on linearly independent kinetic reactions allows some rate equations to be formulated individually and explicitly enforces conservation of component species when component transport equations are solved. The methodology is demonstrated for a case study involving eutrophication reactions in the Des Moines River in Iowa, USA and for two hypothetical examples to illustrate the ability of the model to simulate sediment and chemical transport with both mobile and immobile water phases and with complex reaction networks involving both kinetic and equilibrium reactions.
Extraproximal approach to calculating equilibriums in pure exchange models
Antipin, A. S.
2006-10-01
Models of economic equilibrium are a powerful tool of mathematical modeling of various markets. However, according to many publications, there are as yet no universal techniques for finding equilibrium prices that are solutions to such models. A technique of this kind that is a natural implementation of the Walras idea of tatonnements (i.e., groping for equilibrium prices) is proposed, and its convergence is proved.
Study of Pre-equilibrium Fission Based on Diffusion Model
无
2006-01-01
In terms of numerical method of Smoluchowski equation the behavior of fission process in diffusion model has been described and analyzed, including the reliance upon time, as well as the deformation parameters at several nuclear temperatures in this paper. The fission rates and the residual probabilities inside the saddle point are calculated for fissile nucleus n+238 U reaction and un-fissile nucleus p+208 Pb reaction. The results indicate that there really exists a transient fission process, which means that the pre-equilibrium fission should be taken into account for the fissile nucleus at the high temperature. Oppositely, the pre-equilibrium fission could be neglected for the un-fissile nucleus. In the certain case the overshooting phenomenon of the fission rates will occur, which is mainly determined by the diffusive current at the saddle point. The higher the temperature is, the more obvious the overshooting phenomenon is. However, the emissions of the light particles accompanying the diffusion process may weaken or vanish the overshooting phenomenon.
DSMC modeling of flows with recombination reactions
Gimelshein, Sergey; Wysong, Ingrid
2017-06-01
An empirical microscopic recombination model is developed for the direct simulation Monte Carlo method that complements the extended weak vibrational bias model of dissociation. The model maintains the correct equilibrium reaction constant in a wide range of temperatures by using the collision theory to enforce the number of recombination events. It also strictly follows the detailed balance requirement for equilibrium gas. The model and its implementation are verified with oxygen and nitrogen heat bath relaxation and compared with available experimental data on atomic oxygen recombination in argon and molecular nitrogen.
A direct microscopic approach to transition strengths in pre-equilibrium reactions
Guimaraes, F B
2011-01-01
We present a microscopic formalism that extends the traditional formulation of Williams, Ericson and Bloch and permits to obtain the transition strengths (TS) of pre-equilibrium nuclear reactions directly from their quantum microscopic description. We calculate the TS without resorting to the Laplace transform approach and the use of the saddle point approximation. We also analyze some problems that may appear in connection with these mathematical tools and the Darwin-Fowler approach in this case. We show that, analogously to the nuclear densities, the strengths for transitions that change the exciton number by two or leave it unchanged can be estimated microscopically as convolutions of the functions of simpler states. When using the HO basis for the Model Space we obtained important departure from the results of the exciton model (EXM), which can partially invalidate our previous analysis on the attainment of equilibrium during the PE stage. On the other hand, by using constant grid of energies for the sp-b...
Description of the General Equilibrium Model of Ecosystem Services (GEMES)
Travis Warziniack; David Finnoff; Jenny Apriesnig
2017-01-01
This paper serves as documentation for the General Equilibrium Model of Ecosystem Services (GEMES). GEMES is a regional computable general equilibrium model that is composed of values derived from natural capital and ecosystem services. It models households, producing sectors, and governments, linked to one another through commodity and factor markets. GEMES was...
PEMAHAMAN DASAR ANALISIS MODEL COMPUTABLE GENERAL EQUILIBRIUM (CGE
Mardiyah Hayati
2013-11-01
Full Text Available Simple paper about basic understanding of computable general equilibrium aimed to give basic understanding about CGE. It consist of history of CGE, assumption of CGE model, excess and lack of CGE model, and creation of simple CGE model for closed economy. CGE model is suitable to be used for seeing impact of new policy implementation. It is because CGE model use general equilibrium in which this theory of general equilibrium explaining about inter-relation among markets in the economy system. CGE model was introduced in 1960s known as Johansen model. Next, it is expanded into various models such as: ORANI Model, General Trade Analysis Project (GTAP Model, and Applied General Equilibrium (AGE Model. In Indonesia, there are CGE ORANI Model, Wayang, Indonesia-E3 and IRCGE. CGE Model is created by assumption of perfect competition. Consumer maximizes utility, producer maximizes profit, and company maximizes zero profit condition.
Bursting regimes in a reaction-diffusion system with action potential-dependent equilibrium.
Stephen R Meier
Full Text Available The equilibrium Nernst potential plays a critical role in neural cell dynamics. A common approximation used in studying electrical dynamics of excitable cells is that the ionic concentrations inside and outside the cell membranes act as charge reservoirs and remain effectively constant during excitation events. Research into brain electrical activity suggests that relaxing this assumption may provide a better understanding of normal and pathophysiological functioning of the brain. In this paper we explore time-dependent ionic concentrations by allowing the ion-specific Nernst potentials to vary with developing transmembrane potential. As a specific implementation, we incorporate the potential-dependent Nernst shift into a one-dimensional Morris-Lecar reaction-diffusion model. Our main findings result from a region in parameter space where self-sustaining oscillations occur without external forcing. Studying the system close to the bifurcation boundary, we explore the vulnerability of the system with respect to external stimulations which disrupt these oscillations and send the system to a stable equilibrium. We also present results for an extended, one-dimensional cable of excitable tissue tuned to this parameter regime and stimulated, giving rise to complex spatiotemporal pattern formation. Potential applications to the emergence of neuronal bursting in similar two-variable systems and to pathophysiological seizure-like activity are discussed.
Comparative evaluation of kinetic, equilibrium and semi-equilibrium models for biomass gasification
Buragohain, Buljit [Center for Energy, Indian Institute of Technology Guwahati, Guwahati – 781 039, Assam (India); Chakma, Sankar; Kumar, Peeush [Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati – 781 039, Assam (India); Mahanta, Pinakeswar [Center for Energy, Indian Institute of Technology Guwahati, Guwahati – 781 039, Assam (India); Department of Mechanical Engineering, Indian Institute of Technology Guwahati, Guwahati – 781 039, Assam (India); Moholkar, Vijayanand S. [Center for Energy, Indian Institute of Technology Guwahati, Guwahati – 781 039, Assam (India); Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati – 781 039, Assam (India)
2013-07-01
Modeling of biomass gasification has been an active area of research for past two decades. In the published literature, three approaches have been adopted for the modeling of this process, viz. thermodynamic equilibrium, semi-equilibrium and kinetic. In this paper, we have attempted to present a comparative assessment of these three types of models for predicting outcome of the gasification process in a circulating fluidized bed gasifier. Two model biomass, viz. rice husk and wood particles, have been chosen for analysis, with gasification medium being air. Although the trends in molar composition, net yield and LHV of the producer gas predicted by three models are in concurrence, significant quantitative difference is seen in the results. Due to rather slow kinetics of char gasification and tar oxidation, carbon conversion achieved in single pass of biomass through the gasifier, calculated using kinetic model, is quite low, which adversely affects the yield and LHV of the producer gas. Although equilibrium and semi-equilibrium models reveal relative insensitivity of producer gas characteristics towards temperature, the kinetic model shows significant effect of temperature on LHV of the gas at low air ratios. Kinetic models also reveal volume of the gasifier to be an insignificant parameter, as the net yield and LHV of the gas resulting from 6 m and 10 m riser is same. On a whole, the analysis presented in this paper indicates that thermodynamic models are useful tools for quantitative assessment of the gasification process, while kinetic models provide physically more realistic picture.
Comparative evaluation of kinetic, equilibrium and semi-equilibrium models for biomass gasification
Buljit Buragohain, Sankar Chakma, Peeush Kumar, Pinakeswar Mahanta, Vijayanand S. Moholkar
2013-01-01
Full Text Available Modeling of biomass gasification has been an active area of research for past two decades. In the published literature, three approaches have been adopted for the modeling of this process, viz. thermodynamic equilibrium, semi-equilibrium and kinetic. In this paper, we have attempted to present a comparative assessment of these three types of models for predicting outcome of the gasification process in a circulating fluidized bed gasifier. Two model biomass, viz. rice husk and wood particles, have been chosen for analysis, with gasification medium being air. Although the trends in molar composition, net yield and LHV of the producer gas predicted by three models are in concurrence, significant quantitative difference is seen in the results. Due to rather slow kinetics of char gasification and tar oxidation, carbon conversion achieved in single pass of biomass through the gasifier, calculated using kinetic model, is quite low, which adversely affects the yield and LHV of the producer gas. Although equilibrium and semi-equilibrium models reveal relative insensitivity of producer gas characteristics towards temperature, the kinetic model shows significant effect of temperature on LHV of the gas at low air ratios. Kinetic models also reveal volume of the gasifier to be an insignificant parameter, as the net yield and LHV of the gas resulting from 6 m and 10 m riser is same. On a whole, the analysis presented in this paper indicates that thermodynamic models are useful tools for quantitative assessment of the gasification process, while kinetic models provide physically more realistic picture.
Gavrilenko, A V; Gavrilenko, V I
2008-01-01
Equilibrium atomic configurations and electron energy structure of ethanol adsorbed on the Si (111) surface are studied by the first-principles density functional theory. Geometry optimization is performed by the total energy minimization method. Several equilibrium atomic configurations of ethanol, both undissociated and dissociated, on the Si (111) surface are found. Reaction pathways and predicted transition states are discussed in comparison with available experimental data in terms of the feasibility of the reactions occurring. Analysis of atom and orbital resolved projected density of states indicate substantial modifications of the Si surface valence and conduction bands due to the adsorption of ethanol affecting the electrical properties of the surface.
2002-01-01
The Feshbach-Kerman_Koonin multistep compound theory (MSC) of the pre - equilibrium reaction isfurther improved and perfected. The nucleon is treated as a spin-half particle, target nucleus is allowed toa non-zero spin, the angular momentum coupling is treated rigorously. The expressions of the
Non-equilibrium modelling of arc plasma torches
Trelles, J P; Heberlein, J V R; Pfender, E [Department of Mechanical Engineering, University of Minnesota, Minneapolis, MN 55455 (United States)
2007-10-07
A two-temperature thermal non-equilibrium model is developed and applied to the three-dimensional and time-dependent simulation of the flow inside a dc arc plasma torch. A detailed comparison of the results of the non-equilibrium model with those of an equilibrium model is presented. The fluid and electromagnetic equations in both models are approximated numerically in a fully-coupled approach by a variational multi-scale finite element method. In contrast to the equilibrium model, the non-equilibrium model did not need a separate reattachment model to produce an arc reattachment process and to limit the magnitude of the total voltage drop and arc length. The non-equilibrium results show large non-equilibrium regions in the plasma-cold-flow interaction region and close to the anode surface. Marked differences in the arc dynamics, especially in the arc reattachment process, and in the magnitudes of the total voltage drop and outlet temperatures and velocities between the models are observed. The non-equilibrium results show improved agreement with experimental observations.
Equilibrium of the reaction between dissolved sodium sulfide and biologically produced sulfur
Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.
2005-01-01
The equilibrium of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied. Biologically produced sulfur was obtained from a bioreactor of a hydrogen sulfide removal process in which the dominating organism is Thiobacillus sp. W5.
Equilibrium chemical reaction of supersonic hydrogen-air jets (the ALMA computer program)
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.
Non-Equilibrium Modeling of Arc Plasma Torches
Trelles, J P; Heberlein, J V R
2013-01-01
A two-temperature thermal non-equilibrium model is developed and applied to the three-dimensional and time-dependent simulation of the flow inside a DC arc plasma torch. A detailed comparison of the results of the non-equilibrium model with those of an equilibrium model is presented. The fluid and electromagnetic equations in both models are approximated numerically in a fully-coupled approach by a variational multi-scale finite element method. In contrast to the equilibrium model, the non-equilibrium model did not need a separate reattachment model to produce an arc reattachment process and to limit the magnitude of the total voltage drop and arc length. The non-equilibrium results show large non-equilibrium regions in the plasma - cold-flow interaction region and close to the anode surface. Marked differences in the arc dynamics, especially in the arc reattachment process, and in the magnitudes of the total voltage drop and outlet temperatures and velocities between the models are observed. The non-equilibr...
Parameter Estimation for a Computable General Equilibrium Model
Arndt, Channing; Robinson, Sherman; Tarp, Finn
2002-01-01
We introduce a maximum entropy approach to parameter estimation for computable general equilibrium (CGE) models. The approach applies information theory to estimating a system of non-linear simultaneous equations. It has a number of advantages. First, it imposes all general equilibrium constraints...
Parameter Estimation for a Computable General Equilibrium Model
Arndt, Channing; Robinson, Sherman; Tarp, Finn
We introduce a maximum entropy approach to parameter estimation for computable general equilibrium (CGE) models. The approach applies information theory to estimating a system of nonlinear simultaneous equations. It has a number of advantages. First, it imposes all general equilibrium constraints...
Discrimination and Skill Differences in an Equilibrium Search Model
Bowlus, Audra J.; Eckstein, Zvi
1998-01-01
In this paper we analyze an equilibrium search model with threesources for wage andunemployment differentials among workers with the same (observed) human capital but different appearance (race): unobserved productivity (skill), search intensities and discrimination (Becker 1957)due to an
Discrimination and Skill Differences in an Equilibrium Search Model
Bowlus, Audra J.; Eckstein, Zvi
1998-01-01
In this paper we analyze an equilibrium search model with threesources for wage andunemployment differentials among workers with the same (observed) human capital but different appearance (race): unobserved productivity (skill), search intensities and discrimination (Becker 1957)due to an appearanc
Kinetic, equilibrium and thermodynamic modelling of the sorption of ...
Kinetic, equilibrium and thermodynamic modelling of the sorption of metals ... Batch sorption studies were conducted to assess the potential of a ... negative Ea values, indicating their preference to bind to low-energy sites. ... Article Metrics.
Nyasulu, Frazier; McMills, Lauren; Barlag, Rebecca
2013-01-01
A laboratory to determine the equilibrium constants of weak acid negative weak base reactions is described. The equilibrium constants of component reactions when multiplied together equal the numerical value of the equilibrium constant of the summative reaction. The component reactions are weak acid ionization reactions, weak base hydrolysis…
Nyasulu, Frazier; McMills, Lauren; Barlag, Rebecca
2013-01-01
A laboratory to determine the equilibrium constants of weak acid negative weak base reactions is described. The equilibrium constants of component reactions when multiplied together equal the numerical value of the equilibrium constant of the summative reaction. The component reactions are weak acid ionization reactions, weak base hydrolysis…
Insights: Simple Models for Teaching Equilibrium and Le Chatelier's Principle.
Russell, Joan M.
1988-01-01
Presents three models that have been effective for teaching chemical equilibrium and Le Chatelier's principle: (1) the liquid transfer model, (2) the fish model, and (3) the teeter-totter model. Explains each model and its relation to Le Chatelier's principle. (MVL)
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.
The solubility of (Ba,Sr)SO 4 precipitates: Thermodynamic equilibrium and reaction path analysis
Felmy, Andrew R.; Rai, Dhanpat; Moore, Dean A.
1993-09-01
The solubility of (Ba,Sr)SO 4 precipitates, varying in SrSO 4 mole fraction from 0.05-0.90, was investigated at room temperature with an equilibration period extending to almost three years. The data show that on or before 315 days of equilibration the precipitates reach a reversible equilibrium with the aqueous solution. The reversibility of this equilibrium was verified both by the attainment of steady-state concentrations with time and by heating the samples to perturb the equilibrium and then observing the slow return to the initial equilibrium state. The dissolution of the (Ba,Sr)SO 4 precipitates does not, in general, follow limiting reaction paths as defined by the Lippmann solutus or stoichiometric dissolution curves. In addition, activity coefficient calculations for the BaSO 4 and SrSO 4 components of the solid phase, using either total bulk analysis or near-surface analysis of the component mole fractions, do not satisfy the Gibbs-Duhem equation, demonstrating that a single solid-solution phase does not control both the aqueous Ba and Sr concentrations. Instead, our long-term equilibration data can be explained by the unavoidable formation of small amounts of barite and substitution of Sr into a solid-solution phase with the BaSO 4 component of the solid-solution phase never reaching thermodynamic equilibrium with the aqueous phase.
Computing multi-species chemical equilibrium with an algorithm based on the reaction extents
Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.;
2013-01-01
A mathematical model for the solution of a set of chemical equilibrium equations in a multi-species and multiphase chemical system is described. The computer-aid solution of model is achieved by means of a Newton-Raphson method enhanced with a line-search scheme, which deals with the non-negative...
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.
Wang, Jun; Xu, Ya Zhen; Fu, Ya Fei; Liu, Xiang Dong
2016-12-01
Latent curing systems are widely used in industrial thermosets in applications such as adhesion, coating, and composites. Despite many attempts to improve the practicality of this dormant reaction system, the majority of commercially available latent products still use particulate hardeners or liquid compounds with blocked active groups. These formulations generally lack fluidity or rapid reaction characteristics and thus are problematic in some industry applications. Here we describe a novel concept that stabilizes highly reactive benzoxazine/amine mixtures by reaction equilibrium. These new latent benzoxazine curing systems have a long storable lifetime but very short gel time at 150 °C. The reversible reaction between benzoxazine and amine is further demonstrated by FT-IR spectral measurements and rheological experiments, and it is shown that the overall characteristics of the latent system are promising for many industrial applications.
Phylogenies support out-of-equilibrium models of biodiversity.
Manceau, Marc; Lambert, Amaury; Morlon, Hélène
2015-04-01
There is a long tradition in ecology of studying models of biodiversity at equilibrium. These models, including the influential Neutral Theory of Biodiversity, have been successful at predicting major macroecological patterns, such as species abundance distributions. But they have failed to predict macroevolutionary patterns, such as those captured in phylogenetic trees. Here, we develop a model of biodiversity in which all individuals have identical demographic rates, metacommunity size is allowed to vary stochastically according to population dynamics, and speciation arises naturally from the accumulation of point mutations. We show that this model generates phylogenies matching those observed in nature if the metacommunity is out of equilibrium. We develop a likelihood inference framework that allows fitting our model to empirical phylogenies, and apply this framework to various mammalian families. Our results corroborate the hypothesis that biodiversity dynamics are out of equilibrium.
CHEMICAL REACTIONS SIMULATED BY GROUND-WATER-QUALITY MODELS.
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.
The Chaotic General Economic Equilibrium Model and Monopoly
Vesna D. Jablanovic
2012-09-01
Full Text Available The basic aim of this study is to construct a relatively simple chaotic general economic equilibrium growth model that is capable of generating stable equilibrium, cycles, or chaos. An important example of general economic equilibrium is provided by monopolies. A key hypothesis of this study is based on the idea that the coefficient π = b mRS/m (α-1 (1+1/e mRT plays a crucial role in explaining local stability of the general equilibrium output, where, b: The coefficient of the quadratic marginal-cost function, m: The coefficient of the inverse demand function, mRS: The marginal rate of substitution, mRT: Marginal rate of transformation, α: The coefficient of the monopoly price growth, e: The coefficient of the price elasticity of demand.
Non-equilibrium modelling of distillation
Wesselingh, J.A
This is a lecture on the way that we engineers model distillation. How we have done such modelling, how we would like to do it, and how far we have come at this moment. The ideas that I will be bringing forward are not my own. I owe them mostly to R. Krishna, R. Taylor, H. Kooijman and A. Gorak.
Non-equilibrium modelling of distillation
Wesselingh, J.A
1997-01-01
This is a lecture on the way that we engineers model distillation. How we have done such modelling, how we would like to do it, and how far we have come at this moment. The ideas that I will be bringing forward are not my own. I owe them mostly to R. Krishna, R. Taylor, H. Kooijman and A. Gorak. The
A new atmospheric aerosol phase equilibrium model (UHAERO: organic systems
N. R. Amundson
2007-09-01
Full Text Available In atmospheric aerosols, water and volatile inorganic and organic species are distributed between the gas and aerosol phases in accordance with thermodynamic equilibrium. Within an atmospheric particle, liquid and solid phases can exist at equilibrium. Models exist for computation of phase equilibria for inorganic/water mixtures typical of atmospheric aerosols; when organic species are present, the phase equilibrium problem is complicated by organic/water interactions as well as the potentially large number of organic species. We present here an extension of the UHAERO inorganic thermodynamic model (Amundson et al., 2006c to organic/water systems. Phase diagrams for a number of model organic/water systems characteristic of both primary and secondary organic aerosols are computed. Also calculated are inorganic/organic/water phase diagrams that show the effect of organics on inorganic deliquescence behavior. The effect of the choice of activity coefficient model for organics on the computed phase equilibria is explored.
A new atmospheric aerosol phase equilibrium model (UHAERO: organic systems
N. R. Amundson
2007-06-01
Full Text Available In atmospheric aerosols, water and volatile inorganic and organic species are distributed between the gas and aerosol phases in accordance with thermodynamic equilibrium. Within an atmospheric particle, liquid and solid phases can exist at equilibrium. Models exist for computation of phase equilibria for inorganic/water mixtures typical of atmospheric aerosols; when organic species are present, the phase equilibrium problem is complicated by organic/water interactions as well as the potentially large number of organic species. We present here an extension of the UHAERO inorganic thermodynamic model (Amundson et al., 2006c to organic/water systems. Phase diagrams for a number of model organic/water systems characteristic of both primary and secondary organic aerosols are computed. Also calculated are inorganic/organic/water phase diagrams that show the effect of organics on inorganic deliquescence behavior. The effect of the choice of activity coefficient model for organics on the computed phase equilibria is explored.
The rational expectations equilibrium inventory model theory and applications
1989-01-01
This volume consists of six essays that develop and/or apply "rational expectations equilibrium inventory models" to study the time series behavior of production, sales, prices, and inventories at the industry level. By "rational expectations equilibrium inventory model" I mean the extension of the inventory model of Holt, Modigliani, Muth, and Simon (1960) to account for: (i) discounting, (ii) infinite horizon planning, (iii) observed and unobserved by the "econometrician" stochastic shocks in the production, factor adjustment, storage, and backorders management processes of firms, as well as in the demand they face for their products; and (iv) rational expectations. As is well known according to the Holt et al. model firms hold inventories in order to: (a) smooth production, (b) smooth production changes, and (c) avoid stockouts. Following the work of Zabel (1972), Maccini (1976), Reagan (1982), and Reagan and Weitzman (1982), Blinder (1982) laid the foundations of the rational expectations equilibrium inve...
李明春; 赵中亮; 静宇; 刘家涛; 吴玉胜
2013-01-01
To study the influence of the Soret and Dufour effects on the reactive characteristics of a porous packed bed with endothermic reactions and forced convection, a two-dimensional mathematical model considering the cross-diffusion effects was developed in accordance with the thermodynamics of irreversible processes and the lo-cal thermal non-equilibrium model. The simulation results were validated by comparing with experimental data. The influence of the Soret and Dufour effects on the heat transfer, mass transfer and endothermic chemical reaction in the non-thermal equilibrium packed bed is discussed. It was found that when the Peclet number reaches 1865, the maximum relative error of the concentration of gas product induced by the Soret effect is 34.7% and that of the solid fractional conversion caused by the Dufour effect is 10.8%at reaction time 160 s and initial temperature 1473 K. The differences induced by the Soret and Dufour effects are demonstrated numerically to increase gradually with the initial temperature of feeding gas and the Peclet number.
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.
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.
Equilibrium models in multimodal container transport systems
Corman, F.; Viti, F.; Negenborn, R.R.
2015-01-01
Optimizing the performance of multimodal freight transport networks involves adequately balancing the interplay between costs, volumes, times of departure and arrival, and times of travel. In order to study this interplay, we propose an assignment model that is able to efficiently determine flows an
Estimating Dynamic Equilibrium Models using Macro and Financial Data
Christensen, Bent Jesper; Posch, Olaf; van der Wel, Michel
We show that including financial market data at daily frequency, along with macro series at standard lower frequency, facilitates statistical inference on structural parameters in dynamic equilibrium models. Our continuous-time formulation conveniently accounts for the difference in observation...... of the estimators and estimate the model using 20 years of U.S. macro and financial data....
Fitting Equilibrium Search Models to Labour Market Data
Bowlus, Audra J.; Kiefer, Nicholas M.; Neumann, George R.
1996-01-01
Specification and estimation of a Burdett-Mortensen type equilibrium search model is considered. The estimation is nonstandard. An estimation strategy asymptotically equivalent to maximum likelihood is proposed and applied. The results indicate that specifications with a small number of productiv...... of productivity types fit the data well compared to the homogeneous model....
Numerical equilibrium analysis for structured consumer resource models
de Roos, A.M.; Diekmann, O.; Getto, P.; Kirkilionis, M.A.
2010-01-01
In this paper, we present methods for a numerical equilibrium and stability analysis for models of a size structured population competing for an unstructured re- source. We concentrate on cases where two model parameters are free, and thus existence boundaries for equilibria and stability boundaries
An applied general equilibrium model for Dutch agribusiness policy analysis.
Peerlings, J.H.M.
1993-01-01
The purpose of this thesis was to develop a basic static applied general equilibrium (AGE) model to analyse the effects of agricultural policy changes on Dutch agribusiness. In particular the effects on inter-industry transactions, factor demand, income, and trade are of interest.The model is fairly
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…
Electricity market equilibrium model with resource constraint and transmission congestion
Gao, F. [ABB, Inc., Santa Clara, CA 95050 (United States); Sheble, G.B. [Portland State University, Portland, OR 97207 (United States)
2010-01-15
Electricity market equilibrium model not only helps Independent System Operator/Regulator analyze market performance and market power, but also provides Market Participants the ability to build optimal bidding strategies based on Microeconomics analysis. Supply Function Equilibrium (SFE) is attractive compared to traditional models and many efforts have been made on it before. However, most past research focused on a single-period, single-market model and did not address the fact that GENCOs hold a portfolio of assets in both electricity and fuel markets. This paper first identifies a proper SFE model, which can be applied to a multiple-period situation. Then the paper develops the equilibrium condition using discrete time optimal control considering fuel resource constraints. Finally, the paper discusses the issues of multiple equilibria caused by transmission network and shows that a transmission constrained equilibrium may exist, however the shadow price may not be zero. Additionally, an advantage from the proposed model for merchant transmission planning is discussed. (author)
Phase equilibrium measurements and modelling for separation process design
Dell' Era, C.
2012-07-01
the thermodynamic representation of the equilibrium between phases. For this purpose an extensive experimental work was performed, comprising of vapour-liquid, gas-liquid and solid-liquid equilibrium measurements. Vapour liquid equilibrium of binary mixtures of butane + alcohols was measured with a static total pressure apparatus due to the importance of hydrocarbon and alcohol mixtures in the production of biofuels. The same equipment was used to measure binary systems of diethyl sulphide + C4 - hydrocarbons of importance in refinery applications. The activity coefficients of these systems were modelled with activity coefficients models. The absorption of carbon dioxide in alkanolamine solutions is the leading technology for the removal of carbon dioxide during refining of gas and oil. In recent years, this technology has gained importance also for carbon capture from large point sources. The scarcity of experimental data for some alkanolamine systems affected the accuracy of thermodynamic models. Several experimental techniques were developed to supply new experimental data for aqueous solutions of diisopropanolamine (DIPA) and methyldiethanolamine (MDEA). The solubility of carbon dioxide in solutions of these amines was measured with a static total pressure apparatus for gas solubility, and with a bubbling apparatus. The density of carbonated aqueous DIPA was also measured and modelled. The vapour-liquid equilibrium of water + DIPA and water + MDEA was measured with a static total pressure apparatus. The solid-liquid equilibrium of the same systems was measured with a visual method and a Differential Scanning Calorimeter. The activity coefficients of aqueous DIPA and MDEA solutions were modelled using NRTL, thus providing the first model of this sort for DIPA. A new model of the Henry's law constant of carbon dioxide in binary and ternary aqueous solutions of alkanolamines was developed at temperatures up to 393 K. (orig.)
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.
African wildlife and people : finding solutions where equilibrium models fail
Poshiwa, X.
2013-01-01
Grazing systems, covering about half of the terrestrial surface, tend to be either equilibrial or non-equilibrial in nature, largely depending on the environmental stochasticity.The equilibrium model perspective stresses the importance of biotic feedbacks between herbivores and
An applied general equilibrium model for Dutch agribusiness policy analysis
Peerlings, J.
1993-01-01
The purpose of this thesis was to develop a basic static applied general equilibrium (AGE) model to analyse the effects of agricultural policy changes on Dutch agribusiness. In particular the effects on inter-industry transactions, factor demand, income, and trade are of interest.
African wildlife and people : finding solutions where equilibrium models fail
Poshiwa, X.
2013-01-01
Grazing systems, covering about half of the terrestrial surface, tend to be either equilibrial or non-equilibrial in nature, largely depending on the environmental stochasticity.The equilibrium model perspective stresses the importance of biotic feedbacks between herbivores and thei
An applied general equilibrium model for Dutch agribusiness policy analysis
Peerlings, J.
1993-01-01
The purpose of this thesis was to develop a basic static applied general equilibrium (AGE) model to analyse the effects of agricultural policy changes on Dutch agribusiness. In particular the effects on inter-industry transactions, factor demand, income, and trade are of
An Equilibrium-Correction Model for Dynamic Network Data
D.J. Dekker (David); Ph.H.B.F. Franses (Philip Hans); D. Krackhardt (David)
2001-01-01
textabstractWe propose a two-stage MRQAP to analyze dynamic network data, within the framework of an equilibrium-correction (EC) model. Extensive simulation results indicate practical relevance of our method and its improvement over standard OLS. An empirical illustration additionally shows that the
An equilibrium-correction model for dynamic network data
R. Dekker (Rommert); Ph.H.B.F. Franses (Philip Hans); D. Krackhardt (David)
2003-01-01
textabstractWe propose a two-stage MRQAP to analyze dynamic network data, within the framework of an equilibrium-correction (EC) model. Extensive simulation results indicate practical relevance of our method and its improvement over standard OLS. An empirical illustration additionally shows that the
African wildlife and people : finding solutions where equilibrium models fail
Poshiwa, X.
2013-01-01
Grazing systems, covering about half of the terrestrial surface, tend to be either equilibrial or non-equilibrial in nature, largely depending on the environmental stochasticity.The equilibrium model perspective stresses the importance of biotic feedbacks between herbivores and thei
T. Lukács
2011-01-01
Full Text Available A general overall feasibility methodology of batch reactive distillation of multireaction systems is developed to study all the possible configurations of batch reactive distillation. The general model equations are derived for multireaction system with any number of chemical equilibrium-limited reactions and for any number of components. The present methodology is demonstrated with the detailed study of the transesterification of dimethyl carbonate in two reversible cascade reactions in batch reactive distillation process. Pure methanol is produced as distillate, and pure diethyl carbonate is produced at the bottom simultaneously in middle-vessel column; in each section, continuous feeding of ethanol is necessary. The results of feasibility study are successfully validated by rigorous simulations.
Tel, E.; Kaplan, A.; Aydın, A.; Özkorucuklu, S.; Büyükuslu, H.; Yıldırım, G.
2010-08-01
Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So, working out the systematics of ( n,t) reaction cross sections and triton emission differential data are important for the given reaction taking place on various nuclei at different energies. In this study, ( n,xt) reactions for some target nuclei as 16O, 27Al, 59Co and 209Bi have been investigated up to 45 MeV incident neutron energy. In the calculations of the triton emission spectra, the pre-equilibrium and equilibrium effects have been used. The calculated results have been compared with the experimental data taken from the literature.
Non-Equilibrium Zeldovich-Von Neumann-Doring Theory and Reactive Flow Modeling of Detonation
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
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.
Equilibrium Model Constraints on Baryon Cycling Across Cosmic Time
Mitra, Sourav; Finlator, Kristian
2014-01-01
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
Knowledge Management through the Equilibrium Pattern Model for Learning
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.
Management Model of Resources Equilibrium Distribution among Overlapping-Generations
Jiang Xuemin; Li Ling
2004-01-01
The overlapping generation models the western scholars have designed from various perspectives to address different kinds of issues do not reflect Chinese emerging political and economic problems, and cannot be entirely and blindly applied to Chinese practical situation. In this paper the authors endeavor to incorporate some western scholars' research results into their own research findings to present overlapping generations model theory in a new perspective through establishing an overlapping generations theory on population including articulation of concepts and theorems of biological generation, economic generation and social generation and the overlapping periods in biological generation and two overlapping periods in economic generation among three generations. This management model with equilibrium distribution of resource wealth includes overlapping generations length model (δ),equilibrium transfer model (θ) and a complete model on equilibrium distribution among generations (δ-θ).The model provides quantitative basis for the creation of resource management system, and fills in a theoretical gap in this discipline in China. Besides,it furnishes a new methodology and manipulable tool for Chinese government to establish a comprehensive management information bank for many sectors such as economic trade, population, science and technology, education, human resource, natural resource and environment, agriculture, forestry,industry, mining and energy.
An equilibrium search model of the informal sector
2006-01-01
We use an equilibrium search framework to model a formal- informal sector labour market where the informal sector arises endogenously. In our model large firms will be in the formal sector and pay a wage premium, while small firms are characterised by low wages and tend to be in the informal sector. Using data from the South African labour force survey we illustrate that the data is consistent with these predictions.
The direction of migration: a dynamic general equilibrium model.
Lee, K S
1984-11-01
A two-sector dynamic general equilibrium model is developed "to investigate the direction of migration in response to differing demographic and consumption demand behavior, as well as variations in production conditions." The model, which involves a rural sector and an urban sector, incorporates "returns to scale and the natural rate of sectoral population growth as important determinants of the direction of migration, in addition to price and income elasticities, and the sectoral technical change rate with which...previous studies dealt."
Mathematical modeling of precipitation and dissolution reactions in microbiological systems.
Rittmann, Bruce E; Banaszak, James E; VanBriesen, Jeanne M; Reed, Donald T
2002-01-01
We expand the biogeochemical model CCBATCH to include a precipitation/dissolution sub-model that contains kinetic and equilibrium options. This advancement extends CCBATCH's usefulness to situations in which microbial reactions cause or are affected by formation or dissolution of a solid phase. The kinetic option employs a rate expression that explicitly includes the intrinsic kinetics for reaction or mass-transport control, the difference from thermodynamic equilibrium, and the aqueous concentration of the rate-limiting metal or ligand. The equilibrium feature can be used alone, and it also serves as check that the kinetic rate never is too fast and "overshoots" equilibrium. The features of the expanded CCBATCH are illustrated by an example in which the precipitation of Fe(OH)3(s) allows the biodegradation of citric acid, even though complexes are strong and not bioavailable. Precipitation releases citrate ligand, and biodegradation of the citrate increases the pH.
Rasmussen, Thomas Kjær; Watling, David P.; Prato, Carlo Giacomo
-off is strictly enforced: in a time-only model, if the current equilibrium travel time is 15.3 minutes, then adding a route with travel time of 15.4 minutes will have no impact on routing behaviour, whereas in practice (because of uncertainty, variability and unobserved attributes) the new route is likely....... This issue is further complicated by the fact that typically only a sub-set of possible routes will be identified in numerical algorithms solving for SUE. In the current study, we present new alternative forms of SUE conditions that permit unused alternatives, accommodate behaviour on used alternatives...... algorithms to the behaviourally sound SUE and the efficiency of solution algorithms to the DUE, we introduce a transformation of the cost function. This transformation function opens up a larger array of possible solution algorithms to the SUE, as it allows us to apply any path-based DUE solution algorithm...
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.
Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique
2017-04-28
This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).
Discrimination and Skill Differences in an Equilibrium Search Model
Bowlus, Audra J.; Eckstein, Zvi
1998-01-01
In this paper, we analyse an equilibrium search model with three sources for wage and unemployment differentials among workers with the same (observed) human capital but different appearance (race): unobserved productivity (skill), search intensities and discrimination (Becker 1957) due to an appearance-based employer disutility factor. Because these sources affect the earnings distributions differently, empirical identification of these potential sources for the explanation of wage and unemp...
Reactive Solute Transport in Streams: 1. Development of an Equilibrium-Based Model
Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.
1996-02-01
An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.
Reactive solute transport in streams. 1. Development of an equilibrium- based model
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.
Double-differential spectra of the secondary particles in the frame of pre-equilibrium model
Fotina, O. V.; Kravchuk, V. L.; Barlini, S.; Gramegna, F.; Eremenko, D. O.; Parfenova, Yu. L.; Platonov, S. Yu.; Yuminov, O. A.; Bruno, M.; D'Agostino, M.; Casini, G.; Wieland, O.; Bracco, A.; Camera, F.
2010-08-01
An approach was developed to describe the double-differential spectra of secondary particles formed in heavy-ion reactions. Griffin model of nonequilibrium processes was used to account for the nonequilibrium stage of the compound system formation. Simulation of de-excitation of the compound system was carried out using the Monte-Carlo method. Analysis of the probability of neutron, proton, and α-particle emission was performed both in equilibrium, and in the pre-equilibrium stages of the process. Fission and γ-ray emission were also considered after equilibration. The analysis of the experimental data on the double-differential cross sections of p, α particles for the 16O + 116Sn reaction at the oxygen energy E = 130 and 250 MeV were performed.
