Kinetic exchange models for social opinion formation
Lallouache, Mehdi; Chakrabarti, Bikas K
2010-01-01
We propose a minimal model for the collective dynamics of opinion formation in the society, by modifying kinetic exchange dynamics studied in the context of income, money or wealth distributions in a society.
Kinetic exchange models: From molecular physics to social science
Patriarca, Marco; Chakraborti, Anirban
2013-08-01
We discuss several multi-agent models that have their origin in the kinetic exchange theory of statistical mechanics and have been recently applied to a variety of problems in the social sciences. This class of models can be easily adapted for simulations in areas other than physics, such as the modeling of income and wealth distributions in economics and opinion dynamics in sociology.
Kinetic exchange models: From molecular physics to social science
Patriarca, Marco
2013-01-01
We discuss several multi-agent models that have their origin in the kinetic exchange theory of statistical mechanics and have been recently applied to a variety of problems in the social sciences. This class of models can be easily adapted for simulations in areas other than physics, such as the modeling of income and wealth distributions in economics and opinion dynamics in sociology.
Agent dynamics in kinetic models of wealth exchange
Chatterjee, Arnab
2010-01-01
We study the dynamics of individual agents in some kinetic models of wealth exchange, particularly, the models with savings. For the model with uniform savings, agents perform simple random walks in the `"wealth space". On the other hand, we observe ballistic diffusion in the model with distributed savings. There is an associated skewness in the gain-loss distribution which explains the steady state behavior in such models. We find that in general an agent gains while interacting with an agent with a larger saving propensity.
Kinetic Modeling of Incremental Ambulatory Peritoneal Dialysis Exchanges.
Guest, Steven; Leypoldt, John K; Cassin, Michelle; Schreiber, Martin
2017-01-01
♦ BACKGROUND: Incremental peritoneal dialysis (PD), the gradual introduction of dialysate exchanges at less than full-dose therapy, has been infrequently described in clinical reports. One concern with less than full-dose dialysis is whether urea clearance targets are achievable with an incremental regimen. In this report, we used a large database of PD patients, across all membrane transport types, and performed urea kinetic modeling determinations of possible incremental regimens for an individual membrane type. ♦ METHODS: Using a modified 3-pore model of peritoneal transport, various incremental manual continuous ambulatory PD (CAPD) exchanges employing glucose and/or icodextrin were evaluated. Peritoneal urea clearances from those simulations were added to residual kidney urea clearance for patients with various glomerular filtration rates (GFRs), and the total weekly urea clearance was then compared to the total weekly urea Kt/V target of 1.7. All 4 peritoneal membrane types were modeled. For each simulated prescription, net ultrafiltration and carbohydrate absorption were also calculated. ♦ RESULTS: Incremental CAPD regimens of 2 exchanges a day met adequacy targets if the GFR was 6 mL/min/1.73 m(2) in all membrane types. For regimens employing 3 exchanges a day, Kt/V targets were achieved at GFR levels of 4 to 5 mL/min/1.73 m(2) in high transporters to low transporters but higher tonicity 2.5% glucose solutions or icodextrin were required in some regimens. ♦ CONCLUSIONS: This work demonstrates that with incremental CAPD regimens, urea kinetic targets are achievable in most new starts to PD with residual kidney function. Incremental PD may be a less intrusive, better accepted initial treatment regime and a cost-effective way to initiate chronic dialysis in the incident patient. The key role of intrinsic kidney function in incremental regimens is highlighted in this analysis and would warrant conscientious monitoring. Copyright © 2017 International
Phase transition in kinetic exchange opinion models with independence
Crokidakis, Nuno
2014-01-01
In this work we study the critical behavior of a three-state ($+1$, $-1$, $0$) opinion model with independence. Each agent has a probability $q$ to act as independent, i.e., he/she can choose his/her opinion independently of the opinions of the other agents. On the other hand, with the complementary probability $1-q$ the agent interacts with a randomly chosen individual through a kinetic exchange. Our analytical and numerical results show that the independence mechanism acts as a noise that induce an order-disorder transition at critical points $q_{c}$ that depend on the individuals' flexibility. For a special value of this flexibility the system undergoes a transition to an absorbing state with all opinions $0$.
Isotope exchange kinetics in metal hydrides I : TPLUG model.
Energy Technology Data Exchange (ETDEWEB)
Larson, Rich; James, Scott Carlton; Nilson, Robert H.
2011-05-01
A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show
Isotope exchange kinetics in metal hydrides I : TPLUG model.
Energy Technology Data Exchange (ETDEWEB)
Larson, Rich; James, Scott Carlton; Nilson, Robert H.
2011-05-01
A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show
Stydy on the Model of Ion Exchange Kinetics
Institute of Scientific and Technical Information of China (English)
ChenFengrong; JiangZhixin
1994-01-01
In this paper, a macrokinetics model equation describing the characteristics of the solid-liquid mass transfer has been proposed.The qualitative analysis and experimental verification have been done for this mode equation.The model equation can explain the ion exchange process considerably well.
Stochastic effects in a discretized kinetic model of economic exchange
Bertotti, M. L.; Chattopadhyay, A. K.; Modanese, G.
2017-04-01
Linear stochastic models and discretized kinetic theory are two complementary analytical techniques used for the investigation of complex systems of economic interactions. The former employ Langevin equations, with an emphasis on stock trade; the latter is based on systems of ordinary differential equations and is better suited for the description of binary interactions, taxation and welfare redistribution. We propose a new framework which establishes a connection between the two approaches by introducing random fluctuations into the kinetic model based on Langevin and Fokker-Planck formalisms. Numerical simulations of the resulting model indicate positive correlations between the Gini index and the total wealth, that suggest a growing inequality with increasing income. Further analysis shows, in the presence of a conserved total wealth, a simultaneous decrease in inequality as social mobility increases, in conformity with economic data.
Inequality measures in kinetic exchange models of wealth distributions
Ghosh, Asim; Chatterjee, Arnab; Inoue, Jun-ichi; Chakrabarti, Bikas K.
2016-06-01
In this paper, we study the inequality indices for some models of wealth exchange. We calculated Gini index and newly introduced k-index and compare the results with reported empirical data available for different countries. We have found lower and upper bounds for the indices and discuss the efficiencies of the models. Some exact analytical calculations are given for a few cases. We also exactly compute the quantities for Gamma and double Gamma distributions.
Inequality measures in kinetic exchange models of wealth distributions
Ghosh, Asim; Inoue, Jun-ichi; Chakrabarti, Bikas K
2015-01-01
In this paper, we study the inequality indices for some models of wealth exchange. We calculated Gini index and newly introduced k-index and compare the results with reported empirical data available for different countries. We have found lower and upper bounds for the indices and discuss the efficiencies of the models. Some exact analytical calculations are given for a few cases. We also exactly compute the quantities for Gamma and double Gamma distributions.
Zheng, Weihua; Andrec, Michael; Gallicchio, Emilio; Levy, Ronald M
2009-08-27
We present an approach to recover kinetics from a simplified protein folding model at different temperatures using the combined power of replica exchange (RE), a kinetic network, and effective stochastic dynamics. While RE simulations generate a large set of discrete states with the correct thermodynamics, kinetic information is lost due to the random exchange of temperatures. We show how we can recover the kinetics of a 2D continuous potential with an entropic barrier by using RE-generated discrete states as nodes of a kinetic network. By choosing the neighbors and the microscopic rates between the neighbors appropriately, the correct kinetics of the system can be recovered by running a kinetic simulation on the network. We fine-tune the parameters of the network by comparison with the effective drift velocities and diffusion coefficients of the system determined from short-time stochastic trajectories. One of the advantages of the kinetic network model is that the network can be built on a high-dimensional discretized state space, which can consist of multiple paths not consistent with a single reaction coordinate.
Kinetic exchange opinion model: solution in the single parameter map limit
Chowdhury, Krishanu Roy; Biswas, Soumyajyoti; Chakrabarti, Bikas K
2011-01-01
We study a recently proposed kinetic exchange opinion model (Lallouache et. al., Phys. Rev E 82, 056112 (2010)) in the limit of a single parameter map. Although it does not include the essentially complex behavior of the multiagent version, it provides us with the insight regarding the choice of order parameter for the system as well as some of its other dynamical properties. We also study the generalized two-parameter version of the model, and provide the exact phase diagram. The universal behavior along this phase boundary in terms of the suitably defined order parameter is seen.
Correlation between Gini index and mobility in a stochastic kinetic model of economic exchange
Bertotti, Maria Letizia; Chattopadhyay, Amit K.; Modanese, Giovanni
Starting from a class of stochastically driven kinetic models of economic exchange, here we present results highlighting the correlation of the Gini inequality index with the social mobility rate, close to dynamical equilibrium. Except for the ;canonical-additive case;, our numerical results consistently indicate negative values of the correlation coefficient, in agreement with empirical evidence. This confirms that growing inequality is not conducive to social mobility which then requires an ;external source; to sustain its dynamics. On the other hand, the sign of the correlation between inequality and total income in the canonical ensemble depends on the way wealth enters or leaves the system. At a technical level, the approach involves a generalization of a stochastic dynamical system formulation, that further paves the way for a probabilistic formulation of perturbed economic exchange models.
Scrape-off layer modeling with kinetic or diffusion description of charge-exchange atoms
Tokar, M. Z.
2016-12-01
Hydrogen isotope atoms, generated by charge-exchange (c-x) of neutral particles recycling from the first wall of a fusion reactor, are described either kinetically or in a diffusion approximation. In a one-dimensional (1-D) geometry, kinetic calculations are accelerated enormously by applying an approximate pass method for the assessment of integrals in the velocity space. This permits to perform an exhaustive comparison of calculations done with both approaches. The diffusion approximation is deduced directly from the velocity distribution function of c-x atoms in the limit of charge-exchanges with ions occurring much more frequently than ionization by electrons. The profiles across the flux surfaces of the plasma parameters averaged along the main part of the scrape-off layer (SOL), beyond the X-point and divertor regions, are calculated from the one-dimensional equations where parallel flows of charged particles and energy towards the divertor are taken into account as additional loss terms. It is demonstrated that the heat losses can be firmly estimated from the SOL averaged parameters only; for the particle loss the conditions in the divertor are of importance and the sensitivity of the results to the so-called "divertor impact factor" is investigated. The coupled 1-D models for neutral and charged species, with c-x atoms described either kinetically or in the diffusion approximation, are applied to assess the SOL conditions in a fusion reactor, with the input parameters from the European DEMO project. It is shown that the diffusion approximation provides practically the same profiles across the flux surfaces for the plasma density, electron, and ion temperatures, as those obtained with the kinetic description for c-x atoms. The main difference between the two approaches is observed in the characteristics of these species themselves. In particular, their energy flux onto the wall is underestimated in calculations with the diffusion approximation by 20 %-30
Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F
2016-12-06
In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (ENi(i)), (ii) assess their corresponding kinetic constants (k(i)), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k(i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.
CFD Modeling of Flow and Ion Exchange Kinetics in a Rotating Bed Reactor System
DEFF Research Database (Denmark)
Larsson, Hilde Kristina; Schjøtt Andersen, Patrick Alexander; Byström, Emil
2017-01-01
be achieved by making the baffles deeper. Two-phase simulations were performed, which managed to reproduce the deflection of the gas–liquid interface in an unbaffled system. A chemical reaction was implemented in the model, describing the ion-exchange phenomena in the porous material using four different...
THE KINETICS OF FILM-DIFFUSION-LIMITED ION-EXCHANGE
KRAAIJEVELD, G; WESSELINGH, JA
1993-01-01
The film-diffusion-limited ion exchange kinetics for the HCl-NaCl and HCl-CaCl2 systems on a Lewatit S100 ion exchanger are investigated. The ion exchange processes are modelled using the Maxwell-Stefan transport equations. The model uses only one fitting parameter. the film thickness, the Maxwell-S
Chakrabarti, Anindya S.
2012-12-01
We address the issue of the distribution of firm size. To this end we propose a model of firms in a closed, conserved economy populated with zero-intelligence agents who continuously move from one firm to another. We then analyze the size distribution and related statistics obtained from the model. There are three well known statistical features obtained from the panel study of the firms i.e., the power law in size (in terms of income and/or employment), the Laplace distribution in the growth rates and the slowly declining standard deviation of the growth rates conditional on the firm size. First, we show that the model generalizes the usual kinetic exchange models with binary interaction to interactions between an arbitrary number of agents. When the number of interacting agents is in the order of the system itself, it is possible to decouple the model. We provide exact results on the distributions which are not known yet for binary interactions. Our model easily reproduces the power law for the size distribution of firms (Zipf’s law). The fluctuations in the growth rate falls with increasing size following a power law (though the exponent does not match with the data). However, the distribution of the difference of the firm size in this model has Laplace distribution whereas the real data suggests that the difference of the log of sizes has the same distribution.
Analysis of proton exchange kinetics with time-dependent exchange rate.
Rutkowska-Wlodarczyk, Izabela; Kierdaszuk, Borys; Wlodarczyk, Jakub
2010-04-01
Mass spectrometry is used to probe the kinetics of hydrogen-deuterium exchange in lysozyme in pH 5, 6 and 7.4. An analysis based on a Verhulst growth model is proposed and effectively applied to the kinetics of the hydrogen exchange. The data are described by a power-like function which is based on a time-dependence of the exchange rate. Experimental data ranging over many time scales is considered and accurate fits of a power-like function are obtained. Results of fittings show correlation between faster hydrogen-deuterium exchange and increase of pH. Furthermore a model is presented that discriminates between easily exchangeable hydrogens (located in close proximity to the protein surface) and those protected from the exchange (located in the protein interior). A possible interpretation of the model and its biological significance are discussed.
Glossman, M. D.; Balbás, L. C.; Alonso, J. A.
1995-07-01
The radial electron density obtained for all the atoms of the main groups of the Periodic Table through the solution of the Euler equation associated with the nonlocal weighted density approximation (WDA) for the exchange and kinetic energy density functionals shows an incipient shell structure which is absent in other calculations using kinetic energy functionals based on the electronic density. The WDA radial density reveals two local maxima and the position of the first maximum correlates with the position of the maximum for the 1s orbital in the Hartree-Fock approximation. The cusp condition at the nucleus is fulfilled accurately. Also we study the density-based electron localization function (DELF) as a complementary procedure for the visualization of shells.
Oikawa, P. Y.; Jenerette, D.; Knox, S. H.; Sturtevant, C. S.; Verfaillie, J. G.; Baldocchi, D. D.
2014-12-01
Under California's Cap-and-Trade program, companies are looking to invest in land-use practices that will reduce greenhouse gas (GHG) emissions. The Sacramento-San Joaquin River Delta is a drained cultivated peatland system and a large source of CO2. To slow soil subsidence and reduce CO2 emissions, there is growing interest in converting drained peatlands to wetlands. However, wetlands are large sources of CH4 that could offset CO2-based GHG reductions. The goal of our research is to provide accurate measurements and model predictions of the changes in GHG budgets that occur when drained peatlands are restored to wetland conditions. We have installed a network of eddy covariance towers across multiple land use types in the Delta and have been measuring CO2 and CH4 ecosystem exchange for multiple years. In order to upscale these measurements through space and time we are using these data to parameterize and validate a process-based biogeochemical model. To predict gross primary productivity (GPP), we are using a simple light use efficiency (LUE) model which requires estimates of light, leaf area index and air temperature and can explain 90% of the observed variation in GPP in a mature wetland. To predict ecosystem respiration we have adapted the Dual Arrhenius Michaelis-Menten (DAMM) model. The LUE-DAMM model allows accurate simulation of half-hourly net ecosystem exchange (NEE) in a mature wetland (r2=0.85). We are working to expand the model to pasture, rice and alfalfa systems in the Delta. To predict methanogenesis, we again apply a modified DAMM model, using simple enzyme kinetics. However CH4 exchange is complex and we have thus expanded the model to predict not only microbial CH4 production, but also CH4 oxidation, CH4 storage and the physical processes regulating the release of CH4 to the atmosphere. The CH4-DAMM model allows accurate simulation of daily CH4 ecosystem exchange in a mature wetland (r2=0.55) and robust estimates of annual CH4 budgets. The LUE
Chain exchange kinetics of block copolymer micelles in ionic liquids
Ma, Yuanchi; Lodge, Timothy
The chain exchange kinetics of block copolymer micelles has been studied using time-resolved small-angle neutron scattering (TR-SANS), a key tool in determining the average micelle composition in contrast-matched solvents. In this work, PMMA-block-PnBMA was selected as the model block copolymer, which has a LCST behavior in the common ionic liquids, [EMIM][TFSI] and [BMIM][TFSI]. We examined the chain exchange kinetics of three PMMA-block-PnBMA copolymers, with identical PMMA block length (MPMMA = 25000) and different PnBMA block lengths (MPnBMA = 24000, 35000 and 53000); the Flory-Huggins interaction parameter (χ) between the core (PnBMA) and the solvent were varied by mixing [EMIM][TFSI] and [BMIM][TFSI] in different ratios. We found that the relaxation of the initial segregation of h- and d- micelles followed the same form with the time as previously developed by our group. Assuming that single chain expulsion is the rate limiting step, the thermal barrier was found to depend linearly on the core block length (Ncore) . Furthermore, the effect of χ on the chain exchange kinetics will also be discussed.
Iqbal, Muhammad; Saeed, Asma; Zafar, Saeed Iqbal
2009-05-15
Mango peel waste (MPW) was evaluated as a new sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution. The maximum sorption capacity of Cd(2+) and Pb(2+) was found to be 68.92 and 99.05mgg(-1), respectively. The kinetics of sorption of both metals was fast, reaching at equilibrium in 60min. Sorption kinetics and equilibria followed pseudo-second order and Langmuir adsorption isotherm models. FTIR analysis revealed that carboxyl and hydroxyl functional groups were mainly responsible for the sorption of Cd(2+) and Pb(2+). Chemical modification of MPW for blocking of carboxyl and hydroxyl groups showed that 72.46% and 76.26% removal of Cd(2+) and Pb(2+), respectively, was due to the involvement of carboxylic group, whereas 26.64% and 23.74% was due to the hydroxyl group. EDX analysis of MPW before and after metal sorption and release of cations (Ca(2+), Mg(2+), Na(+), K(+)) and proton H(+) from MPW with the corresponding uptake of Cd(2+) and Pb(2+) revealed that the main mechanism of sorption was ion exchange. The regeneration experiments showed that the MPW could be reused for five cycles without significant loss in its initial sorption capacity. The study points to the potential of new use of MPW as an effective sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution.
A simple nonlocal model for exchange.
Janesko, Benjamin G
2009-12-21
This work presents a new nonlocal model for the exchange energy density. The model is obtained from the product of the Kohn-Sham one-particle density matrix used to construct exact [Hartree-Fock-like (HF)] exchange, and an approximate density matrix used to construct local spin-density approximation (LSDA) exchange. The proposed exchange energy density has useful formal properties, including correct spin and coordinate scaling and the correct uniform limit. It can readily be evaluated in finite basis sets, with a computational scaling intermediate between HF exchange and semilocal quantities such as the noninteracting kinetic energy density. Applications to representative systems indicate that its properties are typically intermediate between HF and LSDA exchange, and often similar to global hybrids of HF and LSDA exchange. The model is proposed as a novel "Rung 3.5" ingredient for constructing approximate exchange-correlation functionals.
Kinetics of polymer adsorption, desorption and exchange.
Dijt, J.C.
1993-01-01
The aim of the study in this thesis was to gain more insight in the kinetics of polymer adsorption. To this end some well-characterised polymers have been systematically investigated.In the process of polymer adsorption one may distinguish three kinetic contributions: transport to the surface, attac
Measuring a hidden coordinate: Rate-exchange kinetics from 3D correlation functions
Berg, Mark A.; Darvin, Jason R.
2016-08-01
Nonexponential kinetics imply the existence of at least one slow variable other than the observable, that is, the system has a "hidden" coordinate. We develop a simple, but general, model that allows multidimensional correlation functions to be calculated for these systems. Homogeneous and heterogeneous mechanisms are both included, and slow exchange of the rates is allowed. This model shows that 2D and 3D correlation functions of the observable measure the distribution and kinetics of the hidden coordinate controlling the rate exchange. Both the mean exchange time and the shape of the exchange relaxation are measurable. However, complications arise because higher correlation functions are sums of multiple "pathways," each of which measures different dynamics. Only one 3D pathway involves exchange dynamics. Care must be used to extract exchange dynamics without contamination from other processes.
Measuring a hidden coordinate: Rate-exchange kinetics from 3D correlation functions.
Berg, Mark A; Darvin, Jason R
2016-08-07
Nonexponential kinetics imply the existence of at least one slow variable other than the observable, that is, the system has a "hidden" coordinate. We develop a simple, but general, model that allows multidimensional correlation functions to be calculated for these systems. Homogeneous and heterogeneous mechanisms are both included, and slow exchange of the rates is allowed. This model shows that 2D and 3D correlation functions of the observable measure the distribution and kinetics of the hidden coordinate controlling the rate exchange. Both the mean exchange time and the shape of the exchange relaxation are measurable. However, complications arise because higher correlation functions are sums of multiple "pathways," each of which measures different dynamics. Only one 3D pathway involves exchange dynamics. Care must be used to extract exchange dynamics without contamination from other processes.
Oxidative desulfurization: kinetic modelling.
Dhir, S; Uppaluri, R; Purkait, M K
2009-01-30
Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.
Ligand Exchange Kinetics of Environmentally Relevant Metals
Energy Technology Data Exchange (ETDEWEB)
Panasci, Adele Frances [Univ. of California, Davis, CA (United States)
2014-07-15
The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as ^{237}Np is a radioactive transuranic element with a half-life of 2 million years.
Kinetic isotope effects for fast deuterium and proton exchange rates.
Canet, Estel; Mammoli, Daniele; Kadeřávek, Pavel; Pelupessy, Philippe; Bodenhausen, Geoffrey
2016-04-21
By monitoring the effect of deuterium decoupling on the decay of transverse (15)N magnetization in D-(15)N spin pairs during multiple-refocusing echo sequences, we have determined fast D-D exchange rates kD and compared them with fast H-H exchange rates kH in tryptophan to determine the kinetic isotope effect as a function of pH and temperature.
Yang, Po-Wei; Lin, Tsang-Lang; Hu, Yuan; Jeng, U-Ser
2015-03-21
Time-resolved small-angle X-ray scattering was applied to study charged lipid exchange between oppositely charged disc-shaped bicelles. The exchange of charged lipids gradually reduces the surface charge density and weakens the electrostatic attraction between the oppositely charged bicelles which form alternately stacked aggregates upon mixing. Initially, at a high surface charge density with almost no free water layer between the stacked bicelles, fast exchange kinetics dominate the exchange process. At a later stage with a lower surface charge density and a larger water gap between the stacked bicelles, slow exchange kinetics take over. The fast exchange kinetics are correlated with the close contact of the bicelles when there is almost no free water layer between the tightly bound bicelles with a charged lipid exchange time constant as short as 20-40 min. When the water gap becomes large enough to have a free water layer between the stacked bicelles, the fast lipid exchange kinetics are taken over by slow lipid exchange kinetics with time constants around 200-300 min, which are comparable to the typical time constant of lipid exchange between vesicles in aqueous solution. These two kinds of exchange mode fit well with the lipid exchange models of transient hemifusion for the fast mode and monomer exchange for the slow mode.
Energy Technology Data Exchange (ETDEWEB)
Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)
1993-12-01
This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.
Diffusion kinetics of the ion exchange of benzocaine on sulfocationites
Al'tshuler, O. G.; Shkurenko, G. Yu.; Gorlov, A. A.; Al'tshuler, G. N.
2016-06-01
The theory of the ion exchange kinetics on strong acid cationites with the participation of weak electrolytes is discussed. The kinetics of desorption of benzocaine in the protonated and molecular forms from strong acid cationites, sulfonated polycalixarene, and KU-23 30/100 sulfocationite, is studied experimentally. It is shown that the flow of protonated benzocaine from cationite upon desorption proceeding by the ion-exchange mechanism is more intense than upon desorption of nonionized benzocaine molecules. It is established that the diffusion coefficient of benzocaine cations is (1.21 ± 0.23) × 10-12 m2/s in KU-23 30/100 sulfocation and (0.65 ± 0.06) × 10-13 m2/s in sulfonated polycalixarene, while the diffusion coefficient of benzocaine molecules is (0.65 ± 0.15) × 10-14 m2/s in sulfonated polycalixarene.
Modelling heart rate kinetics.
Zakynthinaki, Maria S
2015-01-01
The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women).
Modelling heart rate kinetics.
Directory of Open Access Journals (Sweden)
Maria S Zakynthinaki
Full Text Available The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise. Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women.
Zakynthinaki, Maria S.
2015-01-01
The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164
Kinetics of DSB rejoining and formation of simple chromosome exchange aberrations
Cucinotta, F. A.; Nikjoo, H.; O'Neill, P.; Goodhead, D. T.
2000-01-01
PURPOSE: To investigate the role of kinetics in the processing of DNA double strand breaks (DSB), and the formation of simple chromosome exchange aberrations following X-ray exposures to mammalian cells based on an enzymatic approach. METHODS: Using computer simulations based on a biochemical approach, rate-equations that describe the processing of DSB through the formation of a DNA-enzyme complex were formulated. A second model that allows for competition between two processing pathways was also formulated. The formation of simple exchange aberrations was modelled as misrepair during the recombination of single DSB with undamaged DNA. Non-linear coupled differential equations corresponding to biochemical pathways were solved numerically by fitting to experimental data. RESULTS: When mediated by a DSB repair enzyme complex, the processing of single DSB showed a complex behaviour that gives the appearance of fast and slow components of rejoining. This is due to the time-delay caused by the action time of enzymes in biomolecular reactions. It is shown that the kinetic- and dose-responses of simple chromosome exchange aberrations are well described by a recombination model of DSB interacting with undamaged DNA when aberration formation increases with linear dose-dependence. Competition between two or more recombination processes is shown to lead to the formation of simple exchange aberrations with a dose-dependence similar to that of a linear quadratic model. CONCLUSIONS: Using a minimal number of assumptions, the kinetics and dose response observed experimentally for DSB rejoining and the formation of simple chromosome exchange aberrations are shown to be consistent with kinetic models based on enzymatic reaction approaches. A non-linear dose response for simple exchange aberrations is possible in a model of recombination of DNA containing a DSB with undamaged DNA when two or more pathways compete for DSB repair.
STRUCTURAL FEATURE AND EXCHANGE KINETICS OF CARBOXYLATED POLYPROPYLENE ION EXCHANGE RESIN
Institute of Scientific and Technical Information of China (English)
WU Chinyung; YANG Chaoshiung; YANG Chong
1987-01-01
The present article deals with the exchange process of bivalent metal ions, such as Zn2 +, Cd2 + and Hg2+, etc., taken up by non-crosslinked carboxylated polypropylene (CPP) resin. The control factor of the exchange rate deduced from the kinetic data is governed basically by the chemical reaction rather than the mass transfer effect particle diffusion and/or liquid film diffusion. In solution, all the graft chains in the outer shell ofa CPP resin could form a "quasi-macromolecular solution" domain. This opinion further demonstrates the structural pattern of CPP resin proposed in earlier paper[1].
Onsager reciprocity principle for kinetic models and kinetic schemes
Mahendra, Ajit Kumar
2013-01-01
Boltzmann equation requires some alternative simpler kinetic model like BGK to replace the collision term. Such a kinetic model which replaces the Boltzmann collision integral should preserve the basic properties and characteristics of the Boltzmann equation and comply with the requirements of non equilibrium thermodynamics. Most of the research in development of kinetic theory based methods have focused more on entropy conditions, stability and ignored the crucial aspect of non equilibrium thermodynamics. The paper presents a new kinetic model formulated based on the principles of non equilibrium thermodynamics. The new kinetic model yields correct transport coefficients and satisfies Onsager's reciprocity relationship. The present work also describes a novel kinetic particle method and gas kinetic scheme based on this linkage of non-equilibrium thermodynamics and kinetic theory. The work also presents derivation of kinetic theory based wall boundary condition which complies with the principles of non-equili...
A comparative study of ion exchange kinetics in zinc/lead-modified zeolite-clinoptilolite systems.
Trgo, M; Perić, J; Medvidović, N Vukojević
2006-08-25
The kinetics of zinc and lead ions removal by modified zeolite-clinoptilolite has been investigated. The rate of the ion exchange process for lead ions is faster than for zinc ions, as well as the time needed to reach the equilibrium. The ion exchange capacity of zeolite of lead ions is doubly higher than that of zinc ions. Diffusion models according to the Vermeulen's approximation, the parabolic diffusion model and the homogeneous diffusion model have been tested with the experimental data of ion exchange for zinc and lead. For both systems examined, the best fit of the models proposed with the experimental data was shown by the Vermeulen's approximation and the homogeneous diffusion model with t-->t(infinity). The diffusion coefficients are calculated from kinetic models of lead ions they are of the order of 10(-6)cm(2)/min, constant for all examined initial concentrations and not dependent on time. The diffusion coefficients in the system of zinc ions is of the order of 10(-8)cm(2)/min, also independent of initial concentrations, but decreasing with time from the beginning of ion exchange to the equilibrium.
Kinetics Modeling of Cancer Immunology.
1986-05-09
CANCER IMMUNOLOGY -1 DTICS ELECTED SEP 9 8 UNITED STATES NAVAL ACADEMY ANNAPOLIS, MARYLAND V ,1986 %,e docment ha le approved for public A." I and sale...1986 4. TITLE (and Subtitle) S. TYPE OF REPORT & PERIOD COVERED KINETICS MODELING OF CANCER IMMUNOLOGY Final: 1985/1986 6. PERFORMING ORG. REPORT...137 (1986) "Kinetics Modeling of Cancer Immunology " A Trident Scholar Project Report by Midn I/C Scott Helmers, Class of 1986 United States Naval
Crystallization Kinetics within a Generic Modelling Framework
DEFF Research Database (Denmark)
Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist
2013-01-01
An existing generic modelling framework has been expanded with tools for kinetic model analysis. The analysis of kinetics is carried out within the framework where kinetic constitutive models are collected, analysed and utilized for the simulation of crystallization operations. A modelling...... procedure is proposed to gain the information of crystallization operation kinetic model analysis and utilize this for faster evaluation of crystallization operations....
Majoni, Stephen; Hossenlopp, Jeanne M
2010-12-16
Anion exchange reactions of nanodimensional layered metal hydroxide compounds are utilized to create materials with targeted physical and chemical properties and also as a means for controlled release of intercalated anions. The kinetics of this important class of reaction are generally characterized by model-based approaches. In this work, a different approach based on isothermal, isoconversional analysis was utilized to determine effective activation energies with respect to extent of reaction. Two different layered metal hydroxide materials were chosen for reaction with chloride anions, using a temperature range of 30-60 °C. The concentrations of anions released into solution and the changes in polycrystalline solid phases were evaluated using model-based (Avrami-Erofe'ev nucleation-growth model) and model-free (integral isoconversional) methods. The results demonstrate the utility of the isoconversional approach for identifying when fitting to a single model is not appropriate, particularly for characterizing the temperature dependence of the reaction kinetics.
Kinetic analysis of an anion exchange absorbent for CO2 capture from ambient air.
Shi, Xiaoyang; Li, Qibin; Wang, Tao; Lackner, Klaus S
2017-01-01
This study reports a preparation method of a new moisture swing sorbent for CO2 capture from air. The new sorbent components include ion exchange resin (IER) and polyvinyl chloride (PVC) as a binder. The IER can absorb CO2 when surrounding is dry and release CO2 when surrounding is wet. The manuscript presents the studies of membrane structure, kinetic model of absorption process, performance of desorption process and the diffusivity of water molecules in the CO2 absorbent. It has been proved that the kinetic performance of CO2 absorption/desorption can be improved by using thin binder and hot water treatment. The fast kinetics of P-100-90C absorbent is due to the thin PVC binder, and high diffusion rate of H2O molecules in the sample. The impressive is this new CO2 absorbent has the fastest CO2 absorption rate among all absorbents which have been reported by other up-to-date literatures.
Chemical kinetics and combustion modeling
Energy Technology Data Exchange (ETDEWEB)
Miller, J.A. [Sandia National Laboratories, Livermore, CA (United States)
1993-12-01
The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.
On Kinetics Modeling of Vibrational Energy Transfer
Gilmore, John O.; Sharma, Surendra P.; Cavolowsky, John A. (Technical Monitor)
1996-01-01
Two models of vibrational energy exchange are compared at equilibrium to the elementary vibrational exchange reaction for a binary mixture. The first model, non-linear in the species vibrational energies, was derived by Schwartz, Slawsky, and Herzfeld (SSH) by considering the detailed kinetics of vibrational energy levels. This model recovers the result demanded at equilibrium by the elementary reaction. The second model is more recent, and is gaining use in certain areas of computational fluid dynamics. This model, linear in the species vibrational energies, is shown not to recover the required equilibrium result. Further, this more recent model is inconsistent with its suggested rate constants in that those rate constants were inferred from measurements by using the SSH model to reduce the data. The non-linear versus linear nature of these two models can lead to significant differences in vibrational energy coupling. Use of the contemporary model may lead to significant misconceptions, especially when integrated in computer codes considering multiple energy coupling mechanisms.
Kinetic Modeling of Biological Systems
Energy Technology Data Exchange (ETDEWEB)
Resat, Haluk; Petzold, Linda; Pettigrew, Michel F.
2009-04-21
The dynamics of how its constituent components interact define the spatio-temporal response of a natural system to stimuli. Modeling the kinetics of the processes that represent a biophysical system has long been pursued with the aim of improving our understanding of the studied system. Due to the unique properties of biological systems, in addition to the usual difficulties faced in modeling the dynamics of physical or chemical systems, biological simulations encounter difficulties that result from intrinsic multiscale and stochastic nature of the biological processes. This chapter discusses the implications for simulation of models involving interacting species with very low copy numbers, which often occur in biological systems and give rise to significant relative fluctuations. The conditions necessitating the use of stochastic kinetic simulation methods and the mathematical foundations of the stochastic simulation algorithms are presented. How the well-organized structural hierarchies often seen in biological systems can lead to multiscale problems, and possible ways to address the encountered computational difficulties are discussed. We present the details of the existing kinetic simulation methods, and discuss their strengths and shortcomings. A list of the publicly available kinetic simulation tools and our reflections for future prospects are also provided.
Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed
Directory of Open Access Journals (Sweden)
T.M. Zewail
2015-03-01
Full Text Available Spouted bed contactor is a hybrid of fixed and fluidized bed contactors, which retains the advantages of each with good hydrodynamic conditions. The aim of the present study is to investigate the performance of a batch conical air spouted vessel for heavy metal removal by strong cation exchange resins (AMBERJET 1200 Na. The effect of various parameters such as type of heavy metal ions (Ni+2 and Pb+2, contact time, superficial air velocity and initial heavy metal ion concentration on % heavy metal ion removal has been investigated. It has been found that under optimum conditions 98% and 99% removal of Ni+2 and Pb+2 were achieved respectively. Several kinetic models were used to test the experimental data and to examine the controlling mechanism of the sorption process. The present results of Ni+2 and Pb+2 well fit pseudo second order kinetic model with a high correlation coefficient. Both film diffusion and intra-particle diffusion contribute to the ion exchange process. The present study revealed that spouted bed vessel may provide an effective alternative for conducting ion exchange reactions.
Impact of natural organic matter properties on the kinetics of suspended ion exchange process.
Bazri, Mohammad Mahdi; Mohseni, Madjid
2016-03-15
Removal kinetics of four standard organic matter isolates under the application of strongly basic ion exchange resins (IEX) in suspended mode was studied under commercial application conditions. Suwannee River natural organic matter (SRNOM), SR fulvic acid (SRFA), and Pony Lake fulvic acid (PLFA) were greatly removed (>90%) and highly preferred by IEX resins (α > 5, over Cl(-), and HCO3(-)) while SR humic acid (SRHA) was the least preferred organic structure among the four isolates studied (α ≈ 1). Moreover, the efficacy of removal for fulvic acids (i.e., SRFA, PLFA) was consistent over consecutive reuse of IEX resins (i.e., loading cycles) whereas it decreased for SRNOM and SRHA over the course of operation. The stoichiometric correlation between the chloride released from the resins as a result of organic molecules uptake indicated that ion exchange was the dominant mechanism. Results obtained indicated that molecular weight and charge density of isolates played a major role in the performance of ion exchange process for organic matter removal. Furthermore, various empirical and physical models were evaluated using the experimental data and pore diffusion was found to be the rate-liming step during the uptake of organic matters; hence, it was used as the appropriate model to predict the kinetics of removal. Consequently, free liquid diffusivities and effective pore diffusion coefficients of organic molecules were estimated and findings were in agreement with the literature data that were obtained from spectrophotometric methods.