Modeling of turbulent chemical reaction
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.
Equilibrium properties of the reaction H2 ⇌ 2H by classical molecular dynamics simulations.
Skorpa, Ragnhild; Simon, Jean-Marc; Bedeaux, Dick; Kjelstrup, Signe
2014-01-21
We have developed a classical molecular dynamics model for the hydrogen dissociation reaction, containing two- and three-particle potentials derived by Kohen, Tully and Stillinger. Two fluid densities were investigated for a wide range of temperatures, and 11 fluid densities were considered for one temperature. We report the temperature range where the degree of reaction is significant, and also where a stable molecule dominates the population in the energy landscape. The three-particle potential, which is essential for the reaction model and seldom studied, together with the two-particle interaction lead to a large effective excluded volume diameter of the molecules in the molecular fluid. The three-particle interaction was also found to give a large positive contribution to the pressure of the reacting mixture at high density and/or low temperatures. From knowledge of the dissociation constant of the reaction and the fluid pressure, we estimated the standard enthalpy of the dissociation reaction to be 430 kJ mol(-1) (ρ = 0.0695 g cm(-3)) and 380 kJ mol(-1) (ρ = 0.0191 g cm(-3)). These values are in good agreement with the experimental vaule of 436 kJ mol(-1) under ambient pressure. The model is consistent with a Lennard-Jones model of the molecular fluid, and may facilitate studies of the impact of chemical reactions on transport systems.
Partial molar enthalpies and reaction enthalpies from equilibrium molecular dynamics simulation
Schnell, Sondre K. [Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft (Netherlands); Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim (Norway); Skorpa, Ragnhild; Bedeaux, Dick [Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim (Norway); Kjelstrup, Signe [Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim (Norway); Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft (Netherlands); Vlugt, Thijs J. H. [Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft (Netherlands); Simon, Jean-Marc, E-mail: jmsimon@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303, CNRS-Université de Bourgogne, 9, av. Savary, 21000 Dijon (France)
2014-10-14
We present a new molecular simulation technique for determining partial molar enthalpies in mixtures of gases and liquids from single simulations, without relying on particle insertions, deletions, or identity changes. The method can also be applied to systems with chemical reactions. We demonstrate our method for binary mixtures of Weeks-Chandler-Anderson particles by comparing with conventional simulation techniques, as well as for a simple model that mimics a chemical reaction. The method considers small subsystems inside a large reservoir (i.e., the simulation box), and uses the construction of Hill to compute properties in the thermodynamic limit from small-scale fluctuations. Results obtained with the new method are in excellent agreement with those from previous methods. Especially for modeling chemical reactions, our method can be a valuable tool for determining reaction enthalpies directly from a single MD simulation.
3D-model view characterization using equilibrium planes
Theetten, Adrien; Filali Ansary, Tarik; Vandeborre, Jean-Philippe
2008-01-01
International audience; We propose a new method for 3D-mesh model characteristic view selection. It consists in using the views that come from the equilibrium states of a 3D-model: they correspond to the horizontal plane on which an object is stat- ically laying under the effect of gravity. The selected views are then very intuitive for the user. Indeed, to present a query, the user will take a photo or draw a sketch of the object on a table or on a floor, putting thus the object in a static ...
Conversion of Chemical Reaction Energy into Useful Work in the Van't Hoff Equilibrium Box
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.
Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique
2017-03-01
This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub-Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti-Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature. This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'.
Three Stage Equilibrium Model for Coal Gasification in Entrained Flow Gasifiers Based on Aspen Plus
KONG Xiangdong; ZHONG Weimin; DU Wenli; QIAN Feng
2013-01-01
A three stage equilibrium model is developed for coal gasification in the Texaco type coal gasifiers based on Aspen Plus to calculate the composition of product gas,carbon conversion,and gasification temperature.The model is divided into three stages including pyrolysis and combustion stage,char gas reaction stage,and gas phase reaction stage.Part of the water produced in the pyrolysis and combustion stage is assumed to be involved in the second stage to react with the unburned carbon.Carbon conversion is then estimated in the second stage by steam participation ratio expressed as a function of temperature.And the gas product compositions are calculated from gas phase reactions in the third stage.The simulation results are consistent with published experimental data.
Modeling Inflation Using a Non-Equilibrium Equation of Exchange
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
A Parametric Model for Barred Equilibrium Beach Profiles
2014-05-10
A parametric model for barred equilibrium beach profiles Robert A. Holman a,⁎, David M. Lalejini a, Kacey Edwards b, Jay Veeramony b a Marine...a limited cross-shore span. Coastal Engineering 90 (2014) 85–94 ⁎ Corresponding author. Tel.: +1 541 737 2914. E-mail addresses: holman ...coas.oregonstate.edu (R.A. Holman ), David.Lalejini@nrlssc.navy.mil (D.M. Lalejini), kacey.edwards@nrlssc.navy.mil (K. Edwards), jay.veeramony@nrlssc.navy.mil (J
General Relativistic Equilibrium Models of Magnetized Neutron Stars
Pili, A G; Del Zanna, L
2013-01-01
Magnetic fields play a crucial role in many astrophysical scenarios and, in particular, are of paramount importance in the emission mechanism and evolution of Neutron Stars (NSs). To understand the role of the magnetic field in compact objects it is important to obtain, as a first step, accurate equilibrium models for magnetized NSs. Using the conformally flat approximation we solve the Einstein's equations together with the GRMHD equations in the case of a static axisymmetryc NS taking into account different types of magnetic configuration. This allows us to investigate the effect of the magnetic field on global properties of NSs such as their deformation.
Reduction of chemical reaction models
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.
Non-equilibrium statistical mechanical approach for describing heavy ion reactions
Sventek, J.S.
1978-11-01
With the availability of heavy-ion projectiles (A > 4) at low to intermediate energies (4 < E/A < 10), products showing various stages of relaxation for certain macroscopic variables (center-of-mass energy, orbital angular momentum, etc.) were produced in various reactions. The distributions for these macroscopic variables showed a correlation between the stage of relaxation reached and the net amount of mass transfer which had occurred in the reaction. There was also evidence that there was an asymmetry in the number of net transfers necessary for complete relaxation between stripping and pickup reactions. A model for describing the time-evolution of these reactions was formulated, the keystone of which is a master-equation approach for describing the time-dependence of the mass-asymmetry. This, coupled with deterministic equations of motion for the other macroscopic coordinates in the reaction lead to calculated distributions which provide an excellent qualitative description of these reactions, and, in some cases, quantitatively reproduce the experimental data quite well. 61 figures, 2 tables.
Entropy and equilibrium state of free market models
Iglesias, J R
2011-01-01
Many recent models of trade dynamics use the simple idea of wealth exchanges among economic agents in order to obtain a stable or equilibrium distribution of wealth among the agents. In particular, a plain analogy compares the wealth in a society with the energy in a physical system, and the trade between agents to the energy exchange between molecules during collisions. In physical systems, the energy exchange among molecules leads to a state of equipartition of the energy and to an equilibrium situation where the entropy is a maximum. On the other hand, in the majority of exchange models, the system converges to a very unequal condensed state, where one or a few agents concentrate all the wealth of the society while the wide majority of agents shares zero or almost zero fraction of the wealth. So, in those economic systems a minimum entropy state is attained. We propose here an analytical model where we investigate the effects of a particular class of economic exchanges that minimize the entropy. By solving...
Kustova, Elena V.; Kremer, Gilberto M.
2014-12-01
Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman-Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N2 flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.
Wu, Hao; Nüske, Feliks; Paul, Fabian; Klus, Stefan; Koltai, Péter; Noé, Frank
2017-04-01
Markov state models (MSMs) and master equation models are popular approaches to approximate molecular kinetics, equilibria, metastable states, and reaction coordinates in terms of a state space discretization usually obtained by clustering. Recently, a powerful generalization of MSMs has been introduced, the variational approach conformation dynamics/molecular kinetics (VAC) and its special case the time-lagged independent component analysis (TICA), which allow us to approximate slow collective variables and molecular kinetics by linear combinations of smooth basis functions or order parameters. While it is known how to estimate MSMs from trajectories whose starting points are not sampled from an equilibrium ensemble, this has not yet been the case for TICA and the VAC. Previous estimates from short trajectories have been strongly biased and thus not variationally optimal. Here, we employ the Koopman operator theory and the ideas from dynamic mode decomposition to extend the VAC and TICA to non-equilibrium data. The main insight is that the VAC and TICA provide a coefficient matrix that we call Koopman model, as it approximates the underlying dynamical (Koopman) operator in conjunction with the basis set used. This Koopman model can be used to compute a stationary vector to reweight the data to equilibrium. From such a Koopman-reweighted sample, equilibrium expectation values and variationally optimal reversible Koopman models can be constructed even with short simulations. The Koopman model can be used to propagate densities, and its eigenvalue decomposition provides estimates of relaxation time scales and slow collective variables for dimension reduction. Koopman models are generalizations of Markov state models, TICA, and the linear VAC and allow molecular kinetics to be described without a cluster discretization.
Theoretical Model Calculation for d + 8Li Reaction
HAN Yin-Lu; GUO Hai-Rui; ZHANG Yue; ZHANG Jing-Shang
2008-01-01
Based on the theoretical models for light nuclei, the calculations of reaction cross sections and the angular distributions for d+8Li reaction are performed. Since all of the particle emissions are from the compound nucleus to the discrete levels, the angular momentum coupling effect in pre-equilibrium mechanism is taken into account. The three-body break-up process and the recoil effect are involved. The theoretical calculated results are compared to existing experimental data.
Roossien, F.F.; Brink, J.; Robillard, G.T.
1983-01-01
A one step procedure is presented for the preparation of [32P]phosphoenolpyruvate from [γ-32P]ATP using pyruvate kinase. The reaction is carried out at chemical equilibrium and involves only an exchange of isotope between ATP and phosphoenolpyruvate. The initial phosphoenolpyruvate/ATP ratio in the
Closure conditions for non-equilibrium multi-component models
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.
NHPP-Based Software Reliability Models Using Equilibrium Distribution
Xiao, Xiao; Okamura, Hiroyuki; Dohi, Tadashi
Non-homogeneous Poisson processes (NHPPs) have gained much popularity in actual software testing phases to estimate the software reliability, the number of remaining faults in software and the software release timing. In this paper, we propose a new modeling approach for the NHPP-based software reliability models (SRMs) to describe the stochastic behavior of software fault-detection processes. The fundamental idea is to apply the equilibrium distribution to the fault-detection time distribution in NHPP-based modeling. We also develop efficient parameter estimation procedures for the proposed NHPP-based SRMs. Through numerical experiments, it can be concluded that the proposed NHPP-based SRMs outperform the existing ones in many data sets from the perspective of goodness-of-fit and prediction performance.
Modeling dune response using measured and equilibrium bathymetric profiles
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.
Equilibrium Assignment Model with Uncertainties in Traffic Demands
Aiwu Kuang
2013-01-01
Full Text Available In this study, we present an equilibrium traffic assignment model considering uncertainties in traffic demands. The link and route travel time distributions are derived based on the assumption that OD traffic demand follows a log-normal distribution. We postulate that travelers can acquire the variability of route travel times from past experiences and factor such variability into their route choice considerations in the form of mean route travel time. Furthermore, all travelers want to minimize their mean route travel times. We formulate the assignment problem as a variational inequality, which can be solved by a route-based heuristic solution algorithm. Some numerical studies on a small test road network are carried out to validate the proposed model and algorithm, at the same time, some reasonable results are obtained.
Knutz, B.C.; Hjuler, Hans Aage; Berg, Rolf W.;
1993-01-01
corresponding Variation of anode potential, cathode potential, and cell voltage as a function of electrolyte composition. For sulfide containing cells the plateau of lowest potential has been found to be associated with essentially pure nickel sulfide, NiySz. A procedure for model fitting to the cathode...
Equilibrium modeling of the TFCX poloidal field coil system
Strickler, D.J.; Miller, J.B.; Rothe, K.E.; Peng, Y.K.M.
1984-04-01
The Toroidal Fusion Core Experiment (TFCX) isproposed to be an ignition device with a low safety factor (q approx. = 2.0), rf or rf-assisted startup, long inductive burn pulse (approx. 300 s), and an elongated plasma cross section (kappa = 1.6) with moderate triangularity (delta = 0.3). System trade studies have been carried out to assist in choosing an appropriate candidate for TFCX conceptual design. This report describes an important element in these system studies - the magnetohydrodynamic (MHD) equilibrium modeling of the TFCX poloidal field (PF) coil system and its impact on the choice of machine size. Reference design points for the all-super-conducting toroidal field (TF) coil (TFCX-S) and hybrid (TFCX-H) options are presented that satisfy given PF system criteria, including volt-second requirements during burn, mechanical configuration constraints, maximum field constraints at the superconducting PF coils, and plasma shape parameters. Poloidal coil current waveforms for the TFCX-S and TFCX-H reference designs consistent with the equilibrium requirements of the plasma startup, heating, and burn phases of a typical discharge scenario are calculated. Finally, a possible option for quasi-steady-state operation is discussed.
Partial equilibrium model – Case study of the poultry market
Lenka Šobrová
2011-01-01
Full Text Available This paper deals with identifying the main determinants in the poultry agri-food chain in the Czech Republic and examines their relationships. The partial equilibrium model, defined as a seven-equation model in power form, is employed for this purpose. The analysis is based on both time-series and panel data of the main factors in the poultry market. The time-series as well as panel data contain annual data of selected variables for the period from 1995 to 2009. The analysis is focused on supply and demand of poultry meat, specifically on production, consumption and foreign trade in poultry meat in the Czech Republic. Firstly, the main factors influencing the poultry market are determined, then, an appropriate model is employed. The parameters of the model are estimated using the ordinary least squares method in statistical and econometric software. Estimated parameters confirm assumed relationships among the selected variables. Moreover, the long-term tendencies of the selected indicators are proven. Among other, the analysis proves an inertial consumption, the price level as the main factor influencing the consumption and one-way or mutual relationship among the selected variables. The statistical features of the model are satisfied as well – the estimated parameters are statistically significant, the model does not contain, neither the problem of autocorrelation of residuals nor the problem of heteroskedasticity.
Computable general equilibrium model fiscal year 2013 capability development report
Edwards, Brian Keith [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Rivera, Michael Kelly [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Boero, Riccardo [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2016-05-17
This report documents progress made on continued developments of the National Infrastructure Simulation and Analysis Center (NISAC) Computable General Equilibrium Model (NCGEM), developed in fiscal year 2012. In fiscal year 2013, NISAC the treatment of the labor market and tests performed with the model to examine the properties of the solutions computed by the model. To examine these, developers conducted a series of 20 simulations for 20 U.S. States. Each of these simulations compared an economic baseline simulation with an alternative simulation that assumed a 20-percent reduction in overall factor productivity in the manufacturing industries of each State. Differences in the simulation results between the baseline and alternative simulations capture the economic impact of the reduction in factor productivity. While not every State is affected in precisely the same way, the reduction in manufacturing industry productivity negatively affects the manufacturing industries in each State to an extent proportional to the reduction in overall factor productivity. Moreover, overall economic activity decreases when manufacturing sector productivity is reduced. Developers ran two additional simulations: (1) a version of the model for the State of Michigan, with manufacturing divided into two sub-industries (automobile and other vehicle manufacturing as one sub-industry and the rest of manufacturing as the other subindustry); and (2) a version of the model for the United States, divided into 30 industries. NISAC conducted these simulations to illustrate the flexibility of industry definitions in NCGEM and to examine the simulation properties of in more detail.
A reaction-based river/stream water quality model: Model development and numerical schemes
Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Jardine, Philip M.
2008-01-01
SummaryThis paper presents the conceptual and mathematical development of a numerical model of sediment and reactive chemical transport in rivers and streams. The distribution of mobile suspended sediments and immobile bed sediments is controlled by hydrologic transport as well as erosion and deposition processes. The fate and transport of water quality constituents involving a variety of chemical and physical processes is mathematically described by a system of reaction equations for immobile constituents and advective-dispersive-reactive transport equations for mobile constituents. To circumvent stiffness associated with equilibrium reactions, matrix decomposition is performed via Gauss-Jordan column reduction. After matrix decomposition, the system of water quality constituent reactive transport equations is transformed into a set of thermodynamic equations representing equilibrium reactions and a set of transport equations involving no equilibrium reactions. The decoupling of equilibrium and kinetic reactions enables robust numerical integration of the partial differential equations (PDEs) for non-equilibrium-variables. Solving non-equilibrium-variable transport equations instead of individual water quality constituent transport equations also reduces the number of PDEs. A variety of numerical methods are investigated for solving the mixed differential and algebraic equations. Two verification examples are compared with analytical solutions to demonstrate the correctness of the code and to illustrate the importance of employing application-dependent numerical methods to solve specific problems.
Ising Model Reprogramming of a Repeat Protein's Equilibrium Unfolding Pathway.
Millership, C; Phillips, J J; Main, E R G
2016-05-08
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. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.
Stochastic Modeling of Non-equilibrium Bedload Transport
Kuai, Z.; Tsai, C. W.
2009-05-01
Traditional stochastic bed load models aimed to solve for the equilibrium bedload transport rate by matching the rate of bed erosion with the rate of deposition. Bedload transport can be in nonequilibrium even under the steady flow condition, as the quantity of moving particles in the bedload layer may vary. In a nonequilibrium condition, the interchange of sediment particles occurs not only between the bedload layer and the bed surface, but also across the interface between bedload and suspended load. The proposed approach attempts to add a new bedload-suspended load interchange layer to a stochastic bedlod transport model based on the Markov chain. The bedload transport rate is the product of the total particle volume in saltation and the average saltating velocity. We can quantify the number of saltating particles by modeling the occupancy probabilities vector of particles staying in three states (i.e., bed surface, bedload layer, and the interchange layer between the bedload and the suspended load.). The new stochastic bedload relation is validated against existing bedload model. The sudden change of flow and/or sediment condition leads to changes in the transition probabilities. The influence of sudden changes in flow-sediment properties on the bedload transport rate is investigated in this preliminary study. It is found that the neglecting the exchange process between the bedload layer and the suspended layer may lead to non-negligible errors in bedload calculation when the flow and/or sediment conditions change.
Modeling equilibrium adsorption of organic micropollutants onto activated carbon
De Ridder, David J.
2010-05-01
Solute hydrophobicity, polarizability, aromaticity and the presence of H-bond donor/acceptor groups have been identified as important solute properties that affect the adsorption on activated carbon. However, the adsorption mechanisms related to these properties occur in parallel, and their respective dominance depends on the solute properties as well as carbon characteristics. In this paper, a model based on multivariate linear regression is described that was developed to predict equilibrium carbon loading on a specific activated carbon (F400) for solutes reflecting a wide range of solute properties. In order to improve prediction accuracy, groups (bins) of solutes with similar solute properties were defined and solute removals were predicted for each bin separately. With these individual linear models, coefficients of determination (R2) values ranging from 0.61 to 0.84 were obtained. With the mechanistic approach used in developing this predictive model, a strong relation with adsorption mechanisms is established, improving the interpretation and, ultimately, acceptance of the model. © 2010 Elsevier Ltd.
A study of pre-equilibrium emission of neutrons in {sup 93}Nb({alpha},xn) reactions
Sharma, M.K.; Unnati; Singh, P.P.; Singh, B.P.; Prasad, R. [Aligarh Muslim University, Department of Physics, Aligarh (India); Bhardwaj, H.D. [DSN College, Department of Physics, Unnao (India)
2007-01-15
With a view to study the pre-equilibrium emission mechanism in {alpha}-induced reactions the excitation functions for {sup 93}Nb({alpha},n){sup 96m}Tc, {sup 93}Nb({alpha},n){sup 96}Tc, {sup 93}Nb({alpha}, 2n){sup 95m}Tc, {sup 93}Nb({alpha},2n){sup 95g}Tc and {sup 93}Nb({alpha},3n){sup 94}Tc reactions have been measured in the energy range threshold to {approx}10 MeV/nucleon using the activation technique. The measured excitation functions have also been compared with theoretical predictions based on the semi-classical code, which takes into account compound nucleus as well as pre-equilibrium emission. The analysis of the data indicates significant contribution from pre-equilibrium emission at these energies particularly in the high-energy tail portion of EFs. The effect of the variation of the parameters used in the code has been studied. The isomeric cross-section ratios have also been measured. It has been observed that the pre-equilibrium fraction increases rapidly with the increase in {alpha}-particle bombarding energy. (orig.)
Social security as Markov equilibrium in OLG models: A note
Gonzalez Eiras, Martin
2011-01-01
I refine and extend the Markov perfect equilibrium of the social security policy game in Forni (2005) for the special case of logarithmic utility. Under the restriction that the policy function be continuous, instead of differentiable, the equilibrium is globally well defined and its dynamics...
Jesudason, C G
2006-01-01
The rates or formation and concentration distributions of a dimer reaction showing hysteresis behavior are examined in an ab initio chemical reaction designed as elementary and where the hysteresis structure precludes the formation of transition states (TS) with pre-equilibrium and internal sub-reactions. It was discovered that the the reactivity coefficients, defined as a measure of departure from the zero density rate constant for the forward and backward steps had a ratio that was equal to the activity coefficient ratio for the product and reactant species. From the above observations, a theory is developed with the aid of some proven elementary theorems in thermodynamics, and expressions are derived whereby a feasible experimental and computational method for determining the activity coefficients from the rate constants may be obtained The theory developed is applied to ionic reactions where the standard Bronsted-Bjerrum rate equation and exceptions to this are rationalized, and by viewing ion association...
Equilibrium models of coronal loops that involve curvature and buoyancy
Hindman, Bradley W
2013-01-01
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 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.
Equilibrium Models of Coronal Loops That Involve Curvature and Buoyancy
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.
Model Equilibrium and Empirical Study of Rural Labor Transfer
Qinghua; HUANG; Xiuchuan; XU; Ming; ZHANG; Yue; ZHAO
2013-01-01
We establish the two-sector economy model including the urban sector and the rural sector, derive the labor demand curve of the urban sector and rural sector under the condition of balanced production decisions with benefit maximization, and analyze the labor flow when in the short-term or long-term two-sector economic equilibrium. The results show that rising wages caused by short-term internal and external impact increases the pressure on the employment in two sectors, and the urban sector is difficult to absorb the surplus labor of the rural sector. However, under the conditions of free flow of factors and fully competitive market, the wage variation arising from the long-term endogenous evolution, leads to inversely proportional relationship between the demand for labor in the urban and rural sectors, which is conducive to the transfer of rural labor force. Based on microeconomic survey data of labor flow in urban-rural coordination experimental zones in Chongqing City, this paper makes an empirical study of the main factors having a short-term impact on the labor transfer, and the results show that education level and the opportunity to participate in the training are important factors.
Computable General Equilibrium Techniques for Carbon Tax Modeling
Al-Amin
2009-01-01
Full Text Available Problem statement: Lacking of proper environmental models environmental pollution is now a solemn problem in many developing countries particularly in Malaysia. Some empirical studies of worldwide reveal that imposition of a carbon tax significantly decreases carbon emissions and does not dramatically reduce economic growth. To our knowledge there has not been any research done to simulate the economic impact of emission control policies in Malaysia. Approach: Therefore this study developed an environmental computable general equilibrium model for Malaysia and investigated carbon tax policy responses in the economy applying exogenously different degrees of carbon tax into the model. Three simulations were carried out using a Malaysian social accounting matrix. Results: The carbon tax policy illustrated that a 1.21% reduction of carbon emission reduced the nominal GDP by 0.82% and exports by 2.08%; 2.34% reduction of carbon emission reduced the nominal GDP by 1.90% and exports by 3.97% and 3.40% reduction of carbon emission reduced the nominal GDP by 3.17% and exports by 5.71%. Conclusion/Recommendations: Imposition of successively higher carbon tax results in increased government revenue from baseline by 26.67, 53.07 and 79.28% respectively. However, fixed capital investment increased in scenario 1a by 0.43% and decreased in scenarios 1b and 1c by 0.26 and 1.79% respectively from the baseline. According to our policy findings policy makers should consider 1st (scenario 1a carbon tax policy. This policy results in achieving reasonably good environmental impacts without losing the investment, fixed capital investment, investment share of nominal GDP and government revenue.
Monique Florenzano
2008-09-01
Full Text Available General equilibrium is a central concept of economic theory. Unlike partial equilibrium analysis which study the equilibrium of a particular market under the clause “ceteris paribus” that revenues and prices on the other markets stay approximately unaffected, the ambition of a general equilibrium model is to analyze the simultaneous equilibrium in all markets of a competitive economy. Definition of the abstract model, some of its basic results and insights are presented. The important issues of uniqueness and local uniqueness of equilibrium are sketched; they are the condition for a predictive power of the theory and its ability to allow for statics comparisons. Finally, we review the main extensions of the general equilibrium model. Besides the natural extensions to infinitely many commodities and to a continuum of agents, some examples show how economic theory can accommodate the main ideas in order to study some contexts which were not thought of by the initial model
Yohan, D.; Gerald, D.; Magali, G.; Michel, Q.
2008-12-01
The general problem of transport and reaction in multiphase porous media has been a subject of extensive studies during the last decades. For example, biologically mediated porous media have seen a long history of research from the environmental engineering point of view. Biofilms (aggregate of microorganisms coated in a polymer matrix generated by bacteria) have been particularly examined within the context of bioremediation in the subsurface zone. Five types of models may be used to describe these kinds of physical system: 1) one-equation local mass equilibrium models when the assumption of local mass equilibrium is valid 2) two equations models when the assumption of local mass equilibrium is not valid 3) one equation non-equilibrium models 4) mixed models coupling equations solved at two different scales 5) one equation time-asymptotic models. In this presentation, we use the method of volume averaging with closure to extend the time- asymptotic model at the Darcy scale to the reactive case. Closure problems are solved for simple unit cells, and the macro-scale model is validated against pore-scale simulations.
HTR Spherical Super Lattice Model for Equilibrium Fuel Cycle Analysis
Gray S. Cahng
2005-09-01
Advanced High Temperature gas-cooled Reactors (HTR) currently being developed (GFR, VHTR - Very High Temperature gas-cooled Reactor, PBMR, and GT-MHR) are 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. 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. In addition, 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. Although HTR fuel is rather homogeneously dispersed in the fuel graphite matrix, the heterogeneity effects in between fuel kernels and pebbles cannot be ignored. The double-heterogeneous lattice model recently developed at the Idaho National Engineering and Environmental Laboratory (INEEL) contains tens of thousands of cubic fuel kernel cells, which makes it very difficult to deplete the fuel, kernel by kernel (KbK), for the EqFC analysis. In addition, it is not possible to preserve the cubic size and packing factor in a spherical fuel pebble. To avoid these difficulties, a newly developed and validated HTR pebble-bed Kernel-by-Kernel spherical (KbK-sph) model, has been developed and verified in this study. The objective of this research is to introduce the KbK-sph model and super whole Pebble lattice model (PLM). The verified double-heterogeneous KbK-sph and pebble homogeneous lattice model (HLM) are used for the fuel burnup chracteristics analysis and important safety parameters validation. This study summarizes and compares the KbK-sph and HLM burnup analyzed results. Finally, we discus the Monte-Carlo coupling with a fuel depletion and buildup code - Origen-2 as a fuel burnup
Implementation of a vibrationally linked chemical reaction model for DSMC
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.
Park, Ik Kyu; Cho, Heong Kyu; Kim, Jong Tae; Yoon, Han Young; Jeong, Jae Jun
2007-12-15
A computational model for transient, 3 dimensional 2 phase flows was developed by using 'unstructured-FVM-based, non-staggered, semi-implicit numerical scheme' considering the thermally non-equilibrium droplets. The assumption of the thermally equilibrium between liquid and droplets of previous studies was not used any more, and three energy conservation equations for vapor, liquid, liquid droplets were set up. Thus, 9 conservation equations for mass, momentum, and energy were established to simulate 2 phase flows. In this report, the governing equations and a semi-implicit numerical sheme for a transient 1 dimensional 2 phase flows was described considering the thermally non-equilibrium between liquid and liquid droplets. The comparison with the previous model considering the thermally non-equilibrium between liquid and liquid droplets was also reported.
Kramer, K.; Werf, van der D.C.
2010-01-01
The environment is changing and so are forests, in their functioning, in species composition, and in the species’ genetic composition. Many empirical and process-based models exist to support forest management. However, most of these models do not consider the impact of environmental changes and for
Modeling of equilibrium hollow objects stabilized by electrostatics.
Mani, Ethayaraja; Groenewold, Jan; Kegel, Willem K
2011-05-18
The equilibrium size of two largely different kinds of hollow objects behave qualitatively differently with respect to certain experimental conditions. Yet, we show that they can be described within the same theoretical framework. The objects we consider are 'minivesicles' of ionic and nonionic surfactant mixtures, and shells of Keplerate-type polyoxometalates. The finite-size of the objects in both systems is manifested by electrostatic interactions. We emphasize the importance of constant charge and constant potential boundary conditions. Taking these conditions into account, indeed, leads to the experimentally observed qualitatively different behavior of the equilibrium size of the objects.
Modeling of equilibrium hollow objects stabilized by electrostatics
Mani, Ethayaraja; Groenewold, Jan; Kegel, Willem K, E-mail: w.k.kegel@uu.nl [Van' t Hoff Laboratory for Physical and Colloid Chemistry, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht (Netherlands)
2011-05-18
The equilibrium size of two largely different kinds of hollow objects behave qualitatively differently with respect to certain experimental conditions. Yet, we show that they can be described within the same theoretical framework. The objects we consider are 'minivesicles' of ionic and nonionic surfactant mixtures, and shells of Keplerate-type polyoxometalates. The finite-size of the objects in both systems is manifested by electrostatic interactions. We emphasize the importance of constant charge and constant potential boundary conditions. Taking these conditions into account, indeed, leads to the experimentally observed qualitatively different behavior of the equilibrium size of the objects.
Nechyba, Thomas J.
2003-01-01
Synthesizes lessons from school finance research that employs computational structural models to investigate different policy proposals. Suggests that full equilibrium analysis may lead to outcomes that differ from those predicted by partial equilibrium models. (Contains 50 references and 47 notes.) (JOW)
Equilibrium Statistical-Thermal Models in High-Energy Physics
Tawfik, Abdel Nasser
2014-01-01
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 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 analysed 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-par...
Fan, Zhengfeng; Liu, Jie
2016-10-01
We present an ion-electron non-equilibrium model, in which the hot-spot ion temperature is higher than its electron temperature so that the hot-spot nuclear reactions are enhanced while energy leaks are considerably reduced. Theoretical analysis shows that the ignition region would be significantly enlarged in the hot-spot rhoR-T space as compared with the commonly used equilibrium model. Simulations show that shocks could be utilized to create and maintain non-equilibrium conditions within the hot spot, and the hot-spot rhoR requirement is remarkably reduced for achieving self-heating. In NIF high-foot implosions, it is observed that the x-ray enhancement factors are less than unity, which is not self-consistent and is caused by assuming Te =Ti. And from this non-consistency, we could infer that ion-electron non-equilibrium exists in the high-foot implosions and the ion temperature could be 9% larger than the equilibrium temperature.
Dynamic non-equilibrium wall-modeling for large eddy simulation at high Reynolds numbers
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.
Model Calculation of n + 6Li Reactions Below 20 MeV
ZHANG Jing-Shang; HAN Yin-Lu
2001-01-01
Based on the unified Hauser-Feshbach and exciton model for light nuclei, the calculations of reaction cross sections and the double-differential cross sections for n + 6Li are performed. Since all of the first-particle emissions are from the compound nucleus to the discrete levels, the angular momentum coupling effect in pre-equilibrium mechanism must be taken into account. The fitting of the measured data indicates that the three-body break-up process needs to be involved, and the pre-equilibrium reaction mechanism dominates the reaction processes. In light nucleus reactions the recoil effect must be taken into account.``
Nikolaeva, L.S.; Prikhod' ko, N.V.; Evseev, A.M.; Rozen, A.M.; Kolychev, A.E.; Gontar, B.G. (Moskovskij Gosudarstvennyj Univ. (USSR). Khimicheskij Fakul' tet)
1982-07-01
Using as an example regression models of extraction systems HNO/sub 3/-TBP-H/sub 2/O, UO/sub 2/(NO/sub 3/)/sub 2/-TBP-H/sub 2/O it has been shown that disregard of errors of the controlled (independent) variables 3% measurement error of UO/sub 2/(NO/sub 3/)/sub 2/ equilibrium concentration and 3% error of the determination of HNO/sub 3/ activity coefficient results in the displacement of evaluations of certain equilibria constants and leads to incorrect conclusion on the mechanism of chemical equilibria.
JIANG; Tao; CHEN; Yiqing
2005-01-01
Recently, Tang established a local asymptotic relation for the ruin probability to the Cram(e)r-Lunbderg risk model.In this short note we extend the corresponding result to the equilibrium renewal risk model.
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.
Modelling Chemical Reasoning to Predict Reactions
Segler, Marwin H S
2016-01-01
The ability to reason beyond established knowledge allows Organic Chemists to solve synthetic problems and to invent novel transformations. Here, we propose a model which mimics chemical reasoning and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180,000 randomly selected binary reactions. We show that our data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-) discovering novel transformations (even including transition-metal catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph, and because each single reaction prediction is typically ac...
First-principles models of equilibrium tellurium isotope fractionation
Haghnegahdar, M. A.; Schauble, E. A.; Fornadel, A. P.; Spry, P. G.
2013-12-01
In this study, equilibrium mass-dependent isotopic fractionation among representative Te-bearing species is estimated with first-principles thermodynamic calculations. Tellurium is a group 16 element (along with O, S, and Se) with eight stable isotopes ranging in mass from 120Te to 130Te, and six commonly-occurring oxidation states: -II, -I, 0, +II, +IV, and +VI. In its reduced form, Te(-II), tellurium has a unique crystal-chemical role as a bond partner for gold and silver in epithermal and orogenic gold deposits, which likely form when oxidized Te species (e.g., H2TeO3, TeO32-) or perhaps polytellurides (e.g., Te22-) interact with precious metals in hydrothermal solution. Te(IV) is the most common oxidation state at the Earth's surface, including surface outcrops of telluride ore deposits, where tellurite and tellurate minerals form by oxidation. In the ocean, dissolved tellurium tends to be scavenged by particulate matter. Te(VI) is more abundant than Te(IV) in the ocean water (1), even though it is thought to be less stable thermodynamically. This variety of valence states in natural systems and range of isotopic masses suggest that tellurium could exhibit geochemically useful isotope abundance variations. Tellurium isotope fractionations were determined for representative molecules and crystals of varying complexity and chemistry. Gas-phase calculations are combined with supermolecular cluster models of aqueous and solid species. These in turn are compared with plane-wave density functional theory calculations with periodic boundary conditions. In general, heavyTe/lightTe is predicted to be higher for more oxidized species, and lower for reduced species, with 130Te/125Te fractionations as large as 4‰ at 100οC between coexisting Te(IV) and Te(-II) or Te(0) compounds. This is a much larger fractionation than has been observed in naturally occurring redox pairs (i.e., Te (0) vs. Te(IV) species) so far, suggesting that disequilibrium processes may control
Zhu, Huayang; Ricote, Sandrine; Coors, W. Grover;
2014-01-01
A model-based approach is used to interpret equilibrium and transient conductivity measurements for 10% gadolinium-doped ceria: Ce0.9Gd0.1O1.95 − δ (GDC10). The measurements were carried out by AC impedance spectroscopy on slender extruded GDC10 rods. Although equilibrium conductivity measurements...
Generic Model-Based Tailor-Made Design and Analysis of Biphasic Reaction Systems
Anantpinijwatna, Amata
contribution of this thesis is the development of a systematic modelling framework for the biphasic reaction system. The developed framework consists of three modules describing phase equilibria, reactions and mass transfer, and material balances of such processes. Correlative and predictive thermodynamic......-elementary reaction rate laws. Extents of reaction are used to calculate the species material balances. The resulting mathematical model contains temperature dependent reaction rate parameters,equilibrium constants, and partition coefficients; where only the reaction rates are to be regressed to a minimum of time...
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.
LI Xiaoquan; DU Zeyu; YANG Xuguang
2007-01-01
For characteristics of open and far from thermodynamic equilibrium in welding chemical reaction, a new kind of quantitative method, which is used to analyze direction and extent for chemical reaction of SiO2/Fe during quasi-steady state period, is introduced with the concept of non-equilibrium stationary state. The main idea is based on thermodynamic driving forces, which result in non-zero thermodynamic fluxes and lead to chemical reaction far away from thermodynamic equilibrium. There exists certain dynamic equilibrium relationship between rates of diffusion fluxes in liquid phase of reactants or products and the rate equation of chemical reaction when welding is in quasi-steady state. As result of this, a group of non-linear equations containing concentrations of all substances at interface of slag/liquid-metal may be established. Moreover the stability of this non-equilibrium stationary state is discussed using dissipative structure theory and it is concluded theoretically that this non-equilibrium stationary state for welding chemical reaction is of stability.
Douglas, Jack F; Dudowicz, Jacek; Freed, Karl F
2008-06-14
Cooperativity is an emergent many-body phenomenon related to the degree to which elementary entities (particles, molecules, organisms) collectively interact to form larger scale structures. From the standpoint of a formal mean field description of chemical reactions, the cooperativity index m, describing the number of elements involved in this structural self-organization, is the order of the reaction. Thus, m for molecular self-assembly is the number of molecules in the final organized structure, e.g., spherical micelles. Although cooperativity is crucial for regulating the thermodynamics and dynamics of self-assembly, there is a limited understanding of this aspect of self-assembly. We analyze the cooperativity by calculating essential thermodynamic properties of the classical mth order reaction model of self-assembly (FAm model), including universal scaling functions describing the temperature and concentration dependence of the order parameter and average cluster size. The competition between self-assembly and phase separation is also described. We demonstrate that a sequential model of thermally activated equilibrium polymerization can quantitatively be related to the FAm model. Our analysis indicates that the essential requirement for "cooperative" self-assembly is the introduction of constraints (often nonlocal) acting on the individual assembly events to regulate the thermodynamic free energy landscape and, thus, the thermodynamic sharpness of the assembly transition. An effective value of m is defined for general self-assembly transitions, and we find a general tendency for self-assembly to become a true phase transition as m-->infinity. Finally, various quantitative measures of self-assembly cooperativity are discussed in order to identify experimental signatures of cooperativity in self-assembling systems and to provide a reliable metric for the degree of transition cooperativity.
Valence-bond non-equilibrium solvation model for a twisting monomethine cyanine
McConnell, Sean; McKenzie, Ross H.; Olsen, Seth
2015-02-01
We propose and analyze a two-state valence-bond model of non-equilibrium solvation effects on the excited-state twisting reaction of monomethine cyanines. Suppression of this reaction is thought responsible for environment-dependent fluorescence yield enhancement in these dyes. Fluorescence is quenched because twisting is accompanied via the formation of dark twisted intramolecular charge-transfer (TICT) states. For monomethine cyanines, where the ground state is a superposition of structures with different bond and charge localizations, there are two possible twisting pathways with different charge localizations in the excited state. For parameters corresponding to symmetric monomethines, the model predicts two low-energy twisting channels on the excited-state surface, which leads to a manifold of TICT states. For typical monomethines, twisting on the excited state surface will occur with a small barrier or no barrier. Changes in the solvation configuration can differentially stabilize TICT states in channels corresponding to different bonds, and that the position of a conical intersection between adiabatic states moves in response to solvation to stabilize either one channel or the other. There is a conical intersection seam that grows along the bottom of the excited-state potential with increasing solvent polarity. For monomethine cyanines with modest-sized terminal groups in moderately polar solution, the bottom of the excited-state potential surface is completely spanned by a conical intersection seam.
Non equilibrium effects and time scales from 3-body reactions at 20 A. MeV
Maurenzig, P.R. (INFN, Florence (Italy) Florence Univ. (Italy)); Casini, G. (INFN, Florence (Italy) Florence Univ. (Italy)); Olmi, A. (INFN, Florence (Italy) Florence Univ. (Italy)); Stefanini, A.A. (INFN, Florence (Italy) Florence Univ. (Italy))
1994-01-01
Experimental results for various symmetric and quasi-symmetric heavy-ion reactions around 20 A.MeV are presented. In particular the cross sections and some exclusive mass and angular distributions for 2 and 3 heavy fragments (A>20) in the final state are discussed. Evidence for non equilibrated sequential fission are presented. (orig.)
The truthful signalling hypothesis: an explicit general equilibrium model.
Hausken, Kjell; Hirshleifer, Jack
2004-06-21
In mating competition, the truthful signalling hypothesis (TSH), sometimes known as the handicap principle, asserts that higher-quality males signal while lower-quality males do not (or else emit smaller signals). Also, the signals are "believed", that is, females mate preferentially with higher-signalling males. Our analysis employs specific functional forms to generate analytic solutions and numerical simulations that illuminate the conditions needed to validate the TSH. Analytic innovations include: (1) A Mating Success Function indicates how female mating choices respond to higher and lower signalling levels. (2) A congestion function rules out corner solutions in which females would mate exclusively with higher-quality males. (3) A Malthusian condition determines equilibrium population size as related to per-capita resource availability. Equilibria validating the TSH are achieved over a wide range of parameters, though not universally. For TSH equilibria it is not strictly necessary that the high-quality males have an advantage in terms of lower per-unit signalling costs, but a cost difference in favor of the low-quality males cannot be too great if a TSH equilibrium is to persist. And although the literature has paid less attention to these points, TSH equilibria may also fail if: the quality disparity among males is too great, or the proportion of high-quality males in the population is too large, or if the congestion effect is too weak. Signalling being unprofitable in aggregate, it can take off from a no-signalling equilibrium only if the trait used for signalling is not initially a handicap, but instead is functionally useful at low levels. Selection for this trait sets in motion a bandwagon, whereby the initially useful indicator is pushed by male-male competition into the domain where it does indeed become a handicap.
Stability of equilibrium points in intraguild predation model with disease with SI model
Hassan, Aimi Nuraida binti Ali; Bujang, Noriham binti; Mahdi, Ahmad Faisal Bin
2017-04-01
Intraguild Predation (IGP) is classified as killing and eating among potential competitors. Intraguild Predation is a universal interaction, differing from competition or predation. Lotka Volterra competition model and Intraguild predation model has been analyze. The assumption for this model is no any immigration or migration involves. This paper is only considered IGP model for susceptible and infective (SI) only. The analysis of stability of the equilibrium points of Intraguild Predation Models with disease using Routh Hurwitz criteria will be illustrated using some numerical example.
Jagannadham Vandanapu
2012-01-01
Full Text Available The emergence of putative Hammett equation in mid 1930s was a boon to physical-organic chemists to elucidate the reaction mechanisms of several organic reactions. Based on the concept of this equation several hundreds of papers have emerged in chemical literature in the last century on the effect of structure, on reactivity, and very few on thermodynamic stability and kinetic reactivity of intermediates. In this article an attempt is made to explain the effect of hetero atom on Hammett’s reaction constant (ρ taking the dissociation equilibriums of benzoic acids, dithiobenzoic acids, phenols, and thiophenols.
Deng, Yujia; Arenz, Matthias; Wiberg, Gustav Karl Henrik
2015-01-01
We employ a recently developed stripping protocol to examine the equilibrium coverage of oxygenated species and their influence on the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). In particular we aim to distinguish between dynamic and steady state conditions and est...
Wijnen, J.W; Engberts, J.B.F.N.
1997-01-01
The adduct of the Diels-Alder reaction of nitrosobenzene with cyclopentadiene is not stable in solution. The equilibrium constant for the reaction depends strongly on the medium and water induces a spectacular shift to the adduct. Comparison with the bimolecular addition of nitrosobenzene to 1,3-cyc
P.U. Singare
2008-12-01
Full Text Available The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Indion FF-IP. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. For uni-univalent ion exchange reaction systems, the equilibrium constant K’ were also calculated by considering mole fraction of ions in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems were observed to increase with rise in temperature, indicating the endothermic exchange reactions having enthalpy values of 22.45, 28.57, 17.84, 15.97 kJ/mol, respectively.
Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications
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.
A general paradigm to model reaction-based biogeochemical processes in batch systems
Fang, Yilin; Yeh, Gour-Tsyh; Burgos, William D.
2003-04-01
This paper presents the development and illustration of a numerical model of reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions. The objective is to provide a general paradigm for modeling reactive chemicals in batch systems, with expectations that it is applicable to reactive chemical transport problems. The unique aspects of the paradigm are to simultaneously (1) facilitate the segregation (isolation) of linearly independent kinetic reactions and thus enable the formulation and parameterization of individual rates one reaction by one reaction when linearly dependent kinetic reactions are absent, (2) enable the inclusion of virtually any type of equilibrium expressions and kinetic rates users want to specify, (3) reduce problem stiffness by eliminating all fast reactions from the set of ordinary differential equations governing the evolution of kinetic variables, (4) perform systematic operations to remove redundant fast reactions and irrelevant kinetic reactions, (5) systematically define chemical components and explicitly enforce mass conservation, (6) accomplish automation in decoupling fast reactions from slow reactions, and (7) increase the robustness of numerical integration of the governing equations with species switching schemes. None of the existing models to our knowledge has included these scopes simultaneously. This model (BIOGEOCHEM) is a general computer code to simulate biogeochemical processes in batch systems from a reaction-based mechanistic standpoint, and is designed to be easily coupled with transport models. To make the model applicable to a wide range of problems, programmed reaction types include aqueous complexation, adsorption-desorption, ion-exchange, oxidation-reduction, precipitation-dissolution, acid-base reactions, and microbial mediated reactions. In addition, user-specified reaction types can be programmed into the model. Any reaction can be treated as fast/equilibrium or slow
Pudlak, M; Nazmitdinov, R G; Pincak, R
2011-01-01
Creation of electron or exciton by external fields in a system with initially statistically independent unrelaxed vibrational modes leads to an initial condition term. The contribution of this term in the time convolution generalized master equation approach is studied in second order of the perturbation theory for electron-phonon coupling in the parth integral formalism. The developed approach, applied for analysis of dynamics in the photosynthetic reaction center, exhibits the key role of the initial condition term at the primary stage of electron transfer.
An Iterative Method for the Construction of Equilibrium N-Body Models for Stellar Disks
Rodionov, S A
2006-01-01
One widely used technique for the construction of equilibrium models of stellar disks is based on the Jeans equations and the moments of velocity distribution functions derived using these equations. Stellar disks constructed using this technique are shown to be "not entirely" in equilibrium. Our attempt to abandon the epicyclic approximation and the approximation of infinite isothermal layers, which are commonly adopted in this technique, failed to improve the situation substantially. We conclude that the main drawback of techniques based on the Jeans equations is that the system of equations employed is not closed, and therefore requires adopting an essentially ad hoc additional closure condition. A new iterative approach to constructing equilibrium N-body models with a given density distribution is proposed. The main idea behind this approach is that a model is first constructed using some approximation method, and is then allowed to adjust to an equilibrium state with the specified density and the require...
A development of multi-Species mass transport model considering thermodynamic phase equilibrium
Hosokawa, Yoshifumi; Yamada, Kazuo; Johannesson, Björn
2008-01-01
In this paper, a multi-species mass transport model, which can predict time dependent variation of pore solution and solid-phase composition due to the mass transport into the hardened cement paste, has been developed. Since most of the multi-species models established previously, based...... by the penetration of mineral salts during marine seawater exposure conditions. Those phenomena in concrete can be predicted using the coupled multi-species mass transport model and the thermodynamic equilibrium model described in this paper....... on the Poisson-Nernst-Planck theory, did not involve the modeling of chemical process, it has been coupled to thermodynamic equilibrium model in this study. By the coupling of thermodynamic equilibrium model, the multi-species model could simulate many different behaviours in hardened cement paste such as: (i...
An Initial Non-Equilibrium Porous-Media Model for CFD Simulation of Stirling Regenerators
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.
A reaction-based river/stream water quality model Part I: Model development and numerical schemes
Zhang, Fan [ORNL; Gour-Tsyh, Yeh [University of Central Florida, Orlando; Parker, Jack C. [University of Tennessee, Knoxville (UTK); Jardine, Philip M [ORNL
2008-01-01
This paper presents the conceptual and mathematical development of a numerical model of sediment and reactive chemical transport in river/streams. The distribution of mobile suspended sediments and immobile bed sediments is controlled by hydrologic transport as well as erosion and deposition processes. The fate and transport of water quality constituents involving a variety of chemical and physical processes is mathematically described by a system of reaction equations for immobile constituents and advective-dispersive-reactive transport equations for constituents. To circumvent stiffness associated with equilibrium reactions, matrix decomposition is performed via Gauss-Jordan column reduction. After matrix decomposition, the system of water quality constituent reactive transport equations is transformed into a set of thermodynamic equations representing equilibrium reactions and a set of transport equations involving no equilibrium reactions. The decoupling of equilibrium and kinetic reactions enables robust numerical integration of the partial differential equations for non-equilibrium-variables. Solving non-equilibrium-variable transport equations instead of individual water quality constituent transport equations also reduces the number of PDEs. A variety of numerical methods are investigated for solving the mixed differential and algebraic equations. Two verification examples are compared with analytical solutions to demonstrate the correctness of the code and to illustrate the importance of employing application-dependent numerical methods to solve specific problems.
NUMERICAL MODELING OF CHANNEL EQUILIBRIUM PROFILE AND ITS EFFECT ON FLOOD CONTROL
无
2002-01-01
Based on the morphology of Luoshan-Hankou reach at the middle Yangtze River, the one-dimensional, unsteady flow and sediment transport numerical model was adopted to study the generalized channel equilibrium profile. The variation of the longitudinal equilibrium profile, and the relation with the condition of the inflow water and sediment from the upper reach were analyzed. Meanwhile, the numerical simulation results were compared with the corresponding theoretical results. Finally, the equilibrium longitudinal slope variations and its impact on flood control were analyzed after the sediment transport process has changed.
The General Equilibrium Model with Joint Ownership of the Corporation (Voting Stock and the Core),
general equilibrium system. The point specifically is that the Arrow-Debreu treatment of the joint ownership of industry by introducing shares which can be treated, requires further specification. The need for further specification can be seen immediately when this model is examined not for the competitive equilibrium but for the core. It is well known that the competitive equilibrium is contained within the core. However it will be shown that unless extra conditions are imposed on the control of stock the resultant game may have no core whatsoever and hence no competitive
Non-equilibrium Monte Carlo dynamics of the Sherrington-Kirkpatrick mean field spin glass model
Baldassarri, Andrea
1996-01-01
We present a numerical study of the non-equilibrium dynamics of the Sherrington-Kirkpatrick model. We analize the overlap distribution between the configurations visited at the time t and in particular its scaling behaviour with the size of the system. We find two different non-equilibrium dynamical regimes. The first is a proper Out of Equilibrium Regime, that is the relevant regime for the dynamics of an infinite system. The second is an Intermediate Regime that separates the Out of Equilib...
Quantum Cournot equilibrium for the Hotelling-Smithies model of product choice
Rahaman, Ramij; Basu, B
2012-01-01
This paper demonstrates the quantization of a spatial Cournot duopoly model with product choice, a two stage game focusing on non-cooperation in locations and quantities. With quantization, the players can access a continuous set of strategies, using continuous variable quantum mechanical approach. The presence of quantum entanglement in the initial state identifies a quantity equilibrium for every location pair choice with any transport cost. Also higher profit is obtained by the firms at Nash equilibrium. Adoption of quantum strategies rewards us by the existence of a larger quantum strategic space at equilibrium.
Parametrizing coarse grained models for molecular systems at equilibrium
Kalligiannaki, E.
2016-10-18
Hierarchical coarse graining of atomistic molecular systems at equilibrium has been an intensive research topic over the last few decades. In this work we (a) review theoretical and numerical aspects of different parametrization methods (structural-based, force matching and relative entropy) to derive the effective interaction potential between coarse-grained particles. All methods approximate the many body potential of mean force; resulting, however, in different optimization problems. (b) We also use a reformulation of the force matching method by introducing a generalized force matching condition for the local mean force in the sense that allows the approximation of the potential of mean force under both linear and non-linear coarse graining mappings (E. Kalligiannaki, et al., J. Chem. Phys. 2015). We apply and compare these methods to: (a) a benchmark system of two isolated methane molecules; (b) methane liquid; (c) water; and (d) an alkane fluid. Differences between the effective interactions, derived from the various methods, are found that depend on the actual system under study. The results further reveal the relation of the various methods and the sensitivities that may arise in the implementation of numerical methods used in each case.
Parametrizing coarse grained models for molecular systems at equilibrium
Kalligiannaki, E.; Chazirakis, A.; Tsourtis, A.; Katsoulakis, M. A.; Plecháč, P.; Harmandaris, V.
2016-10-01
Hierarchical coarse graining of atomistic molecular systems at equilibrium has been an intensive research topic over the last few decades. In this work we (a) review theoretical and numerical aspects of different parametrization methods (structural-based, force matching and relative entropy) to derive the effective interaction potential between coarse-grained particles. All methods approximate the many body potential of mean force; resulting, however, in different optimization problems. (b) We also use a reformulation of the force matching method by introducing a generalized force matching condition for the local mean force in the sense that allows the approximation of the potential of mean force under both linear and non-linear coarse graining mappings (E. Kalligiannaki, et al., J. Chem. Phys. 2015). We apply and compare these methods to: (a) a benchmark system of two isolated methane molecules; (b) methane liquid; (c) water; and (d) an alkane fluid. Differences between the effective interactions, derived from the various methods, are found that depend on the actual system under study. The results further reveal the relation of the various methods and the sensitivities that may arise in the implementation of numerical methods used in each case.
Xingxing, Chen; Zhihui, Wang; Yongliang, Yu
2016-11-01
Hypersonic chemical non-equilibrium gas flows around blunt nosed bodies are studied in the present paper to investigate the Reynolds analogy relation on curved surfaces. With a momentum and energy transfer model being applied through boundary layers, influences of molecular dissociations and recombinations on skin frictions and heat fluxes are separately modeled. Expressions on the ratio of Cf / Ch (skin friction coefficient to heat flux) are presented along the surface of circular cylinders under the ideal dissociation gas model. The analysis indicates that molecular dissociations increase the linear distribution of Cf / Ch, but the nonlinear Reynolds analogy relation could ultimately be obtained in flows with larger Reynolds numbers and Mach numbers, where the decrease of wall heat flux by molecular recombinations signifies. The present modeling and analyses are also verified by the DSMC calculations on nitrogen gas flows.
Xiaoming Fan
2014-01-01
Full Text Available We discuss multigroup SIRS (susceptible, infectious, and recovered epidemic models with random perturbations. We carry out a detailed analysis on the asymptotic behavior of the stochastic model; when reproduction number ℛ0>1, we deduce the globally asymptotic stability of the endemic equilibrium by measuring the difference between the solution and the endemic equilibrium of the deterministic model in time average. Numerical methods are employed to illustrate the dynamic behavior of the model and simulate the system of equations developed. The effect of the rate of immunity loss on susceptible and recovered individuals is also analyzed in the deterministic model.
Stability Analysis of an Infectious Disease Free Equilibrium of Hepatitis B Model
A.A. Momoh
2011-09-01
Full Text Available In this research study, we proposed an (M-S-E-I-R model to understand the transmission dynamics and control of HBV taking into consideration passive immunisation, treatment of exposed individuals at latent period and infectious Hepatitis B treatment. We established the disease free equilibrium state and epidemic equilibrium state of the model. Stability analysis was carried out on the disease free equilibrium state and it was found that λ1 = -μ, λ2 = -μ, λ3 = -(ε+μ, λ4 = -(γ+μ and λ5 = δB/μ -μ hence the disease free equilibrium is stable if δB/μ is less than μ (where δB/μ is number of susceptible individuals produced.
M. Venkata Ramanan
2008-09-01
Full Text Available Cashew nut shell, a waste product obtained during deshelling of cashew kernels, had in the past been deemed unfit as a fuel for gasification owing to its high occluded oil content. The oil, a source of natural phenol, oozes upon gasification, thereby clogging the gasifier throat, downstream equipment and associated utilities with oil, resulting in ineffective gasification and premature failure of utilities due to its corrosive characteristics. To overcome this drawback, the cashew shells were de-oiled by charring in closed chambers and were subsequently gasified in an autothermal downdraft gasifier. Equilibrium modeling was carried out to predict the producer gas composition under varying performance influencing parameters, viz., equivalence ratio (ER, reaction temperature (RT and moisture content (MC. The results were compared with the experimental output and are presented in this paper. The model is quite satisfactory with the experimental outcome at the ER applicable to gasification systems, i.e., 0.15 to 0.30. The results show that the mole fraction of (i H2, CO and CH4 decreases while (N2 + H2O and CO2 increases with ER, (ii H2 and CO increases while CH4, (N2 + H2O and CO2 decreases with reaction temperature, (iii H2, CH4, CO2 and (N2 + H2O increases while CO decreases with moisture content. However at an equivalence ratio less than 0.15, the model predicts an unrealistic composition and is observed to be non valid below this ER.
Modelling Chemical Reasoning to Predict Reactions
Segler, Marwin H. S.; Waller, Mark P.
2016-01-01
The ability to reason beyond established knowledge allows Organic Chemists to solve synthetic problems and to invent novel transformations. Here, we propose a model which mimics chemical reasoning and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outpe...
Modeling Mathematical Programs with Equilibrium Constraints in Pyomo
Hart, William E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Siirola, John Daniel [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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.
The Equilibrium Analysis of a Closed Economy Model with Government and Money Market Sector
Catalin Angelo Ioan
2011-10-01
Full Text Available In this paper, we first study the static equilibrium of a a closed economy model in terms of dependence on national income and interest rate from the main factors namely the marginal propensity to consume, tax rate, investment rate and the rate of currency demand. In the second part, we study the dynamic equilibrium solutions in terms of stability. We thus obtain the variation functions of national income and interest rate variation and their limit values.
A Tightly Coupled Non-Equilibrium Magneto-Hydrodynamic Model for Inductively Coupled RF Plasmas
2016-02-29
effects are described based on a hybrid State-to-State (StS) approach. A multi-temperature formulation is used to account for thermal non-equilibrium...for Inductively Coupled Radio-Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State...usually obtained through quantum chemistry calculations51–56 or through phenomenological models providing a simplified descrip- tion of the kinetic
Equilibrium study on the reactions of boric acid with some cis-diaqua CrIII-complexes
G N Mukherjee; Ansuman Das
2003-08-01
Substitution inert cis-diaqua CrIII complexes: cis-[(L-)CrIII(H2O)2](3-)+ derived from N-donor ligands (L-) viz., bipyridine and 1,10-phenanthroline ( = 0) and N,O-donor ligands viz., nitrilotriacetate and anthranilate N,N-diacetate ( = 3) titrate as diprotic acids in aqueous solution and enhance the acidity of otherwise weakly acidic boric acid (H3BO3) producing mononuclear and binuclear mixed ligand CrIII-borate complexes: [(L)Cr(H2BO4)]- and [(L)Cr(BO4)Cr(L)](1-2)+ respectively through coordination of the H2O and/or OH- ligands, cis-coordinated in the CrIII-complexes on the electron deficient BIII-atom in H3BO3 with release of protons. Deprotonation of the parent CrIII-complexes and their reactions with H3BO3 have been investigated by potentiometric method in aqueous solution, = 0.1 mol dm-3 (NaNO3) at 25 ± 0.1° C. The equilibrium constants have been evaluated by computerized methods and the tentative stoichiometry of the reactions have been worked out on the basis of the speciation curves.
Modelling non-equilibrium thermodynamic systems from the speed-gradient principle
Khantuleva, Tatiana A.; Shalymov, Dmitry S.
2017-03-01
The application of the speed-gradient (SG) principle to the non-equilibrium distribution systems far away from thermodynamic equilibrium is investigated. The options for applying the SG principle to describe the non-equilibrium transport processes in real-world environments are discussed. Investigation of a non-equilibrium system's evolution at different scale levels via the SG principle allows for a fresh look at the thermodynamics problems associated with the behaviour of the system entropy. Generalized dynamic equations for finite and infinite number of constraints are proposed. It is shown that the stationary solution to the equations, resulting from the SG principle, entirely coincides with the locally equilibrium distribution function obtained by Zubarev. A new approach to describe time evolution of systems far from equilibrium is proposed based on application of the SG principle at the intermediate scale level of the system's internal structure. The problem of the high-rate shear flow of viscous fluid near the rigid plane plate is discussed. It is shown that the SG principle allows closed mathematical models of non-equilibrium processes to be constructed. This article is part of the themed issue 'Horizons of cybernetical physics'.
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".
Soils apart from equilibrium – consequences for soil carbon balance modelling
T. Wutzler
2006-10-01
Full Text Available Many projections of the soil carbon sink or source are based on kinetically defined carbon pool models. Parameters of these models are often determined in a way that the steady state of the model matches observed carbon stocks. The underlying simplifying assumption is that observed carbon stocks are near equilibrium. This assumption is challenged by observations of very old soils that do still accumulate carbon. In this modelling study we explored the consequences of the case where soils are apart from equilibrium. Calculation of equilibrium states of soils that are currently accumulating small amounts of carbon were performed using the Yasso model. It was found that already very small current accumulation rates cause big changes in theoretical equilibrium stocks, which can virtually approach infinity. We conclude that soils that have been disturbed several centuries ago are not in equilibrium but in a transient state because of the slowly ongoing accumulation of the slowest pool. A first consequence is that model calibrations to current carbon stocks that assume equilibrium state, overestimate the decay rate of the slowest pool. A second consequence is that spin-up runs (simulations until equilibrium overestimate stocks of recently disturbed sites. In order to account for these consequences, we propose a transient correction. This correction prescribes a lower decay rate of the slowest pool and accounts for disturbances in the past by decreasing the spin-up-run predicted stocks to match an independent estimate of current soil carbon stocks. Application of this transient correction at a Central European beech forest site with a typical disturbance history resulted in an additional carbon fixation of 5.7±1.5 tC/ha within 100 years. Carbon storage capacity of forest soils is potentially much higher than currently assumed. Simulations that do not adequately account for the transient state of soil carbon stocks neglect a substantial amount of
Towards a model of non-equilibrium binding of metal ions in biological systems.
Beardmore, James; Exley, Christopher
2009-02-01
We have used a systems biology approach to address the hitherto insoluble problem of the quantitative analysis of non-equilibrium binding of aqueous metal ions by competitive ligands in heterogeneous media. To-date, the relative proportions of different metal complexes in aqueous media has only been modelled at chemical equilibrium and there are no quantitative analyses of the approach to equilibrium. While these models have improved our understanding of how metals are used in biological systems they cannot account for the influence of kinetic factors in metal binding, transport and fate. Here we have modelled the binding of aluminium, Al(III), in blood serum by the iron transport protein transferrin (Tf) as it is widely accepted that the biological fate of this non-essential metal is not adequately described by experiments, invitro and insilico, which have consistently demonstrated that at equilibrium 90% of serum Al(III) is bound by Tf. We have coined this paradox 'the blood-aluminium problem' and herein applied a systems biology approach which utilised well-found assumptions to pare away the complexities of the problem such that it was defined by a comparatively simple set of computational rules and, importantly, its solution assumed significant predictive capabilities. Here we show that our novel computational model successfully described the binding of Al(III) by Tf both at equilibrium and as equilibrium for Al(Tf) was approached. The model predicted significant non-equilibrium binding of Al by ligands in competition with Tf and, thereby, provided an explanation of why the distribution of Al(III) in the body cannot be adequately described by its binding and transport by Tf alone. Generically the model highlighted the significance of kinetic in addition to thermodynamic constraints in defining the fate of metal ions in biological systems.
Connectionist and diffusion models of reaction time.
Ratcliff, R; Van Zandt, T; McKoon, G
1999-04-01
Two connectionist frameworks, GRAIN (J. L. McClelland, 1993) and brain-state-in-a-box (J. A. Anderson, 1991), and R. Ratcliff's (1978) diffusion model were evaluated using data from a signal detection task. Dependent variables included response probabilities, reaction times for correct and error responses, and shapes of reaction-time distributions. The diffusion model accounted for all aspects of the data, including error reaction times that had previously been a problem for all response-time models. The connectionist models accounted for many aspects of the data adequately, but each failed to a greater or lesser degree in important ways except for one model that was similar to the diffusion model. The findings advance the development of the diffusion model and show that the long tradition of reaction-time research and theory is a fertile domain for development and testing of connectionist assumptions about how decisions are generated over time.
Chemical-reaction model for Mexican wave
Nagatani, Takashi
2003-05-01
We present a chemical-reaction model to describe the Mexican wave ( La Ola) in football stadia. The spectator's action is described in terms of chemical reactions. The model is governed by three reaction rates k 1, k 2, and k3. We study the nonlinear waves on one- and two-dimensional lattices. The Mexican wave is formulated as a clockwise forwardly propagating wave. Waves are growing or disappear, depending on the values of reaction rates. In the specific case of k1= k2= k3=1, the nonlinear-wave equation produces a propagating pulse like soliton.
Bandres, I.; Giner, B.; Lopez, M.C.; Artigas, H. [Departamento de Quimica Organica y Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain); Lafuente, C. [Departamento de Quimica Organica y Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain)], E-mail: celadi@unizar.es
2008-08-15
Experimental data for the isothermal (vapour + liquid) equilibrium of mixtures formed by several cyclic ethers (tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, and 1,4-dioxane) and chlorohexane at temperatures of (298.15 and 328.15) K are presented. Experimental results have been discussed in terms of both, molecular characteristics of pure compounds and potential intermolecular interaction between them using thermodynamic information of the mixtures obtained earlier. Furthermore, the influence of the temperature on the (vapour + liquid) equilibrium of these mixtures has been explored and discussed. Transferable parameters of the SAFT-VR approach together with standard combining rules have been used to model the phase equilibrium of the mixtures and a description of the (vapour + liquid) equilibrium of them that is in excellent agreement with the experimental data are provided.
Measuring Convergence using Dynamic Equilibrium Models: Evidence from Chinese Provinces
Pan, Lei; Posch, Olaf; van der Wel, Michel
We propose a model to study economic convergence in the tradition of neoclassical growth theory. We employ a novel stochastic set-up of the Solow (1956) model with shocks to both capital and labor. Our novel approach identifies the speed of convergence directly from estimating the parameters which...
Non-equilibrium STLS approach to transport properties of single impurity Anderson model
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.
Python framework for kinetic modeling of electronically excited reaction pathways
Verboncoeur, John; Parsey, Guy; Guclu, Yaman; Christlieb, Andrew
2012-10-01
The use of plasma energy to enhance and control the chemical reactions during combustion, a technology referred to as ``plasma assisted combustion'' (PAC), can result in a variety of beneficial effects: e.g. stable lean operation, pollution reduction, and wider range of p-T operating conditions. While experimental evidence abounds, theoretical understanding of PAC is at best incomplete, and numerical tools still lack in reliable predictive capabilities. In the context of a joint experimental-numerical effort at Michigan State University, we present here an open-source modular Python framework dedicated to the dynamic optimization of non-equilibrium PAC systems. Multiple sources of experimental reaction data, e.g. reaction rates, cross-sections and oscillator strengths, are used in order to quantify the effect of data uncertainty and limiting assumptions. A collisional-radiative model (CRM) is implemented to organize reactions by importance and as a potential means of measuring a non-Maxwellian electron energy distribution function (EEDF), when coupled to optical emission spectroscopy data. Finally, we explore scaling laws in PAC parameter space using a kinetic global model (KGM) accelerated with CRM optimized reaction sequences and sparse stiff integrators.
A Networks Approach to Modeling Enzymatic Reactions.
Imhof, P
2016-01-01
Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes.
Wu, Yi; Sun, Hao; Tanaka, Yasunori; Tomita, Kentaro; Rong, Mingzhe; Yang, Fei; Uesugi, Yoshihiko; Ishijima, Tatsuo; Wang, Xiaohua; Feng, Ying
2016-10-01
The influence of the gas flow rate on the N2 arc behavior was investigated based on a previously established nonchemical equilibrium (non-CE) model. This numerical non-CE model was adopted in the N2 nozzle arc in a model circuit breaker. The arc behaviors of both the arc burning and arc decay phases were obtained at different gas flow rates in both the non-CE and local thermal equilibrium (LTE) model. To better understand the influence of the gas flow rate, in this work we devised the concept of the nonequilibrium parameter. Additionally, the influences of convection, diffusion, and chemical reactions were examined separately to determine which one contributed most to the non-CE behavior. Finally, laser Thomson scattering (LTS) measurements at different gas flow rates were adopted to further demonstrate the validity of the non-CE model. The results of the macroscopic behaviors indicate that the deviations between the non-CE and LTE models during the arc burning phase are much fewer than those during the arc decay phase. By the nonequilibrium parameters, it clearly indicates that with an increase in the gas flow rate, the non-CE effect will be greatly enhanced. During the arc burning phase, this non-CE effect is mainly caused by radial diffusion of the particles. During the arc decay phase, for the charged particles, the chemical reactions had the greatest effect on the time variations of the particle number densities; however, for the neutral particles the time variations of the number densities were mutually influenced by convections, diffusions, and chemical reactions. Finally, the LTS results further demonstrate the validity of the non-CE model at different gas flow rates.
Equilibrium pricing in an order book environment: Case study for a spin model
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.
EMPIRE: Nuclear Reaction Model Code System for Data Evaluation
Herman, M.; Capote, R.; Carlson, B. V.; Obložinský, P.; Sin, M.; Trkov, A.; Wienke, H.; Zerkin, V.
2007-12-01
EMPIRE is a modular system of nuclear reaction codes, comprising various nuclear models, and designed for calculations over a broad range of energies and incident particles. A projectile can be a neutron, proton, any ion (including heavy-ions) or a photon. The energy range extends from the beginning of the unresolved resonance region for neutron-induced reactions (∽ keV) and goes up to several hundred MeV for heavy-ion induced reactions. The code accounts for the major nuclear reaction mechanisms, including direct, pre-equilibrium and compound nucleus ones. Direct reactions are described by a generalized optical model (ECIS03) or by the simplified coupled-channels approach (CCFUS). The pre-equilibrium mechanism can be treated by a deformation dependent multi-step direct (ORION + TRISTAN) model, by a NVWY multi-step compound one or by either a pre-equilibrium exciton model with cluster emission (PCROSS) or by another with full angular momentum coupling (DEGAS). Finally, the compound nucleus decay is described by the full featured Hauser-Feshbach model with γ-cascade and width-fluctuations. Advanced treatment of the fission channel takes into account transmission through a multiple-humped fission barrier with absorption in the wells. The fission probability is derived in the WKB approximation within the optical model of fission. Several options for nuclear level densities include the EMPIRE-specific approach, which accounts for the effects of the dynamic deformation of a fast rotating nucleus, the classical Gilbert-Cameron approach and pre-calculated tables obtained with a microscopic model based on HFB single-particle level schemes with collective enhancement. A comprehensive library of input parameters covers nuclear masses, optical model parameters, ground state deformations, discrete levels and decay schemes, level densities, fission barriers, moments of inertia and γ-ray strength functions. The results can be converted into ENDF-6 formatted files using the
Computable general equilibrium model fiscal year 2014 capability development report
Edwards, Brian Keith [Los Alamos National Laboratory; Boero, Riccardo [Los Alamos National Laboratory
2016-05-11
This report provides an overview of the development of the NISAC CGE economic modeling capability since 2012. This capability enhances NISAC's economic modeling and analysis capabilities to answer a broader set of questions than possible with previous economic analysis capability. In particular, CGE modeling captures how the different sectors of the economy, for example, households, businesses, government, etc., interact to allocate resources in an economy and this approach captures these interactions when it is used to estimate the economic impacts of the kinds of events NISAC often analyzes.
Equilibrium in a random viewer model of television broadcasting
Hansen, Bodil Olai; Keiding, Hans
2014-01-01
The authors considered a model of commercial television market with advertising with probabilistic viewer choice of channel, where private broadcasters may coexist with a public television broadcaster. The broadcasters influence the probability of getting viewer attention through the amount...
Kinetics of Model Reactions for Interfacial Polymerization
Henry Hall
2012-02-01
Full Text Available To model the rates of interfacial polycondensations, the rates of reaction of benzoyl chloride and methyl chloroformate with various aliphatic monoamines in acetonitrile were determined at 25 °C. Buffering with picric acid slowed these extremely fast reactions so the rate constants could be determined from the rate of disappearance of picrate ion. The rates of the amine reactions correlated linearly with their Swain-Scott nucleophilicities.
Geochemical controls on shale groundwaters: Results of reaction path modeling
Von Damm, K.L.; VandenBrook, A.J.
1989-03-01
The EQ3NR/EQ6 geochemical modeling code was used to simulate the reaction of several shale mineralogies with different groundwater compositions in order to elucidate changes that may occur in both the groundwater compositions, and rock mineralogies and compositions under conditions which may be encountered in a high-level radioactive waste repository. Shales with primarily illitic or smectitic compositions were the focus of this study. The reactions were run at the ambient temperatures of the groundwaters and to temperatures as high as 250/degree/C, the approximate temperature maximum expected in a repository. All modeling assumed that equilibrium was achieved and treated the rock and water assemblage as a closed system. Graphite was used as a proxy mineral for organic matter in the shales. The results show that the presence of even a very small amount of reducing mineral has a large influence on the redox state of the groundwaters, and that either pyrite or graphite provides essentially the same results, with slight differences in dissolved C, Fe and S concentrations. The thermodynamic data base is inadequate at the present time to fully evaluate the speciation of dissolved carbon, due to the paucity of thermodynamic data for organic compounds. In the illitic cases the groundwaters resulting from interaction at elevated temperatures are acid, while the smectitic cases remain alkaline, although the final equilibrium mineral assemblages are quite similar. 10 refs., 8 figs., 15 tabs.