Ferrokinetics: a biologic model for plasma iron exchange in man.
Cook, J D; Marsaglia, G; Eschbach, J W; Funk, D D; Finch, C A
1970-02-01
A method is presented for calculating internal iron kinetics. An early reflux associated with extravascular exchange and a late reflux associated with erythropoiesis are described. A biologic model of iron exchange is proposed in which erythron iron turnover is divided into an effective portion (iron fixed in circulating red cells) and wastage iron of erythropoiesis (late reflux). Nonerythroid iron exchange also has a fixed portion (parenchymal uptake) and an early reflux (lymphatic circuit), both of which correlate in amount with the amount of plasma iron. Ferrokinetic measurements in normal subjects and in various pathologic states are presented to validate the model.
Energy Technology Data Exchange (ETDEWEB)
Iqbal, Muhammad [Biotechnology Group, Centre for Environment Protection Studies, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan)], E-mail: iqbalm@fulbrightweb.org; Saeed, Asma [Biotechnology Group, Centre for Environment Protection Studies, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan); Zafar, Saeed Iqbal [School of Biological Sciences, University of Punjab, Lahore 54590 (Pakistan)
2009-05-15
Mango peel waste (MPW) was evaluated as a new sorbent for the removal of Cd{sup 2+} and Pb{sup 2+} from aqueous solution. The maximum sorption capacity of Cd{sup 2+} and Pb{sup 2+} was found to be 68.92 and 99.05 mg g{sup -1}, respectively. The kinetics of sorption of both metals was fast, reaching at equilibrium in 60 min. Sorption kinetics and equilibria followed pseudo-second order and Langmuir adsorption isotherm models. FTIR analysis revealed that carboxyl and hydroxyl functional groups were mainly responsible for the sorption of Cd{sup 2+} and Pb{sup 2+}. Chemical modification of MPW for blocking of carboxyl and hydroxyl groups showed that 72.46% and 76.26% removal of Cd{sup 2+} and Pb{sup 2+}, respectively, was due to the involvement of carboxylic group, whereas 26.64% and 23.74% was due to the hydroxyl group. EDX analysis of MPW before and after metal sorption and release of cations (Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, K{sup +}) and proton H{sup +} from MPW with the corresponding uptake of Cd{sup 2+} and Pb{sup 2+} revealed that the main mechanism of sorption was ion exchange. The regeneration experiments showed that the MPW could be reused for five cycles without significant loss in its initial sorption capacity. The study points to the potential of new use of MPW as an effective sorbent for the removal of Cd{sup 2+} and Pb{sup 2+} from aqueous solution.
Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.
Dang, Liem X; Chang, Tsun-Mei
2016-09-07
In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.
Kinetic modelling of enzymatic starch hydrolysis
Bednarska, K.A.
2015-01-01
Kinetic modelling of enzymatic starch hydrolysis – a summary K.A. Bednarska The dissertation entitled ‘Kinetic modelling of enzymatic starch hydrolysis’ describes the enzymatic hydrolysis and kinetic modelling of liquefaction and saccharification of wheat starch. A
Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes
Institute of Scientific and Technical Information of China (English)
WANG Hai-Feng; LIN Zhen-Quan; KONG Xiang-Mu
2006-01-01
Two catalyzed-birth models of n-species (n≥2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates Amk and Amj of the same species with the rate kernels Km (k,j)=Kmkj (m=1, 2,..., n, n≥2), and aggregates of An species catalyze a monomer-birth of Al species (l=1,2,..., n-1) with the catalysis rate kernel Jl(k,j)=Jlkjυ. The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution alk(t) of Al species depends crucially on the value of the catalysis rate parameter v: (i) alk(t) obeys the conventional scaling law in the case of υ≤0, (ii) alk (t) satisfies a modified scaling form in the case of υ＞0. In the second model,the mechanism of monomer-birth of An-species catalyzed by Al species is added on the basis of the first model, that is,the aggregates of Al and An species catalyze each other to cause monomer-birth. The kinetic behaviors of Al and Anspecies are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ≤0,(ii) gelling at finite time withυ＞0.
Kinetic models of conjugated metabolic cycles
Ershov, Yu. A.
2016-01-01
A general method is developed for the quantitative kinetic analysis of conjugated metabolic cycles in the human organism. This method is used as a basis for constructing a kinetic graph and model of the conjugated citric acid and ureapoiesis cycles. The results from a kinetic analysis of the model for these cycles are given.
Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.
Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind
2014-08-22
Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems.
Anisotropic exchange-interaction model: From the Potts model to the exchange-interaction model
King, T. C.; Chen, H. H.
1995-04-01
A spin model called the anisotropic exchange-interaction model is proposed. The Potts model, the exchange-interaction model, and the spin-1/2 anisotropic Heisenberg model are special cases of the proposed model. Thermodynamic properties of the model on the bcc and the fcc lattices are determined by the constant-coupling approximation.
Lee, Yueh-Lin; Lee, Dongkyu; Wang, Xiao Renshaw; Lee, Ho Nyung; Morgan, Dane; Shao-Horn, Yang
2016-01-21
Through alignment of theoretical modeling with experimental measurements of oxygen surface exchange kinetics on (001)-oriented La2-xSrxMO4+δ (M = Co, Ni, Cu) thin films, we demonstrate here the capability of the theoretical bulk O 2p-band centers to correlate with oxygen surface-exchange kinetics of the Ruddlesden-Popper oxide (RP214) (001)-oriented thin films. In addition, we demonstrate that the bulk O 2p-band centers can also correlate with the experimental activation energies for bulk oxygen transport and oxygen surface exchange of both the RP214 and the perovskite polycrystalline materials reported in the literature, indicating the effectiveness of the bulk O 2p-band centers in describing the associated energetics and kinetics. We propose that the opposite slopes of the bulk O 2p-band center correlations between the RP214 and the perovskite materials are due to the intrinsic mechanistic differences of their oxygen surface exchange kinetics and bulk anionic transport.
Institute of Scientific and Technical Information of China (English)
朱先正; 霍广生; 倪捷; 宋琼
2016-01-01
The equilibrium adsorption isotherm and kinetic of the sorption process for W and Mo on macro chelating resin D403 were investigated on single Na2MoO4 and Na2WO4 solutions. The sorption isotherm results show that the adsorption process of W obeys the Freundlich model very well whereas the exchange process with Mo approximately follows the Henry model. The kinetic experiments show that the intraparticle diffusion process was the rate-determining step for W sorption on the resin, and the corresponding activation energy is calculated to be 21.976 kJ/mol.
Design and comparison of exchange spectroscopy approaches to cryptophane-xenon host-guest kinetics.
Korchak, Sergey; Kilian, Wolfgang; Schröder, Leif; Mitschang, Lorenz
2016-04-01
Exchange spectroscopy is used in combination with a variation of xenon concentration to disentangle the kinetics of the reversible binding of xenon to cryptophane-A. The signal intensity of either free or crytophane-bound xenon decays in a manner characteristic of the underlying exchange reactions when the spins in the other pool are perturbed. Three experimental approaches, including the well-known Hyper-CEST method, are shown to effectively entail a simple linear dependence of the signal depletion rate, or of a related quantity, on free xenon concentration. This occurs when using spin pool saturation or inversion followed by free exchange. The identification and quantification of contributions to the binding kinetics is then straightforward: in the depletion rate plot, the intercept at the vanishing free xenon concentration represents the kinetic rate coefficient for xenon detachment from the host by dissociative processes while the slope is indicative of the kinetic rate coefficient for degenerate exchange reactions. Comparing quantified kinetic rates for hyperpolarized xenon in aqueous solution reveals the high accuracy of each approach but also shows differences in the precision of the numerical results and in the requirements for prior knowledge. Because of their broad range of applicability the proposed exchange spectroscopy experiments can be readily used to unravel the kinetics of complex formation of xenon with host molecules in the various situations appearing in practice.
Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study
Directory of Open Access Journals (Sweden)
Amrit P. Toor
2011-05-01
Full Text Available The kinetic behavior of esterification of lactic acid with isopropanol over an acidic cation exchange resin, Amberlyst 15, was studied under isothermal condition. Isopropyl lactate synthesized in this reaction is an important pharmaceutical intermediate. The experiments were carried out in a stirred batch reactor in the temperature range of 323.15 to 353.15 K. The effect of various parameters such as temperature, molar ratio and catalyst loading was studied. Variation in parameters on rate of reaction demonstrated that the reaction was intrinsically controlled. Kinetic modeling was performed using Eley-Rideal model which acceptably fits the experimental data. The activation energy was found to be 22.007 kJ/mol and frequency factor was 0.036809 l2 g-1 mol-1 min-1 for forward reaction. The value of entropy for the forward reaction was found to be 182.317 J K-1 mol-1 . © 2011 BCREC UNDIP. All rights reserved(Received: 19th January 2011, Revised: 16th March 2011; Accepted: 16th March 2011[How to Cite: A.P. Toor, M. Sharma, S. Thakur, and R. K. Wanchoo. (2011. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 39-45. doi:10.9767/bcrec.6.1.791.39-45][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.791.39-45 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/791 ] | View in
Energy Technology Data Exchange (ETDEWEB)
Thompson, A.S.; Thompson, B.R.
1988-09-01
The analytical model of nuclear reactor transients, incorporating both mechanical and nuclear effects, simulates reactor kinetics. Linear analysis shows the stability borderline for small power perturbations. In a stable system, initial power disturbances die out with time. With an unstable combination of nuclear and mechanical characteristics, initial disturbances persist and may increase with time. With large instability, oscillations of great magnitude occur. Stability requirements set limits on the power density at which particular reactors can operate. The limiting power density depends largely on the product of two terms: the fraction of delayed neutrons and the frictional damping of vibratory motion in reactor core components. As the fraction of delayed neutrons is essentially fixed, mechanical damping largely determines the maximum power density. A computer program, based on the analytical model, calculates and plots reactor power as a nonlinear function of time in response to assigned values of mechanical and nuclear characteristics.
Fielitz, Peter; Borchardt, Günter
2016-08-10
In the dedicated literature the oxygen surface exchange coefficient KO and the equilibrium oxygen exchange rate [Fraktur R] are considered to be directly proportional to each other regardless of the experimental circumstances. Recent experimental observations, however, contradict the consequences of this assumption. Most surprising is the finding that the apparent activation energy of KO depends dramatically on the kinetic regime in which it has been determined, i.e. surface exchange controlled vs. mixed or diffusion controlled. This work demonstrates how the diffusion boundary condition at the gas/solid interface inevitably entails a correlation between the oxygen surface exchange coefficient KO and the oxygen self-diffusion coefficient DO in the bulk ("on top" of the correlation between KO and [Fraktur R] for the pure surface exchange regime). The model can thus quantitatively explain the range of apparent activation energies measured in the different regimes: in the surface exchange regime the apparent activation energy only contains the contribution of the equilibrium exchange rate, whereas in the mixed or in the diffusion controlled regime the contribution of the oxygen self-diffusivity has also to be taken into account, which may yield significantly higher apparent activation energies and simultaneously quantifies the correlation KO ∝ DO(1/2) observed for a large number of oxides in the mixed or diffusion controlled regime, respectively.
Kinetics model for lutate dosimetry
Energy Technology Data Exchange (ETDEWEB)
Lima, M.F.; Mesquita, C.H., E-mail: mflima@ipen.br, E-mail: chmesqui@ipen.br [Instituto de Pesquisas Energeticas (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)
2013-11-01
The use of compartmental analysis to predict the behavior of drugs in the organism is considered the better option among numerous methods employed in pharmacodynamics. A six compartments model was developed to determinate the kinetic constants of 177Lu-DOTATATO biodistribution using data from one published study with 67 patients treated by PRRT (Peptide receptor radionuclide therapy) and followed by CT during 68,25 hours. The compartmental analysis was made using the software AnaComp Registered-Sign . The influence of the time pos-injection over the dose assessment was studied taking into account the renal excretion management by aminoacid coinfusion, whose direct effects persist in the first day. The biodistribution curve was split in five sectors: 0-0.25h; 0-3.25h; 3.25-24.25h; 24.25-68.25h and 3.25-68.25h. After the examination of that influence, the study was concentrated in separate the biodistribution curve in two phases. Phase 1: governed by uptake from the blood, considering the time pos-injection until 3.25h and phase 2: governed by renal excretion, considering the time pos-injection from 3.25h to 68.25h. The model considered the organs and tissues superposition in the CT image acquisition by sampling parameters as the contribution of the the activity concentration in blood and relation between the sizes of the whole body and measured organs. The kinetic constants obtained from each phase (1 and 2) were used in dose assessment to patients in 26 organs and tissues described by MIRD. Dosimetry results were in agreement with the available results from literature, restrict to whole body, kidneys, bone marrow, spleen and liver. The advantage of the proposed model is the compartmental method quickness and power to estimate dose in organs and tissues, including tumor that, in the most part, were not discriminate by voxels of phantoms built using CT images. (author)
Crystallization Kinetics within a Generic Modeling Framework
DEFF Research Database (Denmark)
Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist V.
2014-01-01
to the modeling of various kinetic phenomena like nucleation, growth, agglomeration, and breakage are discussed in terms of model forms, model parameters, their availability and/or estimation, and their selection and application for specific crystallization operational scenarios under study. The advantages......A new and extended version of a generic modeling framework for analysis and design of crystallization operations is presented. The new features of this framework are described, with focus on development, implementation, identification, and analysis of crystallization kinetic models. Issues related...... of employing a well-structured model library for storage, use/reuse, and analysis of the kinetic models are highlighted. Examples illustrating the application of the modeling framework for kinetic model discrimination related to simulation of specific crystallization scenarios and for kinetic model parameter...
Ito, Hiroaki; Fujii, Manabu; Masago, Yoshifumi; Waite, T. David; Omura, Tatsuo
2015-04-01
The effect of ionic strength (I) on the ligand exchange reaction between a mononuclear ferric citrate complex and the siderophore, desferrioxamine B (DFB), was examined in the NaCl concentration range of 0.01-0.5 M, particularly focusing on the kinetics and mechanism of ligand exchange under environmentally relevant conditions. Overall ligand exchange rate constants were determined by spectrophotometrically measuring the time course of ferrioxamine B formation at a water temperature of 25 °C, pH 8.0, and citrate/Fe molar ratios of 500-5000. The overall ligand exchange rate decreased by 2-11-fold (depending on the citrate/Fe molar ratios) as I increased from approximately 0.01 to 0.5 M. In particular, a relatively large decrease was observed at lower I (dissociation of citrate from the parent complexes) dominates in ferrioxamine formation under the experimental conditions used. The model also predicts that the higher rate of ligand exchange at lower I is associated with the decrease in the ferric dicitrate complex stability because of the relatively high electrical repulsion between ferric monocitrate and free citrate at lower I (note that the reactivity of ferric dicitrate with DFB is smaller than that for the monocitrate complex). Overall, the findings of this study contribute to the understanding of the potential effect of I on ligand exchange kinetics in natural waters and provide fundamental knowledge on iron transformation and bioavailability.
Kinetic Behaviors of a Competitive Population and Fitness System in Exchange-Driven Growth
Institute of Scientific and Technical Information of China (English)
LU Ke; LIN Zhen-Quan; SUN Yun-Fei
2008-01-01
We proposed an aggregation model of two species aggregates of fitness and population to study the inter-action between the two species in their exchange-driven processes of the same species by introducing the monomer birth of fitness catalyzed by the population,where the fitness aggregates perform self-death process and the population aggre-gates perform self-birth process.The kinetic behaviors of the aggregate size distributions of the fitness and population were analyzed by the rate equation approach with their exchange rate kernel K1(k,j) = K1kj and K2(k,j) = K2kj,the fitness aggregate's self-death rate kernel J1(k) = J1k,population aggregate's self-birth rate kernel J2(k) = J2k and population-catalyzed fitness birth rate kernel I(k,j) = Ikjv.The kinetic behavior of the fitness was found depending crucially on the parameter v,which reflects the dependence of the population-catalyzed fitness birth rate on the size of the catalyst (population) aggregate.(I) In the v ≤0 case,the effect of catalyzed-birth of fitness is rather weak and the exchange-driven aggregation and self-death of the fitness dominate the process,and the fitness aggregate size distribution ak(t) does not have scale form.(ii) When v > 0,the effect of the population-catalyzed birth of fitness gets strong enough,and the catalyzed-birth and self-death of the fitness aggregates,together with the self-birth of the population aggregates dominate the evolution process of the fitness aggregates.The aggregate size distribution ak(t)approaches a generalized sealing form.
Wealth Distributions in Asset Exchange Models
Krapivsky, P L
2010-01-01
How do individuals accumulate wealth as they interact economically? We outline the consequences of a simple microscopic model in which repeated pairwise exchanges of assets between individuals build the wealth distribution of a population. This distribution is determined for generic exchange rules --- transactions that involve a fixed amount or a fixed fraction of individual wealth, as well as random or greedy exchanges. In greedy multiplicative exchange, a continuously evolving power law wealth distribution arises, a feature that qualitatively mimics empirical observations.
Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming
2014-01-01
Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug-fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug-fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid.
Second order kinetic Kohn-Sham lattice model
Solorzano, Sergio; Herrmann, Hans
2016-01-01
In this work we introduce a new semi-implicit second order correction scheme to the kinetic Kohn-Sham lattice model. The new approach is validated by performing realistic exchange-correlation energy calculations of atoms and dimers of the first two rows of the periodic table finding good agreement with the expected values. Additionally we simulate the ethane molecule where we recover the bond lengths and compare the results with standard methods. Finally, we discuss the current applicability of pseudopotentials within the lattice kinetic Kohn-Sham approach.
NMR studies of proton exchange kinetics in aqueous formaldehyde solutions
Rivlin, Michal; Eliav, Uzi; Navon, Gil
2014-05-01
Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2 ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0 ± 1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1ρ) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ∼104 s-1 at pH 7.4 and 37 °C, the activation energy, 50.2 kJ/mol and its pH dependence at 1.1 °C was fitted to: k (s-1) = 520 + 6.5 × 107[H+] + 3.0 × 109[OH-].
Ion-Isotopic Exchange Reaction Kinetics using Anion Exchange Resins Dowex 550A LC and Indion-930A
Directory of Open Access Journals (Sweden)
P.U. Singare
2014-06-01
Full Text Available The present paper deals with the characterization of ion exchange resins Dowex 550A LC and Indion-930A based on kinetics of ion-isotopic exchange reactions for which the short lived radioactive isotopes 131I and 82Br were used as a tracers. The study was performed for different concentration of ionic solution varying from 0.001 mol/L to 0.004 mol/L and temperature in the range of 30.0 °C to 45.0 °C. The results indicate that as compared to bromide ion-isotopic exchange reaction, iodide exchange reaction take place at the faster rate. For both the ion-isotopic exchange reactions, under identical experimental conditions, the values of specific reaction rate increases with increase in the ionic concentration and decreases with rise in temperature. It was observed that at 35.00C, 1.000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution for iodide ion-isotopic exchange reaction, the values of specific reaction rate (min-1, amount of ion exchanged (mmol, initial rate of ion exchange (mmol/min and log Kd were 0.270, 0.342, 0.092 and 11.8 respectively for Dowex 550A LC resin, which was higher than the respective values of 0.156, 0.241, 0.038 and 7.4 as that obtained for Indion-930A resins. From the results, it appears that Dowex 550A LC resins show superior performance over Indion-930A resins under identical experimental conditions.
Electron-lattice energy exchange in metal nanoparticles. Quantum-kinetic and classical approaches
Tomchuk, Petro; Bilotsky, Yevgen
2014-01-01
We obtained the electron-lattice energy transfer constant in metal nanoparticles (MN), in quantum-mechanical and classical approach using the deformation potential Bardeen-Shockley and found the changes of the electron-lattice energy exchange (due to the finite size MN) in the quantum kinetic approach caused by the discrete phonon spectrum. The condition when the discrete phonon spectrum could be observed via the electron-phonon energy exchange has been obtained. It was shown that the classic...
Chemical Kinetic Modeling of 2-Methylhexane Combustion
Mohamed, Samah Y.
2015-03-30
Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important for investigating the combustion behavior of diesel, gasoline, and aviation fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values and rate rules. These update provides a better agreement with rapid compression machine measurements of ignition delay time, while also strengthening the fundamental basis of the model.
Edge exchangeable models for network data
Crane, Harry
2016-01-01
Exchangeable models for vertex labeled graphs cannot replicate the large sample behaviors of sparsity and power law degree distributions observed in many network datasets. Out of this mathematical impossibility emerges the question of how network data can be modeled in a way that reflects known empirical behaviors and respects basic statistical principles. We address this question by observing that edges, not vertices, act as the statistical units in most network datasets, making a theory of edge labeled networks more natural for most applications. Within this context we introduce the new invariance principle of {\\em edge exchangeability}, which unlike its vertex exchangeable counterpart can produce networks with sparse and/or power law structure. We characterize the class of all edge exchangeable network models and identify a particular two parameter family of models with suitable theoretical properties for statistical inference. We discuss issues of estimation from edge exchangeable models and compare our a...
Modeling of Reactor Kinetics and Dynamics
Energy Technology Data Exchange (ETDEWEB)
Matthew Johnson; Scott Lucas; Pavel Tsvetkov
2010-09-01
In order to model a full fuel cycle in a nuclear reactor, it is necessary to simulate the short time-scale kinetic behavior of the reactor as well as the long time-scale dynamics that occur with fuel burnup. The former is modeled using the point kinetics equations, while the latter is modeled by coupling fuel burnup equations with the kinetics equations. When the equations are solved simultaneously with a nonlinear equation solver, the end result is a code with the unique capability of modeling transients at any time during a fuel cycle.
Modeling Of Proton Exchange Membrane Fuel Cell Systems
DEFF Research Database (Denmark)
Nielsen, Mads Pagh
The objective of this doctoral thesis was to develop reliable steady-state and transient component models suitable to asses-, develop- and optimize proton exchange membrane (PEM) fuel cell systems. Several components in PEM fuel cell systems were characterized and modeled. The developed component...... cell systems. Consequences of indirectly fueling PEM stacks with hydrocarbons using reforming technology were investigated using a PEM stack model including CO poisoning kinetics and a transient Simulink steam reforming system model. Aspects regarding the optimization of PEM fuel cell systems...
Muñoz Burgos, J. M.; Burrell, K. H.; Solomon, W. M.; Grierson, B. A.; Loch, S. D.; Ballance, C. P.; Chrystal, C.
2013-09-01
Charge-exchange spectroscopy is a powerful diagnostic tool for determining ion temperatures, densities and rotational velocities in tokamak plasmas. This technique depends on detailed understanding of the atomic physics processes that affect the measured apparent velocities with respect to the true ion rotational velocities. These atomic effects are mainly due to energy dependence of the charge-exchange cross-sections, and in the case of poloidal velocities, due to gyro-motion of the ion during the finite lifetime of the excited states. Accurate lifetimes are necessary for correct interpretation of measured poloidal velocities, specially for high density plasma regimes on machines such as ITER, where l-mixing effects must be taken into account. In this work, a full nl-resolved atomic collisional radiative model coupled with a full kinetic calculation that includes the effects of electric and magnetic fields on the ion gyro-motion is presented for the first time. The model directly calculates from atomic physics first principles the excited state lifetimes that are necessary to evaluate the gyro-orbit effects. It is shown that even for low density plasmas where l-mixing effects are unimportant and coronal conditions can be assumed, the nl-resolved model is necessary for an accurate description of the gyro-motion effects to determine poloidal velocities. This solution shows good agreement when compared to three QH-mode shots on DIII-D, which contain a wide range of toroidal velocities and high ion temperatures where greater atomic corrections are needed. The velocities obtained from the model are compared to experimental velocities determined from co- and counter-injection of neutral beams on DIII-D.
An equilibrium and kinetic modeling
African Journals Online (AJOL)
SERVER
2007-06-18
Jun 18, 2007 ... Potato dextrose agar medium was prepared by taking 200 g of peeled and sliced potato with .... of glucose as carbon source and ammonium chloride as nitrogen source each. .... Pore and solid diffusion kinetics in fixed bed ...
A formal model of fair exchange protocols
Institute of Scientific and Technical Information of China (English)
QING Sihan; LI Gaicheng
2005-01-01
Based on the study of existing fair exchange protocols, this paper sets up an accurate formal model by stepwise refinement. In the process of refinement an unreliable channel is employed to simulate an attack behavior. The model provides a novel formal definition of exchanged items, and presents the formal goals for fairness, accountability,etc., reflecting the inherent requirements for fair exchange protocols across-the-board. In order to check, prove, and design fair exchange protocols effectively and efficiently, the model puts forward a novel property of abuse-freeness which applies to all fair exchange protocols, gives a formal definition for trust strand of the third party, and presents general criteria of designing a secure and effective fair exchange protocol. Taking a typical fair exchange protocol as an example, this paper presents the analysis steps of fair exchange protocols appealing to our model. An unknown attack is uncovered. The analysis reveals the process of a complete attack, discovering deeper reasons for causing an attack.Finally, we modify the flawed protocol and the revised protocol ensures the desirable properties.
Kinetics of Isovalent (Cd(2+)) and Aliovalent (In(3+)) Cation Exchange in Cd1-xMnxSe Nanocrystals.
Chakraborty, Pradip; Jin, Yu; Barrows, Charles J; Dunham, Scott T; Gamelin, Daniel R
2016-10-05
Ion exchange, in which an in-diffusing ion replaces a lattice ion, has been widely exploited as a synthetic tool for semiconductor doping and solid-to-solid chemical transformations, both in bulk and at the nanoscale. Here, we present a systematic investigation of cation-exchange reactions that involve the displacement of Mn(2+) from CdSe nanocrystals by Cd(2+) or In(3+). For both incoming cations, Mn(2+) displacement is spontaneous but thermally activated, following Arrhenius behavior over a broad experimental temperature range. At any given temperature, cation exchange by In(3+) is approximately 2 orders of magnitude faster than that by Cd(2+), illustrating a critical dependence on the incoming cation. Quantitative analysis of the kinetics data within a Fick's-law diffusion model yields diffusion barriers (ED) and limiting diffusivities (D0) for both incoming ions. Despite their very different kinetics, indistinguishable diffusion barriers of ED ≈ 1.1 eV are found for both reactions (In(3+) and Cd(2+)). A dramatically enhanced diffusivity is found for Mn(2+) cation exchange by In(3+). Overall, these findings provide unique experimental insights into cation diffusion within colloidal semiconductor nanocrystals, contributing to our fundamental understanding of this rich and important area of nanoscience.
Fragmentary model of exchange interactions
Kotov, V M
2000-01-01
This article makes attempt to refusal from using neutrino for explanation continuous distribution of beta particle energy by conversion to characteristic exchange interaction particles in nucleolus. It is taking formulation for nuclear position with many different fragments. It is computing half-value period of spontaneous fission of heavy nucleolus. (author)
DEFF Research Database (Denmark)
Berg, Ronan M G; Taudorf, Sarah; Bailey, Damian M
2012-01-01
. Cerebral blood flow (CBF) and arterial to jugular venous concentration differences of glutamate and glycine were determined before and after a 4-h intravenous infusion of Escherichia coli lipopolysaccharide (LPS, total dose of 0.3 ng/kg) in 12 healthy volunteers. The global cerebral net exchange......, their transcerebral exchange kinetics were unaffected. Inflammation-induced alterations of the circulating levels of glutamate and glycine, do not affect the global transcerebral exchange kinetics of these amino acids in healthy humans....
Validation of the point kinetic neutronic model of the PBMR / Deon Marais
Marais, Deon
2007-01-01
This study introduces a new method for the validation of the point kinetic neutronic model of the PBMR. In this study the diffusion equation solution, as implemented in the TlNTE PBMR 268 MW reactor model, replaces the point kinetic model, as implemented in the Flownex V502 PBMR plant model. An indirect coupling method is devised and implemented in an external program called Flownex-Tinte-Interface (FTI) to facilitate the data exchange between these two codes. The validation...
Chemical Kinetic Modeling of Advanced Transportation Fuels
Energy Technology Data Exchange (ETDEWEB)
PItz, W J; Westbrook, C K; Herbinet, O
2009-01-20
Development of detailed chemical kinetic models for advanced petroleum-based and nonpetroleum based fuels is a difficult challenge because of the hundreds to thousands of different components in these fuels and because some of these fuels contain components that have not been considered in the past. It is important to develop detailed chemical kinetic models for these fuels since the models can be put into engine simulation codes used for optimizing engine design for maximum efficiency and minimal pollutant emissions. For example, these chemistry-enabled engine codes can be used to optimize combustion chamber shape and fuel injection timing. They also allow insight into how the composition of advanced petroleum-based and non-petroleum based fuels affect engine performance characteristics. Additionally, chemical kinetic models can be used separately to interpret important in-cylinder experimental data and gain insight into advanced engine combustion processes such as HCCI and lean burn engines. The objectives are: (1) Develop detailed chemical kinetic reaction models for components of advanced petroleum-based and non-petroleum based fuels. These fuels models include components from vegetable-oil-derived biodiesel, oil-sand derived fuel, alcohol fuels and other advanced bio-based and alternative fuels. (2) Develop detailed chemical kinetic reaction models for mixtures of non-petroleum and petroleum-based components to represent real fuels and lead to efficient reduced combustion models needed for engine modeling codes. (3) Characterize the role of fuel composition on efficiency and pollutant emissions from practical automotive engines.
A kinetic model for predicting biodegradation.
Dimitrov, S; Pavlov, T; Nedelcheva, D; Reuschenbach, P; Silvani, M; Bias, R; Comber, M; Low, L; Lee, C; Parkerton, T; Mekenyan, O
2007-01-01
Biodegradation plays a key role in the environmental risk assessment of organic chemicals. The need to assess biodegradability of a chemical for regulatory purposes supports the development of a model for predicting the extent of biodegradation at different time frames, in particular the extent of ultimate biodegradation within a '10 day window' criterion as well as estimating biodegradation half-lives. Conceptually this implies expressing the rate of catabolic transformations as a function of time. An attempt to correlate the kinetics of biodegradation with molecular structure of chemicals is presented. A simplified biodegradation kinetic model was formulated by combining the probabilistic approach of the original formulation of the CATABOL model with the assumption of first order kinetics of catabolic transformations. Nonlinear regression analysis was used to fit the model parameters to OECD 301F biodegradation kinetic data for a set of 208 chemicals. The new model allows the prediction of biodegradation multi-pathways, primary and ultimate half-lives and simulation of related kinetic biodegradation parameters such as biological oxygen demand (BOD), carbon dioxide production, and the nature and amount of metabolites as a function of time. The model may also be used for evaluating the OECD ready biodegradability potential of a chemical within the '10-day window' criterion.
Figaro, S; Avril, J P; Brouers, F; Ouensanga, A; Gaspard, S
2009-01-30
Adsorption kinetic of molasses wastewaters after anaerobic digestion (MSWD) and melanoidin respectively on activated carbon was studied at different pH. The kinetic parameters could be determined using classical kinetic equations and a recently published fractal kinetic equation. A linear form of this equation can also be used to fit adsorption data. Even with lower correlation coefficients the fractal kinetic equation gives lower normalized standard deviation values than the pseudo-second order model generally used to fit adsorption kinetic data, indicating that the fractal kinetic model is much more accurate for describing the kinetic adsorption data than the pseudo-second order kinetic model.
Nonlinear Inverse Problem for an Ion-Exchange Filter Model: Numerical Recovery of Parameters
Directory of Open Access Journals (Sweden)
Balgaisha Mukanova
2015-01-01
Full Text Available This paper considers the problem of identifying unknown parameters for a mathematical model of an ion-exchange filter via measurement at the outlet of the filter. The proposed mathematical model consists of a material balance equation, an equation describing the kinetics of ion-exchange for the nonequilibrium case, and an equation for the ion-exchange isotherm. The material balance equation includes a nonlinear term that depends on the kinetics of ion-exchange and several parameters. First, a numerical solution of the direct problem, the calculation of the impurities concentration at the outlet of the filter, is provided. Then, the inverse problem, finding the parameters of the ion-exchange process in nonequilibrium conditions, is formulated. A method for determining the approximate values of these parameters from the impurities concentration measured at the outlet of the filter is proposed.
Kinetics and adsorption isotherm of C-phycocyanin from Spirulina platensis on ion-exchange resins
Directory of Open Access Journals (Sweden)
L. Sala
2014-12-01
Full Text Available C-phycocyanin is a natural blue dye extracted from Spirulina platensis, which has many applications in the food and pharmaceutical industries. In this paper the effect of pH and temperature on the adsorption of C-phycocyanin onto two different ion exchange resins (Streamline DEAE and Streamline Q XL for expanded bed adsorption chromatography was investigated. Moreover, the kinetics and adsorption isotherm were evaluated. The equilibrium for the Q XL matrix was reached after 60 min, while for DEAE it was only reached after 140 min. C-phycocyanin showed the highest partition coefficient at pH 7.5 for both resins at 25 ºC. The C-phycocyanin adsorption isotherm was very well represented by the Langmuir, Freundlich and Langmuir-Freundlich models, where the estimated values for Qm and Kd obtained by the Langmuir isotherm were, respectively, 33.92 mg.mL-1 and 0.123 mg.mL-1 for DEAE, and 28.12 mg.mL-1 and 0.082 mg.mL-1 for the Q XL matrix. A negative cooperativity was observed for C-phycocyanin binding when the Q XL matrix was used, while the cooperativity was purely independent using the DEAE matrix.
Smith, Jeremy George; Jain, Prashant
2014-06-01
The realization of common materials transformations in nanocrystalline systems is fostering the development of novel nanostructures and allowing a deep look into the atomistic mechanisms involved. Galvanic corrosion is one such transformation. We studied galvanic replacement within individual metal nanoparticles by using plasmonic spectroscopy. This proved to be a powerful approach to studying materials transformations in the absence of ensemble averaging. Individual nanoscale units act as domains that can be interrogated optically in isolation, whereas the averaging of all such domains provides a bulk reaction trajectory. Single-nanoparticle reaction trajectories showed that a Ag nanoparticle exposed to Au3+ makes an abrupt transition into a nanocage structure. The transition is limited by a critical structural event, which we identified by electron microscopy to comprise the formation of a nanosized void, similar to the pitting process commonly observed in the corrosion of metals. Trajectories also revealed a surprisingly strong nonlinearity of the reaction kinetics, which we explain by a model involving the critical coalescence of vacancies into a growing void. The critical void size for galvanic exchange to spontaneously proceed was found to be 20 atomic vacancies. In the future we hope to extend this approach to examine a wide variety of materials transformations and chemical reactions.