Pusateri, Elise Noel
An Electromagnetic Pulse (EMP) can severely disrupt the use of electronic devices in its path causing a significant amount of infrastructural damage. EMP can also cause breakdown of the surrounding atmosphere during lightning discharges. This makes modeling EMP phenomenon an important research effort in many military and atmospheric physics applications. EMP events include high-energy Compton electrons or photoelectrons that ionize air and produce low energy conduction electrons. A sufficient number of conduction electrons will damp or alter the EMP through conduction current. Therefore, it is important to understand how conduction electrons interact with air in order to accurately predict the EMP evolution and propagation in the air. It is common for EMP simulation codes to use an equilibrium ohmic model for computing the conduction current. Equilibrium ohmic models assume the conduction electrons are always in equilibrium with the local instantaneous electric field, i.e. for a specific EMP electric field, the conduction electrons instantaneously reach steady state without a transient process. An equilibrium model will work well if the electrons have time to reach their equilibrium distribution with respect to the rise time or duration of the EMP. If the time to reach equilibrium is comparable or longer than the rise time or duration of the EMP then the equilibrium model would not accurately predict the conduction current necessary for the EMP simulation. This is because transport coefficients used in the conduction current calculation will be found based on equilibrium reactions rates which may differ significantly from their non-equilibrium values. We see this deficiency in Los Alamos National Laboratory's EMP code, CHAP-LA (Compton High Altitude Pulse-Los Alamos), when modeling certain EMP scenarios at high altitudes, such as upward EMP, where the ionization rate by secondary electrons is over predicted by the equilibrium model, causing the EMP to short
Parameter Estimation for a Computable General Equilibrium Model
Arndt, Channing; Robinson, Sherman; Tarp, Finn
. Second, it permits incorporation of prior information on parameter values. Third, it can be applied in the absence of copious data. Finally, it supplies measures of the capacity of the model to reproduce the historical record and the statistical significance of parameter estimates. The method is applied...
Modelling the ion-exchange equilibrium in nanoporous materials
M. Lukšič
2012-06-01
Full Text Available Distribution of a two component electrolyte mixture between the model adsorbent and a bulk aqueous electrolyte solution was studied using the replica Ornstein-Zernike theory and the grand canonical Monte Carlo method. The electrolyte components were modelled to mimic the HCl/NaCl and HCl/CaCl2 mixtures, respectively. The matrix, invaded by the primitive model electrolyte mixture, was formed from monovalent negatively charged spherical obstacles. The solution was treated as a continuous dielectric with the properties of pure water. Comparison of the pair distribution functions (obtained by the two methods between the various ionic species indicated a good agreement between the replica Ornstein-Zernike results and machine calculations. Among thermodynamic properties, the mean activity coefficient of the invaded electrolyte components was calculated. Simple model for the ion-exchange resin was proposed. The selectivity calculations yielded qualitative agreement with the following experimental observations: (i selectivity increases with the increasing capacity of the adsorbent (matrix concentration, (ii the adsorbent is more selective for the ion having higher charge density if its fraction in mixture is smaller.
General equilibrium basic needs policy model, (updating part).
Kouwenaar A
1985-01-01
ILO pub-WEP pub-PREALC pub. Working paper, econometric model for the assessment of structural change affecting development planning for basic needs satisfaction in Ecuador - considers population growth, family size (households), labour force participation, labour supply, wages, income distribution, profit rates, capital ownership, etc.; examines nutrition, education and health as factors influencing productivity. Diagram, graph, references, statistical tables.
Numerical solution of dynamic equilibrium models under Poisson uncertainty
Posch, Olaf; Trimborn, Timo
2013-01-01
of the retarded type. We apply the Waveform Relaxation algorithm, i.e., we provide a guess of the policy function and solve the resulting system of (deterministic) ordinary differential equations by standard techniques. For parametric restrictions, analytical solutions to the stochastic growth model and a novel...
A Full Disturbance Model for Reaction Wheels
Le, M.P.; Ellenbroek, Marcellinus Hermannus Maria; Seiler, R; van Put, P.; Cottaar, E.J.E.
2014-01-01
Reaction wheels are rotating devices used for the attitude control of spacecraft. However, reaction wheels also generate undesired disturbances in the form of vibrations, which may have an adverse effect on the pointing accuracy and stability of spacecraft (optical) payloads. A disturbance model for
Solid-Liquid equilibrium of n-alkanes using the Chain Delta Lattice Parameter model
Coutinho, João A.P.; Andersen, Simon Ivar; Stenby, Erling Halfdan
1996-01-01
The formation of a solid phase in liquid mixtures with large paraffinic molecules is a phenomenon of interest in the petroleum, pharmaceutical, and biotechnological industries among onters. Efforts to model the solid-liquid equilibrium in these systems have been mainly empirical and with different...... degrees of success.An attempt to describe the equilibrium between the high temperature form of a paraffinic solid solution, commonly known as rotator phase, and the liquid phase is performed. The Chain Delta Lattice Parameter model (CDLP) is developed allowing a successful description of the solid-liquid...... equilibrium of n-alkanes ranging from n-C_20 to n-C_40.The model is further modified to achieve a more correct temperature dependence because it severely underestimates the excess enthalpy. It is shown that the ratio of excess enthalpy and entropy for n-alkane solid solutions, as happens for other solid...
Tavasszy, L.; Davydenko, I.; Ruijgrok, K.
2009-01-01
The integration of Spatial Equilibrium models and Freight transport network models is important to produce consistent scenarios for future freight transport demand. At various spatial scales, we see the changes in production, trade, logistics networking and transportation, being driven by mass-indiv
Restructured electric power systems analysis of electricity markets with equilibrium models
2010-01-01
Electricity market deregulation is driving the power energy production from a monopolistic structure into a competitive market environment. The development of electricity markets has necessitated the need to analyze market behavior and power. Restructured Electric Power Systems reviews the latest developments in electricity market equilibrium models and discusses the application of such models in the practical analysis and assessment of electricity markets.
The matrix model, a driven state variables approach to non-equilibrium thermodynamics
Jongschaap, R.J.J.
2001-01-01
One of the new approaches in non-equilibrium thermodynamics is the so-called matrix model of Jongschaap. In this paper some features of this model are discussed. We indicate the differences with the more common approach based upon internal variables and the more sophisticated Hamiltonian and GENERIC
Robillard, George; Shaw, Elliott; Shulman, R.G.
1974-01-01
N-Acetyl-L-tyrosine semicarbazide is hydrolyzed by chymotrypsin (EC 3.4.21.1) to N-acetyl-L-tyrosine and semicarbazide. If a high concentration of semicarbazide is present, the equilibrium for the reaction can be shifted from hydrolysis to synthesis. Using N-acetyl-L-[13C]tyrosine enriched at the
A marginal revenue equilibrium model for spatial water allocation
王劲峰; 刘昌明; 王智勇; 于静洁
2002-01-01
The outside water is transported into the water-shorted area. It is allocated among many sub-areas that composed the water-shorted area, in order to maximize the total benefit from the input water for the areas. This paper presents a model for spatial water allocation based on the marginal revenue of water utilization, taking the six southern districts of Hebei Province as an example.
An Equilibrium Model of Catastrophe Insurance Futures and Spreads
Knut Aase
1999-01-01
This article presents a valuation model of futures contracts and derivatives on such contracts, when the underlying delivery value is an insurance index, which follows a stochastic process containing jumps of random claim sizes at random time points of accident occurrence. Applications are made on insurance futures and spreads, a relatively new class of instruments for risk management launched by the Chicago Board of Trade in 1993, anticipated to start in Europe and perhaps also in other part...
Modeling hyperelasticity in non-equilibrium multiphase flows
Hank, Sarah; Favrie, Nicolas; Massoni, Jacques
2017-02-01
The aim of this article is the construction of a multiphase hyperelastic model. The Eulerian formulation of the hyperelasticity represents a system of 14 conservative partial differential equations submitted to stationary differential constraints. This model is constructed with an elegant approach where the specific energy is given in separable form. The system admits 14 eigenvalues with 7 characteristic eigenfields. The associated Riemann problem is not easy to solve because of the presence of 7 waves. The shear waves are very diffusive when dealing with the full system. In this paper, we use a splitting approach to solve the whole system using 3 sub-systems. This method reduces the diffusion of the shear waves while allowing to use a classical approximate Riemann solver. The multiphase model is obtained by adapting the discrete equations method. This approach involves an additional equation governing the evolution of a phase function relative to the presence of a phase in a cell. The system is integrated over a multiphase volume control. Finally, each phase admits its own equations system composed of three sub-systems. One and three dimensional test cases are presented.
Fang, Le [Laboratory of Mathematics and Physics, Ecole Centrale de Pékin, Beihang University, Beijing 100191 (China); Zhu, Ying [Laboratory of Mathematics and Physics, Ecole Centrale de Pékin, Beihang University, Beijing 100191 (China); National Key Laboratory of Science and Technology on Aero-Engine Aero-Thermodynamics, School of Energy and Power Engineering, Beihang University, Beijing 100191 (China); Liu, Yangwei, E-mail: liuyangwei@126.com [National Key Laboratory of Science and Technology on Aero-Engine Aero-Thermodynamics, School of Energy and Power Engineering, Beihang University, Beijing 100191 (China); Lu, Lipeng [National Key Laboratory of Science and Technology on Aero-Engine Aero-Thermodynamics, School of Energy and Power Engineering, Beihang University, Beijing 100191 (China)
2015-10-09
The non-equilibrium property in turbulence is a non-negligible problem in large-eddy simulation but has not yet been systematically considered. The generalization from equilibrium turbulence to non-equilibrium turbulence requires a clear recognition of the non-equilibrium property. As a preliminary step of this recognition, the present letter defines a typical non-equilibrium process, that is, the spectral non-equilibrium process, in homogeneous isotropic turbulence. It is then theoretically investigated by employing the skewness of grid-scale velocity gradient, which permits the decomposition of resolved velocity field into an equilibrium one and a time-reversed one. Based on this decomposition, an improved Smagorinsky model is proposed to correct the non-equilibrium behavior of the traditional Smagorinsky model. The present study is expected to shed light on the future studies of more generalized non-equilibrium turbulent flows. - Highlights: • A spectral non-equilibrium process in isotropic turbulence is defined theoretically. • A decomposition method is proposed to divide a non-equilibrium turbulence field. • An improved Smagorinsky model is proposed to correct the non-equilibrium behavior.
Copper removal by algal biomass: Biosorbents characterization and equilibrium modelling
Vilar, Vitor J.P. [LSRE-Laboratory of Separation and Reaction Engineering, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal)], E-mail: vilar@fe.up.pt; Botelho, Cidalia M.S. [LSRE-Laboratory of Separation and Reaction Engineering, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal)], E-mail: cbotelho@fe.up.pt; Pinheiro, Jose P.S.; Domingos, Rute F. [Centro de Biomedicina Molecular e Estrutural, Department of Chemistry and Biochemistry, University of Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); Boaventura, Rui A.R. [LSRE-Laboratory of Separation and Reaction Engineering, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal)], E-mail: bventura@fe.up.pt
2009-04-30
The general principles of Cu(II) binding to algal waste from agar extraction, composite material and algae Gelidium, and different modelling approaches, are discussed. FTIR analyses provided a detailed description of the possible binding groups present in the biosorbents, as carboxylic groups (D-glucuronic and pyruvic acids), hydroxyl groups (cellulose, agar and floridean starch) and sulfonate groups (sulphated galactans). Potentiometric acid-base titrations showed a heterogeneous distribution of two major binding groups, carboxyl and hydroxyl, following the quasi-Gaussian affinity constant distribution suggested by Sips, which permitted to estimate the maximum amount of acid functional groups (0.36, 0.25 and 0.1 mmol g{sup -1}) and proton binding parameters (pK{sup '}{sub H}=5.0,5.3and4.4;m{sub H} = 0.43, 0.37, 0.33), respectively for algae Gelidium, algal waste and composite material. A non-ideal, semi-empirical, thermodynamically consistent (NICCA) isotherm fitted better the experimental ion binding data for different pH values and copper concentrations, considering only the acid functional groups, than the discrete model. Values of pK{sup '}{sub M} (3.2; 3.6 and 3.3), n{sub M} (0.98, 0.91, 1.0) and p (0.67, 0.53 and 0.43) were obtained, respectively for algae Gelidium, algal waste and composite material. NICCA model reflects the complex macromolecular systems that take part in biosorption considering the heterogeneity of the biosorbent, the competition between protons and metals ions to the binding sites and the stoichiometry for different ions.
Copper removal by algal biomass: biosorbents characterization and equilibrium modelling.
Vilar, Vítor J P; Botelho, Cidália M S; Pinheiro, José P S; Domingos, Rute F; Boaventura, Rui A R
2009-04-30
The general principles of Cu(II) binding to algal waste from agar extraction, composite material and algae Gelidium, and different modelling approaches, are discussed. FTIR analyses provided a detailed description of the possible binding groups present in the biosorbents, as carboxylic groups (D-glucuronic and pyruvic acids), hydroxyl groups (cellulose, agar and floridean starch) and sulfonate groups (sulphated galactans). Potentiometric acid-base titrations showed a heterogeneous distribution of two major binding groups, carboxyl and hydroxyl, following the quasi-Gaussian affinity constant distribution suggested by Sips, which permitted to estimate the maximum amount of acid functional groups (0.36, 0.25 and 0.1 mmol g(-1)) and proton binding parameters (pK(H)=5.0, 5.3 and 4.4; m(H)=0.43, 0.37, 0.33), respectively for algae Gelidium, algal waste and composite material. A non-ideal, semi-empirical, thermodynamically consistent (NICCA) isotherm fitted better the experimental ion binding data for different pH values and copper concentrations, considering only the acid functional groups, than the discrete model. Values of pK(M) (3.2; 3.6 and 3.3), n(M) (0.98, 0.91, 1.0) and p (0.67, 0.53 and 0.43) were obtained, respectively for algae Gelidium, algal waste and composite material. NICCA model reflects the complex macromolecular systems that take part in biosorption considering the heterogeneity of the biosorbent, the competition between protons and metals ions to the binding sites and the stoichiometry for different ions.
Celen, Ipek; Buchanan, John R; Burns, Robert T; Robinson, R Bruce; Raman, D Raj
2007-04-01
Precipitation of phosphate minerals from liquid swine manure is an established means of reducing the orthophosphate (OP) concentration. This project investigated the usefulness of a chemical equilibrium model, Visual Minteq, for prescribing the amendments needed to maximize struvite precipitation from liquid swine manure and thus reduce the OP phosphorus concentration. The actual concentrations of Mg(2+), Ca(2+), K(+), OP, NH(4)(+), alkalinity and pH from a liquid swine manure system were used as inputs to the model. The model was modified to remove species with extremely low formation rates, because they would not significantly precipitate in the reaction occurring in a short retention-time process such as those envisioned for swine manure struvite-formation reactors. Using the model's output, a series of 19-L reactors were used to verify the results. Verification results demonstrated that Visual Minteq can be used to pre-determine the concentration of amendments required to maximize struvite recovery.
2009-10-01
Beattie - Bridgeman Virial expansion The above equations are suitable for moderate pressures and are usually based on either empirical constants...CR 2010-013 October 2009 A Review of Equation of State Models, Chemical Equilibrium Calculations and CERV Code Requirements for SHS Detonation...Defence R&D Canada. A Review of Equation of State Models, Chemical Equilibrium Calculations and CERV Code Requirements for SHS Detonation
Game equilibrium models I evolution and game dynamics
1991-01-01
There are two main approaches towards the phenotypic analysis of frequency dependent natural selection. First, there is the approach of evolutionary game theory, which was introduced in 1973 by John Maynard Smith and George R. Price. In this theory, the dynamical process of natural selection is not modeled explicitly. Instead, the selective forces acting within a population are represented by a fitness function, which is then analysed according to the concept of an evolutionarily stable strategy or ESS. Later on, the static approach of evolutionary game theory has been complemented by a dynamic stability analysis of the replicator equations. Introduced by Peter D. Taylor and Leo B. Jonker in 1978, these equations specify a class of dynamical systems, which provide a simple dynamic description of a selection process. Usually, the investigation of the replicator dynamics centers around a stability analysis of their stationary solutions. Although evolutionary stability and dynamic stability both intend to charac...
Overshoot in biological systems modelled by Markov chains: a non-equilibrium dynamic phenomenon.
Jia, Chen; Qian, Minping; Jiang, Daquan
2014-08-01
A number of biological systems can be modelled by Markov chains. Recently, there has been an increasing concern about when biological systems modelled by Markov chains will perform a dynamic phenomenon called overshoot. In this study, the authors found that the steady-state behaviour of the system will have a great effect on the occurrence of overshoot. They showed that overshoot in general cannot occur in systems that will finally approach an equilibrium steady state. They further classified overshoot into two types, named as simple overshoot and oscillating overshoot. They showed that except for extreme cases, oscillating overshoot will occur if the system is far from equilibrium. All these results clearly show that overshoot is a non-equilibrium dynamic phenomenon with energy consumption. In addition, the main result in this study is validated with real experimental data.
He I lines in B stars - Comparison of non-local thermodynamic equilibrium models with observations
Heasley, J. N.; Timothy, J. G.; Wolff, S. C.
1982-01-01
Profiles of He gamma-gamma 4026, 4387, 4471, 4713, 5876, and 6678 have been obtained in 17 stars of spectral type B0-B5. Parameters of the nonlocal thermodynamic equilibrium models appropriate to each star are determined from the Stromgren index and fits to H-alpha line profiles. These parameters yield generally good fits to the observed He I line profiles, with the best fits being found for the blue He I lines where departures from local thermodynamic equilibrium are relatively small. For the two red lines it is found that, in the early B stars and in stars with log g less than 3.5, both lines are systematically stronger than predicted by the nonlocal thermodynamic equilibrium models.
Equilibrium statistical mechanics and energy partition for the shallow water model
Renaud, Antoine; Bouchet, Freddy
2015-01-01
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 discretized model of the continuous shallow water system, and compute the corresponding statistical equilibria. We argue that microcanonical equilibrium states of the discretized 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 v...
Non-equilibrium dynamical phases of the two-atom Dicke model
Bhattacherjee, Aranya B.
2014-09-12
In this paper, we investigate the non-equilibrium dynamical phases of the two-atom Dicke model, which can be realized in a two species Bose–Einstein condensate interacting with a single light mode in an optical cavity. Apart from the usual non-equilibrium normal and inverted phases, a non-equilibrium mixed phase is possible which is a combination of normal and inverted phase. A new kind of dynamical phase transition is predicted from non-superradiant mixed phase to the superradiant phase which can be achieved by tuning the two different atom–photon couplings. We also show that a dynamical phase transition from the non-superradiant mixed phase to the superradiant phase is forbidden for certain values of the two atom–photon coupling strengths. - Highlights: • We investigate the non-equilibrium dynamical phases of the two-atom Dicke model. • The dynamical phase diagram reveals a new kind of non-equilibrium mixed phase. • A new kind of dynamical phase transition is predicted from mixed phase to the superradiant phase. • In the dynamical phase diagram of the mixed phase, there are regions where the superradiant phase cannot exist.
An experiment on radioactive equilibrium and its modelling using the ‘radioactive dice’ approach
Santostasi, Davide; Malgieri, Massimiliano; Montagna, Paolo; Vitulo, Paolo
2017-07-01
In this article we describe an educational activity on radioactive equilibrium we performed with secondary school students (17-18 years old) in the context of a vocational guidance stage for talented students at the Department of Physics of the University of Pavia. Radioactive equilibrium is investigated experimentally by having students measure the activity of 214Bi from two different samples, obtained using different preparation procedures from an uraniferous rock. Students are guided in understanding the mathematical structure of radioactive equilibrium through a modelling activity in two parts. Before the lab measurements, a dice game, which extends the traditional ‘radioactive dice’ activity to the case of a chain of two decaying nuclides, is performed by students divided into small groups. At the end of the laboratory work, students design and run a simple spreadsheet simulation modelling the same basic radioactive chain with user defined decay constants. By setting the constants to realistic values corresponding to nuclides of the uranium decay chain, students can deepen their understanding of the meaning of the experimental data, and also explore the difference between cases of non-equilibrium, transient and secular equilibrium.
LIU Xiaofeng; ZHAO Lei
2012-01-01
Stable operation of aircraft engine compressions is constrained by rotating surge.In this paper,an approximate nonlinear surge margin model of aircraft engine compression system by using equilibrium manifold is presented.Firstly,this paper gives an overview of the current state of modeling aerodynamic flow instabilities in engine compressors.Secondly,the expansion form of equilibrium manifold is introduced,and the choosing scheduling variable method is discussed.Then,this paper also gives the identification procedure of modeling the approximate nonlinear model.Finally,the modeling and simulations with high pressure (HP) compressor surge margin of the aircraft engine show that this real-time model has the same accuracy with the thermodynamic model,but has simpler structure and shorter computation time.
R.S. Lokhande
2008-04-01
Full Text Available The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Duolite A-102 D. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems was observed to increase with rise in temperature, indicating the endothermic exchange reactions having enthalpy values of 13.7, 38.0, 23.9, 22.9 kJ/mol, respectively.
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.
A two-phase restricted equilibrium model for combustion of metalized solid propellants
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.
Chemical Principles Revisited: Chemical Equilibrium.
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)
D Sudarshan Reddy; S Satyanarayana
2003-06-01
Equilibria and kinetics of the reactions of chloromethyl(aquo)cobaloxime with histamine, histidine, glycine and ethyl glycine ester were studied as a function of pH at 25°C, 1.0 M ionic strength (KCl) by spectrophotometric techniques. Comparison of equilibrium constants and rate constants tells that the order is Hisdn > Hiamn > Gly > EtGlyest. The rate of substitution of H2O varies with the p of the incoming ligand and nucleophilic participation of the ligand in the transition state. The rate constants and equilibrium constants are correlated to the hardness and softness of the ligands and the Co(III) of cobaloxime.
Equilibrium microphase separation in the two-leaflet model of lipid membranes
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.
Variational Principle for Non-Equilibrium Steady States of the XX Model
Matsui, T
2003-01-01
We show that non-equilibrium steady states of the one dimensional exactly solved XY model can be characterized by the variational principle of free energy of a long range interaction and that they cannot be a KMS state for any C$^*$-dynamical system.
Solid-Liquid equilibrium of n-alkanes using the Chain Delta Lattice Parameter model
Coutinho, João A.P.; Andersen, Simon Ivar; Stenby, Erling Halfdan
1996-01-01
-liquid equilibrium of n-alkanes ranging from n-C_20 to n-C_40.The model is further modified to achieve a more correct temperature dependence because it severely underestimates the excess enthalpy. It is shown that the ratio of excess enthalpy and entropy for n-alkane solid solutions, as happens for other solid...
A Non-Equilibrium Sediment Transport Model for Coastal Inlets and Navigation Channels
2011-01-01
Navigation Channels Alejandro Sánchez† and Weiming Wu‡ ABSTRACT SANCHEZ, A. and WU, W., 2011. A Non-Equilibrium Sediment Transport Model...2009; accessed January 20, 2009). Nicholson, J.; Brøker, I.; Roelvink, J. A.; Price, D.; Tanguy, J. M., and Moreno , L., 1997. Intercomparison of
Using a Joint-Input, Multi-Product Formulation to Improve Spatial Price Equilibrium Models
Bishop, Phillip M.; Pratt, James E.; Novakovic, Andrew M.
1994-01-01
Mathematical programming models, as typically formulated for international trade applications, may contain certain implied restrictions which lead to solutions which can be shown to be technically infeasible, or if feasible, then not actually an equilibrium. An alternative formulation is presented which allows joint-inputs and multi-products, with pure transshipment and product substitution forms of arbitrage.
A Lotka-Volterra competition model and its global convergence to a definite axial equilibrium.
Sikder, Asim
2002-04-01
We consider a four-species model based on competition and show that the whole four-species system collapses to a definite single species equilibrium at its carrying capacity. To do so, we use the results of Hirsch, Van Den Driessche and Zeeman, Hofbauer and Sigmund, and the product theorem of the Conley connection matrix theory by Mischaikow and Reineck.
Christopher P. Paolini
2012-01-01
Full Text Available The ideal gas (IG model is probably the most well-known gas models in engineering thermodynamics. In this paper, we extend the IG model into an ideal gas equilibrium (IGE model mixture model by incorporating chemical equilibrium calculations as part of the state evaluation. Through a simple graphical interface, users can set the atomic composition of a gas mixture. We have integrated this model into a thermodynamic web portal TEST (http://thermofluids.sdsu.edu/ that contains Java applets for various models for properties of pure substances. In the state panel of the IGE model, the known thermodynamic properties are entered. For a given pressure and temperature, the mixture's Gibbs function is minimized subject to atomic constraints and the equilibrium composition along with thermodynamic properties of the mixture are calculated and displayed. What is unique about this approach is that equilibrium computations are performed in the background, without requiring any major change in the familiar user interface used in other state daemons. Properties calculated by this equilibrium state daemon are compared with results from other established applications such as NASA CEA and STANJAN. Also, two different algorithms, an iterative approach and a direct approach based on minimizing different thermodynamic functions in different situation, are compared.
Development of a bi-equilibrium model for biomass gasification in a downdraft bed reactor.
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.
A parametrized non-equilibrium wall-model for large-eddy simulations
Hickel, Stefan; Bodart, Julien; Larsson, Johan
2015-01-01
Wall-models are essential for enabling large-eddy simulations (LESs) of realistic problems at high Reynolds numbers. The present study is focused on approaches that directly model the wall shear stress, specifically on filling the gap between models based on wall-normal ordinary differential equations (ODEs) that assume equilibrium and models based on full partial differential equations (PDEs) that do not. We develop ideas for how to incorporate non-equilibrium effects (most importantly, strong pressure-gradient effects) in the wall-model while still solving only wall-normal ODEs. We test these ideas using two reference databases: an adverse pressure-gradient turbulent boundary-layer and a shock/boundary-layer interaction problem, both of which lead to separation and re-attachment of the turbulent boundary layer.
Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.
2016-10-01
We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a
Adaptive behaviour and multiple equilibrium states in a predator-prey model.
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.
Consistent post-reaction vibrational energy redistribution in DSMC simulations using TCE model
Borges Sebastião, Israel; Alexeenko, Alina
2016-10-01
The direct simulation Monte Carlo (DSMC) method has been widely applied to study shockwaves, hypersonic reentry flows, and other nonequilibrium flow phenomena. Although there is currently active research on high-fidelity models based on ab initio data, the total collision energy (TCE) and Larsen-Borgnakke (LB) models remain the most often used chemistry and relaxation models in DSMC simulations, respectively. The conventional implementation of the discrete LB model, however, may not satisfy detailed balance when recombination and exchange reactions play an important role in the flow energy balance. This issue can become even more critical in reacting mixtures involving polyatomic molecules, such as in combustion. In this work, this important shortcoming is addressed and an empirical approach to consistently specify the post-reaction vibrational states close to thermochemical equilibrium conditions is proposed within the TCE framework. Following Bird's quantum-kinetic (QK) methodology for populating post-reaction states, the new TCE-based approach involves two main steps. The state-specific TCE reaction probabilities for a forward reaction are first pre-computed from equilibrium 0-D simulations. These probabilities are then employed to populate the post-reaction vibrational states of the corresponding reverse reaction. The new approach is illustrated by application to exchange and recombination reactions relevant to H2-O2 combustion processes.
Wong, Kin-Yiu; Xu, Yuqing; York, Darrin M
2014-06-30
Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2'-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This article significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and nonenzymatic 2'-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a "gold-standard" coupled-cluster level of theory [CCSD(T)]. In addition to the widely used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently developed ab initio path-integral method, that is, automated integration-free path-integral method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis. Copyright © 2014 Wiley Periodicals, Inc.
Econometrics and data of the 9 sector Dynamic General Equilibrium Model. Volume III. Final report
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).
Development of a Chemical Equilibrium Model for a Molten Core-Concrete Interaction Analysis Module
Seo, Jae Uk; Lee, Dae Young; Park, Chang Hwan [FNC Technology Co., Yongin (Korea, Republic of)
2016-10-15
This molten core could interact with the reactor cavity region which consists of concrete. In this process, components of molten core react with components of concrete through a lot of chemical reactions. As a result, many kinds of gas species are generated and those move up forming rising bubbles into the reactor containment atmosphere. These rising bubbles are the carrier of the many kinds of the aerosols coming from the MCCI (Molten Core Concrete Interaction) layers. To evaluate the amount of the aerosols released from the MCCI layers, the amount of the gas species generated from those layers should be calculated. The chemical equilibrium state originally implies the final state of the multiple chemical reactions; therefore, investigating the equilibrium composition of molten core can be applicable to predict the gas generation status. The most common way for finding the chemical equilibrium state is a minimization of total Gibbs free energy of the system. In this paper, the method to make good guess of initial state is suggested and chemical reaction results are compared with results of CSSI report No 164. Total mass of system and the number of atoms of each element are conserved. The tendency of calculation results is similar with results presented in CSNI Report except a few species. These differences may be caused by absence of Gibbs energy data of the species such as Fe{sub 2}SiO{sub 4}, CaFe{sub 2}O{sub 4}, U(OH){sub 3}, UO(OH), UO{sub 2}(OH), U{sub 3}O{sub 7}, La, Ce.
王伟; 孙会君; 吴建军
2015-01-01
The assumption widely used in the user equilibrium model for stochastic network was that the probability distributions of the travel time were known explicitly by travelers. However, this distribution may be unavailable in reality. By relaxing the restrictive assumption, a robust user equilibrium model based on cumulative prospect theory under distribution-free travel time was presented. In the absence of the cumulative distribution function of the travel time, the exact cumulative prospect value (CPV) for each route cannot be obtained. However, the upper and lower bounds on the CPV can be calculated by probability inequalities. Travelers were assumed to choose the routes with the best worst-case CPVs. The proposed model was formulated as a variational inequality problem and solved via a heuristic solution algorithm. A numerical example was also provided to illustrate the application of the proposed model and the efficiency of the solution algorithm.
Ion exchange equilibrium constants
Marcus, Y
2013-01-01
Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and
2009-01-01
This thesis estimates the economic impact of uncertain tourism demand in Hawaii. It does this by incorporating risk into a Computable General Equilibrium (CGE) model. CGE models have been used to investigate a wide range of policy issues. To date, none have investigated how uncertainty regarding future tourism demand impacts on an economy. The context in which this research is set is the US State of Hawaii. The economy of Hawaii is heavily dependent on tourism as a source of income and a...
An Equilibrium Model for an Open Economy. Romania’s case
Catalin Angelo Ioan
2013-02-01
Full Text Available The model presented in this article is an adaptation of the IS-LM model for an openeconomy in which both the static aspects and dynamic ones are approached. Also, based on the modelbuilt, it is determined the level of potential GDP and the natural unemployment rate. Thedetermination of marginal main indicators of GDP and interest rates, allow to identify problems andthe directions of action to achieve economic equilibrium.
Wilmouth, D. M.; Klobas, J. E.; Anderson, J. G.
2015-12-01
Thirty years have now passed since the discovery of the Antarctic ozone hole, and despite comprehensive international agreements being in place to phase out CFCs and halons, polar ozone losses generally remain severe. The relevant halogen compounds have very long atmospheric lifetimes, which ensures that seasonal polar ozone depletion will likely continue for decades to come. Changes in the climate system can further impact stratospheric ozone abundance through changes in the temperature and water vapor structure of the atmosphere and through the potential initiation of solar radiation management efforts. In many ways, the rate at which climate is changing must now be considered fast relative to the slow removal of halogens from the atmosphere. Photochemical models of Earth's atmosphere play a critical role in understanding and projecting ozone levels, but in order for these models to be accurate, they must be built on a foundation of accurate laboratory data. ClOOCl is the centerpiece of the catalytic cycle that accounts for more than 50% of the chlorine-catalyzed ozone loss in the Arctic and Antarctic stratosphere every spring, and so uncertainties in the ultraviolet cross sections of ClOOCl are particularly important. Additionally, the equilibrium constant of the dimerization reaction of ClO merits further study, as there are important discrepancies between in situ measurements and lab-based models, and the JPL-11 recommended equilibrium constant includes high error bars at atmospherically relevant temperatures (~75% at 200 K). Here we analyze available data for the ClOOCl ultraviolet cross sections and equilibrium constant and present new laboratory spectroscopic results.
Equilibrium Statistical Mechanics and Energy Partition for the Shallow Water Model
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.
Cueto-Felgueroso, L.; Fu, X.; Juanes, R.
2016-12-01
The description of multicomponent flows with complex phase behavior remains an open challenge in pore-scale modeling. Darcy-scale general purpose simulators assume local thermodynamic equilibrium, and perform equation-of-state-based calculations to make phase equilibrium predictions; that is, to determine the phase volume fractions and their compositions from overall component mole fractions. What remains unclear is whether the thermodynamic equilibrium assumption is valid given the flow conditions, complex structure of the pore space and characteristic time scales for flow. Diffuse-interface theories of multiphase flow have recently emerged as promising tools to understand and simulate complex processes involving the simultaneous flow of two or more immiscible fluid phases. The common goal in these approaches is to formulate thermodynamically consistent stress tensors and mesoscale balance laws, including the impact of surface tension on the momentum balance, as well as properly tracking interfacial dynamics and mass transfer. We propose a phase-field model of multiphase, multicomponent flow, which we use to address the following research questions: What is the impact of the wetting conditions at the pore scale on upscaled descriptions of multiphase flow? What is the impact of the displacement dynamics, pore space structure and wetting conditions on the phase behavior of multicomponent mixtures? We finally investigate upscaling procedures to incorporate non-equilibrium phase behavior at the continuum scale.
Curing Reaction Model of Epoxy Asphalt Binder
QIAN Zhendong; CHEN Leilei; WANG Yaqi; SHEN Jialin
2012-01-01
In order to understand the strength developing law of the epoxy asphalt mixture,a curing reaction model of the epoxy asphalt binder was proposed based upon the thermokinetic analysis.Given some assumptions,the model was developed by applying the Kissinger law as well as Arrhenius equation,and the differential scanning calorimetry was performed for estimating the model parameters.To monitor the strength development of the epoxy asphalt mixture,a strength test program was employed and then results were compared to those produced from the proposed model.The comparative evaluation shows that a good consistency exists between the outputs from test program and the proposed model,indicating that the proposed model can be used effectively for simulating the curing reaction process for the epoxy asphalt binder and predicting the strength development for the epoxy asphalt mixture.
Modeling Portfolio Optimization Problem by Probability-Credibility Equilibrium Risk Criterion
Ye Wang
2016-01-01
Full Text Available This paper studies the portfolio selection problem in hybrid uncertain decision systems. Firstly the return rates are characterized by random fuzzy variables. The objective is to maximize the total expected return rate. For a random fuzzy variable, this paper defines a new equilibrium risk value (ERV with credibility level beta and probability level alpha. As a result, our portfolio problem is built as a new random fuzzy expected value (EV model subject to ERV constraint, which is referred to as EV-ERV model. Under mild assumptions, the proposed EV-ERV model is a convex programming problem. Furthermore, when the possibility distributions are triangular, trapezoidal, and normal, the EV-ERV model can be transformed into its equivalent deterministic convex programming models, which can be solved by general purpose optimization software. To demonstrate the effectiveness of the proposed equilibrium optimization method, some numerical experiments are conducted. The computational results and comparison study demonstrate that the developed equilibrium optimization method is effective to model portfolio selection optimization problem with twofold uncertain return rates.
ASHEE: a compressible, equilibrium-Eulerian model for volcanic ash plumes
Cerminara, Matteo; Berselli, Luigi Carlo
2015-01-01
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 particles, we adopt an asymptotic expansion strategy to derive a compressible version of the first-order non-equilibrium model, valid for low concentration regimes and small particles Stokes $St<0.2$. When $St < 0.001$ the model reduces to the dusty-gas one. The new model is significantly faster than the Eulerian model while retaining the capability to describe gas-particle non-equilibrium. Direct numerical simulation accurately reproduce the dynamics of isotropic turbulence in subsonic regime. For gas-particle mixtures, it describes the main features of density fluctuations and the preferential concentration of particles by turbulence, verifying the model reliability and suitability for the simulation of high-Reynolds number and high-temperature ...
Nonlinear control of the Salnikov model reaction
Recke, Bodil; Jørgensen, Sten Bay
1999-01-01
This paper explores different nonlinear control schemes, applied to a simple model reaction. The model is the Salnikov model, consisting of two ordinary differential equations. The control strategies investigated are I/O-linearisation, Exact linearisation, exact linearisation combined with LQR...... and Control Lyapunov Functions (CLF's). The results show that based on the lowest possible cost function and shortest settling time, the exact linearisation performs marginally better than the other methods....
Nüske, Feliks; Wu, Hao; Prinz, Jan-Hendrik; Wehmeyer, Christoph; Clementi, Cecilia; Noé, Frank
2017-03-01
Many state-of-the-art methods for the thermodynamic and kinetic characterization of large and complex biomolecular systems by simulation rely on ensemble approaches, where data from large numbers of relatively short trajectories are integrated. In this context, Markov state models (MSMs) are extremely popular because they can be used to compute stationary quantities and long-time kinetics from ensembles of short simulations, provided that these short simulations are in "local equilibrium" within the MSM states. However, over the last 15 years since the inception of MSMs, it has been controversially discussed and not yet been answered how deviations from local equilibrium can be detected, whether these deviations induce a practical bias in MSM estimation, and how to correct for them. In this paper, we address these issues: We systematically analyze the estimation of MSMs from short non-equilibrium simulations, and we provide an expression for the error between unbiased transition probabilities and the expected estimate from many short simulations. We show that the unbiased MSM estimate can be obtained even from relatively short non-equilibrium simulations in the limit of long lag times and good discretization. Further, we exploit observable operator model (OOM) theory to derive an unbiased estimator for the MSM transition matrix that corrects for the effect of starting out of equilibrium, even when short lag times are used. Finally, we show how the OOM framework can be used to estimate the exact eigenvalues or relaxation time scales of the system without estimating an MSM transition matrix, which allows us to practically assess the discretization quality of the MSM. Applications to model systems and molecular dynamics simulation data of alanine dipeptide are included for illustration. The improved MSM estimator is implemented in PyEMMA of version 2.3.