Pan; Green; Maldarelli
1998-09-15
The paper focuses on the measurement of the rate constants for the kinetic steps of adsorption and desorption of surfactant between an air/water surface and the aqueous bulk sublayer adjacent to the surface. Kinetic constants are determined in nonequilibrium experiments in which either a clean surface is contacted with a bulk solution and surfactant diffuses toward and adsorbs onto the interface, or the area of an established monolayer in equilibrium with an underlying solution is changed, and surfactant exchanges between the surface and bulk. The dynamic tension change due to the surfactant exchange is measured, and compared to predictions of kinetic-diffusive transport models in order to infer the kinetic coefficients as well the diffusion coefficients. Model comparisons for highly surface active surfactants have resolved only the diffusion coefficient as the transport was found to be diffusion controlled; kinetic constants have only been established for less active materials such as alcohols or bolaform surfactants. In this study, we demonstrate that kinetics can be differentiated from diffusion in clean interface adsorption and re-equilibration if high bulk concentrations of the surfactant are used, or in re-equilibration, if the surface is compressed sufficiently. We first establish theoretically that mass transfer shifts from diffusion-limited to mixed as the bulk concentration increases in clean interface adsorption, or the surface compression is increased in re-equilibration. We then experimentally verify this idea by using the polyethoxylated surfactant C12E6 (C12H25 (OCH2CH2)6-OH) and by measuring dynamic surface tensions in clean interface adsorption and re-equilibration, respectively by the shape analysis of pendant bubbles. We find values of 6 x 10(-10) m2/s for the diffusion coefficient, and 1.4 x 10(-5) m/sec and 1.4 x 10(-4) s-1 for the adsorption and desorption rate constants, respectively, in a Frumkin kinetic formulation. While the adsorption
Kinetic Behavior of Aggregation-Exchange Growth Process with Catalyzed-Birth
Institute of Scientific and Technical Information of China (English)
HAN An-Jia; CHEN Yu; LIN Zhen-Quan; KE Jian-Hong
2007-01-01
We propose an aggregation model of a two-species system to mimic the growth of cities' population and assets,in which irreversible coagulation reactions and exchange reactions occur between any two aggregates of the same species,and the monomer-birth reactions of one species occur by the catalysis of the other species.In the case with population-catalyzed birth of assets,the rate kernel of an asset aggregate Bκ of size k grows to become an aggregate Bκ+ 1through a monomer-birth catalyzed by a population aggregate Aj of size j is J(k,j) = Jkjλ.And in mutually catalyzed birth model,the birth rate kernels of population and assets are H(k,j) = Hkjη and J(k,j) = Jkjλ,respectively.The kinetics of the system is investigated based on the mean-field theory.In the model of population-catalyzed birth of assets,the long-time asymptotic behavior of the assets aggregate size distribution obeys the conventional or modified scaling form.In mutually catalyzed birth system,the asymptotic behaviors of population and assets obey the conventional scaling form in the case ofη =λ= 0,and they obey the modified scalingform in the case of η = 0,λ= 1.In the case of η = λ = 1,the total mass of population aggregates and that of asset aggregates both grow much faster than those in population-catalyzed birth of assets model,and they approaches to infinite values in finite time.
Chemical Kinetic Models for Advanced Engine Combustion
Energy Technology Data Exchange (ETDEWEB)
Pitz, William J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehl, Marco [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Westbrook, Charles K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
2014-10-22
The objectives for this project are as follows: Develop detailed chemical kinetic models for fuel components used in surrogate fuels for compression ignition (CI), homogeneous charge compression ignition (HCCI) and reactivity-controlled compression-ignition (RCCI) engines; and Combine component models into surrogate fuel models to represent real transportation fuels. Use them to model low-temperature combustion strategies in HCCI, RCCI, and CI engines that lead to low emissions and high efficiency.
Kinetic models with randomly perturbed binary collisions
Bassetti, Federico; Toscani, Giuseppe
2010-01-01
We introduce a class of Kac-like kinetic equations on the real line, with general random collisional rules, which include as particular cases models for wealth redistribution in an agent-based market or models for granular gases with a background heat bath. Conditions on these collisional rules which guarantee both the existence and uniqueness of equilibrium profiles and their main properties are found. We show that the characterization of these stationary solutions is of independent interest, since the same profiles are shown to be solutions of different evolution problems, both in the econophysics context and in the kinetic theory of rarefied gases.
SPEEDUP{trademark} ion exchange column model
Energy Technology Data Exchange (ETDEWEB)
Hang, T.
2000-03-06
A transient model to describe the process of loading a solute onto the granular fixed bed in an ion exchange (IX) column has been developed using the SpeedUp{trademark} software package. SpeedUp offers the advantage of smooth integration into other existing SpeedUp flowsheet models. The mathematical algorithm of a porous particle diffusion model was adopted to account for convection, axial dispersion, film mass transfer, and pore diffusion. The method of orthogonal collocation on finite elements was employed to solve the governing transport equations. The model allows the use of a non-linear Langmuir isotherm based on an effective binary ionic exchange process. The SpeedUp column model was tested by comparing to the analytical solutions of three transport problems from the ion exchange literature. In addition, a sample calculation of a train of three crystalline silicotitanate (CST) IX columns in series was made using both the SpeedUp model and Purdue University's VERSE-LC code. All test cases showed excellent agreement between the SpeedUp model results and the test data. The model can be readily used for SuperLig{trademark} ion exchange resins, once the experimental data are complete.
Indian Academy of Sciences (India)
Amin Jignasa; Thakkar Rakesh; Chudasama Uma
2006-03-01
An advanced inorganic cation exchange material of the class of tetravalent metal acid (TMA) salt, zirconium titanium phosphate (ZTP), has been synthesized by a modified sol-gel technique. ZTP has been characterized by elemental analysis (ICP-AES), thermal analysis (TGA), FTIR and X-ray diffraction studies. The Nernst-Planck equation has been used to study the forward and reverse ion exchange kinetics of Mg (II), Ca (II), Sr (II) and Ba (II) with H (I) at four different temperatures. The mechanism of exchange is particle diffusion, as confirmed by the linear (dimensionless time parameter) vs (time) plots. The exchange process is thus controlled by the diffusion within the exchanger particles for the systems studied herein. Further, various kinetic parameters like self-diffusion coefficient (0), energy of activation () and entropy of activation (*) have been evaluated under conditions favouring a particle diffusion-controlled mechanism.
Kinetic and hydrodynamic models of chemotactic aggregation
Chavanis, Pierre-Henri
2007-01-01
We derive general kinetic and hydrodynamic models of chemotactic aggregation that describe certain features of the morphogenesis of biological colonies (like bacteria, amoebae, endothelial cells or social insects). Starting from a stochastic model defined in terms of N coupled Langevin equations, we derive a nonlinear mean field Fokker-Planck equation governing the evolution of the distribution function of the system in phase space. By taking the successive moments of this kinetic equation and using a local thermodynamic equilibrium condition, we derive a set of hydrodynamic equations involving a damping term. In the limit of small frictions, we obtain a hyperbolic model describing the formation of network patterns (filaments) and in the limit of strong frictions we obtain a parabolic model which is a generalization of the standard Keller-Segel model describing the formation of clusters (clumps). Our approach connects and generalizes several models introduced in the chemotactic literature. We discuss the anal...
Rüdt, Matthias; Gillet, Florian; Heege, Stefanie; Hitzler, Julian; Kalbfuss, Bernd; Guélat, Bertrand
2015-09-25
Application of model-based design is appealing to support the development of protein chromatography in the biopharmaceutical industry. However, the required efforts for parameter estimation are frequently perceived as time-consuming and expensive. In order to speed-up this work, a new parameter estimation approach for modelling ion-exchange chromatography in linear conditions was developed. It aims at reducing the time and protein demand for the model calibration. The method combines the estimation of kinetic and thermodynamic parameters based on the simultaneous variation of the gradient slope and the residence time in a set of five linear gradient elutions. The parameters are estimated from a Yamamoto plot and a gradient-adjusted Van Deemter plot. The combined approach increases the information extracted per experiment compared to the individual methods. As a proof of concept, the combined approach was successfully applied for a monoclonal antibody on a cation-exchanger and for a Fc-fusion protein on an anion-exchange resin. The individual parameter estimations for the mAb confirmed that the new approach maintained the accuracy of the usual Yamamoto and Van Deemter plots. In the second case, offline size-exclusion chromatography was performed in order to estimate the thermodynamic parameters of an impurity (high molecular weight species) simultaneously with the main product. Finally, the parameters obtained from the combined approach were used in a lumped kinetic model to simulate the chromatography runs. The simulated chromatograms obtained for a wide range of gradient lengths and residence times showed only small deviations compared to the experimental data.
A kinetic model of zircon thermoluminescence
Turkin, A.A.; Es, H.J. van; Vainshtein, D.I.; Hartog, H.W. den
A kinetic model of zircon thermoluminescence (TL) has been constructed to simulate the processes and stages relevant to thermoluminescent dating such as: filling of electron and hole traps during the excitation stage both for natural and laboratory irradiation; the time dependence of fading after
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
Gaussian kinetic model for granular gases.
Dufty, James W; Baskaran, Aparna; Zogaib, Lorena
2004-05-01
A kinetic model for the Boltzmann equation is proposed and explored as a practical means to investigate the properties of a dilute granular gas. It is shown that all spatially homogeneous initial distributions approach a universal "homogeneous cooling solution" after a few collisions. The homogeneous cooling solution (HCS) is studied in some detail and the exact solution is compared with known results for the hard sphere Boltzmann equation. It is shown that all qualitative features of the HCS, including the nature of overpopulation at large velocities, are reproduced by the kinetic model. It is also shown that all the transport coefficients are in excellent agreement with those from the Boltzmann equation. Also, the model is specialized to one having a velocity independent collision frequency and the resulting HCS and transport coefficients are compared to known results for the Maxwell model. The potential of the model for the study of more complex spatially inhomogeneous states is discussed.
Neutron scattering from myelin revisited: bilayer asymmetry and water-exchange kinetics
Energy Technology Data Exchange (ETDEWEB)
Denninger, Andrew R. [Boston College, Chestnut Hill, MA 02467 (United States); Demé, Bruno; Cristiglio, Viviana [Institut Laue–Langevin (ILL), CS 20156, F-38042 Grenoble CEDEX 9 (France); LeDuc, Géraldine [European Synchrotron Radiation Facility (ESRF), CS 40220, F-38043 Grenoble CEDEX 9 (France); Feller, W. Bruce [NOVA Scientific Inc., Sturbridge, MA 01566 (United States); Kirschner, Daniel A., E-mail: kirschnd@bc.edu [Boston College, Chestnut Hill, MA 02467 (United States)
2014-12-01
The structure of internodal myelin in the rodent central and peripheral nervous systems has been determined using neutron diffraction. The kinetics of water exchange in these tissues is also described. Rapid nerve conduction in the central and peripheral nervous systems (CNS and PNS, respectively) of higher vertebrates is brought about by the ensheathment of axons with myelin, a lipid-rich, multilamellar assembly of membranes. The ability of myelin to electrically insulate depends on the regular stacking of these plasma membranes and on the presence of a number of specialized membrane-protein assemblies in the sheath, including the radial component, Schmidt–Lanterman incisures and the axo–glial junctions of the paranodal loops. The disruption of this fine-structure is the basis for many demyelinating neuropathies in the CNS and PNS. Understanding the processes that govern myelin biogenesis, maintenance and destabilization requires knowledge of myelin structure; however, the tight packing of internodal myelin and the complexity of its junctional specializations make myelin a challenging target for comprehensive structural analysis. This paper describes an examination of myelin from the CNS and PNS using neutron diffraction. This investigation revealed the dimensions of the bilayers and aqueous spaces of myelin, asymmetry between the cytoplasmic and extracellular leaflets of the membrane, and the distribution of water and exchangeable hydrogen in internodal multilamellar myelin. It also uncovered differences between CNS and PNS myelin in their water-exchange kinetics.
Kinetics model development of cocoa bean fermentation
Kresnowati, M. T. A. P.; Gunawan, Agus Yodi; Muliyadini, Winny
2015-12-01
Although Indonesia is one of the biggest cocoa beans producers in the world, Indonesian cocoa beans are oftenly of low quality and thereby frequently priced low in the world market. In order to improve the quality, adequate post-harvest cocoa processing techniques are required. Fermentation is the vital stage in series of cocoa beans post harvest processing which could improve the quality of cocoa beans, in particular taste, aroma, and colours. During the fermentation process, combination of microbes grow producing metabolites that serve as the precursors for cocoa beans flavour. Microbial composition and thereby their activities will affect the fermentation performance and influence the properties of cocoa beans. The correlation could be reviewed using a kinetic model that includes unstructured microbial growth, substrate utilization and metabolic product formation. The developed kinetic model could be further used to design cocoa bean fermentation process to meet the expected quality. Further the development of kinetic model of cocoa bean fermentation also serve as a good case study of mixed culture solid state fermentation, that has rarely been studied. This paper presents the development of a kinetic model for solid-state cocoa beans fermentation using an empirical approach. Series of lab scale cocoa bean fermentations, either natural fermentations without starter addition or fermentations with mixed yeast and lactic acid bacteria starter addition, were used for model parameters estimation. The results showed that cocoa beans fermentation can be modelled mathematically and the best model included substrate utilization, microbial growth, metabolites production and its transport. Although the developed model still can not explain the dynamics in microbial population, this model can sufficiently explained the observed changes in sugar concentration as well as metabolic products in the cocoa bean pulp.
Gering, Kevin L.
2013-01-01
A system includes an electrochemical cell, monitoring hardware, and a computing system. The monitoring hardware samples performance characteristics of the electrochemical cell. The computing system determines cell information from the performance characteristics. The computing system also analyzes the cell information of the electrochemical cell with a Butler-Volmer (BV) expression modified to determine exchange current density of the electrochemical cell by including kinetic performance information related to pulse-time dependence, electrode surface availability, or a combination thereof. A set of sigmoid-based expressions may be included with the modified-BV expression to determine kinetic performance as a function of pulse time. The determined exchange current density may be used with the modified-BV expression, with or without the sigmoid expressions, to analyze other characteristics of the electrochemical cell. Model parameters can be defined in terms of cell aging, making the overall kinetics model amenable to predictive estimates of cell kinetic performance along the aging timeline.
Computational model for Halorhodopsin photocurrent kinetics
Bravo, Jaime; Stefanescu, Roxana; Talathi, Sachin
2013-03-01
Optogenetics is a rapidly developing novel optical stimulation technique that employs light activated ion channels to excite (using channelrhodopsin (ChR)) or suppress (using halorhodopsin (HR)) impulse activity in neurons with high temporal and spatial resolution. This technique holds enormous potential to externally control activity states in neuronal networks. The channel kinetics of ChR and HR are well understood and amenable for mathematical modeling. Significant progress has been made in recent years to develop models for ChR channel kinetics. To date however, there is no model to mimic photocurrents produced by HR. Here, we report the first model developed for HR photocurrents based on a four-state model of the HR photocurrent kinetics. The model provides an excellent fit (root-mean-square error of 3.1862x10-4, to an empirical profile of experimentally measured HR photocurrents. In combination, mathematical models for ChR and HR photocurrents can provide effective means to design test light based control systems to regulate neural activity, which in turn may have implications for the development of novel light based stimulation paradigms for brain disease control. I would like to thank the University of Florida and the Physics Research Experience for Undergraduates (REU) program, funded through NSF DMR-1156737. This research was also supported through start-up funds provided to Dr. Sachin Talathi
Modeling inhomogeneous DNA replication kinetics.
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Michel G Gauthier
Full Text Available In eukaryotic organisms, DNA replication is initiated at a series of chromosomal locations called origins, where replication forks are assembled proceeding bidirectionally to replicate the genome. The distribution and firing rate of these origins, in conjunction with the velocity at which forks progress, dictate the program of the replication process. Previous attempts at modeling DNA replication in eukaryotes have focused on cases where the firing rate and the velocity of replication forks are homogeneous, or uniform, across the genome. However, it is now known that there are large variations in origin activity along the genome and variations in fork velocities can also take place. Here, we generalize previous approaches to modeling replication, to allow for arbitrary spatial variation of initiation rates and fork velocities. We derive rate equations for left- and right-moving forks and for replication probability over time that can be solved numerically to obtain the mean-field replication program. This method accurately reproduces the results of DNA replication simulation. We also successfully adapted our approach to the inverse problem of fitting measurements of DNA replication performed on single DNA molecules. Since such measurements are performed on specified portion of the genome, the examined DNA molecules may be replicated by forks that originate either within the studied molecule or outside of it. This problem was solved by using an effective flux of incoming replication forks at the model boundaries to represent the origin activity outside the studied region. Using this approach, we show that reliable inferences can be made about the replication of specific portions of the genome even if the amount of data that can be obtained from single-molecule experiments is generally limited.
Modeling foreign exchange risk premium in Armenia
Poghosyan, Tigran; Kocenda, Evnen; Zemcik, Petr
2008-01-01
This paper applies stochastic discount factor methodology to modeling the foreign exchange risk premium in Armenia. We use weekly data on foreign and domestic currency deposits, which coexist in the Armenian banking system. This coexistence implies elimination of the cross-country risks and transact
Farazdaghi, Hadi
2011-02-01
Photosynthesis is the origin of oxygenic life on the planet, and its models are the core of all models of plant biology, agriculture, environmental quality and global climate change. A theory is presented here, based on single process biochemical reactions of Rubisco, recognizing that: In the light, Rubisco activase helps separate Rubisco from the stored ribulose-1,5-bisphosphate (RuBP), activates Rubisco with carbamylation and addition of Mg²(+), and then produces two products, in two steps: (Step 1) Reaction of Rubisco with RuBP produces a Rubisco-enediol complex, which is the carboxylase-oxygenase enzyme (Enco) and (Step 2) Enco captures CO₂ and/or O₂ and produces intermediate products leading to production and release of 3-phosphoglycerate (PGA) and Rubisco. PGA interactively controls (1) the carboxylation-oxygenation, (2) electron transport, and (3) triosephosphate pathway of the Calvin-Benson cycle that leads to the release of glucose and regeneration of RuBP. Initially, the total enzyme participates in the two steps of the reaction transitionally and its rate follows Michaelis-Menten kinetics. But, for a continuous steady state, Rubisco must be divided into two concurrently active segments for the two steps. This causes a deviation of the steady state from the transitional rate. Kinetic models are developed that integrate the transitional and the steady state reactions. They are tested and successfully validated with verifiable experimental data. The single-process theory is compared to the widely used two-process theory of Farquhar et al. (1980. Planta 149, 78-90), which assumes that the carboxylation rate is either Rubisco-limited at low CO₂ levels such as CO₂ compensation point, or RuBP regeneration-limited at high CO₂. Since the photosynthesis rate cannot increase beyond the two-process theory's Rubisco limit at the CO₂ compensation point, net photosynthesis cannot increase above zero in daylight, and since there is always respiration at
ECONOMETRIC MODELS FOR DETERMING THE EXCHANGE RATE
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Mihaela BRATU
2012-05-01
Full Text Available The simple econometric models for the exchange rate, according to recent researches, generates the forecasts with the highest degree of accuracy. This type of models (Simultaneous Equations Model, MA(1 Procedure, Model with lagged variables is used to describe the evolution of the average exchange rate in Romanian in January 1991-March 2012 and to predict it on short run. The best forecasts, in terms of accuracy, on the forecasting horizon April-May 2012 were those based on a Simultaneous Equations Model that takes into account the Granger causality. An almost high degree of accuracy was gotten by combining the predictions based on MA(1 model with those based on the simultaneous equations model, when INV weighting scheme was applied (the forecasts are inversely weighted to their relative mean squared forecast error. The lagged variables Model provided the highest prediction errors. The importance of knowing the best exchange rate forecasts is related to the improvement of decision-making and the building of the monetary policy.
Reduced Chemical Kinetic Model for Titan Entries
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Romain Savajano
2011-01-01
Full Text Available A reduced chemical kinetic model for Titan's atmosphere has been developed. This new model with 18 species and 28 reactions includes the mainfeatures of a more complete scheme, respecting the radiative fluxes. It has been verified against three key elements: a sensitivity analysis, the equilibrium chemical composition using shock tube simulations in CHEMKIN, and the results of computational fluid dynamics (CFDs simulations.
Mathematical Modeling of Spiral Heat Exchanger
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Probal Guha , Vaishnavi Unde
2014-04-01
Full Text Available Compact Heat Exchangers (CHEs are increasingly being used on small and medium scale industries. Due to their compact size and efficient design, they facilitate more efficient heat transfer. Better heat transfer would imply lesser fuel consumption for the operations of the plant, giving improvement to overall efficiency. This reduction in consumption of fuel is a step towards sustainable development. This report exclusively deals with the study the spiral heat exchanger.The design considerations for spiral heat exchanger is that the flow within the spiral has been assumed as flow through a duct and by using Shah London empirical equation for Nusselt number design parameters are further optimized.This is accompanied by a detailed energy balance to generate a concise mathematical model
Multiensemble Markov models of molecular thermodynamics and kinetics.
Wu, Hao; Paul, Fabian; Wehmeyer, Christoph; Noé, Frank
2016-06-07
We introduce the general transition-based reweighting analysis method (TRAM), a statistically optimal approach to integrate both unbiased and biased molecular dynamics simulations, such as umbrella sampling or replica exchange. TRAM estimates a multiensemble Markov model (MEMM) with full thermodynamic and kinetic information at all ensembles. The approach combines the benefits of Markov state models-clustering of high-dimensional spaces and modeling of complex many-state systems-with those of the multistate Bennett acceptance ratio of exploiting biased or high-temperature ensembles to accelerate rare-event sampling. TRAM does not depend on any rate model in addition to the widely used Markov state model approximation, but uses only fundamental relations such as detailed balance and binless reweighting of configurations between ensembles. Previous methods, including the multistate Bennett acceptance ratio, discrete TRAM, and Markov state models are special cases and can be derived from the TRAM equations. TRAM is demonstrated by efficiently computing MEMMs in cases where other estimators break down, including the full thermodynamics and rare-event kinetics from high-dimensional simulation data of an all-atom protein-ligand binding model.
Compartmental modeling and tracer kinetics
Anderson, David H
1983-01-01
This monograph is concerned with mathematical aspects of compartmental an alysis. In particular, linear models are closely analyzed since they are fully justifiable as an investigative tool in tracer experiments. The objective of the monograph is to bring the reader up to date on some of the current mathematical prob lems of interest in compartmental analysis. This is accomplished by reviewing mathematical developments in the literature, especially over the last 10-15 years, and by presenting some new thoughts and directions for future mathematical research. These notes started as a series of lectures that I gave while visiting with the Division of Applied ~1athematics, Brown University, 1979, and have developed in to this collection of articles aimed at the reader with a beginning graduate level background in mathematics. The text can be used as a self-paced reading course. With this in mind, exercises have been appropriately placed throughout the notes. As an aid in reading the material, the e~d of a ...
Hoai-Lam Tran; Maw-Suey Kuo; Wein-Duo Yang; Yu-Chang Huang
2016-01-01
The cobalt (II) ion-exchange process followed the Freundlich and Langmuir adsorption models as well as the pseudo-second-order kinetic model. The cobalt-exchanged contents increased when the initial Co(NO3)2 solution concentration increased up to 0.14 mol L−1 at the optimal pH of 6.05. The N2 adsorption isotherms are mixed types I/II isotherms and H3 type hysteresis. Both the micropore and mesopore adsorptions occurred during the adsorption process. The modification, which is both the cobalt ...
Kinetic Isotope Effect on Transport Mediated by Clc-Type H+/CL- Exchangers
Picollo, Alessandra; Malvezzi, Mattia; Accardi, Alessio
2013-01-01
CLC transporters mediate the stoichiometric exchange of 2 Cl- ions for 1 H+ across the membranes of cellular compartments, mostly endosomes and lysosomes. Despite intense biophysical, structural and electrophysiological scrutiny the H+ transfer mechanism of these exchangers remains largely unknown. Previous work showed that two conserved Glutamates define the extremities of the H+ pathway in CLC exchangers. However, we don't know whether H+ transfer between these residues takes place along a series of protonatable moieties, via a Grotthuss mechanism and by diffusion of an H3+O cation and if at any step H+ tunneling plays a role. To differentiate between these possible mechanisms we measured the deuterium kinetic isotope effect on the transport rate of CLC-ec1 and CLC-5, respectively a prokaryotic and a eukaryotic CLC exchanger. We found that transport mediated by both proteins is slowed by ˜20-40% when H2O is replaced by D2O. This result suggests that the rate limiting step for H+ transport takes place along a hydrogen-bonded pathway, possibly formed by water molecules. However, we found that the voltage dependence of CLC-5 inhibition by extracellular H+ is eliminated by this substitution. This suggests that the voltage dependence of this process arises from a mechanism that is exquisitely sensitive to particle mass such as proton tunneling.
Thermodynamic and kinetic modelling: creep resistant materials
DEFF Research Database (Denmark)
Hald, John; Korcakova, L.; Danielsen, Hilmar Kjartansson
2008-01-01
particles and coarsening of MX, M23C6 and Laves phase particles. The modelling provided new insight into the long term stability of new steels. Modelling of the detrimental precipitation of Z phase Cr(V,Nb)N is described, which points to new approaches in alloy development for higher temperatures......The use of thermodynamic and kinetic modelling of microstructure evolution in materials exposed to high temperatures in power plants is demonstrated with two examples. Precipitate stability in martensitic 9–12%Cr steels is modelled including equilibrium phase stability, growth of Laves phase...
MODELING STYRENE HYDROGENATION KINETICS USING PALLADIUM CATALYSTS
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G. T. Justino
Full Text Available Abstract The high octane number of pyrolysis gasoline (PYGAS explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.
The kinetics of the hydrogen/deuterium exchange of epidermal growth factor receptor ligands.
Iloro, Ibon; Narváez, Daniel; Guillén, Nancy; Camacho, Carlos M; Guillén, Lalisse; Cora, Elsa; Pastrana-Ríos, Belinda
2008-05-15
Five highly homologous epidermal growth factor receptor ligands were studied by mass spectral analysis, hydrogen/deuterium (H/D) exchange via attenuated total reflectance Fourier transform-infrared spectroscopy, and two-dimensional correlation analysis. These studies were performed to determine the order of events during the exchange process, the extent of H/D exchange, and associated kinetics of exchange for a comparative analysis of these ligands. Furthermore, the secondary structure composition of amphiregulin (AR) and heparin-binding-epidermal growth factor (HB-EGF) was determined. All ligands were found to have similar contributions of 3(10)-helix and random coil with varying contributions of beta-sheets and beta-turns. The extent of exchange was 40%, 65%, 55%, 65%, and 98% for EGF, transforming growth factor-alpha (TGF-alpha), AR, HB-EGF, and epiregulin (ER), respectively. The rate constants were determined and classified as fast, intermediate, and slow: for EGF the 0.20 min(-1) (Tyr), 0.09 min(-1) (Arg, beta-turns), and 1.88 x 10(-3) min(-1) (beta-sheets and 3(10)-helix); and for TGF-alpha 0.91 min(-1) (Tyr), 0.27 min(-1) (Arg, beta-turns), and 1.41 x 10(-4) min(-1) (beta-sheets). The time constants for AR 0.47 min(-1) (Tyr), 0.04 min(-1) (Arg), and 1.00 x 10(-4) min(-1) (buried 3(10)-helix, beta-turns, and beta-sheets); for HB-EGF 0.89 min(-1) (Tyr), 0.14 min(-1) (Arg and 3(10)-helix), and 1.00 x 10(-3) min(-1) (buried 3(10)-helix, beta-sheets, and beta-turns); and for epiregulin 0.16 min(-1) (Tyr), 0.03 min(-1) (Arg), and 1.00 x 10(-4) min(-1) (3(10)-helix and beta-sheets). These results provide essential information toward understanding secondary structure, H/D exchange kinetics, and solvation of these epidermal growth factor receptor ligands in their unbound state.
Ion exchange model for α phase proton exchange waveguide in LiNbO3
DEFF Research Database (Denmark)
Veng, Torben Erik; Skettrup, Torben
1998-01-01
An H+/Li+ exchange model is found to be applicable to describe the diffusion of protons when optical waveguides are formed in LiNbO3 by proton exchange methods where the proton doped crystal structure stays in the pure α phase. The H + and Li+ self-diffusion coefficients in the ion exchange model...
Gas exchange kinetics following concentric-eccentric isokinetic arm and leg exercise.
Drescher, U; Mookerjee, S; Steegmanns, A; Knicker, A; Hoffmann, U
2017-06-01
To evaluate the effects of exercise velocity (60, 150, 240deg∙s(-1)) and muscle mass (arm vs leg) on changes in gas exchange and arterio-venous oxygen content difference (avDO2) following high-intensity concentric-eccentric isokinetic exercise. Fourteen subjects (26.9±3.1years) performed a 3×20-repetition isokinetic exercise protocol. Recovery beat-to-beat cardiac output (CO) and breath-by-breath gas exchange were recorded to determine post-exercise half-time (t1/2) for oxygen uptake (V˙O2pulm), carbon dioxide output (V˙CO2pulm), and ventilation (V˙E). Significant differences of the t1/2 values were identified between 60 and 150deg∙s(-1). Significant differences in the t1/2 values were observed between V˙O2pulm and V˙CO2pulm and between V˙CO2pulm and V˙E. The time to attain the first avDO2-peak showed significant differences between arm and leg exercise. The present study illustrates, that V˙O2pulm kinetics are distorted due to non-linear CO dynamics. Therefore, it has to be taken into account, that V˙O2pulm may not be a valuable surrogate for muscular oxygen uptake kinetics in the recovery phases. Copyright © 2017 Elsevier B.V. All rights reserved.
A kinetic model for chemical neurotransmission
Ramirez-Santiago, Guillermo; Martinez-Valencia, Alejandro; Fernandez de Miguel, Francisco
Recent experimental observations in presynaptic terminals at the neuromuscular junction indicate that there are stereotyped patterns of cooperativeness in the fusion of adjacent vesicles. That is, a vesicle in hemifusion process appears on the side of a fused vesicle and which is followed by another vesicle in a priming state while the next one is in a docking state. In this talk we present a kinetic model for this morphological pattern in which each vesicle state previous to the exocytosis is represented by a kinetic state. This chain states kinetic model can be analyzed by means of a Master equation whose solution is simulated with the stochastic Gillespie algorithm. With this approach we have reproduced the responses to the basal release in the absence of stimulation evoked by the electrical activity and the phenomena of facilitation and depression of neuromuscular synapses. This model offers new perspectives to understand the underlying phenomena in chemical neurotransmission based on molecular interactions that result in the cooperativity between vesicles during neurotransmitter release. DGAPA Grants IN118410 and IN200914 and Conacyt Grant 130031.
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Savić Jasmina
2007-01-01
Full Text Available The adsorption kinetics of pyrazol- (РАСА and imidazol-azo-chromo-tropic acid (IACA onto Dowex 1-X8 resin, as a function of the dye concentration and temperature were investigated at pH 4.5. The pseudo-first- and second-order kinetic models and intraparticle diffusion model were used to describe the obtained kinetic data. The adsorption rate constants were found to be in the order of magnitude 10-2 min-1 for all of the used kinetics models. The adsorption capacity increases with increasing initial dye concentration. The study of adsorption kinetics at different temperatures (in the range from 5 to 25 °C reveals an increase in the rate of adsorption and adsorption capacity with increasing temperature. The activation energy (in the case of РАСА 16.6 kJ/mol, and for IACA 11.3 kJ/mol was determined using the Arrhenius dependence. Electrostatic interactions between the dye and resin beads were shown to be the adsorption mechanism.
A continuum model for metabolic gas exchange in pear fruit.
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Q Tri Ho
2008-03-01
Full Text Available Exchange of O(2 and CO(2 of plants with their environment is essential for metabolic processes such as photosynthesis and respiration. In some fruits such as pears, which are typically stored under a controlled atmosphere with reduced O(2 and increased CO(2 levels to extend their commercial storage life, anoxia may occur, eventually leading to physiological disorders. In this manuscript we have developed a mathematical model to predict the internal gas concentrations, including permeation, diffusion, and respiration and fermentation kinetics. Pear fruit has been selected as a case study. The model has been used to perform in silico experiments to evaluate the effect of, for example, fruit size or ambient gas concentration on internal O(2 and CO(2 levels. The model incorporates the actual shape of the fruit and was solved using fluid dynamics software. Environmental conditions such as temperature and gas composition have a large effect on the internal distribution of oxygen and carbon dioxide in fruit. Also, the fruit size has a considerable effect on local metabolic gas concentrations; hence, depending on the size, local anaerobic conditions may result, which eventually may lead to physiological disorders. The model developed in this manuscript is to our knowledge the most comprehensive model to date to simulate gas exchange in plant tissue. It can be used to evaluate the effect of environmental stresses on fruit via in silico experiments and may lead to commercial applications involving long-term storage of fruit under controlled atmospheres.
Modelling Heat Exchangers for Domestic Boilers
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S. F. C. F. Teixeira
2000-01-01
Full Text Available In the present paper the thermal behaviour of fin-tube heat exchangers is modeled. Particular attention has been given to the plate fins. The heat fluxes in the fins are described using a finite volume technique to discretize the energy equation. The thermal interactions with the water in the tubes and the surrounding air are treated as external boundaries, using appropriate relationships for forced convection in pipes and flat plates. The numerical results are presented in terms of dimensionless numbers (Fourier, Biot and geometric ratios which are found to be representative for this particular geometry. Furthermore, the effect of thermal gradients along the fin surface upon the fin efficiency is investigated. Based on a differential model for the heat balances, design charts have been developed for the thermal analysis of heat exchangers.
Forecasting Exchange Rates with Mixed Models
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Laura Maria Badea
2013-06-01
Full Text Available Gaining accuracy in exchange rate forecasting applications provides true benefits for financial activities. Supported today by the advancements in computing power, machine learning techniques provide good alternatives to traditional time series estimation methods. Very approached in time series forecasting are Artificial Neural Networks (ANNs which offer robust results and allow a flexible data manipulation. When integrating both, the “white-box” feature of conventional methods and the complexity of machine learning techniques, forecasting models perform even better in terms of generated errors. In this study, input variables (independent variables are selected using an ARIMA technique and are further employed in differently configured multilayered feed-forward neural networks using Broyden-Fletcher-Goldfarb-Shanno (BFGS optimization algorithm to perform predictions on EUR/RON and CHF/RON exchange rates. Results in terms of mean squared error highlight good results when using mixed models.
Kinetic effects in edge plasma: kinetic modeling for edge plasma and detached divertor
Takizuka, T.
2017-03-01
Detached divertor is considered a solution for the heat control in magnetic-confinement fusion reactors. Numerical simulations using the comprehensive divertor codes based on the plasma fluid modeling are indispensable for the design of the detached divertor in future reactors. Since the agreement in the results between detached-divertor experiments and simulations has been rather fair but not satisfactory, further improvement of the modeling is required. The kinetic effect is one of key issues for improving the modeling. Complete kinetic behaviors are able to be simulated by the kinetic modeling. In this paper at first, major kinetic effects in edge plasma and detached divertor are listed. One of the most powerful kinetic models, particle-in-cell (PIC) model, is described in detail. Several results of PIC simulations of edge-plasma kinetic natures are presented. Future works on PIC modeling and simulation for the deeper understanding of edge plasma and detached divertor are discussed.
Laplacian-level density functionals for the kinetic energy density and exchange-correlation energy
Perdew, John P.; Constantin, Lucian A.
2007-04-01
We construct a Laplacian-level meta-generalized-gradient-approximation (meta-GGA) for the noninteracting (Kohn-Sham orbital) positive kinetic energy density τ of an electronic ground state of density n . This meta-GGA is designed to recover the fourth-order gradient expansion τGE4 in the appropriate slowly varying limit and the von Weizsäcker expression τW=∣∇n∣2/(8n) in the rapidly varying limit. It is constrained to satisfy the rigorous lower bound τW(r)⩽τ(r) . Our meta-GGA is typically a strong improvement over the gradient expansion of τ for atoms, spherical jellium clusters, jellium surfaces, the Airy gas, Hooke’s atom, one-electron Gaussian density, quasi-two-dimensional electron gas, and nonuniformly scaled hydrogen atom. We also construct a Laplacian-level meta-GGA for exchange and correlation by employing our approximate τ in the Tao-Perdew-Staroverov-Scuseria (TPSS) meta-GGA density functional. The Laplacian-level TPSS gives almost the same exchange-correlation enhancement factors and energies as the full TPSS, suggesting that τ and ∇2n carry about the same information beyond that carried by n and ∇n . Our kinetic energy density integrates to an orbital-free kinetic energy functional that is about as accurate as the fourth-order gradient expansion for many real densities (with noticeable improvement in molecular atomization energies), but considerably more accurate for rapidly varying ones.
Lifshitz-Allen-Cahn domain-growth kinetics of Ising models with conserved density
DEFF Research Database (Denmark)
Fogedby, Hans C.; Mouritsen, Ole G.