Pessôa Filho P. A.
2004-01-01
Full Text Available Mixtures containing compounds that undergo hydrogen bonding show large deviations from ideal behavior. These deviations can be accounted for through chemical theory, according to which the formation of a hydrogen bond can be treated as a chemical reaction. This chemical equilibrium needs to be taken into account when applying stability criteria and carrying out phase equilibrium calculations. In this work, we illustrate the application of the stability criteria to establish the conditions under which a liquid-phase split may occur and the subsequent calculation of liquid-liquid equilibrium using a chemical-theory-modified Flory-Huggins equation to describe the non ideality of aqueous two-phase systems composed of poly(ethylene glycol and dextran. The model was found to be able to correlate ternary liquid-liquid diagrams reasonably well by simple adjustment of the polymer-polymer binary interaction parameter.
Dynamical Model of Weak Pion Production Reactions
Sato, T; Lee, T S H
2003-01-01
The dynamical model of pion electroproduction has been extended to investigate the weak pion production reactions. The predicted cross sections of neutrino-induced pion production reactions are in good agreement with the existing data. We show that the renormalized(dressed) axial N-$\\Delta$ form factor contains large dynamical pion cloud effects and this renormalization effects are crucial in getting agreement with the data. We conclude that the N-$\\Delta$ transitions predicted by the constituent quark model are consistent with the existing neutrino induced pion production data in the $\\Delta$ region.
Modeling the Spin Equilibrium of Neutron Stars in LMXBs Without Gravitational Radiation
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.
Giannessi, Franco; Maugeri, Antonino; Equilibrium Problems and Variational Models
2000-01-01
The volume, devoted to variational analysis and its applications, collects selected and refereed contributions, which provide an outline of the field. The meeting of the title "Equilibrium Problems and Variational Models", which was held in Erice (Sicily) in the period June 23 - July 2 2000, was the occasion of the presentation of some of these papers; other results are a consequence of a fruitful and constructive atmosphere created during the meeting. New results, which enlarge the field of application of variational analysis, are presented in the book; they deal with the vectorial analysis, time dependent variational analysis, exact penalization, high order deriva tives, geometric aspects, distance functions and log-quadratic proximal methodology. The new theoretical results allow one to improve in a remarkable way the study of significant problems arising from the applied sciences, as continuum model of transportation, unilateral problems, multicriteria spatial price models, network equilibrium...
QGSM development for spallation reactions modeling
Gudima K.K.
2012-12-01
Full Text Available The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.
QGSM development for spallation reactions modeling
Baznat, M. I.; Chigrinov, S. E.; Gudima, K. K.
2012-12-01
The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM) for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.
Christensen, Bent J.; M. Kiefer, Nicholas
1996-01-01
A thorough econometric analysis of the pure equilibrium search model is given. Minimal data requirements for estimation are unemployment durations, wages, and employment durations. An assessment of the information contribution of each data element is given. The results define the range of potential...... application of the equilibrium search framework and form the foundation for future econometric analysis of related models....
A review of the formulation and application of the spatial equilibrium models to analyze policy
Phan Sy Hieu; Steve Harrison
2011-01-01
This paper reviews alternative market equilibrium models for policy analysis.The origin of spatial equilibrium models and their application to wood and wood-processing industries are described.Three mathematical programming models commonly applied to solve spatial problems - namely linear programming,non-linear programming and mixed complementary programming - are reviewed in terms of forms of objective functions and constraint equalities and inequalities.These programming are illustrated with numerical examples.Linear programming is only applied in transportation problems to solve quantities transported between regions when quantities supplied and demanded in each region are already known.It is argued that linear programming can be applied in broader context to transportation problems where supply and demand quantities are unknown and are linear.In this context,linear programming is seen as a more convenient method for modelers because it has a simpler objective function and does not require as strict conditions,for instance the equal numbers of variables and equations required in mixed complementary programming.Finally,some critical insights are provided on the interpretation of optimal solutions generated by solving spatial equilibrium models.
Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R; Kangawa, Yoshihiro; Kakimoto, Koichi
2017-08-15
Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and Nad-H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on Nad-H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.
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.
Kinetic modeling of reactions in Foods
Boekel, van M.A.J.S.
2008-01-01
The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to effec
Stability Analysis of a Reaction-Diffusion System Modeling Atherogenesis
Ibragimov, Akif
2010-01-01
This paper presents a linear, asymptotic stability analysis for a reaction-diffusionconvection system modeling atherogenesis, the initiation of atherosclerosis, as an inflammatory instability. Motivated by the disease paradigm articulated by Ross, atherogenesis is viewed as an inflammatory spiral with a positive feedback loop involving key cellular and chemical species interacting and reacting within the intimal layer of muscular arteries. The inflammatory spiral is initiated as an instability from a healthy state which is defined to be an equilibrium state devoid of certain key inflammatory markers. Disease initiation is studied through a linear, asymptotic stability analysis of a healthy equilibrium state. Various theorems are proved, giving conditions on system parameters guaranteeing stability of the health state, and a general framework is developed for constructing perturbations from a healthy state that exhibit blow-up, which are interpreted as corresponding to disease initiation. The analysis reveals key features that arterial geometry, antioxidant levels, and the source of inflammatory components (through coupled third-kind boundary conditions or through body sources) play in disease initiation. © 2010 Society for Industrial and Applied Mathematics.
Non-equilibrium structure and dynamics in a microscopic model of thin film active gels
Head, D A; Gompper, G
2013-01-01
In the presence of ATP, molecular motors generate active force dipoles that drive suspensions of protein filaments far from thermodynamic equilibrium, leading to exotic dynamics and pattern formation. Microscopic modelling can help to quantify the relationship between individual motors plus filaments to the large-wavelength properties represented by "hydrodynamic" models. Here we present results of extensive numerical simulations of active gels where the motors and filaments are confined between two infinite parallel plates. Thermal fluctuations and excluded-volume interactions between filaments are included. A systematic variation of rates for motor motion, attachment and detachment, including a differential detachment rate from filament ends, reveals a range of non-equilibrium behaviour. Strong motor binding produces structured filament aggregates that we refer to as asters, bundles or layers, whose stability depends on motor speed and differential end-detachment. The gross features of the dependence of the...
Adsorption of direct dye on palm ash: kinetic and equilibrium modeling.
Ahmad, A A; Hameed, B H; Aziz, N
2007-03-01
Palm ash, an agriculture waste residue from palm-oil industry in Malaysia, was investigated as a replacement for the current expensive methods of removing direct blue 71 dye from an aqueous solution. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Equilibrium data fitted well with Freundlich model in the range of 50-600mg/L. The equilibrium adsorption capacity of the palm ash was determined with the Langmuir equation and found to be 400.01mg dye per gram adsorbent at 30 degrees C. The rates of adsorption were found to conform to the pseudo-second-order kinetics with good correlation. The results indicate that the palm ash could be employed as a low-cost alternative to commercial activated carbon.
Effects of Risk Aversion on Market Outcomes: A Stochastic Two-Stage Equilibrium Model
Kazempour, Jalal; Pinson, Pierre
2016-01-01
This paper evaluates how different risk preferences of electricity producers alter the market-clearing outcomes. Toward this goal, we propose a stochastic equilibrium model for electricity markets with two settlements, i.e., day-ahead and balancing, in which a number of conventional and stochastic...... by its optimality conditions, resulting in a mixed complementarity problem. Numerical results from a case study based on the IEEE one-area reliability test system are derived and discussed....
A metastable equilibrium model for the relative abundances of microbial phyla in a hot spring.
Jeffrey M Dick
Full Text Available 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
Gradzewicz, Michał; Hagemejer, Jan; Zbigniew, Żółkiewski
2007-01-01
The aim of the paper is to quantitatively assess the impact of globalization on the economy of Poland in the medium term. Four channels of the impact of globalization are distinguished: (i) trade openness, (ii) productivity improvement, (iii) labour migrations, (iv) liberalization of the services sector. We employ a computable general equilibrium model with multiple industries and households and imperfect competition features. Our results show positive and quite significant effects of globali...
Assessing the Impacts of Wool Promotion An Equilibrium Displacement Modelling Approach
1995-01-01
The main goal of the International Wool Secretariat (IWS) is to increase the world demand for wool through promotion activities. Australia is a leading wool producer and the world's largest apparel wool exporter. Each year Australian wool producers contribute millions of dollars to the IWS for wool promotion. The principal aims of this paper are to demonstrate the potential for equilibrium displacement modelling to assess the impact of incremental wool promotion on wool producer incomes and p...
A Multiphase First Order Model for Non-Equilibrium Sand Erosion, Transport and Sedimentation
Preziosi, Luigi; Bruno, Luca
2015-01-01
Three phenomena are involved in sand movement: erosion, wind transport, and sedimentation. This paper presents a comprehensive easy-to-use multiphase model that include all three aspects with a particular attention to situations in which erosion due to wind shear and sedimentation due to gravity are not in equilibrium. The interest is related to the fact that these are the situations leading to a change of profile of the sand bed.
Tenure, Experience, Human Capital and Wages: A Tractable Equilibrium Search Model of Wage Dynamics
Bagger, Jesper; Fontaine, François; Postel-Vinay, Fabien; Robin, Jean-Marc
2011-01-01
We develop and estimate an equilibrium job search model of worker careers, allowing for human capital accumulation, employer heterogeneity and individual-level shocks. Career wage growth is decomposed into the contributions of human capital and job search, within and between jobs. Human capital accumulation is largest for highly educated workers, and both human capital accumulation and job search contribute to the observed concavity of wage-experience profiles. The contribution from job searc...
Florin-Marius PAVELESCU
2011-12-01
Full Text Available This paper deals with the consequences of the extension of the number of markets that are taken into consideration in a non-Walrasian equilibrium model. It is reviewed the initial content of the theory of non-Walrasian equilibrium and emphasizes the main modelling factors of the respective equilibrium. It proposes the inclusion of the capital market in the model of non-Walrasian equilibrium and is also reveals the implications of the extension of the respective model to the classification of types of non-Walrasian equilibrium and to the content of macroeconomic and structural policies. Also, it proposes an econometric method for the estimation of the type of unemployment. The respective methodology is practically used in the case of Romania for the period 1991-2004.
Reaction-diffusion pulses: a combustion model
Campos, Daniel [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Llebot, Josep Enric [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Fort, Joaquim [Dept. de FIsica, Univ. de Girona, Campus de Montilivi, 17071 Girona, Catalonia (Spain)
2004-07-02
We focus on a reaction-diffusion approach proposed recently for experiments on combustion processes, where the heat released by combustion follows first-order reaction kinetics. This case allows us to perform an exhaustive analytical study. Specifically, we obtain the exact expressions for the speed of the thermal pulses, their maximum temperature and the condition of self-sustenance. Finally, we propose two generalizations of the model, namely, the case of several reactants burning together, and that of time-delayed heat conduction. We find an excellent agreement between our analytical results and simulations.
Reaction Wheel Disturbance Model Extraction Software - RWDMES
Blaurock, Carl
2009-01-01
The RWDMES is a tool for modeling the disturbances imparted on spacecraft by spinning reaction wheels. Reaction wheels are usually the largest disturbance source on a precision pointing spacecraft, and can be the dominating source of pointing error. Accurate knowledge of the disturbance environment is critical to accurate prediction of the pointing performance. In the past, it has been difficult to extract an accurate wheel disturbance model since the forcing mechanisms are difficult to model physically, and the forcing amplitudes are filtered by the dynamics of the reaction wheel. RWDMES captures the wheel-induced disturbances using a hybrid physical/empirical model that is extracted directly from measured forcing data. The empirical models capture the tonal forces that occur at harmonics of the spin rate, and the broadband forces that arise from random effects. The empirical forcing functions are filtered by a physical model of the wheel structure that includes spin-rate-dependent moments (gyroscopic terms). The resulting hybrid model creates a highly accurate prediction of wheel-induced forces. It accounts for variation in disturbance frequency, as well as the shifts in structural amplification by the whirl modes, as the spin rate changes. This software provides a point-and-click environment for producing accurate models with minimal user effort. Where conventional approaches may take weeks to produce a model of variable quality, RWDMES can create a demonstrably high accuracy model in two hours. The software consists of a graphical user interface (GUI) that enables the user to specify all analysis parameters, to evaluate analysis results and to iteratively refine the model. Underlying algorithms automatically extract disturbance harmonics, initialize and tune harmonic models, and initialize and tune broadband noise models. The component steps are described in the RWDMES user s guide and include: converting time domain data to waterfall PSDs (power spectral
Dominant particles and reactions in a two-temperature chemical kinetic model of a decaying SF6 arc
Wang, Xiaohua; Gao, Qingqing; Fu, Yuwei; Yang, Aijun; Rong, Mingzhe; Wu, Yi; Niu, Chunping; Murphy, Anthony B.
2016-03-01
This paper is devoted to the computation of the non-equilibrium composition of an SF6 plasma, and determination of the dominant particles and reactions, at conditions relevant to high-voltage circuit breakers after current zero (temperatures from 12 000 K to 1000 K and a pressure of 4 atm). The non-equilibrium composition is characterized by departures from both thermal and chemical equilibrium. In thermal non-equilibrium process, the electron temperature (T e) is not equal to the heavy-particle temperature (T h), while for chemical non-equilibrium, a chemical kinetic model is adopted. In order to evaluate the reasonableness and reliability of the non-equilibrium composition, calculation methods for equilibrium composition based on Gibbs free energy minimization and kinetic composition in a one-temperature kinetic model are first considered. Based on the one-temperature kinetic model, a two-temperature kinetic model with the ratio T e/T h varying as a function of the logarithm of electron density ratio (n e/n\\text{e}\\max ) was established. In this model, T* is introduced to allow a smooth transition between T h and T e and to determine the temperatures for the rate constants. The initial composition in the kinetic models is obtained from the asymptotic composition as infinite time is approached at 12 000 K. The molar fractions of neutral particles and ions in the two-temperature kinetic model are consistent with the equilibrium composition and the composition obtained from the one-temperature kinetic model above 10 000 K, while significant differences appear below 10 000 K. Based on the dependence of the particle distributions on temperature in the two-temperature kinetic model, three temperature ranges, and the dominant particles and reactions in the respective ranges, are determined. The full model is then simplified into three models and the accuracy of the simplified models is assessed. The simplified models reduce the number of species and
A non-equilibrium model for soil heating and moisture transport during extreme surface heating
W. J. Massman
2015-03-01
Full Text Available 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
Equilibrium Modeling Study on Thermal Treatment of POPs%热处理POPs的化学平衡计算
田君国; 王贵全; 邓晶; 徐永香; 盛宏至; 蔡伶俐
2013-01-01
为利用等离子体处理持续有机污染物POPs，需要根据某些已有的POPs数据判断其对于各类POPs的销毁能力。基于 Gibbs 自由能最小原理和能量守恒原理建立了平衡计算模型，并与实验结果进行对照。结果表明，模型在给定有机废物组分和产物温度的情况下与实验结果符合较好。利用该模型模拟了加水量对等离子体温度区域范围内处理数种 POPs 的平衡产物，以及不同温度下的摧毁率。该方法可用于预测采用等离子体技术处理各种 POPs 的摧毁效果。%In order to estimate the destruction efficiency for many sorts of POPs (the persistent organic pollutants) based upon the experimental data from several sorts of POPs destructed by plasma technology, this paper sets up an equilibrium model for predicting the reaction product distribution of organic wastes of given constituents under given reaction temperature. The model is based on Gibbs free energy principle and energy conservation, and agrees with experimental data very well. The results show that this model can be applied to predict the reaction products and de-struction efficiency for many sorts of POPs under different reaction temperatures, even under arc plasma temperature, and with water added.
Glowacki, David R; Harvey, Jeremy N
2014-01-01
We describe a parallel linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM. Forces are obtained using the Hellman-Feynmann relationship, giving continuous gradients, and excellent energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to CCSD(T)-F12 electronic structure theory, we built a 64-state MS-EVB model designed to study the F + CD3CN -> DF + CD2CN reaction in CD3CN solvent. This approach allows us to build a reactive potential energy surface (PES) whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We use our PES to run MD simulations, and examine a range of transient observables which follow in the wake of reaction, including transient spectra of the DF vibrational band, time dependent profiles of vibrationally excited DF in CD3CN solvent, and relaxation rates for energy flow from DF into the solvent, all of which agree well with experime...
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.
A Heterogeneous Out-of-Equilibrium Nonlinear $q$-Voter Model with Zealotry
Mellor, Andrew; Zia, R K P
2016-01-01
We study the dynamics of the out-of-equilibrium nonlinear q-voter model with two types of susceptible voters and zealots, introduced in [EPL 113, 48001 (2016)]. In this model, each individual supports one of two parties and is either a susceptible voter of type $q_1$ or $q_2$, or is an inflexible zealot. At each time step, a $q_i$-susceptible voter ($i = 1,2$) consults a group of $q_i$ neighbors and adopts their opinion if all group members agree, while zealots are inflexible and never change their opinion. This model violates detailed balance whenever $q_1 \
Modeling of gamma/gamma-prime phase equilibrium in the nickel-aluminum system
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.
Investigation and Modelling of Diesel Hydrotreating Reactions
Boesen, Rasmus Risum
This project consists of a series of studies, that are related to hydrotreating of diesel. Hy- drotreating is an important refinery process, in which the oil stream is upgraded to meet the required environmental specifications and physical properties. Although hydrotreating is a ma- ture technology...... on a commercial CoMo catalyst, and a simple kinetic model is presented. Hydrogenation of fused aromatic rings are known to be fast, and it is possible, that the reaction rates are limited by either internal or external mass transfer. An experiment conducted at industrial temperatures and pressure, using...... kinetic models. Hydrogenation reactions are quite fast, and in order to avoid mass transfer limitations, and only measure intrinsic rates, experiments are often conducted, at conditions that are milder than in industrial units. A reactor model for a Robinson-Mahoney reactor that takes mass transfer...
Cratering saturation and equilibrium: A new model looks at an old problem
Richardson, James E.
2009-12-01
Recent advances in computing technology and our understanding of the processes involved in crater production, ejecta production, and crater erasure have permitted me to develop a highly-detailed Cratered Terrain Evolution Model (CTEM), which can be used to investigate a variety of questions in the study of impact dominated landscapes. In this work, I focus on the manner in which crater densities on impacted surfaces attain equilibrium conditions (commonly called crater 'saturation') for a variety of impactor population size-frequency distributions: from simple, straight-line power-laws, to complex, multi-sloped distributions. This modeling shows that crater density equilibrium generally occurs near observed relative-density ( R) values of 0.1-0.3 (commonly called 'empirical saturation'), but that when the impactor population has a variable power-law slope, crater density equilibrium values will also be variable, and will continue to reflect, or follow the shape of the production population long after the surface has been 'saturated.' In particular, I demonstrate that the overall level of crater density curves for heavily-cratered regions of the lunar surface are indicative of crater density equilibrium having been reached, while the shape of these curves strongly point to a Main Asteroid Belt (MAB) source for impactors in the near-Earth environment, as originally stipulated in Strom et al. [Strom, R.G., Malhotra, R., Ito, T., Yoshida, F., Kring, D.A., 2005. Science 309 (September), 1847-1850]. This modeling also validates the conclusion by Bottke et al. [Bottke, W.F., Durda, D.D., Nesvorný, D., Jedicke, R., Morbidelli, A., Vokrouhlický, D., Levison, H., 2005. Icarus 175 (May), 111-140] that the modern-day MAB continues to reflect its ancient size-frequency distribution, even though severely depleted in mass since that time.
Montazerolghaem, Maryam; Rahimi, Amir; Seyedeyn-Azad, Fakhry
2010-11-01
In this research, the adsorption of a model sulfur compound, thiophene, from a simulated gasoline onto Ce-Y zeolite in pellet and powder forms was investigated. For this purpose, zeolite Na-Y was synthesized, and Ce-Y zeolite was prepared via solid-state ion-exchanged (SSIE) method. Adsorptive desulfurization of model gasoline was conducted in a batch reactor at ambient conditions to evaluate the equilibrium and kinetics of thiophene adsorption onto Ce-Y zeolite. The equilibrium data were fitted to Langmuire and Toth models. Pseudo-n-order and modified n-order models, LDF-base model, and intra-particle diffusion model were evaluated to fit the kinetic of the adsorption process and to determine the mechanism of it. The corresponding parameters and/or correlation coefficients of each model were reported. The LDF-base model was used also to fit the mass transfer coefficient for both powder and pellet forms of the adsorbent. The best fit estimates for the mass transfer coefficient were obtained 4 × 10-11 m/s and k = 3.1 × 10-12[exp( - t/τ) + 1/(t + 10-4)], for powder and pellet form adsorbents, respectively.
Ohara, N.; Johnson, R. J.
2015-12-01
The inland glacier retreat has often been considered as one of clearest evidences of the global warming last several decades. However, when we try to model the evolution of the inland inter-annual snow storage including glaciers using a standard energy and mass balance snow model, it is impossible to keep the snow storage constant under a constant climate condition. This study treats the inland glaciers as a dynamic equilibrium system that remains constant under static climate condition. We introduced a sub-grid scale parameterization that moves snow/ice from high elevation areas to valleys as the equilibrating factor of the system. This movement of snow/ice occurs by means of wind re-distribution, avalanches, and glaciation. The physically-based model of a dynamic equilibrium snow system at a regional scale was applied to the entire state of Wyoming for long-term simulation. The developed snow model, named RegSnow model, was coupled with the Weather Research and Forecasting (WRF) model to estimate the snow surface energy fluxes during the 33-year-long historical period for transient model calibration. The RegSnow model predicted that 82.2% of interannual snow and ice storage in Wyoming may disappear by 2100 under the RCP4.5 emission scenario based on the climate projection by CMIP5 GCMs.
Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido
2011-01-28
Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF) of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker-Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM) or fluorescence-correlation spectroscopy (FCS) to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates.
Gaikwad, Vaibhav [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Kennedy, Eric, E-mail: Eric.Kennedy@newcastle.edu.au [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Mackie, John [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Holdsworth, Clovia [Centre for Organic Electronics, Chemistry Building, School of Environmental and Life Sciences, University of Newcastle, Callaghan, NSW 2308 (Australia); Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Dlugogorski, Bogdan [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia)
2014-09-15
Highlights: • CCl{sub 4} remediation using non-equilibrium plasma and non-oxidative conditions is proposed. • The reaction mechanism relies on experimental data and quantum chemical analysis. • Comprehensive mass balance for the reaction is provided. • CCl{sub 4} is converted to an environmentally benign and potentially useful polymer. • Characterisation of the polymer structure based on NMR and FTIR analyses is presented. - Abstract: In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.
A simple model for lamellar peritectic coupled growth with peritectic reaction
2007-01-01
The lamellar peritectic coupled growth in Fe-Ni peritectic system was investigated using the equilibrium Boettinger-Jackson-Hunt model.It was found that the slope of the undercooling vs.lamellar spacing is very near zero around the minimum overheating,and the coupled growth can exist under this condition even if the slope of the undercooling vs.lamellar spacing curve is slightly smaller than zero.In addition,the peritectic reaction can never reach completion during the peritectic coupled growth.So the equilibrium peritectic coupled growth was modified by considering the incompletion of the peritectic reaction.It was shown that when the fractions of the peritectic reaction reach 60%-80% completion,the calculated undercooling vs.lamellar spacing curves agree well with the experimental obser-vations in the directionally solidified Fe-Ni alloys.
Non-equilibrium model of two-phase porous media flow with phase change
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.
Plutonium and Minor Actinides Recycling in Standard BWR using Equilibrium Burnup Model
Abdul Waris
2008-03-01
Full Text Available Plutonium (Pu and minor actinides (MA recycling in standard BWR with equilibrium burnup model has been studied. We considered the equilibrium burnup model as a simple time independent burnup method, which can manage all possible produced nuclides in any nuclear system. The equilibrium burnup code was bundled with a SRAC cell-calculation code to become a coupled cell-burnup calculation code system. The results show that the uranium enrichment for the criticality of the reactor, the amount of loaded fuel and the required natural uranium supply per year decrease for the Pu recycling and even much lower for the Pu & MA recycling case compared to those of the standard once-through BWR case. The neutron spectra become harder with the increasing number of recycled heavy nuclides in the reactor core. The total fissile rises from 4.77% of the total nuclides number density in the reactor core for the standard once-through BWR case to 6.64% and 6.72% for the Plutonium recycling case and the Pu & MA recycling case, respectively. The two later data may become the main basis why the required uranium enrichment declines and consequently diminishes the annual loaded fuel and the required natural uranium supply. All these facts demonstrate the advantage of plutonium and minor actinides recycling in BWR.
Non-equilibrium steady states in two-temperature Ising models with Kawasaki dynamics
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
Corner wetting in a far-from-equilibrium magnetic growth model
Manías, V.; Candia, J.; Albano, E. V.
2005-10-01
The irreversible growth of magnetic films is studied in three-dimensional confined geometries of size L×L×M, where M≫L is the growing direction. Competing surface magnetic fields, applied to opposite corners of the growing system, lead to the observation of a localization-delocalization (weakly rounded) transition of the interface between domains of up and down spins on the planes transverse to the growing direction. This effective transition is the precursor of a true far-from-equilibrium corner wetting transition that takes place in the thermodynamic limit. The phenomenon is characterized quantitatively by drawing a magnetic field-temperature phase diagram, firstly for a confined sample of finite size, and then by extrapolating results, obtained with samples of different size, to the thermodynamic limit. The results of this work are a nonequilibrium realization of analogous phenomena recently investigated in equilibrium systems, such as corner wetting transitions in the Ising model.
Equilibrium Solubility of CO2 in Alkanolamines
Waseem Arshad, Muhammad; Fosbøl, Philip Loldrup; von Solms, Nicolas
2014-01-01
Equilibrium solubility of CO2 were measured in aqueous solutions of Monoethanolamine (MEA) and N,N-diethylethanolamine(DEEA). Equilibrium cells are generally used for these measurements. In this study, the equilibrium data were measured from the calorimetry. For this purpose a reaction calorimeter...... (model CPA 122 from ChemiSens AB, Sweden) was used. The advantage of this method is being the measurement of both heats of absorption and equilibrium solubility data of CO2 at the same time. The measurements were performed for 30 mass % MEA and 5M DEEA solutions as a function of CO2 loading at three...... different temperatures 40, 80 and 120 ºC. The measured 30 mass % MEA and 5M DEEA data were compared with the literature data obtained from different equilibrium cells which validated the use of calorimeters for equilibrium solubility measurements....
Application of dynamic stochastic general equilibrium models to the case of the Serbian economy
Urošević Branko
2014-01-01
Full Text Available This paper proposes a dynamic stochastic general equilibrium (DSGE model for the Serbian economy. It is a modification of the existing models of Goodhart, Osorio and Tsomocos (2009 and Martinez and Tsomocos (2012. The model introduces important features of the Serbian economy, financial dollarization and foreign ownership of the banking system, while retaining the most important element of the reference models, financial friction. To solve the model we use Dynare, a specialized Matlab program for solving DSGE models. The model is subject to three different shocks: monetary, productivity, and regulatory, and the results are presented in the form of impulse response functions. It is concluded that the proposed platform has good characteristics, but its complete application to the case of the Serbian economy requires further research. [Projekat Ministarstva nauke Republike Srbije, br. 179005
Vellela, Melissa; Qian, Hong
2009-10-06
Schlögl's model is the canonical example of a chemical reaction system that exhibits bistability. Because the biological examples of bistability and switching behaviour are increasingly numerous, this paper presents an integrated deterministic, stochastic and thermodynamic analysis of the model. After a brief review of the deterministic and stochastic modelling frameworks, the concepts of chemical and mathematical detailed balances are discussed and non-equilibrium conditions are shown to be necessary for bistability. Thermodynamic quantities such as the flux, chemical potential and entropy production rate are defined and compared across the two models. In the bistable region, the stochastic model exhibits an exchange of the global stability between the two stable states under changes in the pump parameters and volume size. The stochastic entropy production rate shows a sharp transition that mirrors this exchange. A new hybrid model that includes continuous diffusion and discrete jumps is suggested to deal with the multiscale dynamics of the bistable system. Accurate approximations of the exponentially small eigenvalue associated with the time scale of this switching and the full time-dependent solution are calculated using Matlab. A breakdown of previously known asymptotic approximations on small volume scales is observed through comparison with these and Monte Carlo results. Finally, in the appendix section is an illustration of how the diffusion approximation of the chemical master equation can fail to represent correctly the mesoscopically interesting steady-state behaviour of the system.
Modeling the Reactions of Energetic Materials in the Condensed Phase
Fried, L E; Manaa, M R; Lewis, J P
2003-12-03
High explosive (HE) materials are unique for having a strong exothermic reactivity, which has made them desirable for both military and commercial applications. Although the history of HE materials is long, condensed-phase properties are poorly understood. Understanding the condensed-phase properties of HE materials is important for determining stability and performance. Information regarding HE material properties (for example, the physical, chemical, and mechanical behaviors of the constituents in plastic-bonded explosive, or PBX, formulations) is necessary in efficiently building the next generation of explosives as the quest for more powerful energetic materials (in terms of energy per volume) moves forward. In addition, understanding the reaction mechanisms has important ramifications in disposing of such materials safely and cheaply, as there exist vast stockpiles of HE materials with corresponding contamination of earth and groundwater at these sites, as well as a military testing sites The ability to model chemical reaction processes in condensed phase energetic materials is rapidly progressing. Chemical equilibrium modeling is a mature technique with some limitations. Progress in this area continues, but is hampered by a lack of knowledge of condensed phase reaction mechanisms and rates. Atomistic modeling is much more computationally intensive, and is currently limited to very short time scales. Nonetheless, this methodology promises to yield the first reliable insights into the condensed phase processes responsible for high explosive detonation. Further work is necessary to extend the timescales involved in atomistic simulations. Recent work in implementing thermostat methods appropriate to shocks may promise to overcome some of these difficulties. Most current work on energetic material reactivity assumes that electronically adiabatic processes dominate. The role of excited states is becoming clearer, however. These states are not accessible in perfect
Achim Ionita
2009-01-01
Full Text Available The oscillation susceptibility of the ADMIRE aircraft along the path of longitudinal flight equilibriums is analyzed numerically in the general and in a simplified flight model. More precisely, the longitudinal flight equilibriums, the stability of these equilibriums, and the existence of bifurcations along the path of these equilibriums are researched in both models. Maneuvers and appropriate piloting tasks for the touch-down moment are simulated in both models. The computed results obtained in the models are compared in order to see if the movement concerning the landing phase computed in the simplified model is similar to that computed in the general model. The similarity we find is not a proof of the structural stability of the simplified system, what as far we know never been made, but can increase the confidence that the simplified system correctly describes the real phenomenon.
General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures
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
An equilibrium model for the coupled ocean-atmosphere boundary layer in the tropics
Sui, C.-H.; Lau, K.-M.; Betts, Alan K.
A coupled model is used to study the equilibrium state of the ocean-atmosphere boundary layer in the tropics. The atmospheric model is a one-dimensional thermodynamic model for a partially mixed, partly cloudy convective boundary layer (CBL), including the effects of cloud-top subsidence, surface momentum and heat (latent and sensible) fluxes, and realistic radiative transfer for both shortwaves and longwaves (Betts and Ridgway, 1988; 1989). The oceanic model is a thermodynamic model for a well-mixed layer, with a closure constraint based on a one-dimensional turbulent kinetic energy (TKE) equation following Kraus and Turner (1967). Results of several sets of experiments are reported in this paper. In the first two sets of experiments, with sea surface temperature (SST) specified, we solve the equilibrium state of the coupled system as a function of SST for a given surface wind (case 1) and as a function of surface wind for a given SST (case 2). In both cases the depth of the CBL and the ocean mixed layer (OML) increases and the upwelling below the OML decreases, corresponding to either increasing SST or increasing surface wind. The deepening of the equilibrium CBL is primarily linked to the increase of CBL moisture with increasing SST and surface wind. The increase of OML depth and decrease of upwelling are due to a decrease of net downward heat flux with increasing SST and the generation of TKE by increasing wind. In another two sets of experiments, we solve for the coupled ocean-atmosphere model iteratively as a function of surface wind for a fixed upwelling (case 3) and a fixed OML depth (case 4). SST falls with increasing wind in both cases, but the fall is steeper in case 4, because the OML depth is fixed, whereas in case 3 the depth is allowed to deepen and the cooling is spread over a larger mass of water. The decrease of evaporation with increasing wind in case 4 leads to a very dry and shallow CBL. Results of further experiments with surface wind and SST
A numerical code for a three-dimensional magnetospheric MHD equilibrium model
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.
Non-existence of Steady State Equilibrium in the Neoclassical Growth Model with a Longevity Trend
Hermansen, Mikkel Nørlem
of steady state equilibrium when considering the empirically observed trend in longevity. We extend a standard continuous time overlapping generations model by a longevity trend and are thereby able to study the properties of mortality-driven population growth. This turns out to be exceedingly complicated......Longevity has been increasing in the developed countries for almost two centuries and further increases are expected in the future. In the neoclassical growth models the case of population growth driven by fertility is well-known, whereas the properties of population growth caused by persistently...
Awan, Javeed; Thomsen, Kaj; Coquelet, Christophe
2010-01-01
In this work, vapor−liquid equilibrium (VLE) measurements of propyl mercaptan (PM) in pure water were performed at three different temperatures, (303, 323, and 365) K, with a pressure variation from (1 to 8) MPa. The total system pressure was maintained by CH4. The inlet mole fraction of propyl...... mercaptan in all experiments was the same, around 4.5·10−4 in the liquid phase. The objective was to provide experimental VLE data points of the propyl mercaptan + methane + water system for modeling since there is a lack of available data. These data will allow the industrial modeling of sulfur emission...
Majda, Andrew J; Gershgorin, Boris
2011-08-02
Understanding and improving the predictive skill of imperfect models for complex systems in their response to external forcing is a crucial issue in diverse applications such as for example climate change science. Equilibrium statistical fidelity of the imperfect model on suitable coarse-grained variables is a necessary but not sufficient condition for this predictive skill, and elementary examples are given here demonstrating this. Here, with equilibrium statistical fidelity of the imperfect model, a direct link is developed between the predictive fidelity of specific test problems in the training phase where the perfect natural system is observed and the predictive skill for the forced response of the imperfect model by combining appropriate concepts from information theory with other concepts based on the fluctuation dissipation theorem. Here a suite of mathematically tractable models with nontrivial eddy diffusivity, variance, and intermittent non-Gaussian statistics mimicking crucial features of atmospheric tracers together with stochastically forced standard eddy diffusivity approximation with model error are utilized to illustrate this link.
Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang
2016-08-01
Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition) at the atmosphere-soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.
Kim, Ki Chul; Kulkarni, Anant D; Johnson, J Karl; Sholl, David S
2011-04-21
Systematic thermodynamics calculations based on density functional theory-calculated energies for crystalline solids have been a useful complement to experimental studies of hydrogen storage in metal hydrides. We report the most comprehensive set of thermodynamics calculations for mixtures of light metal hydrides to date by performing grand canonical linear programming screening on a database of 359 compounds, including 147 compounds not previously examined by us. This database is used to categorize the reaction thermodynamics of all mixtures containing any four non-H elements among Al, B, C, Ca, K, Li, Mg, N, Na, Sc, Si, Ti, and V. Reactions are categorized according to the amount of H(2) that is released and the reaction's enthalpy. This approach identifies 74 distinct single step reactions having that a storage capacity >6 wt.% and zero temperature heats of reaction 15 ≤ΔU(0)≤ 75 kJ mol(-1) H(2). Many of these reactions, however, are likely to be problematic experimentally because of the role of refractory compounds, B(12)H(12)-containing compounds, or carbon. The single most promising reaction identified in this way involves LiNH(2)/LiH/KBH(4), storing 7.48 wt.% H(2) and having ΔU(0) = 43.6 kJ mol(-1) H(2). We also examined the complete range of reaction mixtures to identify multi-step reactions with useful properties; this yielded 23 multi-step reactions of potential interest.