1988-01-01
The domain-growth kinetics of p=fourfold degenerate (2×1) ordering in two-dimensional Ising models with conserved density is studied as a function of temperature and range of Kawasaki spin exchange. It is found by computer simulations that the zero-temperature freezing-in behavior for nearest...
Zhang, Honglei; Ding, Jincheng; Qiu, Yanli; Zhao, Zengdian
2012-05-01
Hybrid catalytic membranes consisting of cation ion-exchange resin particles (CERP) and polyethersulfone (PES) were prepared by immersion phase inversion and used as heterogeneous catalysts for the esterification of acidified oil with methanol, ethanol, propanol and butanol. The membranes were characterized by ion exchange capacity and swelling degree tests. The membranes were annealed at different temperatures to improve catalytic activity and membranes annealed at 393 K had the highest catalytic activity. Butanol allowed the highest free fatty acids (FFAs) conversion of 95.28% since it has better miscibility than the other alcohols which strengthened mass and heat transfer. Furthermore, pseudo-homogeneous kinetic models of the esterification of acidified oil with the four alcohols were established according to the experimental data. The kinetic models can well predict the FFA conversion. Copyright © 2012 Elsevier Ltd. All rights reserved.
Economic inequality and mobility in kinetic models for social sciences
Letizia Bertotti, Maria; Modanese, Giovanni
2016-10-01
Statistical evaluations of the economic mobility of a society are more difficult than measurements of the income distribution, because they require to follow the evolution of the individuals' income for at least one or two generations. In micro-to-macro theoretical models of economic exchanges based on kinetic equations, the income distribution depends only on the asymptotic equilibrium solutions, while mobility estimates also involve the detailed structure of the transition probabilities of the model, and are thus an important tool for assessing its validity. Empirical data show a remarkably general negative correlation between economic inequality and mobility, whose explanation is still unclear. It is therefore particularly interesting to study this correlation in analytical models. In previous work we investigated the behavior of the Gini inequality index in kinetic models in dependence on several parameters which define the binary interactions and the taxation and redistribution processes: saving propensity, taxation rates gap, tax evasion rate, welfare means-testing etc. Here, we check the correlation of mobility with inequality by analyzing the mobility dependence from the same parameters. According to several numerical solutions, the correlation is confirmed to be negative.
MATHEMATICAL MODELING OF ORANGE SEED DRYING KINETICS
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Daniele Penteado Rosa
2015-06-01
Full Text Available Drying of orange seeds representing waste products from juice processing was studied in the temperatures of 40, 50, 60 and 70 °C and drying velocities of 0.6, 1.0 and 1.4 m/s. Experimental drying kinetics of orange seeds were obtained using a convective air forced dryer. Three thin-layer models: Page model, Lewis model, and the Henderson-Pabis model and the diffusive model were used to predict the drying curves. The Henderson-Pabis and the diffusive models show the best fitting performance and statistical evaluations. Moreover, the temperature dependence on the effective diffusivity followed an Arrhenius relationship, and the activation energies ranging from 16.174 to 16.842 kJ/mol
Multidimensional numerical modeling of heat exchangers
Sha, W. T.; Yang, C. I.; Kao, T. T.; Cho, S. M.
A comprehensive, multidimensional, thermal-hydraulic model is developed for the analysis of shell-and-tube heat exchangers for liquid-metal services. For the shellside fluid, the conservation equations of mass, momentum, and energy for continuum fluids are modified using the concept of porosity, surface permeability and distributed resistance to account for the blockage effects due to the presence of heat-transfer tubes, flow baffles/shrouds, the support plates, etc. On the tubeside, the heat-transfer tubes are connected in parallel between the inlet and outlet plenums, and tubeside flow distribution is calculated based on the plenum-to-plenum pressure difference being equal for all tubes. It is assumed that the fluid remains single-phase on the shell side and may undergo phase-change on the tube side, thereby simulating the conditions of Liquid Metal Fast Breeder Reactor (LMFBR) intermediate heat exchangers (IHX) and steam generators (SG).
Kopra, Kari; Ligabue, Alessio; Wang, Qi; Syrjänpää, Markku; Blaževitš, Olga; Veltel, Stefan; van Adrichem, Arjan J; Hänninen, Pekka; Abankwa, Daniel; Härmä, Harri
2014-07-01
A quenching resonance energy transfer (QRET) assay for small GTPase nucleotide exchange kinetic monitoring is demonstrated using nanomolar protein concentrations. Small GTPases are central signaling proteins in all eukaryotic cells acting as a "molecular switches" that are active in the GTP-state and inactive in the GDP-state. GTP-loading is highly regulated by guanine nucleotide exchange factors (GEFs). In several diseases, most prominently cancer, this process in misregulated. The kinetics of the nucleotide exchange reaction reports on the enzymatic activity of the GEF reaction system and is, therefore, of special interest. We determined the nucleotide exchange kinetics using europium-labeled GTP (Eu-GTP) in the QRET assay for small GTPases. After GEF catalyzed GTP-loading of a GTPase, a high time-resolved luminescence signal was found to be associated with GTPase bound Eu-GTP, whereas the non-bound Eu-GTP fraction was quenched by soluble quencher. The association kinetics of the Eu-GTP was measured after GEF addition, whereas the dissociation kinetics could be determined after addition of unlabeled GTP. The resulting association and dissociation rates were in agreement with previously published values for H-Ras(Wt), H-Ras(Q61G), and K-Ras(Wt), respectively. The broader applicability of the QRET assay for small GTPases was demonstrated by determining the kinetics of the Ect2 catalyzed RhoA(Wt) GTP-loading. The QRET assay allows the use of nanomolar protein concentrations, as more than 3-fold signal-to-background ratio was achieved with 50 nM GTPase and GEF proteins. Thus, small GTPase exchange kinetics can be efficiently determined in a HTS compatible 384-well plate format.
Forecasting the Euro exchange rate using vector error correction models
Aarle, B. van; Bos, M.; Hlouskova, J.
2000-01-01
Forecasting the Euro Exchange Rate Using Vector Error Correction Models. — This paper presents an exchange rate model for the Euro exchange rates of four major currencies, namely the US dollar, the British pound, the Japanese yen and the Swiss franc. The model is based on the monetary approach of ex
Modelling dimercaptosuccinic acid (DMSA) plasma kinetics in humans
van Eijkeren, Jan C H; Olie, J Daniël N; Bradberry, Sally M; Vale, J Allister; de Vries, Irma; Meulenbelt, Jan; Hunault, Claudine C
2016-01-01
CONTEXT: No kinetic models presently exist which simulate the effect of chelation therapy on lead blood concentrations in lead poisoning. OBJECTIVE: Our aim was to develop a kinetic model that describes the kinetics of dimercaptosuccinic acid (DMSA; succimer), a commonly used chelating agent, that c
A kinetic model of plasma turbulence
Servidio, S.; Valentini, F.; Perrone, D.; Greco, A.; Califano, F.; Matthaeus, W. H.; Veltri, P.
2015-01-01
A Hybrid Vlasov-Maxwell (HVM) model is presented and recent results about the link between kinetic effects and turbulence are reviewed. Using five-dimensional (2D in space and 3D in the velocity space) simulations of plasma turbulence, it is found that kinetic effects (or non-fluid effects) manifest through the deformation of the proton velocity distribution function (DF), with patterns of non-Maxwellian features being concentrated near regions of strong magnetic gradients. The direction of the proper temperature anisotropy, calculated in the main reference frame of the distribution itself, has a finite probability of being along or across the ambient magnetic field, in general agreement with the classical definition of anisotropy T ⊥/T ∥ (where subscripts refer to the magnetic field direction). Adopting the latter conventional definition, by varying the global plasma beta (β) and fluctuation level, simulations explore distinct regions of the space given by T ⊥/T ∥ and β∥, recovering solar wind observations. Moreover, as in the solar wind, HVM simulations suggest that proton anisotropy is not only associated with magnetic intermittent events, but also with gradient-type structures in the flow and in the density. The role of alpha particles is reviewed using multi-ion kinetic simulations, revealing a similarity between proton and helium non-Maxwellian effects. The techniques presented here are applied to 1D spacecraft-like analysis, establishing a link between non-fluid phenomena and solar wind magnetic discontinuities. Finally, the dimensionality of turbulence is investigated, for the first time, via 6D HVM simulations (3D in both spaces). These preliminary results provide support for several previously reported studies based on 2.5D simulations, confirming several basic conclusions. This connection between kinetic features and turbulence open a new path on the study of processes such as heating, particle acceleration, and temperature
Mathematical Modelling of Thermal Degradation Kinetics of Ascorbic ...
African Journals Online (AJOL)
However, adequate study has not been conducted to exploit the potential of this ... of ascorbic acid in yeabesha gomen fitted first-order reaction kinetic model ... Activation energy for ascorbic degeneration kinetics of yeabesha gomen was ...
Thermodynamic and kinetic modeling of transcriptional pausing.
Tadigotla, Vasisht R; O Maoiléidigh, Dáibhid; Sengupta, Anirvan M; Epshtein, Vitaly; Ebright, Richard H; Nudler, Evgeny; Ruckenstein, Andrei E
2006-03-21
We present a statistical mechanics approach for the prediction of backtracked pauses in bacterial transcription elongation derived from structural models of the transcription elongation complex (EC). Our algorithm is based on the thermodynamic stability of the EC along the DNA template calculated from the sequence-dependent free energy of DNA-DNA, DNA-RNA, and RNA-RNA base pairing associated with (i) the translocational and size fluctuations of the transcription bubble; (ii) changes in the associated DNA-RNA hybrid; and (iii) changes in the cotranscriptional RNA secondary structure upstream of the RNA exit channel. The calculations involve no adjustable parameters except for a cutoff used to discriminate paused from nonpaused complexes. When applied to 100 experimental pauses in transcription elongation by Escherichia coli RNA polymerase on 10 DNA templates, the approach produces statistically significant results. We also present a kinetic model for the rate of recovery of backtracked paused complexes. A crucial ingredient of our model is the incorporation of kinetic barriers to backtracking resulting from steric clashes of EC with the cotranscriptionally generated RNA secondary structure, an aspect not included explicitly in previous attempts at modeling the transcription elongation process.
Thermodynamically consistent model calibration in chemical kinetics
Directory of Open Access Journals (Sweden)
Goutsias John
2011-05-01
Full Text Available Abstract Background The dynamics of biochemical reaction systems are constrained by the fundamental laws of thermodynamics, which impose well-defined relationships among the reaction rate constants characterizing these systems. Constructing biochemical reaction systems from experimental observations often leads to parameter values that do not satisfy the necessary thermodynamic constraints. This can result in models that are not physically realizable and may lead to inaccurate, or even erroneous, descriptions of cellular function. Results We introduce a thermodynamically consistent model calibration (TCMC method that can be effectively used to provide thermodynamically feasible values for the parameters of an open biochemical reaction system. The proposed method formulates the model calibration problem as a constrained optimization problem that takes thermodynamic constraints (and, if desired, additional non-thermodynamic constraints into account. By calculating thermodynamically feasible values for the kinetic parameters of a well-known model of the EGF/ERK signaling cascade, we demonstrate the qualitative and quantitative significance of imposing thermodynamic constraints on these parameters and the effectiveness of our method for accomplishing this important task. MATLAB software, using the Systems Biology Toolbox 2.1, can be accessed from http://www.cis.jhu.edu/~goutsias/CSS lab/software.html. An SBML file containing the thermodynamically feasible EGF/ERK signaling cascade model can be found in the BioModels database. Conclusions TCMC is a simple and flexible method for obtaining physically plausible values for the kinetic parameters of open biochemical reaction systems. It can be effectively used to recalculate a thermodynamically consistent set of parameter values for existing thermodynamically infeasible biochemical reaction models of cellular function as well as to estimate thermodynamically feasible values for the parameters of new
Directory of Open Access Journals (Sweden)
Hoai-Lam Tran
2016-01-01
Full Text Available The cobalt (II ion-exchange process followed the Freundlich and Langmuir adsorption models as well as the pseudo-second-order kinetic model. The cobalt-exchanged contents increased when the initial Co(NO32 solution concentration increased up to 0.14 mol L−1 at the optimal pH of 6.05. The N2 adsorption isotherms are mixed types I/II isotherms and H3 type hysteresis. Both the micropore and mesopore adsorptions occurred during the adsorption process. The modification, which is both the cobalt (II exchange and thermal treatment, significantly improved the surface properties of NaX zeolites. Accordingly, the optimal temperature range is 500 to 600°C for a thermal treatment. This is consistent with the results of XRD analysis.
A kinetic control of the heliospheric interface hydrodynamics of charge-exchanging fluids
Fahr, H J
2004-01-01
It is well known that the Solar System is presently moving through a partially ionized local interstellar medium. This gives rise to a counter-flow situation requiring a consistent description of behaviour of the two fluids -- ions and neutral atoms -- which are dynamically coupled by mutual charge exchange processes. Solutions to this problem have been offered in the literature, all relying on the assumption that the proton fluid, even under evidently nonequilibrium conditions, can be expected to stay in a highly-relaxated distribution function given by mono-Maxwellians shifted by the local proton bulk velocity. Here we check the validity of this assumption, calculating on the basis of a Boltzmann-kinetic approach the actually occurring deviations. As we show, especially for low degrees of ionization, $\\xi \\le 0.3$, both the H-atoms and protons involved do generate in the heliospheric interface clearly pronounced deviations from shifted Maxwellians with asymmetrically shaped distribution functions giving ris...
Modeling in applied sciences a kinetic theory approach
Pulvirenti, Mario
2000-01-01
Modeling complex biological, chemical, and physical systems, in the context of spatially heterogeneous mediums, is a challenging task for scientists and engineers using traditional methods of analysis Modeling in Applied Sciences is a comprehensive survey of modeling large systems using kinetic equations, and in particular the Boltzmann equation and its generalizations An interdisciplinary group of leading authorities carefully develop the foundations of kinetic models and discuss the connections and interactions between model theories, qualitative and computational analysis and real-world applications This book provides a thoroughly accessible and lucid overview of the different aspects, models, computations, and methodology for the kinetic-theory modeling process Topics and Features * Integrated modeling perspective utilized in all chapters * Fluid dynamics of reacting gases * Self-contained introduction to kinetic models * Becker–Doring equations * Nonlinear kinetic models with chemical reactions * Kinet...
Jiang, N; Shelley, J D; Smith, Robin
2014-01-01
The retrofit of heat exchanger networks requires detailed models of the heat exchangers for the detailed assessment of network performance. Network retrofit options include heat transfer enhancement. There is thus a requirement for detailed models of heat exchanger performance, including heat transfer enhancement, suitable for inclusion in network retrofit optimization algorithms. Such models must be robust, computationally efficient and accurate enough to reflect the heat transfer and pressu...
Modeling the Volatility of Exchange Rates: GARCH Models
Directory of Open Access Journals (Sweden)
Fahima Charef
2017-03-01
Full Text Available The modeling of the dynamics of the exchange rate at a long time remains a financial and economic research center. In our research we tried to study the relationship between the evolution of exchange rates and macroeconomic fundamentals. Our empirical study is based on a series of exchange rates for the Tunisian dinar against three currencies of major trading partners (dollar, euro, yen and fundamentals (the terms of trade, the inflation rate, the interest rate differential, of monthly data, from jan 2000 to dec-2014, for the case of the Tunisia. We have adopted models of conditional heteroscedasticity (ARCH, GARCH, EGARCH, TGARCH. The results indicate that there is a partial relationship between the evolution of the Tunisian dinar exchange rates and macroeconomic variables.
Ricardo, Ana R; Carvalho, Gilda; Velizarov, Svetlozar; Crespo, João G; Reis, Maria A M
2012-09-15
The biological degradation of nitrate and perchlorate was investigated in an ion exchange membrane bioreactor (IEMB) using a mixed anoxic microbial culture and ethanol as the carbon source. In this process, a membrane-supported biofilm reduces nitrate and perchlorate delivered through an anion exchange membrane from a polluted water stream, containing 60 mg/L of NO₃⁻ and 100 μg/L of ClO₄⁻. Under ammonia limiting conditions, the perchlorate reduction rate decreased by 10%, whereas the nitrate reduction rate was unaffected. Though nitrate and perchlorate accumulated in the bioreactor, their concentrations in the treated water (2.8 ± 0.5 mg/L of NO₃⁻ and 7.0 ± 0.8 μg/L of ClO₄⁻, respectively) were always below the drinking water regulatory levels, due to Donnan dialysis control of the ionic transport in the system. Kinetic parameters determined for the mixed microbial culture in suspension showed that the nitrate reduction rate was 35 times higher than the maximum perchlorate reduction rate. It was found that perchlorate reduction was inhibited by nitrate, since after nitrate depletion perchlorate reduction rate increased by 77%. The biofilm developed in the IEMB was cryosectioned and the microbial population was analyzed by fluorescence in situ hybridization (FISH). The results obtained seem to indicate that the kinetic advantage of nitrate reduction favored accumulation of denitrifiers near the membrane, whereas per(chlorate) reducing bacteria were mainly positioned at the biofilm outer surface, contacting the biomedium. As a consequence of the biofilm stratification, the reduction of perchlorate and nitrate occur sequentially in space allowing for the removal of both ions in the IEMB.
Assessing chromate availability in tropical ultramafic soils using isotopic exchange kinetics
Energy Technology Data Exchange (ETDEWEB)
Garnier, Jeremie; Quantin, Cecile [Univ. Paris Sud CNRS, Orsay (France); Echevarria, Guillaume [ENSAIA-INPL-INRA, Vandoeuvre-les-Nancy (France); Becquer, Thierry [IRD - Univ. Paris VI and XII, Montpellier (France)
2009-10-15
Background, aim, and scope The presence of labile chromate in the soils is an environmental problem because of its high toxicity. The isotopic exchange kinetics (IEK) methods have been shown to be a useful tool to measure the phytoavailability of major (P, K) and trace elements (Cd, Zn, Ni, Pb) in soils. This study focused on the potential of applying IEK for chromate to characterize its availability in two tropical ultramafic Ferralsols. Materials and methods Two Ferralsols (NIQ II and NIQ III) of the ultramafic complex of Niquelandia (Goias, Brazil), known to have a high content of extractable chromate, were investigated. We adapted IEK for chromate in order to distinguish different pools of available chromate according to their rate of exchange kinetic. Results The extractable Cr(III) ranged from 9 to 132 mg kg{sup -1}, whereas extractable Cr(VI) ranged from 64 to 1,014 mg kg{sup -1}. The intensity factor, i.e., concentration of soluble Cr, ranged from 78 to 231 {mu}g L{sup -1} in profile NIQ II and from 6 to 141 {mu}g L{sup -1} in profile NIQ III. The highest concentrations were found in both topsoils and in the NIQ II-5 horizon. Most of the Cr(VI) was labile in short (E{sub 0-1} {sub min}) or medium-term (E{sub 1} {sub min-24} {sub h}) in both soils. The E{sub 0-1} {sub min} and E{sub 1} {sub min-24} {sub h} represented 39 to 83% of labile Cr (VI) in NIQ II and 69 to 80% in NIQ III. A high quantity of Cr(VI) was thus extremely labile and highly available, particularly in NIQ II. Moreover, both soils had a high buffering capacity of soluble Cr(VI) by labile pools. (orig.)
Hassan, Nouri M; Murimboh, John D; Sekaly, Amina L R; Mandal, Rupasri; Chakrabarti, Chuni L; Grégoire, D Conrad
2006-04-01
Kinetic speciation of nickel, aluminium, and iron in fresh water has been investigated by cascade ultrafiltration followed by competing ligand exchange of the ultrafiltered fractions. Graphite furnace atomic absorption spectrometry was used to measure the kinetics of metal complex dissociation. Dissolved metal species were fractionated by cascade ultrafiltration. Metal speciation in each ultrafiltered fraction was then characterized as free metal ions, "labile" metal complexes (with dissociation rate constants >/=10(-3) s(-1)), "slowly labile" metal complexes (with dissociation rate constants >10(-6) s(-1)), and "inert" metal complexes (with dissociation rate constants measurement of dissociation kinetics alone.
Asset pricing model selection: Indonesian Stock Exchange
Pasaribu, Rowland Bismark Fernando
2010-01-01
The Capital Asset Pricing Model (CAPM) has dominated finance theory for over thirty years; it suggests that the market beta alone is sufficient to explain stock returns. However evidence shows that the cross-section of stock returns cannot be described solely by the one-factor CAPM. Therefore, the idea is to add other factors in order to complete the beta in explaining the price movements in the stock exchange. The Arbitrage Pricing Theory (APT) has been proposed as the first multifactor succ...
STEP - Product Model Data Sharing and Exchange
DEFF Research Database (Denmark)
Kroszynski, Uri
1998-01-01
- Product Data Representation and Exchange", featuring at present some 30 released parts, and growing continuously. Many of the parts are Application Protocols (AP). This article presents an overview of STEP, based upon years of involvement in three ESPRIT projects, which contributed to the development......During the last fifteen years, a very large effort to standardize the product models employed in product design, manufacturing and other life-cycle phases has been undertaken. This effort has the acronym STEP, and resulted in the International Standard ISO-10303 "Industrial Automation Systems...
How not to do kinetics: examples involving GTPases and guanine nucleotide exchange factors.
Goody, Roger S
2014-01-01
Guanine nucleotide exchange factors (GEFs) are crucial regulators of the action of GTPases in signal transduction and cellular regulation. Although their basic mechanism of action has been apparent for almost 20 years, there are still misconceptions concerning their properties, and these are confounded by superficial or incorrect interpretation of experimental results in individual cases. Here, an example is described in which an incorrect mechanism was derived because of an inadequate analysis of kinetic results. In a second example, a case is discussed where certain GTP analogs were erroneously described as being able to function as low molecular mass GEFs. In both cases, a lack of distinction between rates, rate constants, and apparent rate constants, together with a disregard of relative signal amplitudes, led to the misinterpretations. In a final example, it is shown how the lack of an appropriate kinetic investigation led to the false conclusion that a secreted protein from Legionella pneumophila can act not only as a GEF towards eukaryotic Rab1 but also as a factor that is able to actively dissociate the stable complex between Rab1 and GDP dissociation inhibitor.
A Model for Trading the Foreign Exchange Market | Nwokorie | West ...
African Journals Online (AJOL)
A Model for Trading the Foreign Exchange Market. ... interest rates, inflation rates, etc. have significant impacts on the exchange rate fluctuation. Existing ... The predictions from the networks are integrated to get the direction of price movement.
Institute of Scientific and Technical Information of China (English)
刘伟; 李志安; 赵志忠
1996-01-01
Coexistent minerals quartz, feldspar and biotite vary widely in δ18O value and display remarkable 18O/16O disequilibrium relations in the Ertaibei granite pluton, northern Xinjiang. The 18O/16O exchange reaction definitely occurred between granite and water. Initial δ18O values of the granite and exotic water are evaluated by the mass balance consideration. The results show that the 18O/16O exchange reaction is not necessarily accompanied by what geologists describe as petrological and mineralogiesl alteration effects, indicating that the exchange reaction occurs at a comparatively high temperature during subsolidus cooling of magmas. Exchange mechanism is mainly controlled by diffusion. It is demonstrated through quantitative modelling that the hydrothermal system associated with the Ertaibei pluton lived for 0.8-3 Ma, with a fluid flow rate of 3 × 10-14 mol · s-1 and water/rock (W/R) ratio of 0.79 - 3.08. Flow path and initial heterogeneity of the exotic metamorphic fluid are modelled with the δ1
MODELLING OF KINETICS OF FLUORINE ADSORPTION ONTO MODIFIED DIATOMITE
Directory of Open Access Journals (Sweden)
VEACESLAV ZELENTSOV
2017-03-01
Full Text Available The paper presents kinetics modelling of adsorption of fluorine onto modified diatomite, its fundamental characteristics and mathematical derivations. Three models of defluoridation kinetics were used to fit the experimental results on adsorption fluorine onto diatomite: the pseudo-first order model Lagergren, the pseudo-second order model G. McKay and H.S. Ho and intraparticle diffusion model of W.J. Weber and J.C. Morris. Kinetics studies revealed that the adsorption of fluorine followed second-order rate model, complimented by intraparticle diffusion kinetics. The adsorption mechanism of fluorine involved three stages – external surface adsorption, intraparticle diffusion and the stage of equilibrium.
Extended Goldstone-boson-exchange constituent quark model
Wagenbrunn, R F; Plessas, W; Varga, K
2000-01-01
We discuss an updated version of the Goldstone-boson-exchange chiral quark model extended to include in addition to pseudoscalar meson exchanges also vector and scalar meson exchanges. The latter ingredients are viewed as effective parametrizations of multiple Goldstone-boson exchanges in baryons. The extended model allows for an accurate description of all light and strange baryon spectra and at the same time produces the right properties for deducing baryon-baryon interactions.
Tanner, Stephen P.
1997-01-01
One of the goals of the original proposal was to study how cross-linking affects the properties of an ion exchange material(IEM) developed at Lewis Research Center. However, prior to the start of this work, other workers at LERC investigated the effect of cross-linking on the properties of this material. Other than variation in the ion exchange capacity, the chemical characteristics were shown to be independent of the cross-linking agent, and the degree of cross-linking. New physical forms of the film were developed (film, supported film, various sizes of beads, and powder). All showed similar properties with respect to ion exchange equilibria but the kinetics of ion exchange depended on the surface area per unit mass; the powder form of the IEM exchanging much more rapidly than the other forms. The research performed under this grant was directed towards the application of the IEM to the analysis of metal ions at environmental concentrations.
1992-10-01
Wisconsin group shows that a significantly better correlation of the solvent-dependent kinetics are obtained with the Kosower Z parameter than with the...log kh1 for 1+/0 self exchange in nine solvents, including three alcohols, correlates linearly with the Kosower Z or the closely related E?(30
Kinetic depletion model for pellet ablation
Energy Technology Data Exchange (ETDEWEB)
Kuteev, Boris V. [State Technical Univ., St. Petersburg (Russian Federation)
2001-11-01
A kinetic model for depletion effect, which determines pellet ablation when the pellet passes a rational magnetic surface, is formulated. The model predicts a moderate decrease of the ablation rate compared with the earlier considered monoenergy versions [1, 2]. For typical T-10 conditions the ablation rate reduces by a reactor of 2.5 when the 1-mm pellet penetrates through the plasma center. A substantial deceleration of pellets -about 15% per centimeter of low shire rational q region; is predicted. Penetration for Low Field Side and High Field Side injections is considered taking into account modification of the electron distribution function by toroidal magnetic field. It is shown that Shafranov shift and toroidal effects yield the penetration length for HFS injection higher by a factor of 1.5. This fact should be taken into account when plasma-shielding effects on penetration are considered. (author)
Holographic kinetic k-essence model
Energy Technology Data Exchange (ETDEWEB)
Cruz, Norman [Departamento de Fisica, Facultad de Ciencia, Universidad de Santiago de Chile, Casilla 307, Santiago (Chile)], E-mail: ncruz@lauca.usach.cl; Gonzalez-Diaz, Pedro F.; Rozas-Fernandez, Alberto [Colina de los Chopos, Instituto de Fisica Fundamental, Consejo Superior de Investigaciones Cientificas, Serrano 121, 28006 Madrid (Spain)], E-mail: a.rozas@cfmac.csic.es; Sanchez, Guillermo [Departamento de Matematica y Ciencia de la Computacion, Facultad de Ciencia, Universidad de Santiago de Chile, Casilla 307, Santiago (Chile)], E-mail: gsanchez@usach.cl
2009-08-31
We consider a connection between the holographic dark energy density and the kinetic k-essence energy density in a flat FRW universe. With the choice c{>=}1, the holographic dark energy can be described by a kinetic k-essence scalar field in a certain way. In this Letter we show this kinetic k-essential description of the holographic dark energy with c{>=}1 and reconstruct the kinetic k-essence function F(X)
Elementary Processes and Kinetic Modeling for Hydrogen and Helium Plasmas
Directory of Open Access Journals (Sweden)
Roberto Celiberto
2017-05-01
Full Text Available We report cross-sections and rate coefficients for excited states colliding with electrons, heavy particles and walls useful for the description of H 2 /He plasma kinetics under different conditions. In particular, the role of the rotational states in resonant vibrational excitations of the H 2 molecule by electron impact and the calculation of the related cross-sections are illustrated. The theoretical determination of the cross-section for the rovibrational energy exchange and dissociation of H 2 molecule, induced by He atom impact, by using the quasi-classical trajectory method is discussed. Recombination probabilities of H atoms on tungsten and graphite, relevant for the determination of the nascent vibrational distribution, are also presented. An example of a state-to-state plasma kinetic model for the description of shock waves operating in H 2 and He-H 2 mixtures is presented, emphasizing also the role of electronically-excited states in affecting the electron energy distribution function of free electrons. Finally, the thermodynamic properties and the electrical conductivity of non-ideal, high-density hydrogen plasma are finally discussed, in particular focusing on the pressure ionization phenomenon in high-pressure high-temperature plasmas.
Population balance modeling of antibodies aggregation kinetics.
Arosio, Paolo; Rima, Simonetta; Lattuada, Marco; Morbidelli, Massimo
2012-06-21
The aggregates morphology and the aggregation kinetics of a model monoclonal antibody under acidic conditions have been investigated. Growth occurs via irreversible cluster-cluster coagulation forming compact, fractal aggregates with fractal dimension of 2.6. We measured the time evolution of the average radius of gyration, , and the average hydrodynamic radius, , by in situ light scattering, and simulated the aggregation kinetics by a modified Smoluchowski's population balance equations. The analysis indicates that aggregation does not occur under diffusive control, and allows quantification of effective intermolecular interactions, expressed in terms of the Fuchs stability ratio (W). In particular, by introducing a dimensionless time weighed on W, the time evolutions of measured under various operating conditions (temperature, pH, type and concentration of salt) collapse on a single master curve. The analysis applies also to data reported in the literature when growth by cluster-cluster coagulation dominates, showing a certain level of generality in the antibodies aggregation behavior. The quantification of the stability ratio gives important physical insights into the process, including the Arrhenius dependence of the aggregation rate constant and the relationship between monomer-monomer and cluster-cluster interactions. Particularly, it is found that the reactivity of non-native monomers is larger than that of non-native aggregates, likely due to the reduction of the number of available hydrophobic patches during aggregation.
Kinetic modelling of coupled transport across biological membranes.
Korla, Kalyani; Mitra, Chanchal K
2014-04-01
In this report, we have modelled a secondary active co-transporter (symport and antiport), based on the classical kinetics model. Michaelis-Menten model of enzyme kinetics for a single substrate, single intermediate enzyme catalyzed reaction was proposed more than a hundred years ago. However, no single model for the kinetics of co-transport of molecules across a membrane is available in the literature We have made several simplifying assumptions and have followed the basic Michaelis-Menten approach. The results have been simulated using GNU Octave. The results will be useful in general kinetic simulations and modelling.
Electrothermal Model of Kinetic Inductance Detectors
Thomas, Christopher N; Goldie, David J
2014-01-01
An electrothermal model of Kinetic Inductance Detectors (KIDs) is described. The non-equilibrium state of the resonator's quasiparticle system is characterized by an effective temperature, which because of readout-power heating is higher than that of the bath. By balancing the flow of energy into the quasiparticle system, it is possible to calculate the steady-state large-signal, small-signal and noise behaviour. Resonance-curve distortion and hysteretic switching appear naturally within the framework. It is shown that an electrothermal feedback process exists, which affects all aspects of behaviour. It is also shown that generation-recombination noise can be interpreted in terms of the thermal fluctuation noise in the effective thermal conductance that links the quasiparticle and phonon systems of the resonator. Because the scheme is based on electrothermal considerations, multiple elements can be added to simulate the behaviour of complex devices, such as resonators on membranes, again taking into account r...
Zvezdina, S. V.; Chizhova, N. V.; Mamardashvili, N. Zh.
2017-03-01
The reaction of metal exchange between Cd(II) octa(4-bromophenyl)porphyrinate with CuCl2 and ZnCl2 in DMFA and DMSO is studied by means of spectrophotometry. The kinetic parameters of the metal exchange reaction are calculated, a stoichiometric reaction mechanism is proposed. The effect the natures of the solvent, salt solvate, and the chemical modification of tetrapyrrole macrocycle have on the kinetic parameters of the metal exchange reaction are revealed.
A review on solar wind modeling: kinetic and fluid aspects
Echim, Marius; Lie-Svendsen, Oystein
2013-01-01
We review the main advantages and limitations of the kinetic exospheric and fluid models of the solar wind (SW). We discuss the hydrostatic model imagined by Chapman, the first supersonic hydrodynamic models published by Parker and the first generation subsonic kinetic model proposed by Chamberlain. It is shown that a correct estimation of the electric field as in the second generation kinetic exospheric models developed by Lemaire and Scherer, provides a supersonic expansion of the corona, reconciling the hydrodynamic and the kinetic approach. The third generation kinetic exospheric models considers kappa velocity distribution function (VDF) instead of a Maxwellian at the exobase and in addition they treat a non-monotonic variation of the electric potential with the radial distance; the fourth generation exospheric models include Coulomb collisions based on the Fokker--Planck collision term. Multi-fluid models of the solar wind provide a coarse grained description and reproduce with success the spatio-tempor...
Chemical Kinetic Modeling of Biofuel Combustion
Sarathy, Subram Maniam
Bioalcohols, such as bioethanol and biobutanol, are suitable replacements for gasoline, while biodiesel can replace petroleum diesel. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This study's contribution is experimentally validated chemical kinetic combustion mechanisms for biobutanol and biodiesel. Fundamental combustion data and chemical kinetic mechanisms are presented and discussed to improve our understanding of biofuel combustion. The net environmental impact of biobutanol (i.e., n-butanol) has not been studied extensively, so this study first assesses the sustainability of n-butanol derived from corn. The results indicate that technical advances in fuel production are required before commercializing biobutanol. The primary contribution of this research is new experimental data and a novel chemical kinetic mechanism for n-butanol combustion. The results indicate that under the given experimental conditions, n-butanol is consumed primarily via abstraction of hydrogen atoms to produce fuel radical molecules, which subsequently decompose to smaller hydrocarbon and oxygenated species. The hydroxyl moiety in n-butanol results in the direct production of the oxygenated species such as butanal, acetaldehyde, and formaldehyde. The formation of these compounds sequesters carbon from forming soot precursors, but they may introduce other adverse environmental and health effects. Biodiesel is a mixture of long chain fatty acid methyl esters derived from fats and oils. This research study presents high quality experimental data for one large fatty acid methyl ester, methyl decanoate, and models its combustion using an improved skeletal mechanism. The results indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which ultimately lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular
Ishigami, Izumi; Hikita, Masahide; Egawa, Tsuyoshi; Yeh, Syun-Ru; Rousseau, Denis L
2015-01-01
Cytochrome c oxidase is the terminal enzyme in the electron transfer chain. It reduces oxygen to water and harnesses the released energy to translocate protons across the inner mitochondrial membrane. The mechanism by which the oxygen chemistry is coupled to proton translocation is not yet resolved owing to the difficulty of monitoring dynamic proton transfer events. Here we summarize several postulated mechanisms for proton translocation, which have been supported by a variety of vibrational spectroscopic studies. We recently proposed a proton translocation model involving proton accessibility to the regions near the propionate groups of the heme a and heme a3 redox centers of the enzyme based by hydrogen/deuterium (H/D) exchange Raman scattering studies (Egawa et al., PLoS ONE 2013). To advance our understanding of this model and to refine the proton accessibility to the hemes, the H/D exchange dependence of the heme propionate group vibrational modes on temperature and pH was measured. The H/D exchange detected at the propionate groups of heme a3 takes place within a few seconds under all conditions. In contrast, that detected at the heme a propionates occurs in the oxidized but not the reduced enzyme and the H/D exchange is pH-dependent with a pKa of ~8.0 (faster at high pH). Analysis of the thermodynamic parameters revealed that, as the pH is varied, entropy/enthalpy compensation held the free energy of activation in a narrow range. The redox dependence of the possible proton pathways to the heme groups is discussed. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.
Thermoluminescence of zircon: a kinetic model
Turkin, A A; Vainshtein, D I; Hartog, H W D
2003-01-01
The mineral zircon, ZrSiO sub 4 , belongs to a class of promising materials for geochronometry by means of thermoluminescence (TL) dating. The development of a reliable and reproducible method for TL dating with zircon requires detailed knowledge of the processes taking place during exposure to ionizing radiation, long-term storage, annealing at moderate temperatures and heating at a constant rate (TL measurements). To understand these processes one needs a kinetic model of TL. This paper is devoted to the construction of such a model. The goal is to study the qualitative behaviour of the system and to determine the parameters and processes controlling TL phenomena of zircon. The model considers the following processes: (i) Filling of electron and hole traps at the excitation stage as a function of the dose rate and the dose for both (low dose rate) natural and (high dose rate) laboratory irradiation. (ii) Time dependence of TL fading in samples irradiated under laboratory conditions. (iii) Short time anneali...
Kinetic modelling of krypton fluoride laser systems
Energy Technology Data Exchange (ETDEWEB)
Jancaitis, K.S.
1983-11-01
A kinetic model has been developed for the KrF* rare gas halide laser system, specifically for electron-beam pumped mixtures of krypton, fluorine, and either helium or argon. The excitation produced in the laser gas by the e-beam was calculated numerically using an algorithm checked by comparing the predicted ionization yields in the pure rare gases with their experimental values. The excitation of the laser media by multi-kilovolt x-rays was also modeled and shown to be similar to that produced by high energy electrons. A system of equations describing the transfer of the initial gas excitation into the laser upper level was assembled using reaction rate constants from both experiment and theory. A one-dimensional treatment of the interaction of the laser radiation with the gas was formulated which considered spontaneous and stimulated emission and absorption. The predictions of this model were in good agreement with the fluorescence signals and gain and absorption measured experimentally.
Shear-Driven Reconnection in Kinetic Models
Black, C.; Antiochos, S. K.; Germaschewski, K.; Karpen, J. T.; DeVore, C. R.; Bessho, N.
2015-12-01
The explosive energy release in solar eruptive phenomena is believed to be due to magnetic reconnection. In the standard model for coronal mass ejections (CME) and/or solar flares, the free energy for the event resides in the strongly sheared magnetic field of a filament channel. The pre-eruption force balance consists of an upward force due to the magnetic pressure of the sheared field countered by a downward tension due to overlying unsheared field. Magnetic reconnection disrupts this force balance; therefore, it is critical for understanding CME/flare initiation, to model the onset of reconnection driven by the build-up of magnetic shear. In MHD simulations, the application of a magnetic-field shear is a trivial matter. However, kinetic effects are dominant in the diffusion region and thus, it is important to examine this process with PIC simulations as well. The implementation of such a driver in PIC methods is challenging, however, and indicates the necessity of a true multiscale model for such processes in the solar environment. The field must be sheared self-consistently and indirectly to prevent the generation of waves that destroy the desired system. Plasma instabilities can arise nonetheless. In the work presented here, we show that we can control this instability and generate a predicted out-of-plane magnetic flux. This material is based upon work supported by the National Science Foundation under Award No. AGS-1331356.
Reflected kinetics model for nuclear space reactor kinetics and control scoping calculations
Energy Technology Data Exchange (ETDEWEB)
Washington, K.E.
1986-05-01
The objective of this research is to develop a model that offers an alternative to the point kinetics (PK) modelling approach in the analysis of space reactor kinetics and control studies. Modelling effort will focus on the explicit treatment of control drums as reactivity input devices so that the transition to automatic control can be smoothly done. The proposed model is developed for the specific integration of automatic control and the solution of the servo mechanism problem. The integration of the kinetics model with an automatic controller will provide a useful tool for performing space reactor scoping studies for different designs and configurations. Such a tool should prove to be invaluable in the design phase of a space nuclear system from the point of view of kinetics and control limitations.
Model Uncertainty and Exchange Rate Forecasting
Kouwenberg, Roy; Markiewicz, Agnieszka; Verhoeks, Ralph; Zwinkels, Remco
2013-01-01
textabstractWe propose a theoretical framework of exchange rate behavior where investors focus on a subset of economic fundamentals. We find that any adjustment in the set of predictors used by investors leads to changes in the relation between the exchange rate and fundamentals. We test the validity of this framework via a backward elimination rule which captures the current set of fundamentals that best predicts the exchange rate. Out-of-sample forecasting tests show that the backward elimi...
Pizzanelli, Silvia; Forte, Claudia; Pinzino, Calogero; Magrì, Antonio; La Mendola, Diego
2016-02-07
Copper(ii) complexes with short peptides based on the second cell binding site of fibronectin, PHSFN and PHSEN, have been characterized by potentiometric, UV-vis, CD, EPR and NMR spectroscopic methods. The histidine imidazole nitrogen is the anchoring site for the metal ion binding. Thermodynamic and spectroscopic evidence is given that the side chain oxygen donor atom of glutamyl residue in Ac-PHSEN-NH2 is also involved in the binding up to physiological pH. To determine ligand exchange kinetic parameters after the imidazole nitrogen anchoring, proton relaxation enhancement NMR data have been collected for the two hydrogen atoms of the imidazole ring in the temperature range 293-315 K at pH 5.2 and globally treated within different kinetic models for ligand exchange. The best fitting model involves two steps. In the first one, which is slow, a water molecule disengages a carbonyl or a carboxylate group coordinated to the metal ion in the complex formed by PHSFN or PHSEN, respectively. This stage is one order of magnitude slower for PHSEN, due to entropic effects. In the second step, which is fast, the complex just formed exchanges with the ligand. In this step, no appreciable differences are found for the two cases examined.
Gregory, R.T.; Criss, R.E.; Taylor, H.P.
1989-01-01
The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and
Fully implicit kinetic modelling of collisional plasmas
Energy Technology Data Exchange (ETDEWEB)
Mousseau, V.A.
1996-05-01
This dissertation describes a numerical technique, Matrix-Free Newton Krylov, for solving a simplified Vlasov-Fokker-Planck equation. This method is both deterministic and fully implicit, and may not have been a viable option before current developments in numerical methods. Results are presented that indicate the efficiency of the Matrix-Free Newton Krylov method for these fully-coupled, nonlinear integro-differential equations. The use and requirement for advanced differencing is also shown. To this end, implementations of Chang-Cooper differencing and flux limited Quadratic Upstream Interpolation for Convective Kinematics (QUICK) are presented. Results are given for a fully kinetic ion-electron problem with a self consistent electric field calculated from the ion and electron distribution functions. This numerical method, including advanced differencing, provides accurate solutions, which quickly converge on workstation class machines. It is demonstrated that efficient steady-state solutions can be achieved to the non-linear integro-differential equation, obtaining quadratic convergence, without incurring the large memory requirements of an integral operator. Model problems are presented which simulate plasma impinging on a plate with both high and low neutral particle recycling typical of a divertor in a Tokamak device. These model problems demonstrate the performance of the new solution method.
Song, Haiou; Yao, Zhijian; Wang, Mengqiao; Wang, Jinnan; Zhu, Zhaolian; Li, Aimin
2013-01-01
The effects of dissolved organic matter (DOM) on the removal of nitrate-nitrogen from the model contaminated water have been investigated utilizing the strong base anion exchange resins. With the increase of gallic acid concentration from 0 to 400 mg/L, the adsorption amount of nitrate-nitrogen on the commercial resins, including D201, Purolite A 300 (A300) and Purolite A 520E (A520E), would significantly decrease. However, the presence of tannin acid has little impact on nitrate-nitrogen adsorption on them.Compared to D201 and A300 resins, A520E resin exhibited more preferable adsorption ability toward nitrate-nitrogen in the presence of competing organic molecules, such as gallic acid and tannin acid at greater levels in aqueous solution. Attractively, the equilibrium data showed that the adsorption isotherm of nitrate-nitrogen on A520E resin was in good agreement with Langmuir and Freundlich equations. The rate parameters for the intra particle diffusion have been estimated for the different initial concentrations. In batch adsorption processes, nitrate-nitrogen diffuse in porous adsorbent and rate process usually depends on t1/2 rather than the contact time. The pseudo first- and the second-order kinetic models fit better for nitrate-nitrogen adsorption onto A520E resin. The observations reported herein illustrated that A520E resin will be an excellent adsorbent for enhanced removal of nitrate-nitrogen from contaminated groundwater.
Kinetic modeling in pre-clinical positron emission tomography
Energy Technology Data Exchange (ETDEWEB)
Kuntner, Claudia [AIT Austrian Institute of Technology GmbH, Seibersdorf (Austria). Biomedical Systems, Health and Environment Dept.
2014-07-01
Pre-clinical positron emission tomography (PET) has evolved in the last few years from pure visualization of radiotracer uptake and distribution towards quantification of the physiological parameters. For reliable and reproducible quantification the kinetic modeling methods used to obtain relevant parameters of radiotracer tissue interaction are important. Here we present different kinetic modeling techniques with a focus on compartmental models including plasma input models and reference tissue input models. The experimental challenges of deriving the plasma input function in rodents and the effect of anesthesia are discussed. Finally, in vivo application of kinetic modeling in various areas of pre-clinical research is presented and compared to human data.
Institute of Scientific and Technical Information of China (English)
Ping Ao; Lik Wee Lee; Mary E. Lidstrom; Lan Yin; Xiaomei Zhu
2008-01-01
Here we report a systematic method for constructing a large scale kinetic metabolic model and its initial application to the modeling of central metabolism of Methylobacterium extorquens AM1, a methylotrophic and environmental important bacterium. Its central metabolic network includes formaldehyde metabolism, serine cycle, citric acid cycle, pentose phosphate pathway, ghiconeogensis, PHB synthesis and acetyl-CoA conversion pathway, respiration and energy metabolism. Through a systematic and consistent procedure of finding a set of parameters in the physiological range we overcome an outstanding difficulty in large scale kinetic modeling: the requirement for a massive number of enzymatic reaction parameters. We are able to construct the kinetic model based on general biological considerations and incomplete experimental kinetic parameters. Our method consists of the following major steps: 1) using a generic enzymatic rate equation to reduce the number of enzymatic parameters to a minimum set while still preserving their characteristics; 2) using a set of steady state fluxes and metabolite concenwations in the physiological range as the expected output steady state fluxes and metabolite concentrations for the kinetic model to restrict the parametric space of enzymatic reactions; 3) choosing enzyme constants K's and K'eqs optimized for reactions under physiological concentrations, if their experimental values are unknown; 4) for models which do not cover the entire metabolic network of the organisms, designing a dynamical exchange for the coupling between the metabolism represented in the model and the rest not included.
Multiphysics Model of Palladium Hydride Isotope Exchange Accounting for Higher Dimensionality
Energy Technology Data Exchange (ETDEWEB)
Gharagozloo, Patricia E.; Eliassi, Mehdi; Bon, Bradley Luis
2015-03-01
This report summarizes computational model developm ent and simulations results for a series of isotope exchange dynamics experiments i ncluding long and thin isothermal beds similar to the Foltz and Melius beds and a lar ger non-isothermal experiment on the NENG7 test bed. The multiphysics 2D axi-symmetr ic model simulates the temperature and pressure dependent exchange reactio n kinetics, pressure and isotope dependent stoichiometry, heat generation from the r eaction, reacting gas flow through porous media, and non-uniformities in the bed perme ability. The new model is now able to replicate the curved reaction front and asy mmetry of the exit gas mass fractions over time. The improved understanding of the exchange process and its dependence on the non-uniform bed properties and te mperatures in these larger systems is critical to the future design of such sy stems.
Model Uncertainty and Exchange Rate Forecasting
R.R.P. Kouwenberg (Roy); A. Markiewicz (Agnieszka); R. Verhoeks (Ralph); R.C.J. Zwinkels (Remco)
2013-01-01
textabstractWe propose a theoretical framework of exchange rate behavior where investors focus on a subset of economic fundamentals. We find that any adjustment in the set of predictors used by investors leads to changes in the relation between the exchange rate and fundamentals. We test the validit
A Review of Kinetic Modeling Methodologies for Complex Processes
Directory of Open Access Journals (Sweden)
de Oliveira Luís P.
2016-05-01
Full Text Available In this paper, kinetic modeling techniques for complex chemical processes are reviewed. After a brief historical overview of chemical kinetics, an overview is given of the theoretical background of kinetic modeling of elementary steps and of multistep reactions. Classic lumping techniques are introduced and analyzed. Two examples of lumped kinetic models (atmospheric gasoil hydrotreating and residue hydroprocessing developed at IFP Energies nouvelles (IFPEN are presented. The largest part of this review describes advanced kinetic modeling strategies, in which the molecular detail is retained, i.e. the reactions are represented between molecules or even subdivided into elementary steps. To be able to retain this molecular level throughout the kinetic model and the reactor simulations, several hurdles have to be cleared first: (i the feedstock needs to be described in terms of molecules, (ii large reaction networks need to be automatically generated, and (iii a large number of rate equations with their rate parameters need to be derived. For these three obstacles, molecular reconstruction techniques, deterministic or stochastic network generation programs, and single-event micro-kinetics and/or linear free energy relationships have been applied at IFPEN, as illustrated by several examples of kinetic models for industrial refining processes.
SATL MODEL LESSON IN CHEMICAL KINETICS
African Journals Online (AJOL)
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Department of Chemistry, The Federal Urdu University of Arts, Science and ... are several strategies, through which teaching and learning of scientific subjects in ... the linear relationships among various factors involved in chemical kinetics.
Innovative first order elimination kinetics working model for easy learning
Directory of Open Access Journals (Sweden)
Navin Budania
2016-06-01
Conclusions: First order elimination kinetics is easily understood with the help of above working model. More and more working models could be developed for teaching difficult topics. [Int J Basic Clin Pharmacol 2016; 5(3.000: 862-864
Modeling And Forecasting Exchange-Rate Shocks
Andreou, A. S.; Zombanakis, George A.; Likothanassis, S. D.; Georgakopoulos, E.
1998-01-01
This paper considers the extent to which the application of neural networks methodology can be used in order to forecast exchange-rate shocks. Four major foreign currency exchange rates against the Greek Drachma as well as the overnight interest rate in the Greek market are employed in an attempt to predict the extent to which the local currency may be suffering an attack. The forecasting is extended to the estimation of future exchange rates and interest rates. The MLP proved to be highly ...
Borgoo, Alex; Teale, Andrew M; Tozer, David J
2012-01-21
Correlated electron densities, experimental ionisation potentials, and experimental electron affinities are used to investigate the homogeneity of the exchange-correlation and non-interacting kinetic energy functionals of Kohn-Sham density functional theory under density scaling. Results are presented for atoms and small molecules, paying attention to the influence of the integer discontinuity and the choice of the electron affinity. For the exchange-correlation functional, effective homogeneities are highly system-dependent on either side of the integer discontinuity. By contrast, the average homogeneity-associated with the potential that averages over the discontinuity-is generally close to 4/3 when the discontinuity is computed using positive affinities for systems that do bind an excess electron and negative affinities for those that do not. The proximity to 4/3 becomes increasingly pronounced with increasing atomic number. Evaluating the discontinuity using a zero affinity in systems that do not bind an excess electron instead leads to effective homogeneities on the electron abundant side that are close to 4/3. For the non-interacting kinetic energy functional, the effective homogeneities are less system-dependent and the effect of the integer discontinuity is less pronounced. Average values are uniformly below 5/3. The study provides information that may aid the development of improved exchange-correlation and non-interacting kinetic energy functionals. © 2012 American Institute of Physics
Energy Technology Data Exchange (ETDEWEB)
Dang, Liem X. [Physical Science Division, Pacific Northwest National Laboratory, Richland, Washington 93352, USA; Chang, Tsun-Mei [Department of Chemistry, University of Wisconsin - Parkside, Kenosha, Wisconsin 53141, USA
2016-09-02
In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li^{+}(aq) and the kinetics of ion pairings in lithium-ion batteries (LIB). We report one of the first computer simulations of the exchange dynamics around hydrated Li^{+} in acetonitrile (ACN), which is common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li^{+}-[BF_{4}] and Li^{+}-[PF_{6}] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li^{+}(aq). We calculate exchange rates using transition state theory and weighted them with transmission coefficients determined by the reactive flux and Impey, Madden, and McDonald approaches and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li^{+}-[BF_{4}] and Li^{+}-[PF_{6}] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.
MODELLING OF BACTERIAL SULPHATE REDUCTION IN ANAEROBIC PONDS : KINETIC INVESTIGATIONS
Harerimana, Casimir; Vasel, Jean-Luc; Jupsin, Hugues; Ouali, Amira
2011-01-01
The aim of the study was first to develop a simple and practical model of anaerobic digestion including sulphate-reduction in anaerobic ponds. The basic microbiology of our model consists of three steps, namely, acidogenesis, methanogenesis, and sulphate reduction. This model includes multiple reaction stoichiometry and substrate utilization kinetics. The second aim was to determine some kinetic parameters associated with this model. The values of these parameters for sulfidogenic bacteria ar...
Wu, Zhihao; Wang, Shengrui
2017-06-05
Diffusive gradients in thin films (DGT) technique has been newly designed for the identification of formation mechanisms of "internal phosphorus (P)-loading" and the numerical simulation of P exchange at DGT/sediment interface in Lake Dianchi. The primary mechanism was Fe-redox controlled P release from Fe-bound P in sediments, which was revealed by CDGT (P and Fe), total P (Fe) and P (Fe) fractions in NH4Cl and BD phases in sediments and their relationships at sites (N-T). The breakdown of algae biomass in the top layer of sediments at sites (O-T) and the coupled P/Fe/sulfur reactions at two depths at site N played a minor role in P release. The "internal P-loading" was calculated to be 19.23ta(-1), which was 3.0% of the "entering P-loading". At sites (1-9), DGT induced flux in sediments (DIFS) model for P was used to derive curves (i) the resupply parameter (R) against deployment time and (ii) the dissolved/sorbed concentrations against the distance at DGT/sediment interface, the variation characters of which were controlled by kinetics and sediment-P pool. Sulfide microniches in sediments related to P release were evaluated by computer imaging densitometry (CID). DGT-DIFS-CID should be a reliable method to reveal P mobilization in lake sediments.
Srinivasan, Supramaniam; Velev, Omourtag A.; Parthasathy, Arvind; Manko, David J.; Appleby, A. John
1991-01-01
The development of proton exchange membrane (PEM) fuel cell power plants with high energy efficiencies and high power densities is gaining momentum because of the vital need of such high levels of performance for extraterrestrial (space, underwater) and terrestrial (power source for electric vehicles) applications. Since 1987, considerable progress has been made in achieving energy efficiencies of about 60 percent at a current density of 200 mA/sq cm and high power densities (greater than 1 W/sq cm) in PEM fuel cells with high (4 mg/sq cm) or low (0.4 mg/sq cm) platinum loadings in electrodes. The following areas are discussed: (1) methods to obtain these high levels of performance with low Pt loading electrodes - by proton conductor impregnation into electrodes, localization of Pt near front surface; (2) a novel microelectrode technique which yields electrode kinetic parameters for oxygen reduction and mass transport parameters; (3) demonstration of lack of water transport from anode to cathode; (4) modeling analysis of PEM fuel cell for comparison with experimental results and predicting further improvements in performance; and (5) recommendations of needed research and development for achieving the above goals.
Kinetics and equilibrium adsorption studies of dimethylamine (DMA) onto ion-exchange resin
Energy Technology Data Exchange (ETDEWEB)
Hu Qinhai, E-mail: qhhu@zju.edu.cn [College of Environmental and Resources Science, Zhejiang University, Hangzhou 310029, Zhejiang (China); Meng Yuanyuan [College of Environmental and Resources Science, Zhejiang University, Hangzhou 310029, Zhejiang (China); Sun Tongxi [College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Mahmood, Qaisar [Department of Environmental Sciences, COMSATS University, Abbottabad 22060 (Pakistan); Wu Donglei; Zhu Jianhang [College of Environmental and Resources Science, Zhejiang University, Hangzhou 310029, Zhejiang (China); Lu, George [Golden Maple Leaf Corporation of Hangzhou, Hangzhou 310012 (China)
2011-01-30
The fine grained resin ZGSPC106 was used to adsorb dimethylamine (DMA) from aqueous solution in the present research. Batch experiments were performed to examine the effects of initial pH of solution and agitation time on the adsorption process. The thermodynamics and kinetics of adsorption were also analyzed. The maximum adsorption was found at natural pH of DMA solution and equilibrium could be attained within 12 min. The equilibrium adsorption data were conformed satisfactorily to the Langmuir equation. The evaluation based on Langmuir isotherm gave the maximal static saturated adsorption capacity of 138.89 mg/g at 293 K. Various thermodynamic parameters such as free energy ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}) and entropy ({Delta}S{sup o}) showed that the adsorption was spontaneous, endothermic and feasible. DMA adsorption on ZGSPC106 fitted well to the pseudo-second-order kinetic model. Furthermore, the adsorption mechanism was discussed by Fourier transform infrared spectroscopy (FT-IR) analysis.
Kinetics and equilibrium adsorption studies of dimethylamine (DMA) onto ion-exchange resin.
Hu, Qinhai; Meng, Yuanyuan; Sun, Tongxi; Mahmood, Qaisar; Wu, Donglei; Zhu, Jianhang; Lu, George
2011-01-30
The fine grained resin ZGSPC106 was used to adsorb dimethylamine (DMA) from aqueous solution in the present research. Batch experiments were performed to examine the effects of initial pH of solution and agitation time on the adsorption process. The thermodynamics and kinetics of adsorption were also analyzed. The maximum adsorption was found at natural pH of DMA solution and equilibrium could be attained within 12 min. The equilibrium adsorption data were conformed satisfactorily to the Langmuir equation. The evaluation based on Langmuir isotherm gave the maximal static saturated adsorption capacity of 138.89 mg/g at 293K. Various thermodynamic parameters such as free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) showed that the adsorption was spontaneous, endothermic and feasible. DMA adsorption on ZGSPC106 fitted well to the pseudo-second-order kinetic model. Furthermore, the adsorption mechanism was discussed by Fourier transform infrared spectroscopy (FT-IR) analysis. Copyright © 2010 Elsevier B.V. All rights reserved.
A kinetic model for the penicillin biosynthetic pathway in
DEFF Research Database (Denmark)
Nielsen, Jens; Jørgensen, Henrik
1996-01-01
A kinetic model for the first two steps in the penicillin biosynthetic pathway, i.e. the ACV synthetase (ACVS) and the isopenicillin N synthetase (IPNS) is proposed. The model is based on Michaelis-Menten type kinetics with non-competitive inhibition of the ACVS by ACV, and competitive inhibition...... of the IPNS by glutathione. The model predicted flux through the pathway corresponds well with the measured rate of penicillin biosynthesis. From the kinetic model the elasticity coefficients and the flux control coefficients are calculated throughout a fed-batch cultivation, and it is found...
Factor Model Forecasts of Exchange Rates
Charles Engel; Nelson C. Mark; Kenneth D. West
2012-01-01
We construct factors from a cross section of exchange rates and use the idiosyncratic deviations from the factors to forecast. In a stylized data generating process, we show that such forecasts can be effective even if there is essentially no serial correlation in the univariate exchange rate processes. We apply the technique to a panel of bilateral U.S. dollar rates against 17 OECD countries. We forecast using factors, and using factors combined with any of fundamentals suggested by Taylor r...
Chuntonov, Lev; Pazos, Ileana M; Ma, Jianqiang; Gai, Feng
2015-03-26
It has recently been shown that the ester carbonyl stretching vibration can be used as a sensitive probe of local electrostatic field in molecular systems. To further characterize this vibrational probe and extend its potential applications, we studied the kinetics of chemical exchange between differently hydrogen-bonded (H-bonded) ester carbonyl groups of methyl acetate (MA) and ethyl acetate (EA) in methanol. We found that, while both MA and EA can form zero, one, or two H-bonds with the solvent, the population of the 2hb state in MA is significantly smaller than that in EA. Using a combination of linear and nonlinear infrared measurements and numerical simulations, we further determined the rate constants for the exchange between these differently H-bonded states. We found that for MA the chemical exchange reaction between the two dominant states (i.e., 0hb and 1hb states) has a relaxation rate constant of 0.14 ps(-1), whereas for EA the three-state chemical exchange reaction occurs in a predominantly sequential manner with the following relaxation rate constants: 0.11 ps(-1) for exchange between 0hb and 1hb states and 0.12 ps(-1) for exchange between 1hb and 2hb states.
Kinetic models in spin chemistry. 1. The hyperfine interaction
DEFF Research Database (Denmark)
Mojaza, M.; Pedersen, J. B.
2012-01-01
Kinetic models for quantum systems are quite popular due to their simplicity, although they are difficult to justify. We show that the transformation from quantum to kinetic description can be done exactly for the hyperfine interaction of one nuclei with arbitrary spin; more spins are described w...
Modeling the kinetics of essential oil hydrodistillation from plant materials
Directory of Open Access Journals (Sweden)
Milojević Svetomir Ž.
2013-01-01
Full Text Available The present work deals with modeling the kinetics of essential oils extraction from plant materials by water and steam distillation. The experimental data were obtained by studying the hydrodistillation kinetics of essential oil from juniper berries. The literature data on the kinetics of essential oils hydrodistillation from different plant materials were also included into the modeling. A physical model based on simultaneous washing and diffusion of essential oil from plant materials were developed to describe the kinetics of essential oils hydrodistillation, and two other simpler models were derived from this physical model assuming either instantaneous washing followed by diffusion or diffusion with no washing (i.e. the first-order kinetics. The main goal was to compare these models and suggest the optimum ones for water and steam distillation and for different plant materials. All three models described well the experimental kinetic data on water distillation irrespective of the type of distillation equipment and its scale, the type of plant materials and the operational conditions. The most applicable one is the model involving simultaneous washing and diffusion of the essential oil. However, this model was generally inapplicable for steam distillation of essential oils, except for juniper berries. For this hydrodistillation technique, the pseudo first-order model was shown to be the best one. In a few cases, a variation of the essential oil yield with time was observed to be sigmoidal and was modeled by the Boltzmann sigmoid function.
Modeling Philippine Stock Exchange Composite Index Using Time Series Analysis
Gayo, W. S.; Urrutia, J. D.; Temple, J. M. F.; Sandoval, J. R. D.; Sanglay, J. E. A.
2015-06-01
This study was conducted to develop a time series model of the Philippine Stock Exchange Composite Index and its volatility using the finite mixture of ARIMA model with conditional variance equations such as ARCH, GARCH, EG ARCH, TARCH and PARCH models. Also, the study aimed to find out the reason behind the behaviorof PSEi, that is, which of the economic variables - Consumer Price Index, crude oil price, foreign exchange rate, gold price, interest rate, money supply, price-earnings ratio, Producers’ Price Index and terms of trade - can be used in projecting future values of PSEi and this was examined using Granger Causality Test. The findings showed that the best time series model for Philippine Stock Exchange Composite index is ARIMA(1,1,5) - ARCH(1). Also, Consumer Price Index, crude oil price and foreign exchange rate are factors concluded to Granger cause Philippine Stock Exchange Composite Index.
Jiskra, Martin; Saile, Damian; Wiederhold, Jan G; Bourdon, Bernard; Björn, Erik; Kretzschmar, Ruben
2014-11-18
The mobility and bioavailability of toxic Hg(II) in the environment strongly depends on its interactions with natural organic matter (NOM) and mineral surfaces. Using an enriched stable isotope approach, we investigated the exchange of Hg(II) between dissolved species (inorganically complexed or cysteine-, EDTA-, or NOM-bound) and solid-bound Hg(II) (carboxyl-/thiol-resin or goethite) over 30 days under constant conditions (pH, Hg and ligand concentrations). The Hg(II)-exchange was initially fast, followed by a slower phase, and depended on the properties of the dissolved ligands and sorbents. The results were described by a kinetic model allowing the simultaneous determination of adsorption and desorption rate coefficients. The time scales required to reach equilibrium with the carboxyl-resin varied greatly from 1.2 days for Hg(OH)2 to 16 days for Hg(II)-cysteine complexes and approximately 250 days for EDTA-bound Hg(II). Other experiments could not be described by an equilibrium model, suggesting that a significant fraction of total-bound Hg was present in a non-exchangeable form (thiol-resin and NOM: 53-58%; goethite: 22-29%). Based on the slow and incomplete exchange of Hg(II) described in this study, we suggest that kinetic effects must be considered to a greater extent in the assessment of the fate of Hg in the environment and the design of experimental studies, for example, for stability constant determination or metal isotope fractionation during sorption.
Aromatization of light naphtha fractions on zeolites 1: Kinetic model
Directory of Open Access Journals (Sweden)
Rovenskaja Svetlana A.
2003-01-01
Full Text Available On the basis of analyzing kinetic experimental data performed in laboratory integral reactors a lumping kinetic model of the "Zeoforming" process was developed. A reaction scheme of the lumped components was proposed, that was adapted to the technological requirements. The reaction rate constants and activation energies were estimated, that are valid for certain feed compositions. The model is intended for further modeling and optimization of the process.
Kinetic derivation of a Hamilton-Jacobi traffic flow model
Borsche, Raul; Kimathi, Mark
2012-01-01
Kinetic models for vehicular traffic are reviewed and considered from the point of view of deriving macroscopic equations. A derivation of the associated macroscopic traffic flow equations leads to different types of equations: in certain situations modified Aw-Rascle equations are obtained. On the other hand, for several choices of kinetic parameters new Hamilton-Jacobi type traffic equations are found. Associated microscopic models are discussed and numerical experiments are presented discussing several situations for highway traffic and comparing the different models.
Oxygen surface exchange kinetics of SrTi(1-x)Fe(x)O(3-δ) mixed conducting oxides.
Yoo, Chung-Yul; Bouwmeester, Henny J M
2012-09-07
The oxygen surface exchange kinetics of mixed conducting perovskite oxides SrTi(1-x)Fe(x)O(3-δ) (x = 0, 0.01, 0.05, 0.35, 0.5) has been investigated as a function of temperature and oxygen partial pressure using the pulse-response (18)O-(16)O isotope exchange (PIE) technique. Arrhenius activation energies range from 140 kJ mol(-1) for x = 0 to 86 kJ mol(-1) for x = 0.5. Extrapolating the temperature dependence to the intermediate temperature range, 500-600 °C, indicates that the rate of oxygen exchange, in air, increases with increasing iron mole fraction, but saturates at the highest iron mole fraction for the given series. The observed behavior is concomitant with corresponding increases in both electronic and ionic conductivity with increasing x in SrTi(1-x)Fe(x)O(3-δ). Including literature data of related perovskite-type oxides Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-δ), La(0.6)Sr(0.4)CoO(3-δ), and Sm(0.5)Sr(0.5)CoO(3-δ), a linear relationship is observed in the log-log plot between oxygen exchange rate and oxide ionic conductivity with a slope fairly close to unity, suggesting that it is the magnitude of the oxide ionic conductivity that governs the rate of oxygen exchange in these solids. The distribution of oxygen isotopomers ((16)O(2), (16)O(18)O, (18)O(2)) in the effluent pulse can be interpreted on the basis of a two-step exchange mechanism for the isotopic exchange reaction. Accordingly, the observed power law dependence of the overall surface exchange rate on oxygen partial pressure turns out to be an apparent one, depending on the relative rates of both steps involved in the adopted two-step scheme. Supplementary research is, however, required to elucidate which of the two possible reaction schemes better reflects the actual kinetics of oxygen surface exchange on SrTi(1-x)Fe(x)O(3-δ).
Modeling of Crystalline Silicotitanate Ion Exchange Columns
Energy Technology Data Exchange (ETDEWEB)
Walker, D.D.
1999-03-09
Non-elutable ion exchange is being considered as a potential replacement for the In-Tank Precipitation process for removing cesium from Savannah River Site (SRS) radioactive waste. Crystalline silicotitanate (CST) particles are the reference ion exchange medium for the process. A major factor in the construction cost of this process is the size of the ion exchange column required to meet product specifications for decontaminated waste. To validate SRS column sizing calculations, SRS subcontracted two reknowned experts in this field to perform similar calculations: Professor R. G. Anthony, Department of Chemical Engineering, Texas A&038;M University, and Professor S. W. Wang, Department of Chemical Engineering, Purdue University. The appendices of this document contain reports from the two subcontractors. Definition of the design problem came through several meetings and conference calls between the participants and SRS personnel over the past few months. This document summarizes the problem definition and results from the two reports.
Lumping procedure for a kinetic model of catalytic naphtha reforming
Directory of Open Access Journals (Sweden)
H. M. Arani
2009-12-01
Full Text Available A lumping procedure is developed for obtaining kinetic and thermodynamic parameters of catalytic naphtha reforming. All kinetic and deactivation parameters are estimated from industrial data and thermodynamic parameters are calculated from derived mathematical expressions. The proposed model contains 17 lumps that include the C6 to C8+ hydrocarbon range and 15 reaction pathways. Hougen-Watson Langmuir-Hinshelwood type reaction rate expressions are used for kinetic simulation of catalytic reactions. The kinetic parameters are benchmarked with several sets of plant data and estimated by the SQP optimization method. After calculation of deactivation and kinetic parameters, plant data are compared with model predictions and only minor deviations between experimental and calculated data are generally observed.
Modelling atypical CYP3A4 kinetics: principles and pragmatism.
Houston, J Brian; Galetin, Aleksandra
2005-01-15
The Michaelis-Menten model, and the existence of a single active site for the interaction of substrate with drug metabolizing enzyme, adequately describes a substantial number of in vitro metabolite kinetic data sets for both clearance and inhibition determination. However, in an increasing number of cases (involving most notably, but not exclusively, CYP3A4), atypical kinetic features are observed, e.g., auto- and heteroactivation; partial, cooperative, and substrate inhibition; concentration-dependent effector responses (activation/inhibition); limited substrate substitution and inhibitory reciprocity necessitating sub-group classification. The phenomena listed above cannot be readily interpreted using single active site models and the literature indicates that three types of approaches have been adopted. First the 'nai ve' approach of using the Michaelis-Menten model regardless of the kinetic behaviour, second the 'empirical' approach (e.g., employing the Hill or uncompetitive inhibition equations to model homotropic phenomena of sigmoidicity and substrate inhibition, respectively) and finally, the 'mechanistic' approach. The later includes multisite kinetic models derived using the same rapid equilibrium/steady-state assumptions as the single-site model. These models indicate that 2 or 3 binding sites exist for a given CYP3A4 substrate and/or effector. Multisite kinetic models share common features, depending on the substrate kinetics and the nature of the effector response observed in vitro, which allow a generic model to be proposed. Thus although more complex than the other two approaches, they show more utility and can be comprehensively applied in relatively simple versions that can be readily generated from generic model. Multisite kinetic features, observed in isolated hepatocytes as well as in microsomes from hepatic tissue and heterologous expression systems, may be evident in substrate depletion-time profiles as well as in metabolite formation rates
Modeling Biodegradation Kinetics on Benzene and Toluene and Their Mixture
Directory of Open Access Journals (Sweden)
Aparecido N. Módenes
2007-10-01
Full Text Available The objective of this work was to model the biodegradation kinetics of toxic compounds toluene and benzene as pure substrates and in a mixture. As a control, Monod and Andrews models were used. To predict substrates interactions, more sophisticated models of inhibition and competition, and SKIP (sum kinetics interactions parameters model were applied. The models evaluation was performed based on the experimental data from Pseudomonas putida F1 activities published in the literature. In parameter identification procedure, the global method of particle swarm optimization (PSO was applied. The simulation results show that the better description of the biodegradation process of pure toxic substrate can be achieved by Andrews' model. The biodegradation process of a mixture of toxic substrates is modeled the best when modified competitive inhibition and SKIP models are used. The developed software can be used as a toolbox of a kinetics model catalogue of industrial wastewater treatment for process design and optimization.
Rasch models with exchangeable rows and columns
DEFF Research Database (Denmark)
Lauritzen, Steffen Lilholt
The article studies distributions of doubly infinite binary matrices with exchangeable rows and columns which satify the further property that the probability of any $m \\times n$ submatrix is a function of the row- and column sums of that matrix. We show that any such distribution is a (unique...... of existence of measures with given marginals....