Monte Carlo modeling of Lead-Cooled Fast Reactor in adiabatic equilibrium state
Stanisz, Przemysław, E-mail: pstanisz@agh.edu.pl; Oettingen, Mikołaj, E-mail: moettin@agh.edu.pl; Cetnar, Jerzy, E-mail: cetnar@mail.ftj.agh.edu.pl
2016-05-15
Graphical abstract: - Highlights: • We present the Monte Carlo modeling of the LFR in the adiabatic equilibrium state. • We assess the adiabatic equilibrium fuel composition using the MCB code. • We define the self-adjusting process of breeding gain by the control rod operation. • The designed LFR can work in the adiabatic cycle with zero fuel breeding. - Abstract: Nuclear power would appear to be the only energy source able to satisfy the global energy demand while also achieving a significant reduction of greenhouse gas emissions. Moreover, it can provide a stable and secure source of electricity, and plays an important role in many European countries. However, nuclear power generation from its birth has been doomed by the legacy of radioactive nuclear waste. In addition, the looming decrease in the available resources of fissile U235 may influence the future sustainability of nuclear energy. The integrated solution to both problems is not trivial, and postulates the introduction of a closed-fuel cycle strategy based on breeder reactors. The perfect choice of a novel reactor system fulfilling both requirements is the Lead-Cooled Fast Reactor operating in the adiabatic equilibrium state. In such a state, the reactor converts depleted or natural uranium into plutonium while consuming any self-generated minor actinides and transferring only fission products as waste. We present the preliminary design of a Lead-Cooled Fast Reactor operating in the adiabatic equilibrium state with the Monte Carlo Continuous Energy Burnup Code – MCB. As a reference reactor model we apply the core design developed initially under the framework of the European Lead-cooled SYstem (ELSY) project and refined in the follow-up Lead-cooled European Advanced DEmonstration Reactor (LEADER) project. The major objective of the study is to show to what extent the constraints of the adiabatic cycle are maintained and to indicate the phase space for further improvements. The analysis
Cap-and-Trade Modeling and Analysis: Congested Electricity Market Equilibrium
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
General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures
Liu, Yen, E-mail: yen.liu@nasa.gov; Vinokur, Marcel [NASA Ames Research Center, Moffett Field, California 94035 (United States); Panesi, Marco; Sahai, Amal [University of Illinois, Urbana-Champaign, Illinois 61801 (United States)
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
A tightly coupled non-equilibrium model for inductively coupled radio-frequency plasmas
Munafò, A., E-mail: munafo@illinois.edu; Alfuhaid, S. A., E-mail: alfuhai2@illinois.edu; Panesi, M., E-mail: mpanesi@illinois.edu [Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, Talbot Laboratory, 104 S. Wright St., Urbana, Illinois 61801 (United States); Cambier, J.-L., E-mail: jean-luc.cambier@us.af.mil [Edwards Air Force Base Research Laboratory, 10 E. Saturn Blvd., Edwards AFB, California 93524 (United States)
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.
Fernandez-Lafuente, R; Rosell, C M; Guisan, J M
1996-10-01
Parameters relevant to the thermodynamically controlled synthesis of cephalothin utilizing highly active stabilized penicillin G acylase derivatives were studied. These included solubility/stability of substrates, enzyme derivative activity/stability, reaction course and synthetic yields. These parameters were altered by varying the pH, dimethylformamide concentration and temperature. Simultaneous optimization of the selected parameters could not be achieved with a single set of conditions. However, continuous adjustment of conditions throughout the reaction course allowed each parameter to be optimized (dynamic reaction design). This strategy works by optimizing those parameters that are critical to the overall reaction at a given point, whilst leaving others sub-optimal when their contribution to the total is minimal. This strategy has achieved a 90% transformation of antibiotic nucleus to cephalothin at a final concentration of 20 g/l, high enzyme and reactant stability, with a reaction period of 3 h (using 1 ml of derivative/40 ml of reaction solution).
LIN Yangzheng; LI Jiding; ZENG Chuyi; CHEN Cuixian
2005-01-01
The LIQUAC model is often used to predict vapor-liquid equilibria, osmotic coefficients, and mean ion activity coefficients for electrolyte systems. This paper describes a thermodynamic method to analyze solid-liquid equilibrium for electrolytes in mixed solvents solutions using the LIQUAC model. The KCl solubilities in mixed water-ethanol solutions are predicted with the LIQUAC model and its original interaction parameters. This method is also used to obtain new K+-ethanol interaction parameters in the LIQUAC model from the solubility data. The new interaction parameters accurately predict the vapor-liquid equilibrium data of K+ salts (including KCl, KBr, and KCOOCH3) in mixed water-ethanol solutions. The results illustrate the flexibility of the LIQUAC model which can predict not only vapor-liquid equilibrium but also solid-liquid equilibrium in mixed solvent systems.
Chau, Nancy H.
2009-01-01
This paper presents a capability-augmented model of on the job search, in which sweatshop conditions stifle the capability of the working poor to search for a job while on the job. The augmented setting unveils a sweatshop equilibrium in an otherwise archetypal Burdett-Mortensen economy, and reconciles a number of oft noted yet perplexing features of sweatshop economies. We demonstrate existence of multiple rational expectation equilibria, graduation pathways out of sweatshops in complete abs...
El-Khamsa Guechi
2016-09-01
Full Text Available Potato peel (PP was used as a biosorbent to remove malachite green (MG from aqueous solution under various operating conditions. The effect of the experimental parameters such as initial dye concentration, biosorbent dose, initial pH, stirring speed, temperature, ionic strength and biosorbent particle size was investigated through a number of batch sorption experiments. The sorption kinetic uptake for MG by PP at various initial dye concentrations was analyzed by non-linear method using pseudo-first, pseudo-second and pseudo-nth order models. It was found that the pseudo-nth order kinetic model was the best applicable model to describe the sorption kinetic data and the order n of sorption reaction was calculated in the range from 0.71 to 2.71. Three sorption isotherms namely the Langmuir, Freundlich and Redlich–Peterson isotherms in their non-linear forms were applied to the biosorption equilibrium data. Both the Langmuir and Redlich–Peterson models were found to fit the sorption isotherm data well, but the Redlich–Peterson model was better. Thermodynamic parameters show that the sorption process of MG is endothermic and more effective process at high temperatures. The results revealed that PP is very effective for the biosorption of MG from aqueous solutions.
Global asymptotic stability of positive equilibrium in a 3-species cooperating model with time delay
WANG Chang-you
2007-01-01
The asymptotic behavior of the time-dependent solution for a 3-species cooperating model was investigated with the effects of both diffusion and time delay taken into consideration. We proved the global asymptotic stability of a positive steady-state solution to the model problem by using coupled upper and lower solutions for a more general reaction-diffusion system that gives a common framework for 3-species cooperating model problems. The result of global asymptotic stability implies that the model system coexistence is permanent. Some global asymptotic stability results for 2-species cooperating reaction-diffusion systems are included in the discussion, and some known results are extended.
Nakai, Yoichi; Hidaka, Hiroshi; Watanabe, Naoki; Kojima, Takao M.
2016-06-01
We measured equilibrium constants for H3O+(H2O)n-1 + H2O↔H3O+(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, Δ Hn , n - 1 0 and Δ Sn , n - 1 0 , of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O+(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy.
Nakai, Yoichi; Hidaka, Hiroshi; Watanabe, Naoki; Kojima, Takao M
2016-06-14
We measured equilibrium constants for H3O(+)(H2O)n-1 + H2O↔H3O(+)(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, ΔHn,n-1 (0) and ΔSn,n-1 (0), of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O(+)(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy.
Imler, Gregory H; Zdilla, Michael J; Wayland, Bradford B
2014-04-23
A rhodium(II) dibenzotetramethylaza[14]annulene dimer ([(tmtaa)Rh]2) (1) reacts with CO and H2 in toluene and pyridine to form equilibrium distributions with hydride and formyl complexes ((tmtaa)Rh-H (2); (tmtaa)Rh-C(O)H (3)). The rhodium formyl complex ((tmtaa)Rh-C(O)H) was isolated under a CO/H2 atmosphere, and the molecular structure was determined by X-ray diffraction. Equilibrium constants were evaluated for reactions of (tmtaa)Rh-H with CO to produce formyl complexes in toluene (K2(298 K)(tol) = 10.8 (1.0) × 10(3)) and pyridine (K2(298 K)(py) = 2.2 (0.2) × 10(3)). Reactions of 1 and 2 in toluene and pyridine are discussed in the context of alternative radical and ionic pathways. The five-coordinate 18-electron Rh(I) complex ([(py)(tmtaa)Rh(I)](-)) is proposed to function as a nucleophile toward CO to give a two-electron activated bent Rh-CO unit. Results from DFT calculations on the (tmtaa)Rh system correlate well with experimental observations. Reactions of 1 with CO and H2 suggest metal catalyst design features to reduce the activation barriers for homogeneous CO hydrogenation.
Meso-scale modeling: beyond local equilibrium assumption for multiphase flow
Wang, Wei
2015-01-01
This is a summary of the article with the same title, accepted for publication in Advances in Chemical Engineering, 47: 193-277 (2015). Gas-solid fluidization is a typical nonlinear nonequilibrium system with multiscale structure. In particular, the mesoscale structure in terms of bubbles or clusters, which can be characterized by nonequilibrium features in terms of bimodal velocity distribution, energy non equipartition, and correlated density fluctuations, is the critical factor. Traditional two-fluid model (TFM) and relevant closures depend on local equilibrium and homogeneous distribution assumptions, and fail to predict the dynamic, nonequilibrium phenomena in circulating fluidized beds even with fine-grid resolution. In contrast, the mesoscale modeling, as exemplified by the energy-minimization multiscale (EMMS) model, is consistent with the nonequilibrium features in multiphase flows. Thus, the structure-dependent multi-fluid model conservation equations with the EMMS-based mesoscale modeling greatly i...
Reaction-contingency based bipartite Boolean modelling
2013-01-01
Background Intracellular signalling systems are highly complex, rendering mathematical modelling of large signalling networks infeasible or impractical. Boolean modelling provides one feasible approach to whole-network modelling, but at the cost of dequantification and decontextualisation of activation. That is, these models cannot distinguish between different downstream roles played by the same component activated in different contexts. Results Here, we address this with a bipartite Boolean modelling approach. Briefly, we use a state oriented approach with separate update rules based on reactions and contingencies. This approach retains contextual activation information and distinguishes distinct signals passing through a single component. Furthermore, we integrate this approach in the rxncon framework to support automatic model generation and iterative model definition and validation. We benchmark this method with the previously mapped MAP kinase network in yeast, showing that minor adjustments suffice to produce a functional network description. Conclusions Taken together, we (i) present a bipartite Boolean modelling approach that retains contextual activation information, (ii) provide software support for automatic model generation, visualisation and simulation, and (iii) demonstrate its use for iterative model generation and validation. PMID:23835289
Shuva, M. A. H.; Rhamdhani, M. A.; Brooks, G. A.; Masood, S.; Reuter, M. A.
2016-10-01
The distribution ratio of germanium (Ge), L_{{Ge}}^{s/m} during equilibrium reactions between magnesia-saturated FeOx-CaO-SiO2 (FCS) slag and molten copper has been measured under oxygen partial pressures from 10-10 to 10-7 atm and at temperatures 1473 to 1623 K (1200 to 1350 °C). It was observed that the Ge distribution ratio increases with increasing oxygen partial pressure, and with decreasing temperature. It was also observed that the distribution ratio is strongly dependent on slag basicity. The distribution ratio was observed to increase with increasing optical basicity. At fixed CaO concentration in the slag, the distribution ratio was found to increase with increasing Fe/SiO2 ratio, tending to a plateau at L_{{Ge}}^{s/m} = 0.8. This behavior is consistent with the assessment of ionic bond fraction carried out in this study, and suggested the acidic nature of germanium oxide (GeO2) in the slag system studied. The characterisation results of the quenched slag suggested that Ge is present in the FeOx-CaO-SiO2-MgO slag predominantly as GeO2. At 1573 K (1300 °C) and p_{{{{O}}2 }} = 10-8 atm, the activity coefficient of GeO2 in the slag was calculated to be in the range of 0.24 to 1.50. The results from the current study suggested that less-basic slag, high operating temperature, and low oxygen partial pressure promote a low Ge distribution ratio. These conditions are desired for maximizing Ge recovery, for example, during pyrometallurgical processing of Ge-containing e-waste through secondary copper smelting. Overall, the thermodynamics data generated from this study can be used for process modeling purposes for improving recovery of Ge in primary and secondary copper smelting processes.
Microscopic Simulation and Macroscopic Modeling for Thermal and Chemical Non-Equilibrium
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.
A non-equilibrium picture of the chemical freeze-out in hadronic thermal models
De Assis, Leonardo P G; Chiapparini, Marcelo; Hirsch, Luciana R; Delfino, Antonio
2012-01-01
Thermal models have proven to be an useful and simple tool used to make theoretical predictions and data analysis in relativistic and ultra-relativistic heavy ion collisions. A new version of these models is presented here, incorporating a non equilibrium feature to the description of the intermediate fireball state formed at the chemical freeze-out. Two different effective temperatures are attributed to the expanding fireball, regarding its baryonic and mesonic sectors. The proposal is not merely to include an additional degree of freedom to reach a better adjustment to the data, but to open a room in the model conception for considerations on the non-equilibrium scenario of the system evolution. A set of well consolidated data for particles production is used to validated the reformulated version of thermal models presented here. A rather good performance of the extended version was verified, both for the quality of particle ratio data fittings as well as for describing the asymptotic energy behavior of tem...
Bichan, N. G.; Ovchenkova, E. N.; Mozhzhukhina, E. G.; Lomova, T. N.
2017-07-01
The results from thermodynamic and quantum-chemical studies of the reversible reaction between (5,10,15,20-tetra(2-methoxyphenyl)porphinato)chloroindium(III) and pyridine are reported. The main physicochemical parameters of properties of its supramolecular products are obtained and analyzed. The addition of pyridine molecules to metalloporphyrin proceeds in one step to attain an equilibrium state with the formation of supramolecules with a stoichiometry of 2: 1; spectral characteristics and parameters of the stability of the latter are identified. The possibility of using substituted indium(III)porphyrin for further research in the field of hybrid solar cells is discussed.
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.
A theoretical model of metal surface reactions
Shustorovich, E. (Eastman Kodak Co., Rochester, NY); Baetzold, R.C.; Muetterties, E.L.
1983-03-31
Metal surface reactions are modeled with a novel theoretical construct in which periodic trends can be scrutinized. The theoretical model is succinctly presented and a conspectus of periodic trends, based on the model, is explored. Periodic trends are discussed in the contexts of chemisorption bond energies, electron transfer between metal surface and adsorbate, stereochemical features of chemisorption states for closed-shell diatomic and linear X-CN or X-NC molecules, and hydrocarbon reactions. Hydrocarbon C-H bond-breaking processes are analyzed in terms of d-level occupancy, electron transfer, and stereochemistry of intermediates. Conceptually and computationally, the metal surface is characterized as a good electron donor: antibonding molecular orbitals of the adsorbate species appear to be significant contributors to the chemisorption bond and also play a decisive role in bond-breaking processes. No aspect of the model projections is inconsistent with the experimental data although the electronic characterization of some chemisorption states are counter to commonly held perceptions.
A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace
Kruskopf, Ari; Visuri, Ville-Valtteri
2017-08-01
In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.
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
Phase equilibrium of North Sea oils with polar chemicals: Experiments and CPA modeling
Frost, Michael Grynnerup; Kontogeorgis, Georgios M.; von Solms, Nicolas;
2016-01-01
This work consists of a combined experimental and modeling study for oil - MEG - water systems, of relevance to petroleum applications. We present new experimental liquid-liquid equilibrium data for the mutual solubility of two North Sea oils + MEG and North Sea oils + MEG + water systems...... in the temperature range 303.15-323.15 K and at atmospheric pressure. These new data are for North Sea oils which are substantially heavier and with higher aromatic/naphthenic content compared to previous studies. The new data compare favorably with previously reported measurements for other North Sea oils. The data...
Social security in a general equilibrium model with endogenous government behavior.
Drissen, E; Van Winden, F
1991-05-01
"In this paper attention is focused on the economic and political effects of an aging population. For that purpose, a general equilibrium model is used that allows for an endogenous analysis of decision making on government policies. We concentrate here on the effects of an aging population on expenditures and levels of social security benefits, the provision of public goods and services, the private output and intergenerational conflicts. Special attention will be paid to the effects of changes in the retirement age and in capital endowments. Furthermore, the effects of issues related to aging, as changes in the political influence structure and the motive of other-directedness by others, are investigated."
Equilibrium dynamics of the sub-Ohmic spin-boson model under bias
Zheng, Da-Chuan; Tong, Ning-Hua
2017-06-01
Using the bosonic numerical renormalization group method, we studied the equilibrium dynamical correlation function C(ω) of the spin operator σ z for the biased sub-Ohmic spin-boson model. The small-ω behavior C(ω )\\propto {ω }s is found to be universal and independent of the bias ɛ and the coupling strength α (except at the quantum critical point α ={α }{{c}} and ɛ = 0). Our NRG data also show C(ω )\\propto {χ }2{ω }s for a wide range of parameters, including the biased strong coupling regime (\\varepsilon \
Two-Temperature Model of non-equilibrium electron relaxation: A Review
Singh, Navinder
2007-01-01
The present paper is a review of the phenomena related to non-equilibrium electron relaxation in bulk and nano-scale metallic samples. The workable Two-Temperature Model (TTM) based on Boltzmann-Bloch-Peierls (BBP) kinetic equation has been applied to study the ultra-fast(femto-second) electronic relaxation in various metallic systems. The advent of new ultra-fast (femto-second) laser technology and pump-probe spectroscopy has produced wealth of new results for micro and nano-scale electronic...
Indra Maipita
2012-06-01
Full Text Available This study analyzes the impact of increased government spending on macroeconomic performance, using AGEFIS; a Computable General Equilibrium Model. Simulations carried out with the three scenarios in the sector Construction, Electricity, and Land Transportation. The simulation results shows that, in general, an increase in government spending have a positive impact on macroeconomic performance and increase household income. increase in government spending in the Construction sector provides better impact on increasing household income compared with other sectors, while in the electricity sector have no effect
Two-Temperature Model of non-equilibrium electron relaxation: A Review
Singh, Navinder
2007-01-01
The present paper is a review of the phenomena related to non-equilibrium electron relaxation in bulk and nano-scale metallic samples. The workable Two-Temperature Model (TTM) based on Boltzmann-Bloch-Peierls (BBP) kinetic equation has been applied to study the ultra-fast(femto-second) electronic relaxation in various metallic systems. The advent of new ultra-fast (femto-second) laser technology and pump-probe spectroscopy has produced wealth of new results for micro and nano-scale electronic...
Non-equilibrium modeling of the PMSE Overshoot Effect revisited: A comprehensive study
Biebricher, Alexander; Havnes, Ove
2012-06-01
Numerical investigations of the Polar Mesosphere Summer Echoes (PMSE) Overshoot Effect have to date been undertaken under the premise of plasma neutrality and current equilibrium at any time. We find it necessary to revisit the calculations without these restrictions, since electrons and ions are attached to and absorbed by mesospheric dust particles at vastly different rates under PMSE conditions. We find that differences to earlier modeling might be so significant as to warrant further investigation. Furthermore, we conduct comprehensive studies of the PMSE Overshoot Effect and put the results in the context of experimental realities.
A stochastic equilibrium model for the North American natural gas market
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
Regional disaster impact analysis: comparing input-output and computable general equilibrium models
Koks, Elco E.; Carrera, Lorenzo; Jonkeren, Olaf; Aerts, Jeroen C. J. H.; Husby, Trond G.; Thissen, Mark; Standardi, Gabriele; Mysiak, Jaroslav
2016-08-01
A variety of models have been applied 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 number of scholars have developed hybrid approaches: one that combines both or either of them in combination with noneconomic 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 born likely to vary with the chosen modelling approach (IO, CGE, or hybrid). Hence, regional disaster impact loss estimates resulting from a range of models facilitate better decisions and policy making. Therefore, this study analyses the economic consequences for a specific case study, using three regional disaster impact models: two hybrid IO models and a 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 7 between the three models, depending on the type of recovery path. Total economic impact, comprising all Italian regions, is negative in all models though.
Dondi, Daniele; Merli, Daniele; Albini, Angelo; Zeffiro, Alberto; Serpone, Nick
2012-05-01
When a chemical system is submitted to high energy sources (UV, ionizing radiation, plasma sparks, etc.), as is expected to be the case of prebiotic chemistry studies, a plethora of reactive intermediates could form. If oxygen is present in excess, carbon dioxide and water are the major products. More interesting is the case of reducing conditions where synthetic pathways are also possible. This article examines the theoretical modeling of such systems with random-generated chemical networks. Four types of random-generated chemical networks were considered that originated from a combination of two connection topologies (viz., Poisson and scale-free) with reversible and irreversible chemical reactions. The results were analyzed taking into account the number of the most abundant products required for reaching 50% of the total number of moles of compounds at equilibrium, as this may be related to an actual problem of complex mixture analysis. The model accounts for multi-component reaction systems with no a priori knowledge of reacting species and the intermediates involved if system components are sufficiently interconnected. The approach taken is relevant to an earlier study on reactions that may have occurred in prebiotic systems where only a few compounds were detected. A validation of the model was attained on the basis of results of UVC and radiolytic reactions of prebiotic mixtures of low molecular weight compounds likely present on the primeval Earth.
Dynamic behaviour of reactive distillation tray columns described with a non-equilibrium cell model
Baur, R.; Taylor, R.; Krishna, R.
2001-01-01
In this paper we develop a generic, dynamic, nonequilibrium (NEQ) cell model for reactive distillation (RD) tray columns. The features of our model are (1) the use of Maxwell–Stefan equations for describing mass transfer between fluid phases, (2) the reaction is assumed to take place in the liquid
Non equilibrium dynamics of mixing, oscillations, and equilibration: A model study
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.
Reaction-diffusion models of decontamination
Hjorth, Poul G.
A contaminant, which also contains a polymer is in the form of droplets on a solid surface. It is to be removed by the action of a decontaminant, which is applied in aqueous solution. The contaminant is only sparingly soluble in water, so the reaction mechanism is that it slowly dissolves...... in the aqueous solution and then is oxidized by the decontaminant. The polymer is insoluble in water, and so builds up near the interface, where its presence can impede the transport of contaminant. In these circumstances, Dstl wish to have mathematical models that give an understanding of the process, and can...
Gaikwad, Vaibhav; Kennedy, Eric; Mackie, John; Holdsworth, Clovia; Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael; Dlugogorski, Bogdan
2014-09-15
In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.
Zhimiao Tao
2013-01-01
Full Text Available An equilibrium chance-constrained multiobjective programming model with birandom parameters is proposed. A type of linear model is converted into its crisp equivalent model. Then a birandom simulation technique is developed to tackle the general birandom objective functions and birandom constraints. By embedding the birandom simulation technique, a modified genetic algorithm is designed to solve the equilibrium chance-constrained multiobjective programming model. We apply the proposed model and algorithm to a real-world inventory problem and show the effectiveness of the model and the solution method.
Hewitson, Peter; Sutherland, Ian; Kostanyan, Artak E; Voshkin, Andrei A; Ignatova, Svetlana
2013-08-16
This paper describes an equilibrium cell model for intermittent counter-current extraction that is analytically solved for the first time for continuous sample injection between a pair of columns. The model is compared with practice for injections of a model mixture of compounds on a standard high-performance counter-current chromatography instrument giving good agreement for compound elution order and the times to maximum concentration for the eluted components. An improved design of end fittings for the counter-current chromatography bobbins is described which permits on-column switching of the mobile and stationary phases. This on-column switching successfully eliminates the displaced stationary phase seen in fractions when operating ICcE with standard flying leads and gives a 6% reduction in the retention time of compounds and improved resolution due to the elimination of the time delay required to pump the previous mobile phase from standard flying leads.
Regime switches induced by supply-demand equilibrium: a model for power-price dynamics
Mari, Carlo; Tondini, Daniela
2010-11-01
Regime-switching models can be used to describe stochastic movements of electricity prices in deregulated markets. This paper shows that regime-switching dynamics arise quite naturally in an equilibrium context in which the functional form of the supply curve is described by a two-state Markov process. This mechanism is responsible for random switches between regimes and it allows one to describe the main features of the price-formation process. With the interplay between demand and supply, the proposed methodology can be used to capture shortages in electricity generation, forced outages, and peaks in electricity demand. As an example of application, a two-regime model specification is proposed, and it will be shown that the empirical analysis, performed by estimating using the model on the California power market, offers an interesting agreement with observed data.
Evolution and non-equilibrium physics: A study of the Tangled Nature Model
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.
Guitao Zhang
2014-01-01
Full Text Available The advertisement can increase the consumers demand; therefore it is one of the most important marketing strategies in the operations management of enterprises. This paper aims to analyze the impact of advertising investment on a discrete dynamic supply chain network which consists of suppliers, manufactures, retailers, and demand markets associated at different tiers under random demand. The impact of advertising investment will last several planning periods besides the current period due to delay effect. Based on noncooperative game theory, variational inequality, and Lagrange dual theory, the optimal economic behaviors of the suppliers, the manufactures, the retailers, and the consumers in the demand markets are modeled. In turn, the supply chain network equilibrium model is proposed and computed by modified project contraction algorithm with fixed step. The effectiveness of the model is illustrated by numerical examples, and managerial insights are obtained through the analysis of advertising investment in multiple periods and advertising delay effect among different periods.
Prediction of Liquid-Liquid Equilibrium Using the Group Solubility Parameter Model
ZHAO Mo; CHEN Fuming
2005-01-01
The group solubility parameter (GSP) model was used to analyze the liquid-liquid equilibrium (LLE) of ternary and quaternary systems. The GSP parameters are divided into four dimensions representing the four major intermolecular forces. The values of the parameters were determined by regression using the nonlinear SIMPLEX optimization method to fit the LLE data of 548 ternary and 26 quaternary systems selected from the literature. LLE predictions of 8 ternary systems were then made using the fit parameters. Comparison of the results with predictions using the modified UNIFAC model shows that the GSP model has less adjustable parameters to achieve a similar accuracy and that the parameter values are easily acquired by analysis of available data.
Systematic validation of non-equilibrium thermochemical models using Bayesian inference
Miki, Kenji
2015-10-01
© 2015 Elsevier Inc. 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.
Systematic validation of non-equilibrium thermochemical models using Bayesian inference
Miki, Kenji [NASA Glenn Research Center, OAI, 22800 Cedar Point Rd, Cleveland, OH 44142 (United States); Panesi, Marco, E-mail: mpanesi@illinois.edu [Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, 306 Talbot Lab, 104 S. Wright St., Urbana, IL 61801 (United States); Prudhomme, Serge [Département de mathématiques et de génie industriel, Ecole Polytechnique de Montréal, C.P. 6079, succ. Centre-ville, Montréal, QC, H3C 3A7 (Canada)
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.
Jasperson, Louis V.; McDougal, Rubin J.; Diky, Vladimir; Paulechka, Eugene; Chirico, Robert D.; Kroenlein, Kenneth; Iisa, Kristiina; Dutta, Abhijit
2017-01-12
We report liquid-liquid mutual solubilities for binary aqueous mixtures involving 2-, 3-, and 4-ethylphenol, 2-, 3-, and 4-methoxyphenol, benzofuran, and 1H-indene for the temperature range (300 < T/K < 360). Measurements in the water-rich phase for (2-ethylphenol + water) were extended to T = 440 K to facilitate comparison with literature values. Liquid-liquid equilibrium tie-line determinations were made for four ternary systems involving (water + toluene) mixed with a third component; phenol, 3-ethylphenol, 4-methoxyphenol, or 2,4-dimethylphenol. Literature values at higher temperatures are available for the three (ethylphenol + water) systems, and, in general, good agreement is seen. The ternary system (water + toluene + phenol) has been studied previously with inconsistent results reported in the literature, and one report is shown to be anomalous. All systems are modeled with the predictive methods NIST-Modified-UNIFAC and NIST-COSMO-SAC, with generally good success in the temperature range of interest (300 < T/K < 360). This work is part of a larger project on the testing and development of predictive phase equilibrium models for compound types occurring in catalytic fast pyrolysis of biomass, and background information for the larger project is provided.
Modeling sediment transport in the lower Yellow River and dynamic equilibrium threshold value
HU; Chunhong; GUO; Qingchao
2004-01-01
A major problem in the lower Yellow River is the insufficient incoming water and excessive sediment supply, which results in serious deposition, continuous rise of the river bed, and austere flood control situation. To understand the sediment transport regularity of the lower Yellow River and determine the relationship between sedimentation,incoming water and sediment, and zone water diversion, a mathematical model of the sediment suitable for the characteristics of the lower Yellow River has been developed.This model is first rated and verified by large quantity of observed data, and it is then used to analyze silting reduction for the lower Yellow River by Xiaolangdi Reservoir's operation,the relationship between zone water diversion and channel sedimentation, and critical equilibrium of sedimentation in the lower Yellow River. The threshold values of equilibrium of sedimentation in the lower Yellow River are estimated and they suggest that deposition in the lower Yellow River can be effectively reduced by the operation of regulating flow and sediment from Xiaolangdi Reservoir, water-soil conservation, and controlling water diversion along the lower Yellow River.
Ostriker, Eve C; Leroy, Adam K
2010-01-01
We develop a model for regulation of galactic star formation rates Sigma_SFR in disk galaxies, in which ISM heating by stellar UV plays a key role. By requiring simultaneous thermal and (vertical) dynamical equilibrium in the diffuse gas, and star formation at a rate proportional to the mass of the self-gravitating component, we obtain a prediction for Sigma_SFR as a function of the total gaseous surface density Sigma and the density of stars + dark matter, rho_sd. The physical basis of this relationship is that thermal pressure in the diffuse ISM, which is proportional to the UV heating rate and therefore to Sigma_SFR, must adjust to match the midplane pressure set by the vertical gravitational field. Our model applies to regions where Sigma < 100 Msun/pc^2. In low-Sigma_SFR (outer-galaxy) regions where diffuse gas dominates, the theory predicts Sigma_SFR \\propto Sigma (rho_sd)^1/2. The decrease of thermal equilibrium pressure when Sigma_SFR is low implies, consistent with observations, that star formatio...
Castro Ospina, J.M.
1984-01-01
A review is presented of some bioeconomic mathematical models that incorporate constant harvesting. This is followed by a complete qualitative and quantitative analysis of competition and predator-prey Lotka-Volterra bioeconomic models. The trivial and non-trivial equilibrium points of these systems are analyzed and the Routh-Hurwitz criteria are used to determine the necessary and sufficient conditions for stability in relation to the effort parameter eta. Some numerical examples that illustrate the corresponding qualitative stability analysis for the open access and bioeconomic equilibria for the competition and predator-prey systems are given. In the numerical examples analyzed, three different open access and bioeconomic equilibria were found. The non-trivial equilibrium points are unstable and infeasible. A critical level of effort was also derived for the predator-prey numerical example and corresponding management policies were formulated. When only the predator is harvested, it can be shown that the system under analysis undergoes a critical bifurcation at the point E/sub c/.
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.
Equilibrium and kinetic models for colloid release under transient solution chemistry conditions.
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
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
Renormalization-group studies of three model systems far from equilibrium
Georgiev, Ivan Tsvetanov
This thesis describes the development of analytical and computational techniques for systems far from equilibrium and their application to three model systems. Each of the model systems reaches a non-equilibrium steady state and exhibits one or more phase transitions. We first introduce a new position-space renormalization-group approach and illustrate its application using the one-dimensional fully asymmetric exclusion process. We have constructed a recursion relation for the relevant dynamic parameters for this model and have reproduced all of the important critical features of the model, including the exact positions of the critical point and the first and second order phase boundaries. The method yields an approximate value for the critical exponent nu which is very close to the known value. The second major part of this thesis combines information theoretic techniques for calculating the entropy and a Monte Carlo renormalization-group approach. We have used this method to study and compare infinitely driven lattice gases. This approach enables us to calculate the critical exponents associated with the correlation length nu and the order parameter beta. These results are compared to the values predicted from different field theoretic treatments of the models. In the final set of calculations, we build position-space renormalization-group recursion relations from the master equations of small clusters. By obtaining the probability distributions for these clusters numerically, we develop a mapping connecting the parameters specifying the dynamics on different length scales. The resulting flow topology in some ways mimics equilibrium features, with sinks for each phase and fixed points associated with each phase boundary. In addition, though, there are added complexities in the flows, suggesting multiple regions within the ordered phase for some values of parameters, and the presence of an extra "source" fixed point within the ordered phase. Thus, this study
Modeling stochasticity in biochemical reaction networks
Constantino, P. H.; Vlysidis, M.; Smadbeck, P.; Kaznessis, Y. N.
2016-03-01
Small biomolecular systems are inherently stochastic. Indeed, fluctuations of molecular species are substantial in living organisms and may result in significant variation in cellular phenotypes. The chemical master equation (CME) is the most detailed mathematical model that can describe stochastic behaviors. However, because of its complexity the CME has been solved for only few, very small reaction networks. As a result, the contribution of CME-based approaches to biology has been very limited. In this review we discuss the approach of solving CME by a set of differential equations of probability moments, called moment equations. We present different approaches to produce and to solve these equations, emphasizing the use of factorial moments and the zero information entropy closure scheme. We also provide information on the stability analysis of stochastic systems. Finally, we speculate on the utility of CME-based modeling formalisms, especially in the context of synthetic biology efforts.
Benjamin, Ilan; Pohorille, Andrew
1993-01-01
The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.
Benjamin, Ilan; Pohorille, Andrew
1993-01-01
The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.
Voter Model Perturbations and Reaction Diffusion Equations
Cox, J Theodore; Perkins, Edwin
2011-01-01
We consider particle systems that are perturbations of the voter model and show that when space and time are rescaled the system converges to a solution of a reaction diffusion equation in dimensions $d \\ge 3$. Combining this result with properties of the PDE, some methods arising from a low density super-Brownian limit theorem, and a block construction, we give general, and often asymptotically sharp, conditions for the existence of non-trivial stationary distributions, and for extinction of one type. As applications, we describe the phase diagrams of three systems when the parameters are close to the voter model: (i) a stochastic spatial Lotka-Volterra model of Neuhauser and Pacala, (ii) a model of the evolution of cooperation of Ohtsuki, Hauert, Lieberman, and Nowak, and (iii) a continuous time version of the non-linear voter model of Molofsky, Durrett, Dushoff, Griffeath, and Levin. The first application confirms a conjecture of Cox and Perkins and the second confirms a conjecture of Ohtsuki et al in the ...
Peng Yang
2013-02-01
Full Text Available With the constant changes of the market demand trends and modern information technology which greatly influence supply chain operation and management, postponement has been developed to be an important strategy in some of the supply chain processes. This paper studies the multi-period and multi-commodity flow supply chain network equilibrium problem with postponement strategy under a type of supply chain management pattern. Taking the influences of the relationship between orders and inventory management of supply chain into consideration, and employing variational inequality to establish multi-period equilibrium model at each level and network equilibrium model , this paper eventually works out the conditions to make the system achieve equilibrium, and also offers economic interpretation with concrete examples to verify them.
Investigation of Chemical Equilibrium Kinetics by the Electromigration Method
Bozhikov, G A; Bontchev, G D; Maslov, O D; Milanov, M V; Dmitriev, S N
2002-01-01
Measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the complex formation of Hf(IV) and DTPA is determined.
Multi-component vapor-liquid equilibrium model for LES and application to ECN Spray A
Matheis, Jan
2016-01-01
We present and evaluate a detailed multi-species two-phase thermodynamic equilibrium model for large-eddy simulations (LES) of liquid-fuel injection and mixing at high pressure. The model can represent the coexistence of supercritical states and multi-component subcritical two-phase states. LES results for the transcritical Spray A of the Engine Combustion Network (ECN) are found to agree very well to available experimental data. We also address well-known numerical challenges of trans- and supercritical fluid mixing and compare a fully conservative formulation to a quasi conservative formulation of the governing equations. Our results prove physical and numerical consistency of both methods on fine grids and demonstrate the effects of energy conservation errors associated with the quasi conservative formulation on typical LES grids.
Harrison, D. E.; Holland, W. R.
1981-01-01
A mean vorticity budget analysis is presented of Holland's (1978) numerical ocean general circulation experiment. The stable budgets are compared with classical circulation theory to emphasize the ways in which the mesoscale motions of the model alter (or leave unaltered) classical vorticity balances. The basinwide meridional transports of vorticity by the mean flow and by the mesoscale flow in the mean are evaluated to establish the role(s) of the mesoscale in the larger scale equilibrium vorticity transports. The vorticity equation for this model fluid system is presented and the budget analysis method is described. Vorticity budgets over the selected regions and on a larger scale are given, and a summary of budget results is provided along with remarks about the utility of this type of analysis.
Entropy analysis on non-equilibrium two-phase flow models
Karwat, H.; Ruan, Y.Q. [Technische Universitaet Muenchen, Garching (Germany)
1995-09-01
A method of entropy analysis according to the second law of thermodynamics is proposed for the assessment of a class of practical non-equilibrium two-phase flow models. Entropy conditions are derived directly from a local instantaneous formulation for an arbitrary control volume of a structural two-phase fluid, which are finally expressed in terms of the averaged thermodynamic independent variables and their time derivatives as well as the boundary conditions for the volume. On the basis of a widely used thermal-hydraulic system code it is demonstrated with practical examples that entropy production rates in control volumes can be numerically quantified by using the data from the output data files. Entropy analysis using the proposed method is useful in identifying some potential problems in two-phase flow models and predictions as well as in studying the effects of some free parameters in closure relationships.