Real Exchange Rate and Commodity Prices in a Neoclassical Model
Reinhart, Carmen
1988-01-01
This paper represents a neoclassical model that explains the observed empirical relationship between government spending and world commodity supplies and the real exchange rate and real commodity prices. It is shown that fiscal expansion and increasing world commodity supplies simultaneously lead to an appreciation of the real exchange rate and a decline in relative commodity prices. The structural model is estimated and its forecasting performance is compared to a variety of models. We fin...
Biomass torrefaction: modeling of volatile and solid product evolution kinetics.
Bates, Richard B; Ghoniem, Ahmed F
2012-11-01
The aim of this work is the development of a kinetics model for the evolution of the volatile and solid product composition during torrefaction conditions between 200 and 300°C. Coupled to an existing two step solid mass loss kinetics mechanism, this model describes the volatile release kinetics in terms of a set of identifiable chemical components, permitting the solid product composition to be estimated by mass conservation. Results show that most of the volatiles released during the first stage include highly oxygenated species such as water, acetic acid, and carbon dioxide, while volatiles released during the second step are composed primarily of lactic acid, methanol, and acetic acid. This kinetics model will be used in the development of a model to describe reaction energy balance and heat release dynamics.
Kinetic, equilibrium and thermodynamic modelling of the sorption of ...
African Journals Online (AJOL)
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.
Institute of Scientific and Technical Information of China (English)
Haiou Song; Zhijian Yao; Mengqiao Wang; Jinnan Wang; Zhaolian Zhu; Aimin Li
2013-01-01
The effects of dissolved organic matter (DOM) on the removal of nitrate-nitrogen from the model contaminated water have been investigated utilizing the strong base anion exchange resins.With the increase of gallic acid concentration from 0 to 400 mg/L,the adsorption amount of nitrate-nitrogen on the commercial resins,including D201,Purolite A 300 (A300) and Purolite A 520E (A520E),would significantly decrease.However,the presence of tannin acid has little impact on nitrate-nitrogen adsorption on them.Compared to D201 and A300 resins,A520E resin exhibited more preferable adsorption ability toward nitrate-nitrogen in the presence of competing organic molecules,such as gallic acid and tannin acid at greater levels in aqueous solution.Attractively,the equilibrium data showed that the adsorption isotherm of nitrate-nitrogen on A520E resin was in good agreement with Langmuir and Freundlich equations.The rate parameters for the intra particle diffusion have been estimated for the different initial concentrations.In batch adsorption processes,nitrate-nitrogen diffuse in porous adsorbent and rate process usually depends on t1/2 rather than the contact time.The pseudo first-and the second-order kinetic models fit better for nitrate-nitrogen adsorption onto A520E resin.The observations reported herein illustrated that A520E resin will be an excellent adsorbent for enhanced removal of nitrate-nitrogen from contaminated groundwater.
Energy Technology Data Exchange (ETDEWEB)
Zvejnieks, G. [Institute for Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Ibenskas, A., E-mail: ibenskas@pfi.lt [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania); Tornau, E.E. [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania)
2015-11-15
Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p, and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R, increases with p), (ii) intermediate regime (weak p–dependence), and (iii) fast homogeneous flow (R decreases with p). We find that only Au–Ni exchange, contrary to both Ni–CO and Au–CO exchanges, significantly reduces the number of screened Ni atoms inside the Au clusters and stimulates the occurrence of Ni-free Au clusters. The size of Au islands depends on both pressure and temperature. At a fixed temperature it decreases with pressure due to an increased step flow rate. In the high temperature limit, despite the step flow rate exponential increase with temperature, the cluster size increases due to an enhanced Au mobility. - Highlights: • Kinetic Monte Carlo study of Au–Ni surface alloy instability to CO pressure and temperature. • Three reaction front propagation regimes. • In channel-like regime, the step flow rate increases with CO pressure as in experiment. • Ni-free Au islands are obtained when Au-Ni adatom exchange mechanism is considered. • The size of Au islands decreases with pressure and increases with temperature.
Jellium-with-gap model applied to semilocal kinetic functionals
Constantin, Lucian A.; Fabiano, Eduardo; Śmiga, Szymon; Della Sala, Fabio
2017-03-01
We investigate a highly nonlocal generalization of the Lindhard function, given by the jellium-with-gap model. We find a band-gap-dependent gradient expansion of the kinetic energy, which performs noticeably well for large atoms. Using the static linear response theory and the simplest semilocal model for the local band gap, we derive a nonempirical generalized gradient approximation (GGA) of the kinetic energy. This GGA kinetic-energy functional is remarkably accurate for the description of weakly interacting molecular systems within the subsystem formulation of density functional theory.
Kinetic models in industrial biotechnology - Improving cell factory performance.
Almquist, Joachim; Cvijovic, Marija; Hatzimanikatis, Vassily; Nielsen, Jens; Jirstrand, Mats
2014-07-01
An increasing number of industrial bioprocesses capitalize on living cells by using them as cell factories that convert sugars into chemicals. These processes range from the production of bulk chemicals in yeasts and bacteria to the synthesis of therapeutic proteins in mammalian cell lines. One of the tools in the continuous search for improved performance of such production systems is the development and application of mathematical models. To be of value for industrial biotechnology, mathematical models should be able to assist in the rational design of cell factory properties or in the production processes in which they are utilized. Kinetic models are particularly suitable towards this end because they are capable of representing the complex biochemistry of cells in a more complete way compared to most other types of models. They can, at least in principle, be used to in detail understand, predict, and evaluate the effects of adding, removing, or modifying molecular components of a cell factory and for supporting the design of the bioreactor or fermentation process. However, several challenges still remain before kinetic modeling will reach the degree of maturity required for routine application in industry. Here we review the current status of kinetic cell factory modeling. Emphasis is on modeling methodology concepts, including model network structure, kinetic rate expressions, parameter estimation, optimization methods, identifiability analysis, model reduction, and model validation, but several applications of kinetic models for the improvement of cell factories are also discussed.
An integral representation of functions in gas-kinetic models
Perepelitsa, Misha
2016-08-01
Motivated by the theory of kinetic models in gas dynamics, we obtain an integral representation of lower semicontinuous functions on {{{R}}^d,} {d≥1}. We use the representation to study the problem of compactness of a family of the solutions of the discrete time BGK model for the compressible Euler equations. We determine sufficient conditions for strong compactness of moments of kinetic densities, in terms of the measures from their integral representations.
Mathematical and Computational Modeling of Polymer Exchange Membrane Fuel Cells
Ulusoy, Sehribani
In this thesis a comprehensive review of fuel cell modeling has been given and based on the review, a general mathematical fuel cell model has been developed in order to understand the physical phenomena governing the fuel cell behavior and in order to contribute to the efforts investigating the optimum performance at different operating conditions as well as with different physical parameters. The steady state, isothermal model presented here accounts for the combined effects of mass and species transfer, momentum conservation, electrical current distribution through the gas channels, the electrodes and the membrane, and the electrochemical kinetics of the reactions in the anode and cathode catalyst layers. One of the important features of the model is that it proposes a simpler modified pseudo-homogeneous/agglomerate catalyst layer model which takes the advantage of the simplicity of pseudo-homogenous modeling while taking into account the effects of the agglomerates in the catalyst layer by using experimental geometric parameters published. The computation of the general mathematical model can be accomplished in 3D, 2D and 1D with the proper assumptions. Mainly, there are two computational domains considered in this thesis. The first modeling domain is a 2D Membrane Electrode Assembly (MEA) model including the modified agglomerate/pseudo-homogeneous catalyst layer modeling with consistent treatment of water transport in the MEA while the second domain presents a 3D model with different flow filed designs: straight, stepped and tapered. COMSOL Multiphysics along with Batteries and Fuel Cell Module have been used for 2D & 3D model computations while ANSYS FLUENT PEMFC Module has been used for only 3D two-phase computation. Both models have been validated with experimental data. With 2D MEA model, the effects of temperature and water content of the membrane as well as the equivalent weight of the membrane on the performance have been addressed. 3D COMSOL simulation
BINARY AND TERNARY ION EXCHANGE KINETICS SO42——Cl——NO3——201×7SYSTEM
Institute of Scientific and Technical Information of China (English)
TAOZuyi; ZHOUHaimei; 等
1993-01-01
Kinetics of chloride/sulfate,chloride/nitrate and nitrate/sulfate forward exchanges and reverse exchanges at solution concentrations of 1N,0.2N and 0.02 N on 201×7 strong base anion exchange resin,respectively,have been examined at 25℃.It is found that the forward and the reverse exchange rates of the two given ions at low solution concentration,respectively,under identical conditions can be controlled by different mechanisms,while those at high solution concentration are all controlled by particle diffusion.The ternary exchange rates of sulfate/(chloride+nitrate) and nitrate/(chloride+sulfate)have also been examined.
Kinetic Modelling of Pesticidal Degradation and Microbial Growth in Soil
Institute of Scientific and Technical Information of China (English)
LIUDUO－SEN; WANGZONG－SHENG; 等
1994-01-01
This paper discusses such models for the degradation kinetics of pesticides in soil as the model expressing the degradation rate as a function of two varables:the pesticide concentration and the number of pesticide degrading microorganisms,the model expressing the pesticide concentration as explicit or implicit function of time ,and the model exprssing the pesticide loss rate constants as functions of temperature,These models may interpret the degradation curves with an inflection point.A Kinetic model describing the growth processes of microbial populations in a closed system is reported as well.
New mass loss kinetic model for thermal decomposition of biomass
Institute of Scientific and Technical Information of China (English)
无
2001-01-01
Based on non-isothermal experimental results for eight Chinese biomass species, a new kinetic model,named as the "pseudo bi-component separate-stage model (PBSM)", is developed in this note to describe the mass loss behavior of biomass thermal decomposition. This model gains an advantage over the commonly used "pseudo single-component overall model (PSOM)" and "pseudo multi-component overall model (PMOM)". By means of integral analysis it is indicated that the new model is suitable to describe the mass loss kinetics of wood and leaf samples under relatively low heating rates (e.g. 10°C/rin, used in this work).``
Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation
Energy Technology Data Exchange (ETDEWEB)
Silke, E J; Pitz, W J; Westbrook, C K; Ribaucour, M
2006-11-10
A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O{sub 2} through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO{sub 2} from RO{sub 2} is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O{sub 2}QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.
Kinetic modelling of the Fischer-Tropsch synthesis
Energy Technology Data Exchange (ETDEWEB)
Gambaro, C.; Pollesel, P.; Zennaro, R. [Eni S.p.A., San Donato Milanese (Italy); Lietti, L.; Tronconi, E. [Politecnico di Milano (Italy)
2006-07-01
In this work the development of a CO conversion kinetic model of the Fischer-Tropsch process will be presented. Kinetic data were produced testing a Co-based catalyst on two lab units, equipped with a slurry autoclave and a fixed bed reactor respectively. Accordingly, information on the catalytic performances of the same catalyst in two reactor configurations were also obtained. The experimental results were then analyzed with different kinetic models, available in the literature: two mechanistic models, derived by Sarup-Wojciechowski and Yates-Satterfield, and a simple power law rate expression were compared. The parameters of the different rate expressions were estimated by non-linear regression of the kinetic data collected on the two lab units. (orig.)
Energy Technology Data Exchange (ETDEWEB)
Boltz, J.C. (ed.)
1992-09-01
EXCHANGE is published monthly by the Idaho National Engineering Laboratory (INEL), a multidisciplinary facility operated for the US Department of Energy (DOE). The purpose of EXCHANGE is to inform computer users about about recent changes and innovations in both the mainframe and personal computer environments and how these changes can affect work being performed at DOE facilities.
Mathematical Modeling of Spiral Heat Exchanger
Probal Guha , Vaishnavi Unde
2014-01-01
Compact Heat Exchangers (CHEs) are increasingly being used on small and medium scale industries. Due to their compact size and efficient design, they facilitate more efficient heat transfer. Better heat transfer would imply lesser fuel consumption for the operations of the plant, giving improvement to overall efficiency. This reduction in consumption of fuel is a step towards sustainable development. This report exclusively deals with the study the spiral heat ...
Monetary models and exchange rate determination: The Nigerian ...
African Journals Online (AJOL)
Monetary models and exchange rate determination: The Nigerian evidence. ... income levels and real interest rate differentials provide better forecasts of the naira-US dollar ... in this regard is that monetary policy should be positively predicted.
Directory of Open Access Journals (Sweden)
Janković Milovan R.
2004-01-01
Full Text Available Mathematical models that describe the kinetics of reaction systems for the in situ epoxidation of unsaturated fatty acid esters or triglycérides with organic peracids are reviewed in this paper. The advantages and inadequacies of each model are discussed. A mono-phase pseudo-first order kinetic model was compared with a two phase model based on the Langmuir-Hinshelwood-Hougen-Watson (LHHW postulates proposed by the authors of this paper. The comparison was performed on the experimentally determined values for the in situ epoxidation of soybean oil by peracetic acid in the presence of different quantities of ion exchange resin used as the catalyst. It was concluded that a complete model for in situ epoxidation in the presence of ion exchange resin as the catalyst was still not given for perorganic acid formation. In particular, we report here the possibilities of the creation of an "ideal" model for in situ epoxidation.
Directory of Open Access Journals (Sweden)
Krivtcova Nadezhda
2016-01-01
Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.
Modeling of Heat Exchange with Developed Nucleate Boiling on Tenons
Directory of Open Access Journals (Sweden)
A. V. Оvsiannik
2007-01-01
Full Text Available The paper proposes a thermal and physical model for heat exchange processes with developed nucleate boiling on the developed surfaces (tenons with various contours of heat transfer surface. Dependences for calculating convective heat exchange factor have been obtained on the basis of modeling representation. Investigations have shown that an intensity of convective heat exchange does not depend on tenon profile when boiling takes place on the tenons. The intensity is determined by operating conditions, thermal and physical properties of liquid, internal characteristics of boiling processes and geometrical characteristics of a tenon.
Modeling canopy CO2 exchange in the European Russian Arctic
DEFF Research Database (Denmark)
Kiepe, Isabell; Friborg, Thomas; Herbst, Mathias
2013-01-01
In this study, we use the coupled photosynthesis-stomatal conductance model of Collatz et al. (1991) to simulate the current canopy carbon dioxide exchange of a heterogeneous tundra ecosystem in European Russia. For the parameterization, we used data obtained from in situ leaf level measurements...... in combination with meteorological data from 2008. The modeled CO2 fluxes were compared with net ecosystem exchange (NEE), measured by the eddy covariance technique during the snow-free period in 2008. The findings from this study indicated that the main state parameters of the exchange processes were leaf area...
Modeling radial flow ion exchange performance for condensate polisher conditions
Energy Technology Data Exchange (ETDEWEB)
Shallcross, D. [University of Melbourne, Melbourne, VIC (Australia). Department of Chemical Engineering; Renouf, P.
2001-11-01
A theoretical model is developed which simulates ion exchange performance within an annular resin bed. Flow within the mixed ion exchange bed is diverging, with the solution flowing outwards away from the bed's axis. The model is used to simulate performance of a mixed annular bed operating under condensate polisher conditions. The simulation predictions are used to develop design envelope curves for practical radial flow beds and to estimate potential cost savings flowing from less expensive polisher vessels. (orig.)
Chemical Kinetic Models for HCCI and Diesel Combustion
Energy Technology Data Exchange (ETDEWEB)
Pitz, W J; Westbrook, C K; Mehl, M; Sarathy, S M
2010-11-15
Predictive engine simulation models are needed to make rapid progress towards DOE's goals of increasing combustion engine efficiency and reducing pollutant emissions. These engine simulation models require chemical kinetic submodels to allow the prediction of the effect of fuel composition on engine performance and emissions. Chemical kinetic models for conventional and next-generation transportation fuels need to be developed so that engine simulation tools can predict fuel effects. The objectives are to: (1) Develop detailed chemical kinetic models for fuel components used in surrogate fuels for diesel and HCCI engines; (2) Develop surrogate fuel models to represent real fuels and model low temperature combustion strategies in HCCI and diesel engines that lead to low emissions and high efficiency; and (3) Characterize the role of fuel composition on low temperature combustion modes of advanced combustion engines.
Hybrid fluid/kinetic model for parallel heat conduction
Energy Technology Data Exchange (ETDEWEB)
Callen, J.D.; Hegna, C.C.; Held, E.D. [Univ. of Wisconsin, Madison, WI (United States)
1998-12-31
It is argued that in order to use fluid-like equations to model low frequency ({omega} < {nu}) phenomena such as neoclassical tearing modes in low collisionality ({nu} < {omega}{sub b}) tokamak plasmas, a Chapman-Enskog-like approach is most appropriate for developing an equation for the kinetic distortion (F) of the distribution function whose velocity-space moments lead to the needed fluid moment closure relations. Further, parallel heat conduction in a long collision mean free path regime can be described through a combination of a reduced phase space Chapman-Enskog-like approach for the kinetics and a multiple-time-scale analysis for the fluid and kinetic equations.
Energy Technology Data Exchange (ETDEWEB)
Li, Yulan; Hu, Shenyang Y.; Sun, Xin; Khaleel, Mohammad A.
2011-06-15
Microstructure evolution kinetics in irradiated materials has strongly spatial correlation. For example, void and second phases prefer to nucleate and grow at pre-existing defects such as dislocations, grain boundaries, and cracks. Inhomogeneous microstructure evolution results in inhomogeneity of microstructure and thermo-mechanical properties. Therefore, the simulation capability for predicting three dimensional (3-D) microstructure evolution kinetics and its subsequent impact on material properties and performance is crucial for scientific design of advanced nuclear materials and optimal operation conditions in order to reduce uncertainty in operational and safety margins. Very recently the meso-scale phase-field (PF) method has been used to predict gas bubble evolution, void swelling, void lattice formation and void migration in irradiated materials,. Although most results of phase-field simulations are qualitative due to the lake of accurate thermodynamic and kinetic properties of defects, possible missing of important kinetic properties and processes, and the capability of current codes and computers for large time and length scale modeling, the simulations demonstrate that PF method is a promising simulation tool for predicting 3-D heterogeneous microstructure and property evolution, and providing microstructure evolution kinetics for higher scale level simulations of microstructure and property evolution such as mean field methods. This report consists of two parts. In part I, we will present a new phase-field model for predicting interstitial loop growth kinetics in irradiated materials. The effect of defect (vacancy/interstitial) generation, diffusion and recombination, sink strength, long-range elastic interaction, inhomogeneous and anisotropic mobility on microstructure evolution kinetics is taken into account in the model. The model is used to study the effect of elastic interaction on interstitial loop growth kinetics, the interstitial flux, and sink
Reinisch, Guillaume; Leyssale, Jean-Marc; Vignoles, Gérard L.
2010-10-01
We present an extension of some popular hindered rotor (HR) models, namely, the one-dimensional HR (1DHR) and the degenerated two-dimensional HR (d2DHR) models, allowing for a simple and accurate treatment of internal rotations. This extension, based on the use of a variable kinetic function in the Hamiltonian instead of a constant reduced moment of inertia, is extremely suitable in the case of rocking/wagging motions involved in dissociation or atom transfer reactions. The variable kinetic function is first introduced in the framework of a classical 1DHR model. Then, an effective temperature and potential dependent constant is proposed in the cases of quantum 1DHR and classical d2DHR models. These methods are finally applied to the atom transfer reaction SiCl3+BCl3→SiCl4+BCl2. We show, for this particular case, that a proper accounting of internal rotations greatly improves the accuracy of thermodynamic and kinetic predictions. Moreover, our results confirm (i) that using a suitably defined kinetic function appears to be very adapted to such problems; (ii) that the separability assumption of independent rotations seems justified; and (iii) that a quantum mechanical treatment is not a substantial improvement with respect to a classical one.
Kinetic Modelling of Macroscopic Properties Changes during Crosslinked Polybutadiene Oxidation
Audouin, Ludmila; Coquillat, Marie; Colin, Xavier; Verdu, Jacques; Nevière, Robert
2008-08-01
The thermal oxidation of additive free hydroxyl-terminated polybutadiene (HTPB) isocyanate crosslinked rubber bulk samples has been studied at 80, 100 and 120 °C in air. The oxidation kinetics has been monitored by gravimetry and thickness distribution of oxidation products was determined by FTIR mapping. Changes of elastic shear modulus G' during oxidation were followed during oxidation at the same temperatures. The kinetic model established previously for HTPB has been adapted for bulk sample oxidation using previously determined set of kinetic parameters. Oxygen diffusion control of oxidation has been introduced into the model. The mass changes kinetic curves and oxidation products profiles were simulated and adequate fit was obtained. Using the rubber elasticity theory the elastic modulus changes were simulated taking into account the elastically active chains concentration changes due to chain scission and crosslinking reactions. The reasonable fit of G' as a function of oxidation time experimental curves was obtained.
Breakdown parameter for kinetic modeling of multiscale gas flows.
Meng, Jianping; Dongari, Nishanth; Reese, Jason M; Zhang, Yonghao
2014-06-01
Multiscale methods built purely on the kinetic theory of gases provide information about the molecular velocity distribution function. It is therefore both important and feasible to establish new breakdown parameters for assessing the appropriateness of a fluid description at the continuum level by utilizing kinetic information rather than macroscopic flow quantities alone. We propose a new kinetic criterion to indirectly assess the errors introduced by a continuum-level description of the gas flow. The analysis, which includes numerical demonstrations, focuses on the validity of the Navier-Stokes-Fourier equations and corresponding kinetic models and reveals that the new criterion can consistently indicate the validity of continuum-level modeling in both low-speed and high-speed flows at different Knudsen numbers.
A Kinetic Model of Chromium in a Flame
Institute of Scientific and Technical Information of China (English)
无
2000-01-01
Chromium has been identified as a carcinogenic metal.Incineration is the useful method for disposal of toxic chromium hazard waste and a chromium kinetic model in a flame is very important to study chromium oxidation.Chromium chemical kinetics over a range of temperatures of a hydrogen/air flame is proposed.Nine chromium compounds and fifty-eight reversible chemical reactions were considered The forward reaction rates are calculated based on the molecular collision approach for unknown ones and Arrhenius's Law for known ones.The backward reaction rates were calculated according to forward reaction rates, the equilibrium constants and chemical thermodynamics.It is verified by several equilibrium cases and is tested by a hydrogen/air diffusion flame.The results show that the kinetic model could be used in cases in which the chromium kinetics play an important role in a flame
Directory of Open Access Journals (Sweden)
Marwa Khaldi
2015-01-01
Full Text Available Few investigations have attempted to connect the mechanism of dairy fouling to the chemical reaction of denaturation (unfolding and aggregation occurring in the bulk. The objective of this study is to contribute to this aspect in order to propose innovative controls to limit fouling deposit formation. Experimental investigations have been carried out to observe the relationship between the deposit mass distribution generated in plate heat exchangers (PHE by a whey protein isolate (WPI mainly composed of β-lactoglobulin (β-Lg and the ratio between the unfolding and aggregation rate constants. Experiments using a PHE were carried out at a pilot scale to identify the deposit distribution of a model fouling solution with different calcium contents. In parallel, laboratory experiments were performed to determine the unfolding/aggregation rate constants. Data analysis showed that (i β-Lg denaturation is highly dependent on the calcium content, (ii for each fouling solution, irrespective of the imposed temperature profile, the deposit mass in each channel and the ratio between the unfolding and aggregation rate constants seem to be well correlated. This study demonstrates that both the knowledge of the thermal profile and the β-Lg denaturation rate constants are required in order to predict accurately the deposit distribution along the PHE.
Physiologically based kinetic modeling of the bioactivation of myristicin
Al-Malahmeh, Amer J.; Al-Ajlouni, Abdelmajeed; Wesseling, Sebastiaan; Soffers, Ans E.M.F.; Al-Subeihi, A.; Kiwamoto, Reiko; Vervoort, Jacques; Rietjens, Ivonne M.C.M.
2016-01-01
The present study describes physiologically based kinetic (PBK) models for the alkenylbenzene myristicin that were developed by extension of the PBK models for the structurally related alkenylbenzene safrole in rat and human. The newly developed myristicin models revealed that the formation of th
Proton exchange membrane fuel cells modeling
Gao, Fengge; Miraoui, Abdellatif
2013-01-01
The fuel cell is a potential candidate for energy storage and conversion in our future energy mix. It is able to directly convert the chemical energy stored in fuel (e.g. hydrogen) into electricity, without undergoing different intermediary conversion steps. In the field of mobile and stationary applications, it is considered to be one of the future energy solutions.Among the different fuel cell types, the proton exchange membrane (PEM) fuel cell has shown great potential in mobile applications, due to its low operating temperature, solid-state electrolyte and compactness.This book pre
RESULTS OF INTERBANK EXCHANGE RATES FORECASTING USING STATE SPACE MODEL
Directory of Open Access Journals (Sweden)
Muhammad Kashif
2008-07-01
Full Text Available This study evaluates the performance of three alternative models for forecasting daily interbank exchange rate of U.S. dollar measured in Pak rupees. The simple ARIMA models and complex models such as GARCH-type models and a state space model are discussed and compared. Four different measures are used to evaluate the forecasting accuracy. The main result is the state space model provides the best performance among all the models.
Chemical kinetic modeling of H{sub 2} applications
Energy Technology Data Exchange (ETDEWEB)
Marinov, N.M.; Westbrook, C.K.; Cloutman, L.D. [Lawrence Livermore National Lab., CA (United States)] [and others
1995-09-01
Work being carried out at LLNL has concentrated on studies of the role of chemical kinetics in a variety of problems related to hydrogen combustion in practical combustion systems, with an emphasis on vehicle propulsion. Use of hydrogen offers significant advantages over fossil fuels, and computer modeling provides advantages when used in concert with experimental studies. Many numerical {open_quotes}experiments{close_quotes} can be carried out quickly and efficiently, reducing the cost and time of system development, and many new and speculative concepts can be screened to identify those with sufficient promise to pursue experimentally. This project uses chemical kinetic and fluid dynamic computational modeling to examine the combustion characteristics of systems burning hydrogen, either as the only fuel or mixed with natural gas. Oxidation kinetics are combined with pollutant formation kinetics, including formation of oxides of nitrogen but also including air toxics in natural gas combustion. We have refined many of the elementary kinetic reaction steps in the detailed reaction mechanism for hydrogen oxidation. To extend the model to pressures characteristic of internal combustion engines, it was necessary to apply theoretical pressure falloff formalisms for several key steps in the reaction mechanism. We have continued development of simplified reaction mechanisms for hydrogen oxidation, we have implemented those mechanisms into multidimensional computational fluid dynamics models, and we have used models of chemistry and fluid dynamics to address selected application problems. At the present time, we are using computed high pressure flame, and auto-ignition data to further refine the simplified kinetics models that are then to be used in multidimensional fluid mechanics models. Detailed kinetics studies have investigated hydrogen flames and ignition of hydrogen behind shock waves, intended to refine the detailed reactions mechanisms.
A unifying kinetic framework for modeling oxidoreductase-catalyzed reactions
Chang, Ivan; Baldi, Pierre
2013-01-01
Motivation: Oxidoreductases are a fundamental class of enzymes responsible for the catalysis of oxidation–reduction reactions, crucial in most bioenergetic metabolic pathways. From their common root in the ancient prebiotic environment, oxidoreductases have evolved into diverse and elaborate protein structures with specific kinetic properties and mechanisms adapted to their individual functional roles and environmental conditions. While accurate kinetic modeling of oxidoreductases is thus imp...
The Nonlinear Magnetosphere: Expressions in MHD and in Kinetic Models
Hesse, Michael; Birn, Joachim
2011-01-01
Like most plasma systems, the magnetosphere of the Earth is governed by nonlinear dynamic evolution equations. The impact of nonlinearities ranges from large scales, where overall dynamics features are exhibiting nonlinear behavior, to small scale, kinetic, processes, where nonlinear behavior governs, among others, energy conversion and dissipation. In this talk we present a select set of examples of such behavior, with a specific emphasis on how nonlinear effects manifest themselves in MHD and in kinetic models of magnetospheric plasma dynamics.
Application of Detailed Chemical Kinetics to Combustion Instability Modeling
2016-01-04
under two different conditions corresponding to marginally stable and unstable operation in order to evaluate the performance of the chemical kinetics...instability is a complex interaction between acoustics and the heat release due to combustion.In rocket engines, which are acoustically compact, there is...and amplitudes remains a challenge. The present article is an attempt towards addressing such discrepancies by enhancing the chemical kinetics model
Kinetic model for hydroisomerization reaction of C8-aromatics
Institute of Scientific and Technical Information of China (English)
Ouguan XU; Hongye SU; Xiaoming JIN; Jian CHU
2008-01-01
Based on the reported reaction networks, a novel six-component hydroisomerization reaction net-work with a new lumped species including C8-naphthenes and Cs-paraffins is proposed and a kinetic model for a commercial unit is also developed. An empirical catalyst deactivation function is incorporated into the model accounting for the loss in activity because of coke forma-tion on the catalyst surface during the long-term opera-tion. The Runge-Kutta method is used to solve the ordinary differential equations of the model. The reaction kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential vari-able metric optimization method (BFGS). The kinetic model is validated by an industrial unit with sets of plant data under different operating conditions and simulation results show a good agreement between the model predic-tions and the plant observations.
A tool model for predicting atmospheric kinetics with sensitivity analysis
Institute of Scientific and Technical Information of China (English)
无
2001-01-01
A package( a tool model) for program of predicting atmospheric chemical kinetics with sensitivity analysis is presented. The new direct method of calculating the first order sensitivity coefficients using sparse matrix technology to chemical kinetics is included in the tool model, it is only necessary to triangularize the matrix related to the Jacobian matrix of the model equation. The Gear type procedure is used to integrate amodel equation and its coupled auxiliary sensitivity coefficient equations. The FORTRAN subroutines of the model equation, the sensitivity coefficient equations, and their Jacobian analytical expressions are generated automatically from a chemical mechanism. The kinetic representation for the model equation and its sensitivity coefficient equations, and their Jacobian matrix is presented. Various FORTRAN subroutines in packages, such as SLODE, modified MA28, Gear package, with which the program runs in conjunction are recommended.The photo-oxidation of dimethyl disulfide is used for illustration.
Wang, Zhandong
2015-07-01
Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O
Modeling ion exchange in clinoptilolite using the EQ3/6 geochemical modeling code
Energy Technology Data Exchange (ETDEWEB)
Viani, B.E.; Bruton, C.J.
1992-06-01
Assessing the suitability of Yucca Mtn., NV as a potential repository for high-level nuclear waste requires the means to simulate ion-exchange behavior of zeolites. Vanselow and Gapon convention cation-exchange models have been added to geochemical modeling codes EQ3NR/EQ6, allowing exchange to be modeled for up to three exchangers or a single exchanger with three independent sites. Solid-solution models that are numerically equivalent to the ion-exchange models were derived and also implemented in the code. The Gapon model is inconsistent with experimental adsorption isotherms of trace components in clinoptilolite. A one-site Vanselow model can describe adsorption of Cs or Sr on clinoptilolite, but a two-site Vanselow exchange model is necessary to describe K contents of natural clinoptilolites.
Modeling ion exchange in clinoptilolite using the EQ3/6 geochemical modeling code
Energy Technology Data Exchange (ETDEWEB)
Viani, B.E.; Bruton, C.J. [Lawrence Livermore National Lab., CA (United States)
1992-12-31
Potential disposal of high-level nuclear waste at Yucca Mtn., Nevada requires the means to simulate ion-exchange behavior of clays and zeolites. Vanselow and Gapon convention cation-exchange models have been added to geochemical modeling codes EQ3NR/EQ6, allowing exchange to be modeled for up to three exchangers or a single exchanger with three independent sites. Solid-solution models that are numerically equivalent to the ion-exchange models were derived and also implemented in the code. The Gapon model is inconsistent with experimental adsorption isotherms of trace components in clinoptilolite. A one-site Vanselow model can describe adsorption of Cs and Sr on clinoptilolite, but a two-site Vanselow exchange model is necessary to describe K contents of natural clinoptilolites. 15 refs., 5 figs., 1 tab.
Kinetic models of collective decision-making in the presence of equality bias
Pareschi, Lorenzo; Zanella, Mattia
2016-01-01
We introduce and discuss kinetic models describing the influence of the competence in the evolution of decisions in a multi-agent system. The original exchange mechanism, which is based on the human tendency to compromise and change opinion through self-thinking, is here modified to include the role of the agents' competence. In particular, we take into account the agents' tendency to behave in the same way as if they were as good, or as bad, as their partner: the so-called equality bias. This occurred in a situation where a wide gap separated the competence of group members. We discuss the main properties of the kinetic models and numerically investigate some examples of collective decision under the influence of the equality bias. The results confirm that the equality bias leads the group to suboptimal decisions.
Kinetic models of collective decision-making in the presence of equality bias
Pareschi, Lorenzo; Vellucci, Pierluigi; Zanella, Mattia
2017-02-01
We introduce and discuss kinetic models describing the influence of the competence in the evolution of decisions in a multi-agent system. The original exchange mechanism, which is based on the human tendency to compromise and change opinion through self-thinking, is here modified to include the role of the agents' competence. In particular, we take into account the agents' tendency to behave in the same way as if they were as good, or as bad, as their partner: the so-called equality bias. This occurred in a situation where a wide gap separated the competence of group members. We discuss the main properties of the kinetic models and numerically investigate some examples of collective decision under the influence of the equality bias. The results confirm that the equality bias leads the group to suboptimal decisions.
Identification and Estimation of Exchange Rate Models with Unobservable Fundamentals
Chambers, M.J.; McCrorie, J.R.
2004-01-01
This paper is concerned with issues of model specification, identification, and estimation in exchange rate models with unobservable fundamentals.We show that the model estimated by Gardeazabal, Reg´ulez and V´azquez (International Economic Review, 1997) is not identified and demonstrate how to spec
Repopulation Kinetics and the Linear-Quadratic Model
O'Rourke, S. F. C.; McAneney, H.; Starrett, C.; O'Sullivan, J. M.
2009-08-01
The standard Linear-Quadratic (LQ) survival model for radiotherapy is used to investigate different schedules of radiation treatment planning for advanced head and neck cancer. We explore how these treament protocols may be affected by different tumour repopulation kinetics between treatments. The laws for tumour cell repopulation include the logistic and Gompertz models and this extends the work of Wheldon et al. [1], which was concerned with the case of exponential repopulation between treatments. Treatment schedules investigated include standarized and accelerated fractionation. Calculations based on the present work show, that even with growth laws scaled to ensure that the repopulation kinetics for advanced head and neck cancer are comparable, considerable variation in the survival fraction to orders of magnitude emerged. Calculations show that application of the Gompertz model results in a significantly poorer prognosis for tumour eradication. Gaps in treatment also highlight the differences in the LQ model with the effect of repopulation kinetics included.
Study on Isomerous CAD Model Exchange Based on Feature
Institute of Scientific and Technical Information of China (English)
SHAO Xiaodong; CHEN Feng; XU Chenguang
2006-01-01
A model-exchange method based on feature between isomerous CAD systems is put forward in this paper. In this method, CAD model information is accessed at both feature and geometry levels and converted according to standard feature operation. The feature information including feature tree, dimensions and constraints, which will be lost in traditional data conversion, as well as geometry are converted completely from source CAD system to destination one. So the transferred model can be edited through feature operation, which cannot be implemented by general model-exchange interface.
Kinetic modeling of the Townsend breakdown in argon
Macheret, S. O.; Shneider, M. N.
2013-10-01
Kinetic modeling of the Townsend breakdown in argon was performed in the "forward-back" approximation. The kinetic model was found to adequately describe the left branch of the Paschen curve, and the important role of ionization by fast ions and atoms near the cathode, as well as the increase in secondary emission coefficient in strong electric fields described in the literature, was confirmed. The modeling also showed that the electron energy distribution function develops a beam of high-energy electrons and that the runaway effect, i.e., the monotonic increase of the mean electron energy with the distance from the cathode, occurs at the left branch of the Paschen curve.
Thermal performance modeling of cross-flow heat exchangers
Cabezas-Gómez, Luben; Saíz-Jabardo, José Maria
2014-01-01
This monograph introduces a numerical computational methodology for thermal performance modeling of cross-flow heat exchangers, with applications in chemical, refrigeration and automobile industries. This methodology allows obtaining effectiveness-number of transfer units (e-NTU) data and has been used for simulating several standard and complex flow arrangements configurations of cross-flow heat exchangers. Simulated results have been validated through comparisons with results from available exact and approximate analytical solutions. Very accurate results have been obtained over wide ranges
Hard-sphere kinetic models for inert and reactive mixtures
Polewczak, Jacek
2016-10-01
I consider stochastic variants of a simple reacting sphere (SRS) kinetic model (Xystris and Dahler 1978 J. Chem. Phys. 68 387-401, Qin and Dahler 1995 J. Chem. Phys. 103 725-50, Dahler and Qin 2003 J. Chem. Phys. 118 8396-404) for dense reacting mixtures. In contrast to the line-of-center models of chemical reactive models, in the SRS kinetic model, the microscopic reversibility (detailed balance) can be easily shown to be satisfied, and thus all mathematical aspects of the model can be fully justified. In the SRS model, the molecules behave as if they were single mass points with two internal states. Collisions may alter the internal states of the molecules, and this occurs when the kinetic energy associated with the reactive motion exceeds the activation energy. Reactive and non-reactive collision events are considered to be hard sphere-like. I consider a four component mixture A, B, A *, B *, in which the chemical reactions are of the type A+B\\rightleftharpoons {{A}\\ast}+{{B}\\ast} , with A * and B * being distinct species from A and B. This work extends the joined works with George Stell to the kinetic models of dense inert and reactive mixtures. The idea of introducing smearing-type effect in the collisional process results in a new class of stochastic kinetic models for both inert and reactive mixtures. In this paper the important new mathematical properties of such systems of kinetic equations are proven. The new results for stochastic revised Enskog system for inert mixtures are also provided.
A Biophysically Based Mathematical Model for the Kinetics of Mitochondrial Na+-Ca2+ Antiporter
Pradhan, Ranjan K.; Beard, Daniel A.; Dash, Ranjan K.
2010-01-01
Sodium-calcium antiporter is the primary efflux pathway for Ca2+ in respiring mitochondria, and hence plays an important role in mitochondrial Ca2+ homeostasis. Although experimental data on the kinetics of Na+-Ca2+ antiporter are available, the structure and composition of its functional unit and kinetic mechanisms associated with the Na+-Ca2+ exchange (including the stoichiometry) remains unclear. To gain a quantitative understanding of mitochondrial Ca2+ homeostasis, a biophysical model of Na+-Ca2+ antiporter is introduced that is thermodynamically balanced and satisfactorily describes a number of independent data sets under a variety of experimental conditions. The model is based on a multistate catalytic binding mechanism for carrier-mediated facilitated transport and Eyring's free energy barrier theory for interconversion and electrodiffusion. The model predicts the activating effect of membrane potential on the antiporter function for a 3Na+:1Ca2+ electrogenic exchange as well as the inhibitory effects of both high and low pH seen experimentally. The model is useful for further development of mechanistic integrated models of mitochondrial Ca2+ handling and bioenergetics to understand the mechanisms by which Ca2+ plays a role in mitochondrial signaling pathways and energy metabolism. PMID:20338843
2016-01-01
Isotope exchange depth profiling and electrochemical impedance spectroscopy are usually regarded as complementary tools for measuring the surface oxygen exchange activity of mixed conducting oxides, for example used in solid oxide fuel cell (SOFC) electrodes. Only very few studies compared electrical (kq) and tracer (k*) exchange coefficients of solid–gas interfaces measured under identical conditions. The 1:1 correlation between kq and k* often made is thus more an assumption than experimentally verified. In this study it is shown that the measured rates of electrical and tracer exchange of oxygen may strongly differ. Simultaneous acquisition of kq and k* on La0.6Sr0.4FeO3-δ and SrTi0.3Fe0.7O3-δ thin film electrodes revealed that k* > 100 kq in humid oxidizing (16O2 + H218O) and humid reducing (H2 + H218O) atmospheres. These results are explained by fast water adsorption and dissociation on surface oxygen vacancies, forming two surface hydroxyl groups. Hence, interpreting experimentally determined k* values in terms of electrochemically relevant oxygen exchange is not straightforward. PMID:27389420
Strain in the mesoscale kinetic Monte Carlo model for sintering
DEFF Research Database (Denmark)
Bjørk, Rasmus; Frandsen, Henrik Lund; Tikare, V.
2014-01-01
Shrinkage strains measured from microstructural simulations using the mesoscale kinetic Monte Carlo (kMC) model for solid state sintering are discussed. This model represents the microstructure using digitized discrete sites that are either grain or pore sites. The algorithm used to simulate...
Some models for the adsorption kinetics of pesticides in soil
Leistra, M.; Dekkers, W.A.
1977-01-01
Three models describing adsorption‐desorption kinetics of pesticides in soil, that could be incorporated into computer programs on pesticide movement in soil, were discussed, the first model involved single first‐order rate equations for adsorption and desorption. Results from an analytical and a
Simplified kinetic models of methanol oxidation on silver
DEFF Research Database (Denmark)
Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten;
2005-01-01
Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5–23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...
Simplified kinetic models of methanol oxidation on silver
DEFF Research Database (Denmark)
Andreasen, A.; Lynggaard, H.; Stegelmann, C.;
2005-01-01
Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...
Computer-Aided Construction of Chemical Kinetic Models
Energy Technology Data Exchange (ETDEWEB)
Green, William H. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
2014-12-31
The combustion chemistry of even simple fuels can be extremely complex, involving hundreds or thousands of kinetically significant species. The most reasonable way to deal with this complexity is to use a computer not only to numerically solve the kinetic model, but also to construct the kinetic model in the first place. Because these large models contain so many numerical parameters (e.g. rate coefficients, thermochemistry) one never has sufficient data to uniquely determine them all experimentally. Instead one must work in “predictive” mode, using theoretical rather than experimental values for many of the numbers in the model, and as appropriate refining the most sensitive numbers through experiments. Predictive chemical kinetics is exactly what is needed for computer-aided design of combustion systems based on proposed alternative fuels, particularly for early assessment of the value and viability of proposed new fuels before those fuels are commercially available. This project was aimed at making accurate predictive chemical kinetics practical; this is a challenging goal which requires a range of science advances. The project spanned a wide range from quantum chemical calculations on individual molecules and elementary-step reactions, through the development of improved rate/thermo calculation procedures, the creation of algorithms and software for constructing and solving kinetic simulations, the invention of methods for model-reduction while maintaining error control, and finally comparisons with experiment. Many of the parameters in the models were derived from quantum chemistry calculations, and the models were compared with experimental data measured in our lab or in collaboration with others.
Information cascade, Kirman's ant colony model, and kinetic Ising model
Hisakado, Masato
2014-01-01
In this paper, we discuss a voting model in which voters can obtain information from a finite number of previous voters. There exist three groups of voters: (i) digital herders and independent voters, (ii) analog herders and independent voters, and (iii) tanh-type herders. In our previous paper, we used the mean field approximation for case (i). In that study, if the reference number r is above three, phase transition occurs and the solution converges to one of the equilibria. In contrast, in the current study, the solution oscillates between the two equilibria, that is, good and bad equilibria. In this paper, we show that there is no phase transition when r is finite. If the annealing schedule is adequately slow from finite r to infinite r, the voting rate converges only to the good equilibrium. In case (ii), the state of reference votes is equivalent to that of Kirman's ant colony model, and it follows beta binomial distribution. In case (iii), we show that the model is equivalent to the finite-size kinetic...
Directory of Open Access Journals (Sweden)
Nicola H. Perry
2016-10-01
Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.
Comparison of linear modes in kinetic plasma models
Camporeale, Enrico
2016-01-01
We compare, in an extensive and systematic way, linear theory results obtained with the hybrid (ion-kinetic and electron-fluid), the gyrokinetic and the fully-kinetic plasma models. We present a test case with parameters that are relevant for solar wind turbulence at small scales, which is a topic now recognized to need a kinetic treatment, to a certain extent. We comment on the comparison of low-frequency single modes (Alfv\\'{e}n/ion-cyclotron, ion-acoustic, and fast modes) for a wide range of propagation angles, and on the overall spectral properties of the linear operators, for quasi-perpendicular propagation. The methodology and the results presented in this paper will be valuable when choosing which model should be used in regimes where the assumptions of each model are not trivially satisfied.
Kinetic modelling for zinc (II) ions biosorption onto Luffa cylindrica
Energy Technology Data Exchange (ETDEWEB)
Oboh, I., E-mail: innocentoboh@uniuyo.edu.ng [Department of Chemical and Petroleum Engineering, University of Uyo, Uyo (Nigeria); Aluyor, E.; Audu, T. [Department of Chemical Engineering, University of Uyo, BeninCity, BeninCity (Nigeria)
2015-03-30
The biosorption of Zinc (II) ions onto a biomaterial - Luffa cylindrica has been studied. This biomaterial was characterized by elemental analysis, surface area, pore size distribution, scanning electron microscopy, and the biomaterial before and after sorption, was characterized by Fourier Transform Infra Red (FTIR) spectrometer. The kinetic nonlinear models fitted were Pseudo-first order, Pseudo-second order and Intra-particle diffusion. A comparison of non-linear regression method in selecting the kinetic model was made. Four error functions, namely coefficient of determination (R{sup 2}), hybrid fractional error function (HYBRID), average relative error (ARE), and sum of the errors squared (ERRSQ), were used to predict the parameters of the kinetic models. The strength of this study is that a biomaterial with wide distribution particularly in the tropical world and which occurs as waste material could be put into effective utilization as a biosorbent to address a crucial environmental problem.
A Detailed Chemical Kinetic Model for TNT
Energy Technology Data Exchange (ETDEWEB)
Pitz, W J; Westbrook, C K
2005-01-13
A detailed chemical kinetic mechanism for 2,4,6-tri-nitrotoluene (TNT) has been developed to explore problems of explosive performance and soot formation during the destruction of munitions. The TNT mechanism treats only gas-phase reactions. Reactions for the decomposition of TNT and for the consumption of intermediate products formed from TNT are assembled based on information from the literature and on current understanding of aromatic chemistry. Thermodynamic properties of intermediate and radical species are estimated by group additivity. Reaction paths are developed based on similar paths for aromatic hydrocarbons. Reaction-rate constant expressions are estimated from the literature and from analogous reactions where the rate constants are available. The detailed reaction mechanism for TNT is added to existing reaction mechanisms for RDX and for hydrocarbons. Computed results show the effect of oxygen concentration on the amount of soot precursors that are formed in the combustion of RDX and TNT mixtures in N{sub 2}/O{sub 2} mixtures.
Kinetic models for irreversible processes on a lattice
Energy Technology Data Exchange (ETDEWEB)
Wolf, N.O.
1979-04-01
The development and application of kinetic lattice models are considered. For the most part, the discussions are restricted to lattices in one-dimension. In Chapter 1, a brief overview of kinetic lattice model formalisms and an extensive literature survey are presented. A review of the kinetic models for non-cooperative lattice events is presented in Chapter 2. The development of cooperative lattice models and solution of the resulting kinetic equations for an infinite and a semi-infinite lattice are thoroughly discussed in Chapters 3 and 4. The cooperative models are then applied to the problem of theoretically dtermining the sticking coefficient for molecular chemisorption in Chapter 5. In Chapter 6, other possible applications of these models and several model generalizations are considered. Finally, in Chapter 7, an experimental study directed toward elucidating the mechanistic factors influencing the chemisorption of methane on single crystal tungsten is reported. In this it differs from the rest of the thesis which deals with the statistical distributions resulting from a given mechanism.
Transperitoneal transport of creatinine. A comparison of kinetic models
DEFF Research Database (Denmark)
Fugleberg, S; Graff, J; Joffe, P;
1994-01-01
Six kinetic models of transperitoneal creatinine transport were formulated and validated on the basis of experimental results obtained from 23 non-diabetic patients undergoing peritoneal dialysis. The models were designed to elucidate the presence or absence of diffusive, non-lymphatic convective...... including all three forms of transport is superior to other models. We conclude that the best model of transperitoneal creatinine transport includes diffusion, non-lymphatic convective transport and lymphatic convective transport....
MODELING RESULTS FROM CESIUM ION EXCHANGE PROCESSING WITH SPHERICAL RESINS
Energy Technology Data Exchange (ETDEWEB)
Nash, C.; Hang, T.; Aleman, S.
2011-01-03
Ion exchange modeling was conducted at the Savannah River National Laboratory to compare the performance of two organic resins in support of Small Column Ion Exchange (SCIX). In-tank ion exchange (IX) columns are being considered for cesium removal at Hanford and the Savannah River Site (SRS). The spherical forms of resorcinol formaldehyde ion exchange resin (sRF) as well as a hypothetical spherical SuperLig{reg_sign} 644 (SL644) are evaluated for decontamination of dissolved saltcake wastes (supernates). Both SuperLig{reg_sign} and resorcinol formaldehyde resin beds can exhibit hydraulic problems in their granular (nonspherical) forms. SRS waste is generally lower in potassium and organic components than Hanford waste. Using VERSE-LC Version 7.8 along with the cesium Freundlich/Langmuir isotherms to simulate the waste decontamination in ion exchange columns, spherical SL644 was found to reduce column cycling by 50% for high-potassium supernates, but sRF performed equally well for the lowest-potassium feeds. Reduced cycling results in reduction of nitric acid (resin elution) and sodium addition (resin regeneration), therefore, significantly reducing life-cycle operational costs. These findings motivate the development of a spherical form of SL644. This work demonstrates the versatility of the ion exchange modeling to study the effects of resin characteristics on processing cycles, rates, and cold chemical consumption. The value of a resin with increased selectivity for cesium over potassium can be assessed for further development.
Plasma interfacial mixing layers: Comparisons of fluid and kinetic models
Vold, Erik; Yin, Lin; Taitano, William; Albright, B. J.; Chacon, Luis; Simakov, Andrei; Molvig, Kim
2016-10-01
We examine plasma transport across an initial discontinuity between two species by comparing fluid and kinetic models. The fluid model employs a kinetic theory approximation for plasma transport in the limit of small Knudsen number. The kinetic simulations include explicit particle-in-cell simulations (VPIC) and a new implicit Vlasov-Fokker-Planck code, iFP. The two kinetic methods are shown to be in close agreement for many aspects of the mixing dynamics at early times (to several hundred collision times). The fluid model captures some of the earliest time dynamic behavior seen in the kinetic results, and also generally agrees with iFP at late times when the total pressure gradient relaxes and the species transport is dominated by slow diffusive processes. The results show three distinct phases of the mixing: a pressure discontinuity forms across the initial interface (on times of a few collisions), the pressure perturbations propagate away from the interfacial mixing region (on time scales of an acoustic transit) and at late times the pressure relaxes in the mix region leaving a non-zero center of mass flow velocity. The center of mass velocity associated with the outward propagating pressure waves is required to conserve momentum in the rest frame. Work performed under the auspices of the U.S. DOE by the LANS, LLC, Los Alamos National Laboratory under Contract No. DE-AC52-06NA25396. Funding provided by the Advanced Simulation and Computing (ASC) Program.
Modeling Of Proton Exchange Membrane Fuel Cell Systems
DEFF Research Database (Denmark)
Nielsen, Mads Pagh
The objective of this doctoral thesis was to develop reliable steady-state and transient component models suitable to asses-, develop- and optimize proton exchange membrane (PEM) fuel cell systems. Several components in PEM fuel cell systems were characterized and modeled. The developed component...
Exchange Rate Forecasting Using Entropy Optimized Multivariate Wavelet Denoising Model
Directory of Open Access Journals (Sweden)
Kaijian He
2014-01-01
Full Text Available Exchange rate is one of the key variables in the international economics and international trade. Its movement constitutes one of the most important dynamic systems, characterized by nonlinear behaviors. It becomes more volatile and sensitive to increasingly diversified influencing factors with higher level of deregulation and global integration worldwide. Facing the increasingly diversified and more integrated market environment, the forecasting model in the exchange markets needs to address the individual and interdependent heterogeneity. In this paper, we propose the heterogeneous market hypothesis- (HMH- based exchange rate modeling methodology to model the micromarket structure. Then we further propose the entropy optimized wavelet-based forecasting algorithm under the proposed methodology to forecast the exchange rate movement. The multivariate wavelet denoising algorithm is used to separate and extract the underlying data components with distinct features, which are modeled with multivariate time series models of different specifications and parameters. The maximum entropy is introduced to select the best basis and model parameters to construct the most effective forecasting algorithm. Empirical studies in both Chinese and European markets have been conducted to confirm the significant performance improvement when the proposed model is tested against the benchmark models.
Cluster variation studies of the anisotropic exchange interaction model
King, T. C.; Chen, H. H.
The cluster variation method is applied to study critical properties of the Potts-like ferromagnetic anisotropic exchange interaction model. Phase transition temperatures, order parameter discontinuities and latent heats of the model on the triangular and the fcc lattices are determined by the triangle approximation; and those on the square and the sc lattices are determined by the square approximation.
Tallarek, U.; Vergeldt, F.J.; As, van H.
1999-01-01
Pulsed field gradient nuclear magnetic resonance has been successfully applied to a direct and detailed experimental study of topological and dynamic aspects involved in the exchange of small, nonsorbed fluid molecules between the intraparticle pore network and the interparticle void space in chroma
Institute of Scientific and Technical Information of China (English)
王亚军; 于蕾; 郑裕国; 王远山; 沈寅初
2013-01-01
Acarbose, a potentα-glucosidase inhibitor, is widely used as an oral anti-diabetic drug for the treatment of the type 2, non-insulin-dependent diabetes. In this work, a gel type strong acid cation exchange resin 001×4 was applied to isolate acarbose from fermentation broth. It was demonstrated that cation exchanger 001×4 displayed a large adsorption capacity and quick exchange rate for acarbose. The static adsorption equilibrium data were well fitted to the Langmuir equation. Column adsorption experiments demonstrated that high dynamic adsorption capacity was reached at bed height of 104.4 mm, feed flow rate of 1.0 ml·min-1 and acarbose concentration of 4.0 mg·ml-1. Under the optimized conditions, the column chromatography packed with cation exchanger 001×4 recovered 74.3%(by mass) of acarbose from Actinoplanes utahensis ZJB-08196 fermentation broth with purity of 80.1%(by mass), demonstrating great potential in the practical applications in acarbose separation.
A kinetic assay of mitochondrial ADP-ATP exchange rate in permeabilized cells.
Kawamata, Hibiki; Starkov, Anatoly A; Manfredi, Giovanni; Chinopoulos, Christos
2010-12-01
We previously described a method to measure ADP-ATP exchange rates in isolated mitochondria by recording the changes in free extramitochondrial [Mg(2+)] reported by an Mg(2+)-sensitive fluorescent indicator, exploiting the differential affinity of ADP and ATP to Mg(2+). In the current article, we describe a modification of this method suited for following ADP-ATP exchange rates in environments with competing reactions that interconvert adenine nucleotides such as in permeabilized cells that harbor phosphorylases and kinases, ion pumps exhibiting substantial ATPase activity, and myosin ATPase activity. Here we report that the addition of BeF(3)(-) and sodium orthovanadate (Na(3)VO(4)) to medium containing digitonin-permeabilized cells inhibits all ADP-ATP-using reactions except the adenine nucleotide translocase (ANT)-mediated mitochondrial ADP-ATP exchange. An advantage of this assay is that mitochondria that may have been also permeabilized by digitonin do not contribute to ATP consumption by the exposed F(1)F(o)-ATPase due to its sensitivity to BeF(3)(-) and Na(3)VO(4). With this assay, ADP-ATP exchange rate mediated by the ANT in permeabilized cells is measured for the entire range of mitochondrial membrane potential titrated by stepwise additions of an uncoupler and expressed as a function of citrate synthase activity per total amount of protein. Copyright © 2010 Elsevier Inc. All rights reserved.
Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface
Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; Sturchio, Neil C.
2017-06-01
Ion exchange at charged solid-liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here we report temporal variation in the distribution of Rb+ species at the muscovite (001)-water interface during exchange with Na+. Time-resolved resonant anomalous X-ray reflectivity measurements at 25 °C reveal that Rb+ desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb+ slowly transforms to a less stable outer-sphere Rb+. In contrast, Rb+ adsorption is about twice as fast, proceeding from Rb+ in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55 °C shows that the pre-exponential factor for desorption is significantly smaller than that for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.
Thermodynamic and Kinetic Modeling of Transcriptional Pausing
National Research Council Canada - National Science Library
Vasisht R. Tadigotla; Dáibhid Ó. Maoiléidigh; Anirvan M. Sengupta; Vitaly Epshtein; Richard H. Ebright; Evgeny Nudler; Andrei E. Ruckenstein
2006-01-01
We present a statistical mechanics approach for the prediction of backtracked pauses in bacterial transcription elongation derived from structural models of the transcription elongation complex (EC...
Bayesian inference of chemical kinetic models from proposed reactions
Galagali, Nikhil
2015-02-01
© 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.
3D Building Model Fitting Using A New Kinetic Framework
Brédif, Mathieu; Pierrot-Deseilligny, Marc; Maître, Henri
2008-01-01
We describe a new approach to fit the polyhedron describing a 3D building model to the point cloud of a Digital Elevation Model (DEM). We introduce a new kinetic framework that hides to its user the combinatorial complexity of determining or maintaining the polyhedron topology, allowing the design of a simple variational optimization. This new kinetic framework allows the manipulation of a bounded polyhedron with simple faces by specifying the target plane equations of each of its faces. It proceeds by evolving continuously from the polyhedron defined by its initial topology and its initial plane equations to a polyhedron that is as topologically close as possible to the initial polyhedron but with the new plane equations. This kinetic framework handles internally the necessary topological changes that may be required to keep the faces simple and the polyhedron bounded. For each intermediate configurations where the polyhedron looses the simplicity of its faces or its boundedness, the simplest topological mod...
Kinetic models of opinion formation in the presence of personal conviction
Brugna, Carlo
2015-01-01
We consider a nonlinear kinetic equation of Boltzmann type which takes into account the influence of conviction during the formation of opinion in a system of agents which interact through the binary exchanges introduced in [G. Toscani, Commun. Math. Sci. 4, 481 (2006)]. The original exchange mechanism, which is based on the human tendency to compromise and change of opinion through self-thinking, is here modified in the parameters of the compromise and diffusion terms, which now are assumed to depend on the personal degree of conviction. The numerical simulations show that the presence of conviction has the potential to break symmetry, and to produce clusters of opinions. The model is partially inspired by the recent work [L. Pareschi, G. Toscani, Phil. Trans. R. Soc. A 372, 20130396 (2014)], in which the role of knowledge in the formation of wealth distribution has been investigated.
Oxygen reduction kinetics on mixed conducting SOFC model cathodes
Energy Technology Data Exchange (ETDEWEB)
Baumann, F.S.
2006-07-01
The kinetics of the oxygen reduction reaction at the surface of mixed conducting solid oxide fuel cell (SOFC) cathodes is one of the main limiting factors to the performance of these promising systems. For ''realistic'' porous electrodes, however, it is usually very difficult to separate the influence of different resistive processes. Therefore, a suitable, geometrically well-defined model system was used in this work to enable an unambiguous distinction of individual electrochemical processes by means of impedance spectroscopy. The electrochemical measurements were performed on dense thin film microelectrodes, prepared by PLD and photolithography, of mixed conducting perovskite-type materials. The first part of the thesis consists of an extensive impedance spectroscopic investigation of La0.6Sr0.4Co0.8Fe0.2O3 (LSCF) microelectrodes. An equivalent circuit was identified that describes the electrochemical properties of the model electrodes appropriately and enables an unambiguous interpretation of the measured impedance spectra. Hence, the dependencies of individual electrochemical processes such as the surface exchange reaction on a wide range of experimental parameters including temperature, dc bias and oxygen partial pressure could be studied. As a result, a comprehensive set of experimental data has been obtained, which was previously not available for a mixed conducting model system. In the course of the experiments on the dc bias dependence of the electrochemical processes a new and surprising effect was discovered: It could be shown that a short but strong dc polarisation of a LSCF microelectrode at high temperature improves its electrochemical performance with respect to the oxygen reduction reaction drastically. The electrochemical resistance associated with the oxygen surface exchange reaction, initially the dominant contribution to the total electrode resistance, can be reduced by two orders of magnitude. This &apos
A kinetic model of carbon burnout in pulverized coal combustion
Energy Technology Data Exchange (ETDEWEB)
Hurt, R.; Jian-Kuan Sun; Lunden, M. [Brown University, Providence, RI (United States). Division of Engineering
1998-04-01
The degree of carbon burnout is an important operating characteristic of full-scale suspension-fired coal combustion systems affecting boiler efficiency, electrostatic precipitator operation and the value of fly ash as a saleable product. Prediction of carbon loss requires special char combustion kinetics valid through the very high conversions targeted in industry (typically {gt} 99.5%), and valid for a wide-range of particle temperature histories occurring in full-scale furnaces. The paper presents high-temperature kinetic data for five coal chars in the form of time-resolved burning profiles that include the late stages of combustion. It then describes the development and validation of the Carbon Burnout Kinetic Model (CBK), a coal-general kinetics package that is specifically designed to predict the total extent of carbon burnout and ultimate fly ash carbon content for prescribed temperature/oxygen histories typical of pulverized coal combustion systems. The model combines the single-film treatment of cha oxidation with quantitative descriptions of thermal annealing, statistical kinetics, statistical densities, and ash inhibition in the late stages of combustion. In agreement with experimental observations, the CBK model predicts (1) low reactivities for unburned carbon residues extracted from commercial ash samples, (2) reactivity loss in the late stages of laboratory combustion, (3) the observed sensitivity of char reactivity to high-temperature heat treatment on second and subsecond time scales, and (4) the global reaction inhibition by mineral matter in the late stages of combustion observed in single-particle imaging studies. The model ascribes these various char deactivation phenomena to the combined effects of thermal annealing, ash inhibition, and the preferential consumption of more reactive particles (statistical kinetics), the relative contributions of which vary greatly with combustion conditions. 39 refs., 4 figs., 4 tabs., 1 app.
Jiang, Liangbao; Guo, Xintao; Li, Xiaoyu; Li, Lei; Zhang, Guanli; Yan, Yue
2013-01-01
The difference between the inter-diffusion kinetics of K+-Na+ in the air and tin sides of an ion-exchanged float aluminosilicate glass was investigated as a function of the exchange temperature and time. The potassium concentration profiles of the ion-exchanged glass surface were experimentally measured by electron microprobe analysis, and the diffusion coefficient was calculated by the Boltzmann-Montano approach. On the tin side of the ion-exchanged glass, the diffusion of K+-Na+ ions is hindered by tin. The diffusion coefficient is also more sensitive to temperature and time on the tin than on the air sides. The results would be useful in guiding the strengthening process of float glass by one step ion-exchange or two step ion-exchange to obtain engineered stress profile (ESP) glasses.
Modeling uptake kinetics of cadmium by field-grown lettuce
Energy Technology Data Exchange (ETDEWEB)
Chen Weiping [Department of Environmental Sciences, University of California, 900 University Avenue, Riverside, CA 92521 (United States)], E-mail: chenweip@yahoo.com.cn; Li Lianqing [Institute of Resources, Ecosystem and Environment of Agriculture, Nanjing Agricultural University, Nanjing 210095 (China); Chang, Andrew C.; Wu Laosheng [Department of Environmental Sciences, University of California, 900 University Avenue, Riverside, CA 92521 (United States); Kwon, Soon-Ik [Agricultural Environmental and Ecology Division, National Institute of Agricultural Science and Technology, Suwon 441-707 (Korea, Republic of); Bottoms, Rick [Desert Research and Extension Center, 1004 East Holton Road, El Centro, CA 92243 (United States)
2008-03-15
Cadmium uptake by field grown Romaine lettuce treated with P-fertilizers of different Cd levels was investigated over an entire growing season. Results indicated that the rate of Cd uptake at a given time of the season can be satisfactorily described by the Michaelis-Menten kinetics, that is, plant uptake increases as the Cd concentration in soil solution increases, and it gradually approaches a saturation level. However, the rate constant of the Michaelis-Menten kinetics changes over the growing season. Under a given soil Cd level, the cadmium content in plant tissue decreases exponentially with time. To account for the dynamic nature of Cd uptake, a kinetic model integrating the time factor was developed to simulate Cd plant uptake over the growing season: C{sub Plant} = C{sub Solution} . PUF{sub max} . exp[-b . t], where C{sub Plant} and C{sub Solution} refer to the Cd content in plant tissue and soil solution, respectively, PUF{sub max} and b are kinetic constants. - A kinetic model was developed to evaluate the uptake of Cd under field conditions.
Phase transitions and relaxation dynamics of Ising models exchanging particles
Goh, Segun; Fortin, Jean-Yves; Choi, M. Y.
2017-01-01
A variety of systems in nature and in society are open and subject to exchanging their constituents with other systems (e.g., environments). For instance, in biological systems, cells collect necessary energy and material by exchange of molecules or ions. Similarly, countries, cities or research institutes evolve as their constituents move in or out. To probe the corresponding particle exchange dynamics in such systems, we consider two Ising models exchanging particles and establish a master equation describing the equilibrium phases as well as the non-equilibrium dynamics of the system. It is found that an additional stable phase emerges as a consequence of the particle exchange process. Furthermore, we formulate the Ginzburg-Landau theory which allows to probe correlation effects. Accordingly, critical slowing down is manifested and the associated dynamic exponent is computed in the linear relaxation regime. In particular, this approach is relevant for investigating the grand canonical description of the system plus environment, with particle exchange and state transitions taken into account explicitly.
A physical model of nicotinic ACh receptor kinetics
Nurowska, Ewa; Bratiichuk, Mykola; Dworakowska, Beata; Nowak, Roman J.
2008-01-01
We present a new approach to nicotinic receptor kinetics and a new model explaining random variabilities in the duration of open events. The model gives new interpretation on brief and long receptor openings and predicts (for two identical binding sites) the presence of three components in the open time distribution: two brief and a long. We also present the physical model of the receptor block. This picture naturally and universally explains receptor desensitization, the phenomenon of centra...
A Discrete Velocity Traffic Kinetic Model Including Desired Speed
Directory of Open Access Journals (Sweden)
Shoufeng Lu
2013-05-01
Full Text Available We introduce the desired speed variable into the table of games and formulate a new table of games and the corresponding discrete traffic kinetic model. We use the hybrid programming technique of VB and MATLAB to develop the program. Lastly, we compared the proposed model result and the detector data. The results show that the proposed model can describe the traffic flow evolution.
Electrochemical kinetic and mass transfer model for direct ethanol alkaline fuel cell (DEAFC)
Abdullah, S.; Kamarudin, S. K.; Hasran, U. A.; Masdar, M. S.; Daud, W. R. W.
2016-07-01
A mathematical model is developed for a liquid-feed DEAFC incorporating an alkaline anion-exchange membrane. The one-dimensional mass transport of chemical species is modelled using isothermal, single-phase and steady-state assumptions. The anode and cathode electrochemical reactions use the Tafel kinetics approach, with two limiting cases, for the reaction order. The model fully accounts for the mixed potential effects of ethanol oxidation at the cathode due to ethanol crossover via an alkaline anion-exchange membrane. In contrast to a polymer electrolyte membrane model, the current model considers the flux of ethanol at the membrane as the difference between diffusive and electroosmotic effects. The model is used to investigate the effects of the ethanol and alkali inlet feed concentrations at the anode. The model predicts that the cell performance is almost identical for different ethanol concentrations at a low current density. Moreover, the model results show that feeding the DEAFC with 5 M NaOH and 3 M ethanol at specific operating conditions yields a better performance at a higher current density. Furthermore, the model indicates that crossover effects on the DEAFC performance are significant. The cell performance decrease from its theoretical value when a parasitic current is enabled in the model.
Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas
2017-07-19
Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.
A Kinetic Model for Vapor-liquid Flows
2005-07-13
A Kinetic Model for Vapor-liquid Flows Aldo Frezzotti, Livio Gibelli and Silvia Lorenzani Dipartimento di Matematica del Politecnico di Milano Piazza...ES) Dipartimento di Matematica del Politecnico di Milano Piazza Leonardo da Vinci 32 - 20133 Milano - Italy 8. PERFORMING ORGANIZATION REPORT NUMBER
Development of simple kinetic models and parameter estimation for ...
African Journals Online (AJOL)
PANCHIGA
Key words: Exponential feed, growth modeling, Monod kinetic equation, Pichia pastoris, recombinant human ... Author(s) agree that this article remains permanently open access under the terms of the Creative Commons .... Methanol was the only energy and carbon source ..... A potential explanation for the decline in cell.
Commute Maps: Separating Slowly Mixing Molecular Configurations for Kinetic Modeling.
Noé, Frank; Banisch, Ralf; Clementi, Cecilia
2016-11-08
Identification of the main reaction coordinates and building of kinetic models of macromolecular systems require a way to measure distances between molecular configurations that can distinguish slowly interconverting states. Here we define the commute distance that can be shown to be closely related to the expected commute time needed to go from one configuration to the other, and back. A practical merit of this quantity is that it can be easily approximated from molecular dynamics data sets when an approximation of the Markov operator eigenfunctions is available, which can be achieved by the variational approach to approximate eigenfunctions of Markov operators, also called variational approach of conformation dynamics (VAC) or the time-lagged independent component analysis (TICA). The VAC or TICA components can be scaled such that a so-called commute map is obtained in which Euclidean distance corresponds to the commute distance, and thus kinetic models such as Markov state models can be computed based on Euclidean operations, such as standard clustering. In addition, the distance metric gives rise to a quantity we call total kinetic content, which is an excellent score to rank input feature sets and kinetic model quality.
Estimation of Kinetic Parameters in an Automotive SCR Catalyst Model
DEFF Research Database (Denmark)
Åberg, Andreas; Widd, Anders; Abildskov, Jens;
2016-01-01
A challenge during the development of models for simulation of the automotive Selective Catalytic Reduction catalyst is the parameter estimation of the kinetic parameters, which can be time consuming and problematic. The parameter estimation is often carried out on small-scale reactor tests, or p...
Exchange Rate Prediction using Neural – Genetic Model
Directory of Open Access Journals (Sweden)
MECHGOUG Raihane
2012-10-01
Full Text Available Neural network have successfully used for exchange rate forecasting. However, due to a large number of parameters to be estimated empirically, it is not a simple task to select the appropriate neural network architecture for exchange rate forecasting problem.Researchers often overlook the effect of neural network parameters on the performance of neural network forecasting. The performance of neural network is critically dependant on the learning algorithms, thenetwork architecture and the choice of the control parameters. Even when a suitable setting of parameters (weight can be found, the ability of the resulting network to generalize the data not seen during learning may be far from optimal. For these reasons it seemslogical and attractive to apply genetic algorithms. Genetic algorithms may provide a useful tool for automating the design of neural network. The empirical results on foreign exchange rate prediction indicate that the proposed hybrid model exhibits effectively improved accuracy, when is compared with some other time series forecasting models.
Towards cleaner combustion engines through groundbreaking detailed chemical kinetic models.
Battin-Leclerc, Frédérique; Blurock, Edward; Bounaceur, Roda; Fournet, René; Glaude, Pierre-Alexandre; Herbinet, Olivier; Sirjean, Baptiste; Warth, V
2011-09-01
In the context of limiting the environmental impact of transportation, this critical review discusses new directions which are being followed in the development of more predictive and more accurate detailed chemical kinetic models for the combustion of fuels. In the first part, the performance of current models, especially in terms of the prediction of pollutant formation, is evaluated. In the next parts, recent methods and ways to improve these models are described. An emphasis is given on the development of detailed models based on elementary reactions, on the production of the related thermochemical and kinetic parameters, and on the experimental techniques available to produce the data necessary to evaluate model predictions under well defined conditions (212 references). This journal is © The Royal Society of Chemistry 2011
Chemical kinetics and combustion modelling with CFX 4
Energy Technology Data Exchange (ETDEWEB)
Stopford, P. [AEA Technology, Computational Fluid Dynamics Services Harwell, Oxfordshire (United Kingdom)
1997-12-31
The presentation describes some recent developments in combustion and kinetics models used in the CFX software of AEA Technology. Three topics are highlighted: the development of coupled solvers in a traditional `SIMPLE`-based CFD code, the use of detailed chemical kinetics mechanism via `look-up` tables and the application of CFD to large-scale multi-burner combustion plant. The aim is identify those physical approximations and numerical methods that are likely to be most useful in the future and those areas where further developments are required. (author) 6 refs.