Model Data Fusion: developing Bayesian inversion to constrain equilibrium and mode structure
Hole, M J; Bertram, J; Svensson, J; Appel, L C; Blackwell, B D; Dewar, R L; Howard, J
2010-01-01
Recently, a new probabilistic "data fusion" framework based on Bayesian principles has been developed on JET and W7-AS. The Bayesian analysis framework folds in uncertainties and inter-dependencies in the diagnostic data and signal forward-models, together with prior knowledge of the state of the plasma, to yield predictions of internal magnetic structure. A feature of the framework, known as MINERVA (J. Svensson, A. Werner, Plasma Physics and Controlled Fusion 50, 085022, 2008), is the inference of magnetic flux surfaces without the use of a force balance model. We discuss results from a new project to develop Bayesian inversion tools that aim to (1) distinguish between competing equilibrium theories, which capture different physics, using the MAST spherical tokamak; and (2) test the predictions of MHD theory, particularly mode structure, using the H-1 Heliac.
Harrison, D. E.; Holland, W. R.
1981-01-01
A mean vorticity budget analysis is presented of Holland's (1978) numerical ocean general circulation experiment. The stable budgets are compared with classical circulation theory to emphasize the ways in which the mesoscale motions of the model alter (or leave unaltered) classical vorticity balances. The basinwide meridional transports of vorticity by the mean flow and by the mesoscale flow in the mean are evaluated to establish the role(s) of the mesoscale in the larger scale equilibrium vorticity transports. The vorticity equation for this model fluid system is presented and the budget analysis method is described. Vorticity budgets over the selected regions and on a larger scale are given, and a summary of budget results is provided along with remarks about the utility of this type of analysis.
Out-of-equilibrium mean-field dynamics of a model for wave-particle interaction
de Buyl, Pierre; Bachelard, Romain; De Ninno, Giovanni
2009-01-01
The out-of-equilibrium mean-field dynamics of a model for wave-particle interaction is investigated. Such a model can be regarded as a general formulation for all those applications where the complex interplay between particles and fields is known to be central, e.g., electrostatic instabilities in plasma physics, particle acceleration and free-electron lasers. The latter case is here assumed as a paradigmatic example. A transition separating different macroscopic regimes is numerically identified and interpreted by making use of the so-called violent relaxation theory. In this context, the transition is explained as a dynamical switch between two metastable regimes, and related to the change of nature of a stationary point of an entropic functional.
Golinelli, Olivier; Mallick, Kirone
2006-10-01
The asymmetric simple exclusion process (ASEP) plays the role of a paradigm in non-equilibrium statistical mechanics. We review exact results for the ASEP obtained by the Bethe ansatz and put emphasis on the algebraic properties of this model. The Bethe equations for the eigenvalues of the Markov matrix of the ASEP are derived from the algebraic Bethe ansatz. Using these equations we explain how to calculate the spectral gap of the model and how global spectral properties such as the existence of multiplets can be predicted. An extension of the Bethe ansatz leads to an analytic expression for the large deviation function of the current in the ASEP that satisfies the Gallavotti-Cohen relation. Finally, we describe some variants of the ASEP that are also solvable by the Bethe ansatz.
Golinelli, Olivier [Service de Physique Theorique, CEA Saclay, 91191 Gif-sur-Yvette Cedex (France); Mallick, Kirone [Service de Physique Theorique, CEA Saclay, 91191 Gif-sur-Yvette Cedex (France)
2006-10-13
The asymmetric simple exclusion process (ASEP) plays the role of a paradigm in non-equilibrium statistical mechanics. We review exact results for the ASEP obtained by the Bethe ansatz and put emphasis on the algebraic properties of this model. The Bethe equations for the eigenvalues of the Markov matrix of the ASEP are derived from the algebraic Bethe ansatz. Using these equations we explain how to calculate the spectral gap of the model and how global spectral properties such as the existence of multiplets can be predicted. An extension of the Bethe ansatz leads to an analytic expression for the large deviation function of the current in the ASEP that satisfies the Gallavotti-Cohen relation. Finally, we describe some variants of the ASEP that are also solvable by the Bethe ansatz.
de Koning, Maurice; Antonelli, Alex
2008-01-01
We present a model for the determination of the thermal equilibrium concentrations of Bjerrum defects, molecular point defects, and their aggregates in ice I(h). First, using a procedure which minimizes the free energy of an ice crystal with respect to the numbers of defect species, we derive a set of equations for the equilibrium concentrations of free Bjerrum and point defects, as well their complexes. Using density-functional-theory calculations, we then evaluate the binding energies of Bj...
Eze, Valentine C; Phan, Anh N; Harvey, Adam P
2014-03-01
A more robust kinetic model of base-catalysed transesterification than the conventional reaction scheme has been developed. All the relevant reactions in the base-catalysed transesterification of rapeseed oil (RSO) to fatty acid methyl ester (FAME) were investigated experimentally, and validated numerically in a model implemented using MATLAB. It was found that including the saponification of RSO and FAME side reactions and hydroxide-methoxide equilibrium data explained various effects that are not captured by simpler conventional models. Both the experiment and modelling showed that the "biodiesel reaction" can reach the desired level of conversion (>95%) in less than 2min. Given the right set of conditions, the transesterification can reach over 95% conversion, before the saponification losses become significant. This means that the reaction must be performed in a reactor exhibiting good mixing and good control of residence time, and the reaction mixture must be quenched rapidly as it leaves the reactor.
Modelled glacier equilibrium line altitudes during the mid-Holocene in the southern mid-latitudes
C. Bravo
2015-03-01
Full Text Available Glacier behaviour during the mid-Holocene (MH, 6000 year BP in the Southern Hemisphere provides observational data to constrain our understanding of the origin and propagation of palaeo-climatic signals. We examine the climatic forcing of glacier expansion in the MH by evaluating modelled glacier equilibrium line altitude (ELA and climate conditions during the MH compared with pre-industrial time (PI, year 1750 in the mid latitudes of the Southern Hemisphere, specifically in Patagonia and the South Island of New Zealand. Climate conditions for the MH are obtained from PMIP2 models simulations, which in turn force a simple glacier mass balance model to simulate changes in equilibrium-line altitude during this period. Climate conditions during the MH show significantly (p ≤ 0.05 colder temperatures in summer, autumn and winter, and significantly (p ≤ 0.05 warmer temperatures in spring. These changes are a consequence of insolation differences between the two periods. Precipitation does not show significant changes, but exhibits a temporal pattern with less precipitation from August to September and more precipitation from October to April during the MH. In response to these climatic changes, glaciers in both analysed regions have an ELA that is 15–33 m lower than PI during the MH. The main causes of this difference are the colder temperature during the MH, reinforcing previous results that mid-latitude glaciers are more sensitive to temperature change compared to precipitation changes. Differences in temperature have a dual effect on mass balance. First, during summer and early autumn less energy is available for melting. Second in late autumn and winter, lower temperatures cause more precipitation to fall as snow rather than rain, resulting in more accumulation and higher surface albedo. For these reasons, we postulate that the modelled ELA changes, although small, may help to explain larger glacier extents observed in the mid Holocene in
Xiaopeng Cui; Shouting Gao
2008-01-01
The effects of zonal perturbations of sea surface temperature (SST) on tropical equilibrium states are investigated based on a series of two-dimensional cloud-resolving simulations with imposed zero vertical velocity, constant zonal wind, and a zonal model domain of 768 km. Four experiments with zonal SST perturbations of wavenumbers 1 (Cl), 2 (C2), 4 (C3), and 8 (C4) are compared to a control experiment with zonally uniform SST (CO). The 40-day integrations show that the temperatures reach quasi-equilibrium states with distinct differences. Cl and C2 produce warmer equilibrium states whereas C3 and C4 generate colder equilibrium states than CO does. The heat budgets in the five experiments are analyzed. Compared to CO, less IR cooling over smaller clear-sky regions in Cl and more condensational heating in C2 are responsible for wanner equilibrium states. A reduced condensational heating leads to the cold equilibrium state in C3. The interaction between convective systems in C4 causes a decrease of condensational heating, which accounts for the cold equilibrium state.
Milad Haghani
2016-06-01
Further investigations with respect to the relative importance of STA model estimation (or equivalently, parameter calibration and model specification (or equivalently, error term formulation are also conducted. A paired combinatorial logit (PCL assignment model with an origin–destination-specific-parameter, along with a heuristic method of model estimation (calibration, is proposed. The proposed model cannot only accommodate the correlation between path utilities, but also accounts for the fact that travelling between different origin–destination (O–D pairs can correspond to different levels of stochasticity and choice randomness. Results suggest that the estimation of the stochastic user equilibrium (SUE models can affect the outcome of the flow prediction far more meaningfully than the complexity of the choice model (i.e., model specification.
Liquid-vapour equilibrium in the restricted primitive model for ionic liquids
Gillan, M. J.
We study the thermodynamic equilibrium between liquid and vapour for the restricted primitive model (charged hard spheres of equal diameters) of a two component ionic liquid. We point out that physical clustering of ions will have a crucial effect on this equilibrium. The calculations presented are based on the representation of the vapour as a mixture of clusters of different types, the interactions between clusters being neglected. The relative proportions of the different types are governed by the law of mass action. We show that neglect of interactions yields a lower bound to the true vapour pressure. The internal free energies of the clusters in the vapour are obtained from a combination of analytic and Monte Carlo calculations and the thermodynamic properties of the liquid phase are derived from Larsen's published Monte Carlo results. We present numerical results for the densities of different cluster types in the vapour phase, for the overall liquid and vapour densities and for the vapour pressure. A comparison with the predictions of the mean spherical approximation and of Larsen's empirical equation show that these yield vapour pressures which are far below our lower bound and are therefore erroneous. We point out that Larsen's equation implies a weak subsidiary critical point on the liquid branch of the coexistence curve, an effect which we suggest is spurious. Finally, we discuss the relation between our work and that of Stell, Wu and Larsen.
THERMAL NON-EQUILIBRIUM REVISITED: A HEATING MODEL FOR CORONAL LOOPS
Lionello, Roberto; Linker, Jon A.; Mikic, Zoran [Predictive Science, Inc., 9990 Mesa Rim Rd., Ste. 170, San Diego, CA 92121-2910 (United States); Winebarger, Amy R. [NASA Marshall Space Flight Center, ZP 13, Huntsville, AL 35812 (United States); Mok, Yung, E-mail: lionel@predsci.com, E-mail: linkerj@predsci.com, E-mail: mikicz@predsci.com, E-mail: amy.r.winebarger@nasa.gov, E-mail: ymok@uci.edu [Department of Physics and Astronomy, University of California, 4129 Reines Hall, Irvine, CA 92697 (United States)
2013-08-20
The location and frequency of events that heat the million-degree corona are still a matter of debate. One potential heating scenario is that the energy release is effectively steady and highly localized at the footpoints of coronal structures. Such an energy deposition drives thermal non-equilibrium solutions in the hydrodynamic equations in longer loops. This heating scenario was considered and discarded by Klimchuk et al. on the basis of their one-dimensional simulations as incapable of reproducing observational characteristics of loops. In this paper, we use three-dimensional simulations to generate synthetic emission images, from which we select and analyze six loops. The main differences between our model and that of Klimchuk et al. concern (1) dimensionality, (2) resolution, (3) geometrical properties of the loops, (4) heating function, and (5) radiative function. We find evidence, in this small set of simulated loops, that the evolution of the light curves, the variation of temperature along the loops, the density profile, and the absence of small-scale structures are compatible with the characteristics of observed loops. We conclude that quasi-steady footpoint heating that drives thermal non-equilibrium solutions cannot yet be ruled out as a viable heating scenario for EUV loops.
Serapinas, Petras, E-mail: serapinas@pfi.l [Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, 01108 Vilnius (Lithuania); Salkauskas, Julius; Ezerinskis, Zilvinas; Acus, Arturas [Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, 01108 Vilnius (Lithuania)
2010-01-15
Essentially higher ionization degree of small concentrations of elements in inductively coupled plasma in comparison to the ionization of pure elements is emphasized. This conclusion is used to determine the relative dependence of the sensitivity of the inductively coupled plasma mass spectrometer on the atomic mass. The possibility of evaluation of the ionization temperature and electron density from mass spectrometric signals is proposed. Temperatures about 7000 K and 8000 K were obtained from the ionization ratio dependences on ionization potentials. Electron densities of the order of magnitude 10{sup 15} cm{sup -3}, in excess to the local thermodynamic equilibrium values, follow from the application of the Saha equation to the measurement results and indicate the recombining character of the plasma in the mass spectrometer measurement region. Effects due to additional ionization from matrix were discussed. The effect is largest on minor abundant ionization state components. Matrix effect is restricted to some temperature interval, which depends on the whole matrix composition and the plasma state. The results show that the local thermodynamic equilibrium modeling, if adequately matching the sample composition, can be useful as a quantitative basis for both description of the plasma state and indication of the character of the nonequilibrium effects.
Equilibrium points in the restricted synchronous three-body problem using a mass dipole model
Barbosa Torres dos Santos, Leonardo; Bertachini de Almeida Prado, Antonio F.; Merguizo Sanchez, Diogo
2017-03-01
The objective of the present paper is to investigate the zero velocity curves, using the Jacobi constant C, and to determine the positions of the libration points in the restricted synchronous three-body problem. To perform this task, it is necessary to obtain the equations of motion of a negligible mass traveling in a system composed of two other massive bodies. One of them is assumed to have a spherical shape, while the other one is irregular shaped and modeled as a rotating mass dipole. The locations of the equilibrium points are determined and then, for several values C of the Jacobi constant, the boundary regions are obtained where the motion of the particle is allowed. The zero velocity curves are plotted. Next, the stability of these equilibrium points examined, including the collinear and non-collinear ones. It is found that the collinear points are unstable and the non-collinear ones are linearly stable for lower values of the mass parameter. A comparison with the equivalent results for the dynamics considering three points of mass is made, to emphasize the influence of the elongation of one of the bodies.
Testing a Dynamical Equilibrium Model of the Extraplanar Diffuse Ionized Gas in NGC 891
Boettcher, Erin; Gallagher, J S; Benjamin, Robert A
2016-01-01
The observed scale heights of extraplanar diffuse ionized gas (eDIG) layers exceed their thermal scale heights by a factor of a few in the Milky Way and other nearby edge-on disk galaxies. Here, we test a dynamical equilibrium model of the extraplanar diffuse ionized gas layer in NGC 891, where we ask whether the thermal, turbulent, magnetic field, and cosmic ray pressure gradients are sufficient to support the layer. In optical emission line spectroscopy from the SparsePak integral field unit on the WIYN 3.5-meter telescope, the H-alpha emission in position-velocity space suggests that the eDIG is found in a ring between galactocentric radii of R_min = 2 kpc. We find that the thermal (sigma_th = 11 km/s) and turbulent (sigma_turb = 25 km/s) velocity dispersions are insufficient to satisfy the hydrostatic equilibrium equation given an exponential electron scale height of h_z = 1.0 kpc. Using a literature analysis of radio continuum observations from the CHANG-ES survey, we demonstrate that the magnetic field ...
Borah, B
2014-01-01
A theoretical model is developed to study the equilibrium electromagnetic properties of a spherically symmetric dust molecular cloud (DMC) structure on the Jeans scale. It applies a technique based on the modified Lane-Emden equation (m-LEE). It considers an inhomogeneous distribution of dust grains in field-free hydrodynamic equilibrium configuration within the framework of exact gravito-electrostatic pressure balancing condition. Although weak relative to the massive grains, but finite, the efficacious inertial roles of the thermal species (electrons and ions) are included. A full portrayal of the lowest-order cloud surface boundary (CSB) and associated parameter signatures on the Jeans scale is made numerically for the first time. The multi-order extremization of the m-LEE solutions specifies the CSB at a radial point m relative to the centre. It gets biased negatively due to the interplay of plasma-boundary wall interaction (global) and plasma sheath-sheath coupling (local) processes. The CSB acts as an i...
Charin, Rafael M. [Department of Chemical Engineering, Federal University of Parana (UFPR), Polytechnic Center (DTQ/ST/UFPR), Jardim das Americas, Curitiba 82530-990, PR (Brazil); Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil); Corazza, Marcos L.; Ndiaye, Papa M. [Department of Chemical Engineering, Federal University of Parana (UFPR), Polytechnic Center (DTQ/ST/UFPR), Jardim das Americas, Curitiba 82530-990, PR (Brazil); Rigo, Aline A.; Mazutti, Marcio A. [Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil); Vladimir Oliveira, J., E-mail: vladimir@uricer.edu.b [Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil)
2011-03-15
Reported in this work are phase equilibrium data at high pressures for the binary and ternary systems formed by {l_brace}propane + N,N-dimethylformamide (DMF) + methanol{r_brace}. Phase equilibrium measurements were performed in a high-pressure, variable-volume view cell, following the static synthetic method for obtaining the experimental bubble and dew points transition data over the temperature range of (363 to 393) K, pressures up to 11.5 MPa and overall mole fraction of the lighter component varying from 0.1 to 0.995. For the systems investigated, vapour-liquid (VLE), liquid-liquid (LLE) and vapour-liquid-liquid (VLLE) phase transitions were visually recorded. Results show that the systems investigated present UCST (upper critical solution temperature) phase transition curves with an UCEP (upper critical end point) at a temperature higher than the propane critical temperature. The experimental data were modelled using the Peng-Robinson equation of state with the Wong-Sandler and the classical quadratic mixing rules, affording a satisfactory representation of the experimental data.
Marco Villani
2013-09-01
Full Text Available In this work we introduce some preliminary analyses on the role of a semi-permeable membrane in the dynamics of a stochastic model of catalytic reaction sets (CRSs of molecules. The results of the simulations performed on ensembles of randomly generated reaction schemes highlight remarkable differences between this very simple protocell description model and the classical case of the continuous stirred-tank reactor (CSTR. In particular, in the CSTR case, distinct simulations with the same reaction scheme reach the same dynamical equilibrium, whereas, in the protocell case, simulations with identical reaction schemes can reach very different dynamical states, despite starting from the same initial conditions.
Chen, Sheng; Täuber, Uwe C.
2015-03-01
Spatially extended stochastic models for predator-prey competition and coexistence display complex, correlated spatio-temporal structures and are governed by remarkably large fluctuations. Both populations are characterized by damped erratic oscillations whose properties are governed by the reaction rates. Here, we specifically study a stochastic lattice Lotka-Volterra model by means of Monte Carlo simulations that impose spatial restrictions on the number of occupants per site. The system tends to relax into a quasi-stationary state, independent of the imposed initial conditions. We investigate the non-equilibrium relaxation between two such quasi-stationary states, following an instantaneous change of the predation rate. The ensuing relaxation times are measured via the peak width of the population density Fourier transforms. As expected, we find that the initial state only influences the oscillations for the duration of this relaxation time, implying that the system quickly loses any memory of the initial configuration. Research supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-09ER46613.
Qazi, Sanjive; Beltukov, Aleksei; Trimmer, Barry A
2004-01-01
The first event in signal transduction at a synapse is the binding of transmitters to receptors. Because of rapidly changing transmitter levels this binding is unlikely to occur at equilibrium. We describe a mathematical approach that models complex receptor interactions in which the timing and amplitude of transmitter release are noisy. We show that exact solutions for simple bimolecular interactions and receptor transitions can be used to model complex reaction schemes by expressing them in sets of difference equations. Results from the difference equation method to describe binding and channel opening at extended time points compare well with standard solutions using ordinary differential equations. Because it is applicable to noisy systems we used the difference method to investigate the information processing capabilities of GABA receptors and predict how pharmacological agents may modify these properties. As previously demonstrated, the response to a single pulse of GABA is prolonged through entry into a desensitized state. During trains of stimuli the signal to noise ratio can change, and even increase progressively, but the overall transmitted fidelity of the signal decreases with increased driving frequency. The GABA modulator chlorpromazine (primarily affects agonist on and off rates) is predicated to increase receptor signal to noise ratio at all frequencies whereas pregnenolone sulfate (affects receptor desensitization) completely inhibits information transfer.
Modeling of Reaction Processes Controlled by Diffusion
Revelli, J
2003-01-01
Stochastic modeling is quite powerful in science and technology.The technics derived from this process have been used with great success in laser theory, biological systems and chemical reactions.Besides, they provide a theoretical framework for the analysis of experimental results on the field of particle's diffusion in ordered and disordered materials.In this work we analyze transport processes in one-dimensional fluctuating media, which are media that change their state in time.This fact induces changes in the movements of the particles giving rise to different phenomena and dynamics that will be described and analyzed in this work.We present some random walk models to describe these fluctuating media.These models include state transitions governed by different dynamical processes.We also analyze the trapping problem in a lattice by means of a simple model which predicts a resonance-like phenomenon.Also we study effective diffusion processes over surfaces due to random walks in the bulk.We consider differe...
PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC
Parkhurst, David L.; Wissmeier, Laurin
2015-09-01
PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst-Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants. PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.
Meirui Zhong
2014-01-01
Full Text Available This paper combines intergenerational equity equilibrium and social preferences equilibrium with Cournot equilibrium solving the technological problem of intergenerational equity and strategic value compensation confirmation, achieving the effective combination between sustainable development concept and value evaluation, thinking and expanding the theoretical framework for the lack of pricing power of mineral resources. The conclusion of the theoretical model and the numerical simulation shows that intergenerational equity equilibrium and social preferences equilibrium enhance international trade market power of preponderant metal mineral resources owing to the production of intergenerational equity compensation value and strategic value. However, the impact exerted on Cournot market power by social preferences is inconsistent: that is, changes of altruistic Cournot equilibrium and reciprocal inequity Cournot equilibrium are consistent, while inequity aversion Cournot equilibrium has the characteristic of loss aversion, namely, under the consideration of inequity aversion Cournot competition, Counot-Nash equilibrium transforms monotonically with sympathy and jealousy of inequity aversion.
Heterogeneous out-of-equilibrium nonlinear q -voter model with zealotry
Mellor, Andrew; Mobilia, Mauro; Zia, R. K. P.
2017-01-01
We study the dynamics of the out-of-equilibrium nonlinear q -voter model with two types of susceptible voters and zealots, introduced in Mellor et al. [Europhys. Lett. 113, 48001 (2016), 10.1209/0295-5075/113/48001]. In this model, each individual supports one of two parties and is either a susceptible voter of type q1 or q2, or is an inflexible zealot. At each time step, a qi-susceptible voter (i =1 ,2 ) consults a group of qi neighbors and adopts their opinion if all group members agree, while zealots are inflexible and never change their opinion. This model violates detailed balance whenever q1≠q2 and is characterized by two distinct regimes of low and high density of zealotry. Here, by combining analytical and numerical methods, we investigate the nonequilibrium stationary state of the system in terms of its probability distribution, nonvanishing currents, and unequal-time two-point correlation functions. We also study the switching time properties of the model by exploiting an approximate mapping onto the model of Mobilia [Phys. Rev. E 92, 012803 (2015), 10.1103/PhysRevE.92.012803] that satisfies the detailed balance, and we outline some properties of the model near criticality.
Chemical equilibrium modeling of organic acids, pH, aluminum, and iron in Swedish surface waters.
Sjöstedt, Carin S; Gustafsson, Jon Petter; Köhler, Stephan J
2010-11-15
A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.
Silverberg, Lee J.; Raff, Lionel M.
2015-01-01
Thermodynamic spontaneity-equilibrium criteria require that in a single-reaction system, reactions in either the forward or reverse direction at equilibrium be nonspontaneous. Conversely, the concept of dynamic equilibrium holds that forward and reverse reactions both occur at equal rates at equilibrium to the extent allowed by kinetic…
An alternative order-parameter for non-equilibrium generalized spin models on honeycomb lattices
Sastre, Francisco; Henkel, Malte
2016-04-01
An alternative definition for the order-parameter is proposed, for a family of non-equilibrium spin models with up-down symmetry on honeycomb lattices, and which depends on two parameters. In contrast to the usual definition, our proposal takes into account that each site of the lattice can be associated with a local temperature which depends on the local environment of each site. Using the generalised voter motel as a test case, we analyse the phase diagram and the critical exponents in the stationary state and compare the results of the standard order-parameter with the ones following from our new proposal, on the honeycomb lattice. The stationary phase transition is in the Ising universality class. Finite-size corrections are also studied and the Wegner exponent is estimated as ω =1.06(9).
A non-equilibrium thermodynamic model for tumor extracellular matrix with enzymatic degradation
Xue, Shi-Lei; Li, Bo; Feng, Xi-Qiao; Gao, Huajian
2017-07-01
The extracellular matrix (ECM) of a solid tumor not only affords scaffolding to support tumor architecture and integrity but also plays an essential role in tumor growth, invasion, metastasis, and therapeutics. In this paper, a non-equilibrium thermodynamic theory is established to study the chemo-mechanical behaviors of tumor ECM, which is modeled as a poroelastic polyelectrolyte consisting of a collagen network and proteoglycans. By using the principle of maximum energy dissipation rate, we deduce a set of governing equations for drug transport and mechanosensitive enzymatic degradation in ECM. The results reveal that osmosis is primarily responsible for the compression resistance of ECM. It is suggested that a well-designed ECM degradation can effectively modify the tumor microenvironment for improved efficiency of cancer therapy. The theoretical predictions show a good agreement with relevant experimental observations. This study aimed to deepen our understanding of tumor ECM may be conducive to novel anticancer strategies.
Impacts of integration of Brazil with the European Union through a general equilibrium model
Ezequiel Insaurriaga Megiato
2016-01-01
Full Text Available This study analyses the bilateral trade between Brazil and the European Union (EU in the period 2002–2012, examining the trade opportunities based on a full integration process. It employs a computable general equilibrium model from the Global Trade Analysis Project (GTAP, aiming at identifying the sectors that would benefit most from the agreement, according to their technological intensity. The results show that Brazil benefits most from the agreement in terms of welfare and would also increase the country's exports of primary products. However, it would cause a decrease in production and exports of products with higher technological intensity, increasing the country's imports from the EU, in line with their comparative advantages.
Thermal-hydraulic analysis of the HL-2M divertor using an homogeneous equilibrium model
Lu, Yong; Cai, Lijun; Liu, Yuxiang; Liu, Jian; Yuan, Yinglong; Zheng, Guoyao; Liu, Dequan
2017-09-01
The heat flux of the HL-2M divertor would reach 10 MW m-2 or more at the local area when the device operates at high parameters. Subcooled boiling could occur at high thermal load, which would be simulated based on the homogeneous equilibrium model. The results show that the current design of the HL-2M divertor could withstand the local heat flux 10 MW m-2 at a plasma pulse duration of 5 s, inlet coolant pressure of 1.5 MPa and flow velocity of 4 m s-1. The pulse duration that the HL-2M divertor could withstand is closely related to the coolant velocity. In addition, at the time of 2 min after plasma discharge, the flow velocity decreased from 4 m s-1 to 1 m s-1, and the divertor could also be cooled to the initial temperature before the next plasma discharge commences.
Equilibrium dynamical correlations in the Toda chain and other integrable models
Kundu, Aritra; Dhar, Abhishek
2016-12-01
We investigate the form of equilibrium spatiotemporal correlation functions of conserved quantities in the Toda lattice and in other integrable models. From numerical simulations we find that the correlations satisfy ballistic scaling with a remarkable collapse of data from different times. We examine special limiting choices of parameter values, for which the Toda lattice tends to either the harmonic chain or the equal mass hard-particle gas. In both these limiting cases, one can obtain the correlations exactly and we find excellent agreement with the direct Toda simulation results. We also discuss a transformation to "normal mode" variables, as commonly done in hydrodynamic theory of nonintegrable systems, and find that this is useful, to some extent, even for the integrable system. The striking differences between the Toda chain and a truncated version, expected to be nonintegrable, are pointed out.
Equilibrium dynamical correlations in the Toda chain and other integrable models
Kundu, Aritra
2016-01-01
We investigate the form of equilibrium spatio-temporal correlation functions of conserved quantities, and of energy transport in the Toda lattice and in other integrable models. From numerical simulations we find that the correlations satisfy ballistic scaling with a remarkable collapse of data from different times. We examine special limiting choices of parameter values, for which the Toda lattice tends to either the harmonic chain or the equal mass hard-particle gas. In both these limiting cases, one can obtain the correlations exactly and we find excellent agreement with the direct Toda simulation results. We also discuss a transformation to "normal mode" variables, as commonly done in hydrodynamic theory of non-integrable systems, and find that this is useful, to some extent, even for the integrable system.
R. Rodrigues
Full Text Available Abstract Coal and biomass are energy sources with great potential for use in Brazil. Coal-biomass co-gasification enables the combination of the positive characteristics of each fuel, besides leading to a cleaner use of coal. The present study evaluates the potential of co-gasification of binary coal-biomass blends using sources widely available in Brazil. This analysis employs computational simulations using a reliable thermodynamic equilibrium model. Favorable operational conditions at high temperatures are determined in order to obtain gaseous products suitable for energy cogeneration and chemical synthesis. This study shows that blends with biomass ratios of 5% and equivalence ratios ≤ 0.3 lead to high cold gas efficiencies. Suitable gaseous products for chemical synthesis were identified at biomass ratios ≤ 35% and moisture contents ≥ 40%. Formation of undesirable nitrogen and sulfur compounds was also analyzed.
Santra, Dhiman; Joarder, Rajib; Sarkar, Mitali
2014-10-13
The cooperative influence of operational variables for fluoride adsorption on cerium loaded cellulose nanocomposite bead (CCNB) was assessed using Taguchi design tool. The percentage contribution of each operational variable was determined. The solution pH, with a maximum contribution of 80.78%, indicates its highest influence on the response, the adsorption percent of fluoride. The quality and validity of the experimental design were assessed from ANOVA and subsequently by the confirmation experiment. The equilibrium adsorption data showed that the Temkin isotherm is the most suited one compared to the Langmuir and Freundlich model. It is found that almost 90% adsorbed fluoride can be eluted with 0.01 (N) NaOH and the regenerated bead can successively be reused for at least three times. Copyright © 2014 Elsevier Ltd. All rights reserved.
Large deviation statistics of non-equilibrium fluctuations in a sheared model-fluid
Dolai, Pritha; Simha, Aditi
2016-08-01
We analyse the statistics of the shear stress in a one dimensional model fluid, that exhibits a rich phase behaviour akin to real complex fluids under shear. We show that the energy flux satisfies the Gallavotti-Cohen FT across all phases in the system. The theorem allows us to define an effective temperature which deviates considerably from the equilibrium temperature as the noise in the system increases. This deviation is negligible when the system size is small. The dependence of the effective temperature on the strain rate is phase-dependent. It doesn’t vary much at the phase boundaries. The effective temperature can also be determined from the large deviation function of the energy flux. The local strain rate statistics obeys the large deviation principle and satisfies a fluctuation relation. It does not exhibit a distinct kink near zero strain rate because of inertia of the rotors in our system.
Shogin, Dmitry
2015-01-01
We test the physical relevance of the full and truncated versions of the Israel-Stewart theory of irreversible thermodynamics in a cosmological setting. Using a dynamical systems method, we determine the asymptotic future of plane symmetric Bianchi type I spacetimes filled with a viscous {\\gamma}-fluid, keeping track of the magnitude of relative dissipative fluxes, which determines the applicability of the Israel-Stewart theory. We consider the situations when the dissipative mechanisms of shear and bulk viscosity are involved separately and simultaneously. Also, we apply two different temperature models in the full version of the theory in order to compare the results. We demonstrate that the only case when the fluid asymptotically approaches local equilibrium, and the underlying assumptions of the IS theory are therefore not violated, is that of a dissipative fluid with vanishing bulk viscosity. The truncated Israel-Stewart equations for shear viscosity are found to produce solutions which manifest patholog...
Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel
2014-01-01
This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm(3) at a gasification temperature of 1500 K and equivalence ratio of 0.15.
Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel
2014-01-01
This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm3 at a gasification temperature of 1500 K and equivalence ratio of 0.15. PMID:27433487
Continuum modeling and limit equilibrium analysis of slope movement due to rainfall infiltration
Borja, Ronaldo; White, Joshua; Wu, Wei
2010-05-01
Hydrologically-driven landslides and debris flows are highly destructive events that threaten lives and critical infrastructure worldwide. Despite decades of extensive slope stability model development, the fundamental controls connecting the hydrologic and geotechnical processes that trigger slope failure are not well quantified. We use a fully coupled, physics-based finite element model to address this shortcoming. We develop and test a 3D continuum slope-deformation model that couples solid-deformation with fluid-flow processes in variably saturated soils, and assess the capability of the coupled model to predict stresses and deformation necessary to trigger slope failure. We then compare the continuum model with traditional limit equilibrium solutions based on the modified Bishop method of slices to assess the stability of the slope as a function of rainfall infiltration using a scalar stability indicator called factor of safety. For this assessment, we use extensive measurements from a densely instrumented mountain slope (The Coos Bay Experimental Catchment) where a large, rainfall-triggered slope failure occurred. The use of sophisticated, fully coupled numerical simulations combined with comprehensive field-measurements provides an unprecedented opportunity to advance the state of understanding of landslide failure processes and effective mitigation measures.
Rolando Barrera
2014-01-01
Full Text Available The production of synthetic or substitute natural gas (SNG from coal is a process of interest in Colombia where the reserves-to-production ratio (R/P for natural gas is expected to be between 7 and 10 years, while the R/P for coal is forecasted to be around 90 years. In this work, the process to produce SNG by means of coal-entrained flow gasifiers is modeled under thermochemical equilibrium with the Gibbs free energy approach. The model was developed using a complete and comprehensive Aspen Plus model. Two typical technologies used in entrained flow gasifiers such as coal dry and coal slurry are modeled and simulated. Emphasis is put on interactions between the fuel feeding technology and selected energy output parameters of coal-SNG process, that is, energy efficiencies, power, and SNG quality. It was found that coal rank does not significantly affect energy indicators such as cold gas, process, and global efficiencies. However, feeding technology clearly has an effect on the process due to the gasifying agent. Simulations results are compared against available technical data with good accuracy. Thus, the proposed model is considered as a versatile and useful computational tool to study and optimize the coal to SNG process.
Felmy, A.R.
1990-04-01
This document is a user's manual and technical reference for the computerized chemical equilibrium model GMIN. GMIN calculates the chemical composition of systems composed of pure solid phases, solid-solution phases, gas phases, adsorbed phases, and the aqueous phase. In the aqueous phase model, the excess solution free energy is modeled by using the equations developed by PITZER and his coworkers, which are valid to high ionic strengths. The Davies equation can also be used. Activity coefficients for nonideal soild-solution phases are calculated using parameters of polynomial expansion in mole fraction of the excess free energy of mixing. The free energy of adsorbed phase species is described by the triple-layer site-binding model. The mathematical algorithm incorporated into GMIN is based upon a constrained minimization of the Gibbs free energy. This algorithm is numerically stable and reliably converges to a free energy minimum. The data base for GMIN contains all standard chemical potentials and Pitzer ion-interaction parameters necessary to model the system Na-K-Ca-Mg-H-Cl-SO{sub 4}-CO{sub 2}-B(OH){sub 4}-H{sub 2}0 at 25{degrees}C.
Computable General Equilibrium Model Fiscal Year 2013 Capability Development Report - April 2014
Edwards, Brian Keith [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). National Infrastructure Simulation and Analysis Center (NISAC); Rivera, Michael K. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). National Infrastructure Simulation and Analysis Center (NISAC); Boero, Riccardo [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). National Infrastructure Simulation and Analysis Center (NISAC)
2014-04-01
This report documents progress made on continued developments of the National Infrastructure Simulation and Analysis Center (NISAC) Computable General Equilibrium Model (NCGEM), developed in fiscal year 2012. In fiscal year 2013, NISAC the treatment of the labor market and tests performed with the model to examine the properties of the solutions computed by the model. To examine these, developers conducted a series of 20 simulations for 20 U.S. States. Each of these simulations compared an economic baseline simulation with an alternative simulation that assumed a 20-percent reduction in overall factor productivity in the manufacturing industries of each State. Differences in the simulation results between the baseline and alternative simulations capture the economic impact of the reduction in factor productivity. While not every State is affected in precisely the same way, the reduction in manufacturing industry productivity negatively affects the manufacturing industries in each State to an extent proportional to the reduction in overall factor productivity. Moreover, overall economic activity decreases when manufacturing sector productivity is reduced. Developers ran two additional simulations: (1) a version of the model for the State of Michigan, with manufacturing divided into two sub-industries (automobile and other vehicle manufacturing as one sub-industry and the rest of manufacturing as the other subindustry); and (2) a version of the model for the United States, divided into 30 industries. NISAC conducted these simulations to illustrate the flexibility of industry definitions in NCGEM and to examine the simulation properties of in more detail.
Equilibrium-eulerian les model for turbulent poly-dispersed particle-laden flow
Icardi, Matteo
2013-04-01
An efficient Eulerian method for poly-dispersed particles in turbulent flows is implemented, verified and validated for a channel flow. The approach couples a mixture model with a quadrature-based moment method for the particle size distribution in a LES framework, augmented by an approximate deconvolution method to reconstructs the unfiltered velocity. The particle velocity conditioned on particle size is calculated with an equilibrium model, valid for low Stokes numbers. A population balance equation is solved with the direct quadrature method of moments, that efficiently represents the continuous particle size distribution. In this first study particulate processes are not considered and the capability of the model to properly describe particle transport is investigated for a turbulent channel flow. First, single-phase LES are validated through comparison with DNS. Then predictions for the two-phase system, with particles characterised by Stokes numbers ranging from 0.2 to 5, are compared with Lagrangian DNS in terms of particle velocity and accumulation at the walls. Since this phenomenon (turbophoresis) is driven by turbulent fluctuations and depends strongly on the particle Stokes number, the approximation of the particle size distribution, the choice of the sub-grid scale model and the use of an approximate deconvolution method are important to obtain good results. Our method can be considered as a fast and efficient alternative to classical Lagrangian methods or Eulerian multi-fluid models in which poly-dispersity is usually neglected.