Kinetics and modeling of anaerobic digestion process
DEFF Research Database (Denmark)
2003-01-01
Anaerobic digestion modeling started in the early 1970s when the need for design and efficient operation of anaerobic systems became evident. At that time not only was the knowledge about the complex process of anaerobic digestion inadequate but also there were computational limitations. Thus...
Laplace transform in tracer kinetic modeling
Energy Technology Data Exchange (ETDEWEB)
Hauser, Eliete B., E-mail: eliete@pucrs.br [Instituto do Cerebro (InsCer/FAMAT/PUC-RS), Porto Alegre, RS, (Brazil). Faculdade de Matematica
2013-07-01
The main objective this paper is to quantify the pharmacokinetic processes: absorption, distribution and elimination of radiopharmaceutical(tracer), using Laplace transform method. When the drug is administered intravenously absorption is complete and is available in the bloodstream to be distributed throughout the whole body in all tissues and fluids, and to be eliminated. Mathematical modeling seeks to describe the processes of distribution and elimination through compartments, where distinct pools of tracer (spatial location or chemical state) are assigned to different compartments. A compartment model is described by a system of differential equations, where each equation represents the sum of all the transfer rates to and from a specific compartment. In this work a two-tissue irreversible compartment model is used for description of tracer, [{sup 18}F]2-fluor-2deoxy-D-glucose. In order to determine the parameters of the model, it is necessary to have information about the tracer delivery in the form of an input function representing the time-course of tracer concentration in arterial blood or plasma. We estimate the arterial input function in two stages and apply the Levenberg-Marquardt Method to solve nonlinear regressions. The transport of FDG across de arterial blood is very fast in the first ten minutes and then decreases slowly. We use de Heaviside function to represent this situation and this is the main contribution of this study. We apply the Laplace transform and the analytical solution for two-tissue irreversible compartment model is obtained. The only approach is to determinate de arterial input function. (author)
Ensemble Kinetic Modeling of Metabolic Networks from Dynamic Metabolic Profiles
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Gengjie Jia
2012-11-01
Full Text Available Kinetic modeling of metabolic pathways has important applications in metabolic engineering, but significant challenges still remain. The difficulties faced vary from finding best-fit parameters in a highly multidimensional search space to incomplete parameter identifiability. To meet some of these challenges, an ensemble modeling method is developed for characterizing a subset of kinetic parameters that give statistically equivalent goodness-of-fit to time series concentration data. The method is based on the incremental identification approach, where the parameter estimation is done in a step-wise manner. Numerical efficacy is achieved by reducing the dimensionality of parameter space and using efficient random parameter exploration algorithms. The shift toward using model ensembles, instead of the traditional “best-fit” models, is necessary to directly account for model uncertainty during the application of such models. The performance of the ensemble modeling approach has been demonstrated in the modeling of a generic branched pathway and the trehalose pathway in Saccharomyces cerevisiae using generalized mass action (GMA kinetics.
Intrinsic Kinetic Modeling of Thermal Dimerization of C5 Fraction
Institute of Scientific and Technical Information of China (English)
Guo Liang; Wang Tiefeng; Li Dongfeng; Wang Jinfu
2016-01-01
This work aims to investigate the intrinsic kinetics of thermal dimerization of C5 fraction in the reactive distilla-tion process. Experiments are conducted in an 1000-mL stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy Ea is equal to 6.58×104 J/mol for the cyclopentadiene dimerization re-action. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.
Kinetics of Model Reactions for Interfacial Polymerization
Directory of Open Access Journals (Sweden)
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.
Thermodynamic and kinetic modeling of transcriptional pausing
Tadigotla, Vasisht R.; Maoiléidigh, Dáibhid Ó; Sengupta, Anirvan M.; Epshtein, Vitaly; Ebright, Richard H.; Nudler, Evgeny; Ruckenstein, Andrei E.
2006-01-01
We present a statistical mechanics approach for the prediction of backtracked pauses in bacterial transcription elongation derived from structural models of the transcription elongation complex (EC). Our algorithm is based on the thermodynamic stability of the EC along the DNA template calculated from the sequence-dependent free energy of DNA–DNA, DNA–RNA, and RNA–RNA base pairing associated with (i) the translocational and size fluctuations of the transcription bubble; (ii) changes in the as...
Homogeneous gas phase models of relaxation kinetics in neon afterglow
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Marković Vidosav Lj.
2007-01-01
Full Text Available The homogeneous gas phase models of relaxation kinetics (application of the gas phase effective coefficients to represent surface losses are applied for the study of charged and neutral active particles decay in neon afterglow. The experimental data obtained by the breakdown time delay measurements as a function of the relaxation time td (τ (memory curve is modeled in early, as well as in late afterglow. The number density decay of metastable states can explain neither the early, nor the late afterglow kinetics (memory effect, because their effective lifetimes are of the order of milliseconds and are determined by numerous collision quenching processes. The afterglow kinetics up to hundreds of milliseconds is dominated by the decay of molecular neon Ne2 + and nitrogen ions N2 + (present as impurities and the approximate value of N2 + ambipolar diffusion coefficient is determined. After the charged particle decay, the secondary emitted electrons from the surface catalyzed excitation of nitrogen atoms on the cathode determine the breakdown time delay down to the cosmic rays and natural radioactivity level. Due to the neglecting of number density spatial profiles, the homogeneous gas phase models give only the approximate values of the corresponding coefficients, but reproduce correctly other characteristics of afterglow kinetics from simple fits to the experimental data.
Enzymatic hydrolysis of protein:mechanism and kinetic model
Institute of Scientific and Technical Information of China (English)
Qi Wei; He Zhimin
2006-01-01
The bioreaction mechanism and kinetic behavior of protein enzymatic hydrolysis for preparing active peptides were investigated to model and characterize the enzymatic hydrolysis curves.Taking into account single-substrate hydrolysis,enzyme inactivation and substrate or product inhibition,the reaction mechanism could be deduced from a series of experimental results carried out in a stirred tank reactor at different substrate concentrations,enzyme concentrations and temperatures based on M-M equation.An exponential equation dh/dt = aexp(-bh) was also established,where parameters a and b have different expressions according to different reaction mechanisms,and different values for different reaction systems.For BSA-trypsin model system,the regressive results agree with the experimental data,i.e.the average relative error was only 4.73%,and the reaction constants were determined as Km = 0.0748 g/L,Ks = 7.961 g/L,kd = 9.358/min,k2 =38.439/min,Ea= 64.826 kJ/mol,Ed= 80.031 kJ/mol in accordance with the proposed kinetic mode.The whole set of exponential kinetic equations can be used to model the bioreaction process of protein enzymatic hydrolysis,to calculate the thermodynamic and kinetic constants,and to optimize the operating parameters for bioreactor design.
Multisite Kinetic Modeling of 13C Metabolic MR Using [1-13C]Pyruvate
Directory of Open Access Journals (Sweden)
Pedro A. Gómez Damián
2014-01-01
Full Text Available Hyperpolarized 13C imaging allows real-time in vivo measurements of metabolite levels. Quantification of metabolite conversion between [1-13C]pyruvate and downstream metabolites [1-13C]alanine, [1-13C]lactate, and [13C]bicarbonate can be achieved through kinetic modeling. Since pyruvate interacts dynamically and simultaneously with its downstream metabolites, the purpose of this work is the determination of parameter values through a multisite, dynamic model involving possible biochemical pathways present in MR spectroscopy. Kinetic modeling parameters were determined by fitting the multisite model to time-domain dynamic metabolite data. The results for different pyruvate doses were compared with those of different two-site models to evaluate the hypothesis that for identical data the uncertainty of a model and the signal-to-noise ratio determine the sensitivity in detecting small physiological differences in the target metabolism. In comparison to the two-site exchange models, the multisite model yielded metabolic conversion rates with smaller bias and smaller standard deviation, as demonstrated in simulations with different signal-to-noise ratio. Pyruvate dose effects observed previously were confirmed and quantified through metabolic conversion rate values. Parameter interdependency allowed an accurate quantification and can therefore be useful for monitoring metabolic activity in different tissues.
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.
Energy Technology Data Exchange (ETDEWEB)
Dursch, Thomas J. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Ciontea, Monica A. [Univ. of California, Berkeley, CA (United States); Radke, Clayton J. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Weber, Adam Z. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
2011-12-01
Nucleation and growth of ice in the fibrous gas-diffusion layer (GDL) of a proton-exchange membrane fuel cell (PEMFC) are studied using isothermal differential scanning calorimetry (DSC). Isothermal crystallization rates and pseudo-steady-state nucleation rates are obtained as a function of subcooling from heat-flow and induction-time measurements. Kinetics of ice nucleation and growth are studied at two polytetrafluoroethylene (PTFE) loadings (0 and 10 wt %) in a commercial GDL for temperatures between 240 and 273 K. A nonlinear ice-crystallization rate expression is developed using Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory, in which the heat-transfer-limited growth rate is determined from the moving-boundary Stefan problem. Induction times follow a Poisson distribution and increase upon addition of PTFE, indicating that nucleation occurs more slowly on a hydrophobic fiber than on a hydrophilic fiber. The determined nucleation rates and induction times follow expected trends from classical nucleation theory. Finally, a validated rate expression is now available for predicting ice-crystallization kinetics in GDLs.
Institute of Scientific and Technical Information of China (English)
吴朝安
2014-01-01
Dispersion in time-oscillatory electro-osmotic flows in a slit micro-channel under the effect of kinetic sorptive exchange at walls is theoretically investigated using the homogenization method. The two walls of the channel are considered to be made up of different materials, and therefore have different zeta potentials and sorption coefficients. A general expression for the Taylor disper-sion coefficient under different zeta potentials as well as various sorption conditions at the walls is derived analytically. The disper-sion coefficient is found to be dependent on the oscillation frequency, the Debye parameter, the species partition coefficient, the rea-ction kinetics and the ratio of the wall potentials. The results demonstrate that the presence of wall sorption tends to enhance the dispersion when the oscillation frequency is low, but the effect is negligible in high-frequency oscillatory flows. Moreover, it is found that the dispersion coefficient could be significantly changed by adjusting the relative wall potentials for low-frequency flows.
Vlasov models for kinetic Weibel-type instabilities
Ghizzo, A.; Sarrat, M.; Del Sarto, D.
2017-02-01
The Weibel instability, driven by a temperature anisotropy, is investigated within different kinetic descriptions based on the semi-Lagrangian full kinetic and relativistic Vlasov-Maxwell model, on the multi-stream approach, which is based on a Hamiltonian reduction technique, and finally, with the full pressure tensor fluid-type description. Dispersion relations of the Weibel instability are derived using the three different models. A qualitatively different regime is observed in Vlasov numerical experiments depending on the excitation of a longitudinal plasma electric field driven initially by the combined action of the stream symmetry breaking and weak relativistic effects, in contrast with the existing theories of the Weibel instability based on their purely transverse characters. The multi-stream model offers an alternate way to simulate easily the coupling with the longitudinal electric field and particularly the nonlinear regime of saturation, making numerical experiments more tractable, when only a few moments of the distribution are considered. Thus a numerical comparison between the reduced Hamiltonian model (the multi-stream model) and full kinetic (relativistic) Vlasov simulations has been investigated in that regime. Although nonlinear simulations of the fluid model, including the dynamics of the pressure tensor, have not been carried out here, the model is strongly relevant even in the three-dimensional case.
Developments in kinetic modelling of chalcocite particle oxidation
Energy Technology Data Exchange (ETDEWEB)
Jaervi, J.; Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy
1997-12-31
A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.
Modeling Kinetics of Distortion in Porous Bi-layered Structures
DEFF Research Database (Denmark)
Tadesse Molla, Tesfaye; Frandsen, Henrik Lund; Bjørk, Rasmus;
2013-01-01
Shape distortions during constrained sintering experiment of bi-layer porous and dense cerium gadolinium oxide (CGO) structures have been modeled. Technologies like solid oxide fuel cells require co-firing thin layers with different green densities, which often exhibit differential shrinkage...... because of different sintering rates of the materials resulting in undesired distortions of the component. An analytical model based on the continuum theory of sintering has been developed to describe the kinetics of densification and distortion in the sintering processes. A new approach is used...... to extract the material parameters controlling shape distortion through optimizing the model to experimental data of free shrinkage strains. The significant influence of weight of the sample (gravity) on the kinetics of distortion is taken in to consideration. The modeling predictions indicate good agreement...
Chemistry Resolved Kinetic Flow Modeling of TATB Based Explosives
Energy Technology Data Exchange (ETDEWEB)
Vitello, P A; Fried, L E; Howard, W M; Levesque, G; Souers, P C
2011-07-21
Detonation waves in insensitive, TATB based explosives are believed to have multi-time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. They use the thermo-chemical code CHEETAH linked to an ALE hydrodynamics code to model detonations. They term their model chemistry resolved kinetic flow as CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculates EOS values based on the concentrations. A HE-validation suite of model simulations compared to experiments at ambient, hot, and cold temperatures has been developed. They present here a new rate model and comparison with experimental data.
Ab initio and kinetic modeling studies of formic acid oxidation
DEFF Research Database (Denmark)
Marshall, Paul; Glarborg, Peter
2015-01-01
A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... as the fate of HOCO, determines the oxidation rate of formic acid. At lower temperatures HO2, formed from HOCO + O2, is an important chain carrier and modeling predictions become sensitive to the HOCHO + HO2 reaction. © 2014 The Combustion Institute....... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...
Kinetic model for the pathogenesis of radiation lung damage
Energy Technology Data Exchange (ETDEWEB)
Collis, C.H. (Institute of Cancer Research, Sutton (UK). Surrey Branch)
1982-09-01
The development of radiation-induced lung damage can be explained by a kinetic model, based on the assumption that this damage becomes manifest only when a critical proportion (K) of essential cells have ceased to function, and that the rate of loss of these cells following irradiation is linear and dose-dependent. The kinetic model relates the surviving fraction to the time to manifestation of radiation-induced lung damage and to constants, K and the cell cycle time, T. Predictions made from the model about the nature of the response to irradiation are, for the most part, fulfilled. The model can also be used to interpret the response to combined treatment with irradiation and cytotoxic drugs, including the much earlier manifestation of lung damage sometimes seen with such treatment.
Study on Kinetics for Desulfurization of Model Diesel
Institute of Scientific and Technical Information of China (English)
Qian Jianhua; Zhou Yuenan; Liu Lin; Wang Yue; Xing Jinjuan; Lü Hong
2009-01-01
In this study, by means of the experiments for desulfurization of model diesel through oxi-dative extraction, the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides in diesel were explored. Through studying the mechanism for oxidation of sulfides and the principle of solvent extraction, the kinetic equation of desulfurization via oxidative extraction were determined. By means of the evaluation of model parameters and curve fitting, the reaction order between organic sulfide and sulfone, the intrinsic oxidation rate constant of organic sulfide and sulfone, and the equilibrium constant between suifone in model diesel and extractive sol-vent were determined. The experimental values of the desulfurization rate and the theoretical values of the corresponding model equation had closely demonstrated that the desulfurization reaction rate had high accuracy. And the reaction kinetics could provide an important basis for diesel desulfurization process in the future.
Cleaner combustion developing detailed chemical kinetic models
Battin-Leclerc, Frédérique; Blurock, Edward
2013-01-01
This overview compiles the on-going research in Europe to enlarge and deepen the understanding of the reaction mechanisms and pathways associated with the combustion of an increased range of fuels. Focus is given to the formation of a large number of hazardous minor pollutants and the inability of current combustion models to predict the Â formation of minor products such as alkenes, dienes, aromatics, aldehydes and soot nano-particles which have a deleterious impact on both the environment and on human health. Cleaner Combustion describes, at a fundamental level, the reactive chemistry of min
Behavior of human serum albumin on strong cation exchange resins: II. model analysis.
Voitl, Agnes; Butté, Alessandro; Morbidelli, Massimo
2010-08-20
Experiments with human serum albumin on a strong cation exchange resin exhibit a peculiar elution pattern: the protein elutes with two peaks in a modifier gradient. This behavior is modeled with a general rate model, where the two elution peaks are modeled with two binding conformations, one of which is at equilibrium conditions, while for the other, the adsorption process is rate limited. Isocratic experiments under nonadsorbing conditions were used to characterize the mass transfer process. The isotherm of both adsorption conformations as well as the kinetic of adsorption and desorption for the second conformation are functions of the modifier concentration. They are evaluated with linear modifier gradient experiments and step experiments with various adsorption times. All experimental features are well reproduced by the proposed modified general rate model.
Directory of Open Access Journals (Sweden)
Amrit Pal Toor
2011-05-01
Full Text Available Esters are an important pharmaceutical intermediates and very useful perfumery agents. In this study the esterification of acetic acid with n-butanol and iso-butanol over an acidic cation exchange resin, Amberlyst 15 were carried out. The effects of certain parameters such as temperature, catalyst loading, initial molar ratio between reactants on the rate of reaction were studied. The experiments were conducted in a stirred batch reactor in the temperature range of 351.15 K to 366.15K.Variation of parameters on rate of reaction demonstrated that the reaction was intrinsically controlled.The activation energy for the esterification of acetic acid with n-butanol and iso butanol is found to be 28.45 k J/mol and 23.29 kJ/mol respectively. ©2011 BCREC UNDIP. All rights reserved.(Received: 16th December 2010, Revised: 19th March 2011; Accepted: 7th April 2011[How to Cite: A.P. Toor, M. Sharma, G. Kumar, and R. K. Wanchoo. (2011. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 23-30. doi:10.9767/bcrec.6.1.665.23-30][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.665.23-30 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/665 ] | View in
Van Ginkel, Steven W; Ahn, Chang Hoon; Badruzzaman, Mohammad; Roberts, Deborah J; Lehman, S Geno; Adham, Samer S; Rittmann, Bruce E
2008-09-01
Several sources of bacterial inocula were tested for their ability to reduce nitrate and perchlorate in synthetic ion-exchange spent brine (30-45 g/L) using a hydrogen-based membrane biofilm reactor (MBfR). Nitrate and perchlorate removal fluxes reached as high as 5.4 g Nm(-2)d(-1) and 5.0 g ClO(4)m(-2)d(-1), respectively, and these values are similar to values obtained with freshwater MBfRs. Nitrate and perchlorate removal fluxes decreased with increasing salinity. The nitrate fluxes were roughly first order in H(2) pressure, but roughly zero-order with nitrate concentration. Perchlorate reduction rates were higher with lower nitrate loadings, compared to high nitrate loadings; this is a sign of competition for H(2). Nitrate and perchlorate reduction rates depended strongly on the inoculum. An inoculum that was well acclimated (years) to nitrate and perchlorate gave markedly faster removal kinetics than cultures that were acclimated for only a few months. These results underscore that the most successful MBfR bioreduction of nitrate and perchlorate in ion-exchange brine demands a well-acclimated inoculum and sufficient hydrogen availability.
Kinetic modelling of molecular hydrogen transport in microporous carbon materials.
Hankel, Marlies; Zhang, Hong; Nguyen, Thanh X; Bhatia, Suresh K; Gray, Stephen K; Smith, Sean C
2011-05-07
The proposal of kinetic molecular sieving of hydrogen isotopes is explored by employing statistical rate theory methods to describe the kinetics of molecular hydrogen transport in model microporous carbon structures. A Lennard-Jones atom-atom interaction potential is utilized for the description of the interactions between H(2)/D(2) and the carbon framework, while the requisite partition functions describing the thermal flux of molecules through the transition state are calculated quantum mechanically in view of the low temperatures involved in the proposed kinetic molecular sieving application. Predicted kinetic isotope effects for initial passage from the gas phase into the first pore mouth are consistent with expectations from previous modeling studies, namely, that at sufficiently low temperatures and for sufficiently narrow pore mouths D(2) transport is dramatically favored over H(2). However, in contrast to expectations from previous modeling, the absence of any potential barrier along the minimum energy pathway from the gas phase into the first pore mouth yields a negative temperature dependence in the predicted absolute rate coefficients-implying a negative activation energy. In pursuit of the effective activation barrier, we find that the minimum potential in the cavity is significantly higher than in the pore mouth for nanotube-shaped models, throwing into question the common assumption that passage through the pore mouths should be the rate-determining step. Our results suggest a new mechanism that, depending on the size and shape of the cavity, the thermal activation barrier may lie in the cavity rather than at the pore mouth. As a consequence, design strategies for achieving quantum-mediated kinetic molecular sieving of H(2)/D(2) in a microporous membrane will need, at the very least, to take careful account of cavity shape and size in addition to pore-mouth size in order to ensure that the selective step, namely passage through the pore mouth, is also
Multiphysics Numerical Modeling of a Fin and Tube Heat Exchanger
DEFF Research Database (Denmark)
Singh, Shobhana; Sørensen, Kim; Condra, Thomas Joseph
2015-01-01
). For the purposes here, only gas flowing over the fin side is simulated assuming constant inner tube wall temperature. The study couples conjugate heat transfer mechanism with turbulent flow in order to describe the temperature and velocity profile. In addition, performance characteristics of the heat exchanger...... design in terms of heat transfer and pressure loss are determined by parameters such as overall heat transfer coefficient, Colburn j-factor, flow resistance factor, and efficiency index. The model provides useful insights necessary for optimization of heat exchanger design....
Stochastic Model of Maturation and Vesicular Exchange in Cellular Organelles
Vagne, Quentin
2016-01-01
The dynamical organization of membrane-bound organelles along intracellular transport pathways relies on vesicular exchange between organelles and on biochemical maturation of the organelle content by specific enzymes. The relative importance of each mechanism in controlling organelle dynamics remains controversial, in particular for transport through the Golgi apparatus. Using a stochastic model, we show that full maturation of membrane-bound compartments can be seen as the stochastic escape from a steady-state in which export is dominated by vesicular exchange. We show that full maturation can contribute a significant fraction of the total out-flux for small organelles such as endosomes and Golgi cisternae.
Extraction of lycopene from tomato processing waste: kinetics and modelling.
Poojary, Mahesha M; Passamonti, Paolo
2015-04-15
Lycopene, a nutraceutical compound, was extracted from tomato processing waste, an abundantly available food industry by-product in Italy. The extraction kinetics was mathematically described using the first order kinetic model, the mass transfer model and Peleg's model to understand the physicochemical behaviour of the extraction. Samples were extracted using acetone/n-hexane mixtures at different ratios (1:3, 2:2 and 3:1, v/v) and at different temperatures (30, 40 and 50 °C) and simultaneously analysed using UV-VIS spectrophotometry. The lycopene yield was in the range 3.47-4.03 mg/100g, which corresponds to a percentage recovery of 65.22-75.75. All kinetic models gave a good fit to the experimental data, but the best one was Peleg's model, having the highest RAdj(2) and the lowest RMSE, MBE and χ(2) values. All the models confirmed that a temperature of 30 °C and solvent mixture of acetone/n-hexane 1:3 (v/v) provided optimal conditions for extraction of lycopene.
Kinetic bottlenecks to respiratory exchange rates in the deep-sea – Part 1: Oxygen
Directory of Open Access Journals (Sweden)
A. F. Hofmann
2013-07-01
Full Text Available Ocean warming is now reducing dissolved oxygen concentrations, which can pose challenges to marine life. Oxygen limits are traditionally reported simply as a static concentration threshold with no temperature, pressure or flow rate dependency. Here we treat the oceanic oxygen supply potential for heterotrophic consumption as a dynamic molecular exchange problem analogous to familiar gas exchange processes at the sea surface. A combination of the purely physico-chemical oceanic properties temperature, hydrostatic pressure, and oxygen concentration defines the ability of the ocean to provide the oxygen supply to the external surface of a respiratory membrane. This general oceanic oxygen supply potential is modulated by further properties such as the diffusive boundary layer thickness to define an upper limit to oxygen supply rates. While the true maximal oxygen uptake rate of any organism is limited by gas transport either across the respiratory interface of the organism itself or across the diffusive boundary layer around an organism, controlled by physico-chemical oceanic properties, it can never be larger than the latter. Here, we define and calculate quantities that describe this upper limit to oxygen uptake posed by physico-chemical properties around an organism and show examples of their oceanic profiles.
Toda, S.; Nakata, M.; Nunami, M.; Ishizawa, A.; Watanabe, T.-H.; Sugama, H.
2016-10-01
A reduced model of the turbulent ion heat diffusivity is proposed by the gyrokinetic simulation code (GKV-X) with the adiabatic electrons for the high-Ti Large Helical Device discharge. The plasma parameter region of the short poloidal wavelength is studied, where the ion temperature gradient mode becomes unstable. The ion heat diffusivity by the nonlinear simulation with the kinetic electrons is found to be several times larger than the simulation results using the adiabatic electrons in the radial region 0.46 ion energy flux. The model of the turbulent diffusivity is derived as the function of the squared electrostatic potential fluctuation and the squared zonal flow potential. Next, the squared electrostatic potential fluctuation is approximated with the mixing length estimate. The squared zonal flow potential fluctuation is shown as the linear zonal flow response function. The reduced model of the turbulent diffusivity is derived as the function of the physical parameters by the linear GKV-X simulation with the kinetic electrons. This reduced model is applied to the transport code with the same procedure as.
Jovanovic, Mina; Rajic, Nevenka; Obradovic, Bojana
2012-09-30
Removal of heavy metal ions from aqueous solutions using zeolites is widely described by pseudo-second order kinetics although this model may not be valid under all conditions. In this work, we have extended approaches used for derivation of this model in order to develop a novel kinetic model that is related to the ion exchange mechanism underlying sorption of metal ions in zeolites. The novel model assumed two reversible steps, i.e. release of sodium ions from the zeolite lattice followed by bonding of the metal ion. The model was applied to experimental results of Cu(II) sorption by natural clinoptilolite-rich zeolitic tuff at different initial concentrations and temperatures and then validated by predictions of ion exchange kinetics of other divalent heavy metal ions (i.e. Mn(II), Zn(II) and Pb(II)). Model predictions were in excellent agreements with experimental data for all investigated systems. In regard to the proposed mechanism, modeling results implied that the sodium ion release rate was constant for all investigated metals while the overall rate was mainly determined by the rate of heavy metal ion bonding to the lattice. In addition, prediction capabilities of the novel model were demonstrated requiring one experimentally determined parameter, only.
Modeling and predicting historical volatility in exchange rate markets
Lahmiri, Salim
2017-04-01
Volatility modeling and forecasting of currency exchange rate is an important task in several business risk management tasks; including treasury risk management, derivatives pricing, and portfolio risk evaluation. The purpose of this study is to present a simple and effective approach for predicting historical volatility of currency exchange rate. The approach is based on a limited set of technical indicators as inputs to the artificial neural networks (ANN). To show the effectiveness of the proposed approach, it was applied to forecast US/Canada and US/Euro exchange rates volatilities. The forecasting results show that our simple approach outperformed the conventional GARCH and EGARCH with different distribution assumptions, and also the hybrid GARCH and EGARCH with ANN in terms of mean absolute error, mean of squared errors, and Theil's inequality coefficient. Because of the simplicity and effectiveness of the approach, it is promising for US currency volatility prediction tasks.
Kinetic Model of Biodiesel Processing Using Ultrasound
Directory of Open Access Journals (Sweden)
Bambang Susilo
2009-04-01
Full Text Available Ultrasound is predicted to be able to accelerate the chemical reaction, to increase the conversion of plant oil into biodiesel, and to decrease the need of catalyst and energy input. The application of ultrasound for processing of biodiesel and the mathematical model were conducted in this research. The result of the experiments showed that the ultrasound increased reaction rate and the conversion of palm oil into biodiesel up to 100%. It was better than the process with mechanical stirrer that the conversion was just 96%. The duration to complete the process using ultrasound was 1 minute. It was 30 to 120 times faster than that with mechanical stirrer. Ultrasound transforms mechanical energy into inner energy of the fluids and causes an increasing of temperature. Simultaneously, natural mixing process undergo because of acoustic circulation. Simulation with experiment data showed that the acceleration of transesterification with ultrasound was affected not only by natural mixing and increasing temperature. The cavitation, surface tension of micro bubble, and hot spot accelerate chemical reaction. In fact, transesterification of palm oil with ultrasound still needs catalyst. It needs only about 20% of catalyst compared to the process with mechanical stirrer.
Kinetic model of induced codeposition of Ni-Mo alloys
Institute of Scientific and Technical Information of China (English)
ZENG, Yue; MA, Ming; XIAO, Xiao-Ming; LI, Ze-Lin; LIAN, Shi-Xun; ZHOU, Shao-Min
2000-01-01
The kinetic model of induced codeposition of nickel-molybdenum alloys from ammoniun citrate solution was studied on rotating disk electrodes to predict the behavior of the electrodeposition. Ihe molybdate (MoO42-) could be firstly electrochemically reduced to MoO2, and subsequently undergoes a chemical reduction with atomic hydrogen previously adsorbed on the inducing metal nickel to form molybdenum in alloys.The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The electrochemical rate constants for discharge of nickel, molybdenum and water could been expressed as k1 ( E ) = 1. 23 × 10-9 CNexp( - 0. 198FE/ RT )mol/(dm2. s), k2 (E) = 3.28 × 10-10 CMoexp ( - 0.208FE/RT) mol/(dm2·s) and k3(E) = 1.27 × 10-6exp( - 0.062FE/RT) mol/(dm2 ·s), where CN and CMo are the concentrations of the nickel ion and molybdate, respectively, and E is the applied potential vs, saturated calornel electrode (SCE).The codeposition process could be well simulated by this model.
Modeling of karst aquifer genesis: Influence of exchange flow
Bauer, Sebastian; Liedl, Rudolf; Sauter, Martin
2003-10-01
This paper presents a numerical model study simulating the early karstification of a single conduit embedded in a fissured system. A hybrid continuum-discrete pipe flow model (CAVE) is used for the modeling. The effects of coupling of the two flow systems on type and duration of early karstification are studied for different boundary conditions. Assuming fixed head boundaries at both ends of the conduit, coupling of the two flow systems via exchange flow between the conduit and the fissured system leads to an enhanced evolution of the conduit. This effect is valid over a wide range of initial conduit diameters, and karstification is accelerated by a factor of about 100 as compared to the case of no exchange flow. Parameter studies reveal the influence of the exchange coefficient and of the hydraulic conductivity of the fissured system on the development time for the conduit. In a second scenario the upstream fixed head boundary is switched to a fixed flow boundary at a specified flow rate during the evolution, limiting the amount of water draining toward the evolving conduit. Depending on the flow rate specified, conduit evolution may be slowed down or greatly impaired if exchange flow is considered.
Kinetic model of the Buyers’ market
Zhykharsky, Alexander V.
2013-09-01
In this work the following results are received. The closed mathematical apparatus describing the process of interaction of the Buyers’ market with retail Shop is created. The “statistical analogy” between the vacuum electrostatic diode and the Buyers’ market co-operating with retail Shop is considered. On the basis of the spent analysis the closed mathematical apparatus describing process of interaction of the Buyers’ market with retail Shop is created. The analytical expressions connecting a stream of Buyers, come to Shop, and a stream of the gain of Shop, with parameters of the Buyers’ market are received. For check of adequacy of the received model it is solved of some real “market” problems. On the basis of the spent researches principles of construction of Information-analytical Systems of new type which provide direct measurements of parameters of the Buyers’ market are developed. Actually these Systems are devices for measurement of parameters of this market. In this work it is shown that by means of the device developed for measurement of parameters of the Buyers’ market, creation of a new science-“demandodynamics” the Buyers’ market, is possible. Here the term “demandodynamics the Buyers’ market” is accepted by analogy to the term “thermodynamics” in physics. (In this work it is shown that for the Buyers’ market concept “demand” is similar to concept “temperature” in physics.) The construction methodology “demandodynamics” the Buyers’ market is defined and is shown that within the limits of this science working out of a technique of a direct control by a condition of the Buyers’ market is possible.
Kinetic models for historical processes of fast invasion and aggression
Aristov, Vladimir V.; Ilyin, Oleg V.
2015-04-01
In the last few decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological, and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France, and the USSR based on kinetic theory. We simulate this process with the Cauchy boundary problem for two-element kinetic equations. The solution of the problem is given in the form of a traveling wave. The propagation velocity of a front line depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the front-line velocities agree with the historical data.
Kinetic Modeling of Paraffin Aromatization over Zeolites: A Design Perspective
Bhan, Aditya; Katare, Santhoji; Caruthers, James; Lauterbach, Jochen; Venkatasubramanian, Venkat; Delgass, Nicholas
2002-03-01
A generic framework for catalyst design involving the solution of a forward predictive problem using hybrid models and the inverse problem using evolutionary algorithms has been proposed. In that context, we investigate the aromatization of light paraffins over HZSM-5 to obtain the catalyst descriptors and associated kinetic parameters that predict performance. A detailed kinetic model that can fundamentally quantify the catalytic properties of acid sites in terms of intrinsic parameters such as rate constants and activation energies of elementary steps is developed on the basis of the following types of reactions: adsorption/desorption, oligomerization/ beta-scission, hydride transfer, protolysis and aromatization. The reaction network so generated has been grouped under various reaction families taking into account the different stabilities and reactivities of the adsorbed carbenium/carbonium ions. The detailed parameterization of each reaction type, optimizing fits to data, linking catalyst descriptors to performance, and means of improving the robustness of the model will be presented.
5-Lump kinetic model for gas oil catalytic cracking
Energy Technology Data Exchange (ETDEWEB)
Ancheyta-Juarez, Jorge; Aguilar-Rodriguez, Enrique [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, Mexico 07730 DF (Mexico); Lopez-Isunza, Felipe [Universidad Autonoma Metropolitana-Iztapalapa, Mexico 09340 DF (Mexico)
1999-02-22
A new 5-lump kinetic model is proposed to describe the gas oil catalytic cracking (FCC) process. The model contains eight kinetic constants, including one for catalyst deactivation, taking into account LPG (combined C{sub 3}-C{sub 4}), dry gas (C{sub 2} and lighter) and coke yields separately from other lumps (unconverted gas oil and gasoline). Apparent activation energies were determined from experiments obtained in a microactivity reactor (MAT) at temperatures: 480C, 500C and 520C; for a catalyst-to-oil ratio of 5 using vacuum gas oil and equilibrium catalyst, both recovered from an industrial FCC unit. Product yields predicted by this model show good agreement with experimental data
Pre-reheating magnetogenesis in the kinetic coupling model
Fujita, Tomohiro; Namba, Ryo
2016-08-01
Recent blazar observations provide growing evidence for the presence of magnetic fields in the extragalactic regions. While natural speculation is to associate the production with inflationary physics, it is known that magnetogenesis solely from inflation is quite challenging. We therefore study a model in which a noninflaton field χ coupled to the electromagnetic field through its kinetic term, -I2(χ )F2/4 , continues to move after inflation until the completion of reheating. This leads to a postinflationary amplification of the electromagnetic field. We compute all the relevant contributions to the curvature perturbation, including gravitational interactions, and impose the constraints from the CMB scalar fluctuations on the strength of magnetic fields. We, for the first time, explicitly verify both the backreaction and CMB constraints in a simple yet successful magnetogenesis scenario without invoking a dedicated low-scale inflationary model in the weak-coupling regime of the kinetic coupling model.
Modelling of an ASR countercurrent pyrolysis reactor with nonlinear kinetics
Energy Technology Data Exchange (ETDEWEB)
Chiarioni, A.; Reverberi, A.P.; Dovi, V.G. [Universita degli Studi di Genova (Italy). Dipartimento di Ingegneria Chimica e di Processo ' G.B. Bonino' ; El-Shaarawi, A.H. [National Water Research Institute, Burlington, Ont. (Canada)
2003-10-01
The main objective of this work is focused on the modelling of a steady-state reactor where an automotive shredder residue (ASR) is subject to pyrolysis. The gas and solid temperature inside the reactor and the relevant density profiles of both phases are simulated for fixed values of the geometry