Model uncertainties of local-thermodynamic-equilibrium K-shell spectroscopy
Nagayama, T.; Bailey, J. E.; Mancini, R. C.; Iglesias, C. A.; Hansen, S. B.; Blancard, C.; Chung, H. K.; Colgan, J.; Cosse, Ph.; Faussurier, G.; Florido, R.; Fontes, C. J.; Gilleron, F.; Golovkin, I. E.; Kilcrease, D. P.; Loisel, G.; MacFarlane, J. J.; Pain, J.-C.; Rochau, G. A.; Sherrill, M. E.; Lee, R. W.
2016-09-01
Local-thermodynamic-equilibrium (LTE) K-shell spectroscopy is a common tool to diagnose electron density, ne, and electron temperature, Te, of high-energy-density (HED) plasmas. Knowing the accuracy of such diagnostics is important to provide quantitative conclusions of many HED-plasma research efforts. For example, Fe opacities were recently measured at multiple conditions at the Sandia National Laboratories Z machine (Bailey et al., 2015), showing significant disagreement with modeled opacities. Since the plasma conditions were measured using K-shell spectroscopy of tracer Mg (Nagayama et al., 2014), one concern is the accuracy of the inferred Fe conditions. In this article, we investigate the K-shell spectroscopy model uncertainties by analyzing the Mg spectra computed with 11 different models at the same conditions. We find that the inferred conditions differ by ±20-30% in ne and ±2-4% in Te depending on the choice of spectral model. Also, we find that half of the Te uncertainty comes from ne uncertainty. To refine the accuracy of the K-shell spectroscopy, it is important to scrutinize and experimentally validate line-shape theory. We investigate the impact of the inferred ne and Te model uncertainty on the Fe opacity measurements. Its impact is small and does not explain the reported discrepancies.
Shim S.M.
2012-01-01
Full Text Available The performance of the CO2 absorber column using mono-ethanolamine (MEA solution as chemical solvent are predicted by a One-Dimensional (1-D rate based model in the present study. 1-D Mass and heat balance equations of vapor and liquid phase are coupled with interfacial mass transfer model and vapor-liquid equilibrium model. The two-film theory is used to estimate the mass transfer between the vapor and liquid film. Chemical reactions in MEA-CO2-H2O system are considered to predict the equilibrium pressure of CO2 in the MEA solution. The mathematical and reaction kinetics models used in this work are calculated by using in-house code. The numerical results are validated in the comparison of simulation results with experimental and simulation data given in the literature. The performance of CO2 absorber column is evaluated by the 1-D rate based model using various reaction rate coefficients suggested by various researchers. When the rate of liquid to gas mass flow rate is about 8.3, 6.6, 4.5 and 3.1, the error of CO2 loading and the CO2 removal efficiency using the reaction rate coefficients of Aboudheir et al. is within about 4.9 % and 5.2 %, respectively. Therefore, the reaction rate coefficient suggested by Aboudheir et al. among the various reaction rate coefficients used in this study is appropriate to predict the performance of CO2 absorber column using MEA solution. [Acknowledgement. This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF, funded by the Ministry of Education, Science and Technology (2011-0017220].
Model for reaction kinetics in pyrolysis of wood
Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kumar, S. [Banaras Hindu Univ., Varanasi (India)
1996-12-31
A reaction model for the pyrolysis of small and large particles of wood Is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The of heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 7 refs., 3 figs., 2 tabs.
Model for reaction kinetics in pyrolysis of wood
Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kuma, S. [Banaras Hindu Univ., Varanasi (India)
1996-12-31
A reaction model for the pyrolysis of small and large particles of wood is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 6 refs., 3 figs., 2 tabs.
Computable general equilibrium modelling in the context of trade and environmental policy
Koesler, Simon Tobias
2014-10-14
This thesis is dedicated to the evaluation of environmental policies in the context of climate change. Its objectives are twofold. Its first part is devoted to the development of potent instruments for quantitative impact analysis of environmental policy. In this context, the main contributions include the development of a new computable general equilibrium (CGE) model which makes use of the new comprehensive and coherent World Input-Output Dataset (WIOD) and which features a detailed representation of bilateral and bisectoral trade flows. Moreover it features an investigation of input substitutability to provide modellers with adequate estimates for key elasticities as well as a discussion and amelioration of the standard base year calibration procedure of most CGE models. Building on these tools, the second part applies the improved modelling framework and studies the economic implications of environmental policy. This includes an analysis of so called rebound effects, which are triggered by energy efficiency improvements and reduce their net benefit, an investigation of how firms restructure their production processes in the presence of carbon pricing mechanisms, and an analysis of a regional maritime emission trading scheme as one of the possible options to reduce emissions of international shipping in the EU context.
Thermal equilibrium solution to new model of bipolar hybrid quantum hydrodynamics
Di Michele, Federica; Mei, Ming; Rubino, Bruno; Sampalmieri, Rosella
2017-08-01
In this paper we study the hybrid quantum hydrodynamic model for nano-sized bipolar semiconductor devices in thermal equilibrium. By introducing a hybrid version of the Bhom potential, we derive a bipolar hybrid quantum hydrodynamic model, which is able to account for quantum effects in a localized region of the device for both electrons and holes. Coupled with Poisson equation for the electric potential, the steady-state system is regionally degenerate in its ellipticity, due to the quantum effect only in part of the device. This regional degeneracy of ellipticity makes the study more challenging. The main purpose of the paper is to investigate the existence and uniqueness of the weak solutions to this new type of equations. We first establish the uniform boundedness of the smooth solutions to the modified bipolar quantum hydrodynamic model by the variational method, then we use the compactness technique to prove the existence of weak solutions to the original hybrid system by taking hybrid limit. In particular, we account for two different kinds of hybrid behaviour. We perform the first hybrid limit when both electrons and holes behave quantum in a given region of the device, and the second one when only one carrier exhibits hybrid behaviour, whereas the other one is presented classically in the whole domain. The semi-classical limit results are also obtained. Finally, the theoretical results are tested numerically on a simple toy model.
Testing the recent charge-on-spring type polarizable water models. II. Vapor-liquid equilibrium
Kiss, Péter T.; Baranyai, András
2012-11-01
We studied the vapor-liquid coexistence region of seven molecular models of water. All models use the charge-on-spring (COS) method to express polarization. The studied models were the COS/G2, COS/G3 [H. Yu and W. F. van Gunsteren, J. Chem. Phys. 121, 9549 (2004), 10.1063/1.1805516], the SWM4-DP [G. Lamoureux, A. D. MacKerell, Jr., and B. Roux, J. Chem. Phys. 119, 5185 (2003), 10.1063/1.1598191], the SWM4-NDP [G. Lamoureux, E. Harder, I. V. Vorobyov, B. Roux, and A. D. MacKerell, Jr., Chem. Phys. Lett. 418, 245 (2006), 10.1016/j.cplett.2005.10.135], and three versions of our model, the BKd1, BKd2, and BKd3. The BKd1 is the original Gaussian model [P. T. Kiss, M. Darvas, A. Baranyai, and P. Jedlovszky, J. Chem. Phys. 136, 114706 (2012), 10.1063/1.3692602] with constant polarization and with a simple exponential repulsion. The BKd2 applies field-dependent polarizability [A. Baranyai and P. T. Kiss, J. Chem. Phys. 135, 234110 (2011), 10.1063/1.3670962], while the BKd3 model has variable size to approximate the temperature-density (T-ρ) curve of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 137, 194102 (2012), 10.1063/1.4767063]. We calculated the second virial coefficient, the heat of vaporization, equilibrium vapor pressure, the vapor-liquid coexistence curve, and the surface tension in terms of the temperature. We determined and compared the critical temperatures, densities, and pressures of the models. We concluded that the high temperature slope of the (T-ρ) curve accurately predicts the critical temperature. We found that Gaussian charge distributions have clear advantages over the point charges describing the critical region. It is impossible to describe the vapor-liquid coexistence properties consistently with nonpolarizable models, even if their critical temperature is correct.
Testing the recent charge-on-spring type polarizable water models. II. Vapor-liquid equilibrium.
Kiss, Péter T; Baranyai, András
2012-11-21
We studied the vapor-liquid coexistence region of seven molecular models of water. All models use the charge-on-spring (COS) method to express polarization. The studied models were the COS∕G2, COS∕G3 [H. Yu and W. F. van Gunsteren, J. Chem. Phys. 121, 9549 (2004)], the SWM4-DP [G. Lamoureux, A. D. MacKerell, Jr., and B. Roux, J. Chem. Phys. 119, 5185 (2003)], the SWM4-NDP [G. Lamoureux, E. Harder, I. V. Vorobyov, B. Roux, and A. D. MacKerell, Jr., Chem. Phys. Lett. 418, 245 (2006)], and three versions of our model, the BKd1, BKd2, and BKd3. The BKd1 is the original Gaussian model [P. T. Kiss, M. Darvas, A. Baranyai, and P. Jedlovszky, J. Chem. Phys. 136, 114706 (2012)] with constant polarization and with a simple exponential repulsion. The BKd2 applies field-dependent polarizability [A. Baranyai and P. T. Kiss, J. Chem. Phys. 135, 234110 (2011)], while the BKd3 model has variable size to approximate the temperature-density (T-ρ) curve of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 137, 194102 (2012)]. We calculated the second virial coefficient, the heat of vaporization, equilibrium vapor pressure, the vapor-liquid coexistence curve, and the surface tension in terms of the temperature. We determined and compared the critical temperatures, densities, and pressures of the models. We concluded that the high temperature slope of the (T-ρ) curve accurately predicts the critical temperature. We found that Gaussian charge distributions have clear advantages over the point charges describing the critical region. It is impossible to describe the vapor-liquid coexistence properties consistently with nonpolarizable models, even if their critical temperature is correct.
Liechty, Derek S.; Lewis, Mark J.
2010-01-01
Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.
A Reaction-based Diagonalization Approach to Modeling Surface Water Quality
Yu, J.; Yeh, G.; Zhang, F.; Wu, T.; Hu, G.
2005-12-01
There are many water quality models (e.g., WASP, QAUL2E/QUAL2K, CE-QUAL-ICM, RCA, RMA11, etc.) that have been employed by practitioners in surface water quality modeling. All of these models are similar to each others. The major differences among them are the number of water quality parameters included and the number of biogeochemical processes considered. Because of the limitation on the number of biogeochemical processes considered and, in a lesser extent, on the number of water quality parameters included, these models often perform only fairly in validation and their predictions may be unreliable, even though they can be adequately calibrated in most occasions and excellently in some occasions. Obviously, there is a need to develop a model that would allow the inclusion of any number of water quality parameters and enable the hypothesis of any number of biogeochemical processes. This paper presents the development of a numerical water quality model using a general paradigm of reaction-based approaches. In a reaction-based approach, all conceptualized biogoechemical processes are transformed into a reaction network. Through the decomposition of species governing equations via Gauss-Jordan column reduction of the reaction network, (1) redundant fast reactions and irrelevant kinetic reactions are removed from the system, which alleviates the problem of unnecessary and erroneous formulation and parameterization of these reactions, and (2) fast reactions and slow reactions are decoupled, which enables robust numerical integrations. The system of species governing equations is transformed into two sets: algebraic equations (either mass action equations or users' specified) of equilibrium variables and differential equations of kinetic variables. As a result, the model alleviates the needs of using simple partitions for fast reactions and uses kinetic-variables instead of biogeochemical species as primary dependent variables. With the diagonalization strategy, it
Xiao, Ye; Huang, Zaixing, E-mail: huangzx@nuaa.edu.cn [State Key Laboratory of Mechanics and Control of Mechanical Structures, Nanjing University of Aeronautics and Astronautics, Nanjing (China)
2015-11-15
The equilibrium configuration equations of DNA chain with elastic rod model are derived in detail by the variation of the free energy functional, which depends on the curvature, torsion, twisting angle and its derivative with respect to the arc-length of central axis curve of rod. With the different shapes of rod, we obtain the equilibrium equations of DNA with circular and noncircular cross sections, which provide an approach to describe the physical behaviors of A-, B-, Z-DNA. The results show that the elastic rod model with circular cross section can accurately characterize the equilibrium configurations of A-, B-DNA, while the model with elliptical cross sections is more suitable for Z-DNA.
Thermodynamic forward modeling of retrogressive hydration reactions induced by geofluid infiltration
Kuwatani, Tatsu; Toriumi, Mitsuhiro
2017-01-01
We have developed a new methodology for forward analysis of retrogressive hydration (rehydration) reactions by an improved thermodynamic forward modeling technique based on a differential thermodynamic approach (Gibbs' method). Based on natural observations and theoretical considerations, the progress of a rehydration reaction is modeled by incorporating a change in the effective bulk composition on account of the breakdown of the non-equilibrated phase and the amount of water infiltration into the system. Forward analyses of rehydration reactions under greenschist-facies conditions show that (1) the reaction progress of rehydration is proportional to the external water supply, and (2) the mineral compositions of equilibrated minerals are mainly controlled by P- T conditions and are similar to those in the global equilibrium model. Calculated results are in accordance with natural observations of rehydration reactions in greenschist-facies rocks, which supports the validity of the proposed model. The proposed model can be used as a basic forward model for various inversion analyses and numerical simulations and thus to understand the distribution and behavior of geofluids.[Figure not available: see fulltext.
A corresponding-states analysis of the liquid-vapor equilibrium properties of common water models
Fugel, Malte; Weiss, Volker C.
2017-02-01
Many atomistic potential models have been proposed to reproduce the properties of real water and to capture as many of its anomalies as possible. The large number of different models indicates that this task is by no means an easy one. Some models are reasonably successful for various properties, while others are designed to account for only a very few specific features of water accurately. Among the most popular models are SPC/E, TIP4P, TIP4P/2005, TIP4P/Ice, and TIP5P-E. Here, we report the equilibrium properties of the liquid-vapor coexistence, such as the densities of the liquid phase and the vapor phase, the interfacial tension between them, and the vapor pressure at saturation. From these data, the critical parameters are determined and subsequently used to cast the liquid-vapor coexistence properties into a corresponding-states form following Guggenheim's suggestions. Doing so reveals that the three TIP4P-based models display the same corresponding-states behavior and that the SPC/E model behaves quite similarly. Only the TIP5P-E model shows clear deviations from the corresponding-states properties of the other models. A comparison with data for real water shows that the reduced surface tension is well described, while the reduced coexistence curve is too wide. The models underestimate the critical compressibility factor and overestimate Guggenheim's ratio as well as the reduced boiling temperature (Guldberg's ratio). As demonstrated by the collapse of the data for the TIP4P-based models, these deviations are inherent to the specific model and cannot be corrected by a simple reparametrization. For comparison, the results for two recent polarizable models, HBP and BK3, are shown, and both models are seen to perform well in terms of absolute numbers and in a corresponding-states framework. The kind of analysis applied here can therefore be used as a guideline in the design of more accurate and yet simple multi-purpose models of water.
A corresponding-states analysis of the liquid-vapor equilibrium properties of common water models.
Fugel, Malte; Weiss, Volker C
2017-02-14
Many atomistic potential models have been proposed to reproduce the properties of real water and to capture as many of its anomalies as possible. The large number of different models indicates that this task is by no means an easy one. Some models are reasonably successful for various properties, while others are designed to account for only a very few specific features of water accurately. Among the most popular models are SPC/E, TIP4P, TIP4P/2005, TIP4P/Ice, and TIP5P-E. Here, we report the equilibrium properties of the liquid-vapor coexistence, such as the densities of the liquid phase and the vapor phase, the interfacial tension between them, and the vapor pressure at saturation. From these data, the critical parameters are determined and subsequently used to cast the liquid-vapor coexistence properties into a corresponding-states form following Guggenheim's suggestions. Doing so reveals that the three TIP4P-based models display the same corresponding-states behavior and that the SPC/E model behaves quite similarly. Only the TIP5P-E model shows clear deviations from the corresponding-states properties of the other models. A comparison with data for real water shows that the reduced surface tension is well described, while the reduced coexistence curve is too wide. The models underestimate the critical compressibility factor and overestimate Guggenheim's ratio as well as the reduced boiling temperature (Guldberg's ratio). As demonstrated by the collapse of the data for the TIP4P-based models, these deviations are inherent to the specific model and cannot be corrected by a simple reparametrization. For comparison, the results for two recent polarizable models, HBP and BK3, are shown, and both models are seen to perform well in terms of absolute numbers and in a corresponding-states framework. The kind of analysis applied here can therefore be used as a guideline in the design of more accurate and yet simple multi-purpose models of water.
State-to-state modeling of non equilibrium low-temperature atomic plasmas
Bultel, Arnaud; Morel, Vincent; Annaloro, Julien; Druguet, Marie-Claude
2017-03-01
The most relevant approach leading to a thorough understanding of the behavior of non equilibrium atomic plasmas is to elaborate state-to-state models in which the mass conservation equation is applied directly to atoms or ions on their excited states. The present communication reports the elaboration of such models and the results obtained. Two situations close to each other are considered. First, the plasmas produced behind shock fronts obtained in ground test facilities (shock tubes) or during planetary atmospheric entries of spacecrafts are discussed. We focused our attention on the nitrogen case for which a complete implementation of the CoRaM-N2 collisional-radiative model has been performed in a steady one-dimensional computation code based on the Rankine-Hugoniot assumptions. Second, the plasmas produced by the interaction between an ultra short laser pulse and a tungsten sample are discussed in the framework of the elaboration of the Laser-Induced Breakdown Spectroscopy (LIBS) technique. In the present case, tungsten has been chosen in the purpose of validating an in situ experimental method able to provide the elemental composition of the divertor wall of a tokamak like WEST or ITER undergoing high energetic deuterium and tritium nuclei fluxes.
Fluids with competing interactions. II. Validating a free energy model for equilibrium cluster size
Bollinger, Jonathan A.; Truskett, Thomas M.
2016-08-01
Using computer simulations, we validate a simple free energy model that can be analytically solved to predict the equilibrium size of self-limiting clusters of particles in the fluid state governed by a combination of short-range attractive and long-range repulsive pair potentials. The model is a semi-empirical adaptation and extension of the canonical free energy-based result due to Groenewold and Kegel [J. Phys. Chem. B 105, 11702-11709 (2001)], where we use new computer simulation data to systematically improve the cluster-size scalings with respect to the strengths of the competing interactions driving aggregation. We find that one can adapt a classical nucleation like theory for small energetically frustrated aggregates provided one appropriately accounts for a size-dependent, microscopic energy penalty of interface formation, which requires new scaling arguments. This framework is verified in part by considering the extensive scaling of intracluster bonding, where we uncover a superlinear scaling regime distinct from (and located between) the known regimes for small and large aggregates. We validate our model based on comparisons against approximately 100 different simulated systems comprising compact spherical aggregates with characteristic (terminal) sizes between six and sixty monomers, which correspond to wide ranges in experimentally controllable parameters.
Equilibrium model and algorithm of urban transit assignment based on augmented network
无
2009-01-01
The passenger flow assignment problem for the urban transit network is relatively complicated due to the complexity of the network structure and many factors influencing the passengers’ route and line choices. In the past three decades, many models have been proposed to solve the passenger flow assignment problem. However, the common-line problem remains challenging in transit flow assignment. In this paper, the characteristics of the urban transit network is analysed and a new technique of augmented network is proposed to represent the urban transit system. The purpose is to eliminate the complex common-line problem when modeling transit passenger flow assignment. Through this augmentation technique, the urban transit system can be represented by an augmented network-it then behaves like a simple network and can be used as a generalized network for traffic assignment or network analysis. This paper presents a user equilibrium model for the urban transit assignment problem based on such a technique. A numerical example is also provided to illustrate the approach.
Christensen, K. A.; Livbjerg, Hans
2000-01-01
multicomponent growth models are treated. The local gas phase composition is determined from a gas phase chemical equilibrium calculation combined with finite reaction rate kinetics for slower reactions. The model is useful in the analysis of boiler operation with respect to the formation of particles, HCl, SO2......The paper presents a numerical model for the simulation of gas to particle conversion and the chemical changes during cooling of a flue gas from the combustion of fuels rich in volatile alkali species. For the homogeneous nucleation of alkali species the model uses the classical theory modified...
The Use of VMD Data/Model to Test Different Thermodynamic Models for Vapour-Liquid Equilibrium
Abildskov, Jens; Azquierdo-Gil, M.A.; Jonsson, Gunnar Eigil
2004-01-01
Vacuum membrane distillation (VMD) has been studied as a separation process to remove volatile organic compounds from aqueous streams. A vapour pressure difference across a microporous hydrophobic membrane is the driving force for the mass transport through the membrane pores (this transport take...... values; membrane type: PTFE/PP/PVDF; feed flow rate; feed temperature. A comparison is made between different thermodynamic models for calculating the vapour-liquid equilibrium at the membrane/pore interface. (C) 2004 Elsevier B.V. All rights reserved....
T. P. V. B. Dias
2015-09-01
Full Text Available AbstractPhase equilibria of the reaction components are essential data for the design and process operations of biodiesel production. Despite their importance for the production of ethylic biodiesel, the reaction mixture, reactant (oil and ethanol and the product (fatty acid ethyl esters up to now have received less attention than the corresponding systems formed during the separation and purification phases of biodiesel production using ethanol. In this work, new experimental measurements were performed for the liquid-liquid equilibrium (LLE of the system containing vegetable oil (sunflower oil and canola oil + ethylic biodiesel of refined vegetable oil + anhydrous ethanol at 303.15 and at 323.15 K and the system containing refined palm oil + ethylic biodiesel of refined palm oil + ethanol at 318.15 K. The experimental data were successfully correlated by the nonrandom two-liquid (NRTL model; the average deviations between calculated and experimental data were smaller than 1.00%.
Ahmed, Khaliq; Fӧger, Karl
2017-03-01
The SOFC is well-established as a high-efficiency energy conversion technology with demonstrations of micro-CHP systems delivering 60% net electrical efficiency [1]. However, there are key challenges in the path to commercialization. Foremost among them is stack durability. Operating at high temperatures, the SOFC invariably suffers from thermally induced material degradation. This is compounded by thermal stresses within the SOFC stack which are generated from a number of interacting factors. Modelling is used as a tool for predicting undesirable temperature and current density gradients. For an internal reforming SOFC, fidelity of the model is strongly linked to the representation of the fuel reforming reactions, which dictate species concentrations and net heat release. It is critical for simulation of these profiles that the set of reaction rate expressions applicable for the particular anode catalyst are chosen in the model. A relatively wide spectrum of kinetic correlations has been reported in the literature. This work presents a comparative analysis of the internal distribution of temperature, current, voltage and compositions on a SOFC anode, using various combinations of reaction kinetics and equilibrium expressions for the reactions. The results highlight the significance of the fuel reforming chemistry and kinetics in the prediction of cell performance.
Comparison between phenomenological and ab-initio reaction and relaxation models in DSMC
Sebastião, Israel B.; Kulakhmetov, Marat; Alexeenko, Alina
2016-11-01
New state-specific vibrational-translational energy exchange and dissociation models, based on ab-initio data, are implemented in direct simulation Monte Carlo (DSMC) method and compared to the established Larsen-Borgnakke (LB) and total collision energy (TCE) phenomenological models. For consistency, both the LB and TCE models are calibrated with QCT-calculated O2+O data. The model comparison test cases include 0-D thermochemical relaxation under adiabatic conditions and 1-D normal shockwave calculations. The results show that both the ME-QCT-VT and LB models can reproduce vibrational relaxation accurately but the TCE model is unable to reproduce nonequilibrium rates even when it is calibrated to accurate equilibrium rates. The new reaction model does capture QCT-calculated nonequilibrium rates. For all investigated cases, we discuss the prediction differences based on the new model features.
GEM-E3: A computable general equilibrium model applied for Switzerland
Bahn, O. [Paul Scherrer Inst., CH-5232 Villigen PSI (Switzerland); Frei, C. [Ecole Polytechnique Federale de Lausanne (EPFL) and Paul Scherrer Inst. (Switzerland)
2000-01-01
The objectives of the European Research Project GEM-E3-ELITE, funded by the European Commission and coordinated by the Centre for European Economic Research (Germany), were to further develop the general equilibrium model GEM-E3 (Capros et al., 1995, 1997) and to conduct policy analysis through case studies. GEM-E3 is an applied general equilibrium model that analyses the macro-economy and its interaction with the energy system and the environment through the balancing of energy supply and demand, atmospheric emissions and pollution control, together with the fulfillment of overall equilibrium conditions. PSI's research objectives within GEM-E3-ELITE were to implement and apply GEM-E3 for Switzerland. The first objective required in particular the development of a Swiss database for each of GEM-E3 modules (economic module and environmental module). For the second objective, strategies to reduce CO{sub 2} emissions were evaluated for Switzerland. In order to develop the economic, PSI collaborated with the Laboratory of Applied Economics (LEA) of the University of Geneva and the Laboratory of Energy Systems (LASEN) of the Federal Institute of Technology in Lausanne (EPFL). The Swiss Federal Statistical Office (SFSO) and the Institute for Business Cycle Research (KOF) of the Swiss Federal Institute of Technology (ETH Zurich) contributed also data. The Swiss environmental database consists mainly of an Energy Balance Table and of an Emission Coefficients Table. Both were designed using national and international official statistics. The Emission Coefficients Table is furthermore based on know-how of the PSI GaBE Project. Using GEM-E3 Switzerland, two strategies to reduce the Swiss CO{sub 2} emissions were evaluated: a carbon tax ('tax only' strategy), and the combination of a carbon tax with the buying of CO{sub 2} emission permits ('permits and tax' strategy). In the first strategy, Switzerland would impose the necessary carbon tax to achieve
Rapid-Equilibrium Enzyme Kinetics
Alberty, Robert A.
2008-01-01
Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…
Shogin, Dmitry; Amund Amundsen, Per
2016-10-01
We test the physical relevance of the full and the truncated versions of the Israel–Stewart (IS) theory of irreversible thermodynamics in a cosmological setting. Using a dynamical systems method, we determine the asymptotic future of plane symmetric Bianchi type I spacetimes with a viscous mathematical fluid, keeping track of the magnitude of the relative dissipative fluxes, which determines the applicability of the IS theory. We consider the situations where the dissipative mechanisms of shear and bulk viscosity are involved separately and simultaneously. It is demonstrated that the only case in the given model when the fluid asymptotically approaches local thermal equilibrium, and the underlying assumptions of the IS theory are therefore not violated, is that of a dissipative fluid with vanishing bulk viscosity. The truncated IS equations for shear viscosity are found to produce solutions which manifest pathological dynamical features and, in addition, to be strongly sensitive to the choice of initial conditions. Since these features are observed already in the case of an oversimplified mathematical fluid model, we have no reason to assume that the truncation of the IS transport equations will produce relevant results for physically more realistic fluids. The possible role of bulk and shear viscosity in cosmological evolution is also discussed.
Equilibrium model prediction for the scatter in the star-forming main sequence
Mitra, Sourav; Davé, Romeel; Simha, Vimal; Finlator, Kristian
2017-01-01
The analytic `equilibrium model' for galaxy evolution using a mass balance equation is able to reproduce mean observed galaxy scaling relations between stellar mass, halo mass, star formation rate (SFR), and metallicity across the majority of cosmic time with a small number of parameters related to feedback. Here, we aim to test this data-constrained model to quantify deviations from the mean relation between stellar mass and SFR, i.e. the star-forming galaxy main sequence (MS). We implement fluctuation in halo accretion rates parametrized from merger-based simulations, and quantify the intrinsic scatter introduced into the MS under the assumption that fluctuations in star formation follow baryonic inflow fluctuations. We predict the 1σ MS scatter to be ˜0.2-0.25 dex over the stellar mass range 108-1011 M⊙ and a redshift range 0.5 ≲ z ≲ 3 for SFRs averaged over 100 Myr. The scatter increases modestly at z ≳ 3, as well as by averaging over shorter time-scales. The contribution from merger-induced star formation is generally small, around 5 per cent today and 10-15 per cent during the peak epoch of cosmic star formation. These results are generally consistent with available observations, suggesting that deviations from the MS primarily reflect stochasticity in the inflow rate owing to halo mergers.
Electrical characteristics of TIG arcs in argon from non-equilibrium modelling and experiment
Baeva, Margarita; Uhrlandt, Dirk; Siewert, Erwan
2016-09-01
Electric arcs are widely used in industrial processes so that a thorough understanding of the arc characteristics is highly important to industrial research and development. TIG welding arcs operated with pointed electrodes made of tungsten, doped with cerium oxide, have been studied in order to analyze in detail the electric field and the arc voltage. Newly developed non-equilibrium model of the arc is based on a complete diffusion treatment of particle fluxes, a generalized form of Ohm's law, and boundary conditions accounting for the space-charge sheaths within the magneto-hydrodynamic approach. Experiments have been carried out for electric currents in the range 5-200 A. The electric arc has been initiated between a WC20 cathode and a water-cooled copper plate placed 0.8 mm from each other. The arc length has been continuously increased by 0.1 mm up to 15 mm and the arc voltage has been simultaneously recorded. Modelling and experimental results will be presented and discussed.
Equilibrium Reconstructions with V3FIT and Current Evolution Modeling for 3-D Stellarator Plasmas
Schmitt, J. C.; Cianciosa, M.; Geiger, J.; Lazerson, S.
2016-10-01
V3FIT is a powerful equilibrium reconstruction tool for magnetic confinement fusion experiments which are inherently 3-D in nature (i.e. stellarators) or have 3-D components (tokamaks with 3-D shaping, reversed field pinches with helical states, etc). Here, we present details of the diagnostic modeling, constraints and the user interface for reconstructions of W7-X plasmas. For typical discharges during the OP1.1 run campaign of W7-X, the net toroidal current and current density profile do not reach steady-state. When modeling the current evolution in 3-D plasmas, both poloidal and toroidal currents are linked with both poloidal and toroidal fluxes. In contrast, in toroidally axisymmetric plasmas, the poloidal flux is linked only with the toroidal current and the toroidal current is linked only with the poloidal flux. Compared to an equivalently-sized axisymmetric configuration, the current diffusion in 3-D plasmas is enhanced, leading to a faster relaxation of the current profile to its steady-state. Implications for the time-evolution of the current and rotational transform profiles in stellarator plasmas are discussed. This work is supported by DoE Grant DE-SC00014529.
Analysis of strategic and deterrence equilibrium by modeling with a Van der Waals gas
Angaroni, Fabrizio
2016-01-01
In this paper we are going to propose a physical model that can represent a simple deterrence equilibrium situation, it is on based theory of unitary rational actors. This theory takes in account that a state is composed of a large number of people and a detailed study of the dynamics of any individual it is impossible. This situation, in Physics, is similar for gases, which are composed by a huge number of molecules and the study dynamics for one is impossible. Then a common approach, in this case, is the thermodynamics one. We only look to the macroscopic properties of the gas such as pressure, temperature and volume. Then in this sense thermodynamics could help to use theory of unitary rational actors also considering some non-rational factors. Firstly we are going to see how this model represents the Mutual assured destruction (MAD) theory if the influence of internal (economical, political,due to non state actors) instability and o conventional military forces are not taken in account. Secondly we are go...
Chirenti, Cecilia; Yoshida, Shin'ichirou
2013-01-01
Newly born neutron stars can present differential rotation, even if later it should be suppressed by viscosity or a sufficiently strong magnetic field. And in this early stage of its life, a neutron star is expected to have a strong emission of gravitational waves, which could be influenced by the differential rotation. We present here a new formalism for modelling differentially rotating neutron stars: working on the slow rotation approximation and assuming a small degree of differential rotation, we show that it is possible to separate variables in the Einstein field equations. The dragging of inertial frames is determined by solving three decoupled ODEs. After we establish our equilibrium model, we explore the influence of the differential rotation on the f and r-modes of oscillation of the neutron star in the Cowling approximation, and we also analyze an effect of the differential rotation on the emission of gravitational radiation from the f-modes. We see that the gravitational radiation from the f-modes...
Equilibrium model prediction for the scatter in the star-forming main sequence
Mitra, Sourav; Davé, Romeel; Simha, Vimal; Finlator, Kristian
2016-10-01
The analytic "equilibrium model" for galaxy evolution using a mass balance equation is able to reproduce mean observed galaxy scaling relations between stellar mass, halo mass, star formation rate (SFR) and metallicity across the majority of cosmic time with a small number of parameters related to feedback. Here we aim to test this data-constrained model to quantify deviations from the mean relation between stellar mass and SFR, i.e. the star-forming galaxy main sequence (MS). We implement fluctuation in halo accretion rates parameterised from merger-based simulations, and quantify the intrinsic scatter introduced into the MS under the assumption that fluctuations in star formation follow baryonic inflow fluctuations. We predict the 1-σ MS scatter to be ˜0.2 - 0.25 dex over the stellar mass range 108M⊙ to 1011M⊙ and a redshift range 0.5⪉ z⪉ 3 for SFRs averaged over 100 Myr. The scatter increases modestly at z⪆ 3, as well as by averaging over shorter timescales. The contribution from merger-induced star formation is generally small, around 5% today and 10 - 15% during the peak epoch of cosmic star formation. These results are generally consistent with available observations, suggesting that deviations from the MS primarily reflect stochasticity in the inflow rate owing to halo mergers.
Awalina; Harimawan, A.; Haryani, G. S.; Setiadi, T.
2017-05-01
The Biosorption of cadmium (II) ions on dried biomass of Aphanothece sp.which previously grown in a photobioreactor system with atmospheric carbon dioxide fed input, was studied in a batch system with respect to initial pH, biomass concentration, contact time, and temperature. The biomass exhibited the highest cadmium (II) uptake capacity at 30ºC, initial pH of 8.0±0.2 in 60 minute and initial cadmium (II) ion concentration of 7.76 mg/L. Maximum biosorption capacities were 16.47 mg/g, 54.95 mg/g and 119.05 mg/g at range of initial cadmium (II) 0.96-3.63 mg/L, 1.99-8.10 mg/L and 6.48-54.38 mg/L, respectively. Uptake kinetics follows the pseudo-second order model while equilibrium is best described by Langmuir isotherm model. Isotherms have been used to determine thermodynamic parameter process (free energy change, enthalpy change and entropy change). FTIR analysis of microalgae biomass revealed the presence of amino acids, carboxyl, hydroxyl, sulfhydryl and carbonyl groups, which are responsible for biosorption of metal ions. During repeated sorption/desorption cycles, the ratio of Cd (II) desorption to biosorption decreased from 81% (at first cycle) to only 27% (at the third cycle). Nevertheless, due to its higher biosorption capability than other adsorbent, Aphanothece sp appears to be a good biosorbent for removing metal Cd (II) ions from aqueous phase.
Wolery, T.J.; Daveler, S.A.
1992-10-09
EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ``single-point`` thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics.
Kang, Yoonyoung
While vast resources have been invested in the development of computational models for cost-benefit analysis for the "whole world" or for the largest economies (e.g. United States, Japan, Germany), the remainder have been thrown together into one model for the "rest of the world." This study presents a multi-sectoral, dynamic, computable general equilibrium (CGE) model for Korea. This research evaluates the impacts of controlling COsb2 emissions using a multisectoral CGE model. This CGE economy-energy-environment model analyzes and quantifies the interactions between COsb2, energy and economy. This study examines interactions and influences of key environmental policy components: applied economic instruments, emission targets, and environmental tax revenue recycling methods. The most cost-effective economic instrument is the carbon tax. The economic effects discussed include impacts on main macroeconomic variables (in particular, economic growth), sectoral production, and the energy market. This study considers several aspects of various COsb2 control policies, such as the basic variables in the economy: capital stock and net foreign debt. The results indicate emissions might be stabilized in Korea at the expense of economic growth and with dramatic sectoral allocation effects. Carbon dioxide emissions stabilization could be achieved to the tune of a 600 trillion won loss over a 20 year period (1990-2010). The average annual real GDP would decrease by 2.10% over the simulation period compared to the 5.87% increase in the Business-as-Usual. This model satisfies an immediate need for a policy simulation model for Korea and provides the basic framework for similar economies. It is critical to keep the central economic question at the forefront of any discussion regarding environmental protection. How much will reform cost, and what does the economy stand to gain and lose? Without this model, the policy makers might resort to hesitation or even blind speculation. With
A computational study of pyrolysis reactions of lignin model compounds
Thomas Elder
2010-01-01
Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...
Brignole, Esteban Alberto
2013-01-01
Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and
Polymerization as a Model Chain Reaction
Morton, Maurice
1973-01-01
Describes the features of the free radical, anionic, and cationic mechanisms of chain addition polymerization. Indicates that the nature of chain reactions can be best taught through the study of macromolecules. (CC)
Reaction Wheel Disturbance Model Extraction Software Project
National Aeronautics and Space Administration — Reaction wheel mechanical noise is one of the largest sources of disturbance forcing on space-based observatories. Such noise arises from mass imbalance, bearing...
Reaction Wheel Disturbance Model Extraction Software Project
National Aeronautics and Space Administration — Reaction wheel disturbances are some of the largest sources of noise on sensitive telescopes. Such wheel-induced mechanical noises are not well characterized....
Modelling Chemical Reasoning to Predict and Invent Reactions.
Segler, Marwin H S; Waller, Mark P
2016-11-11
The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery.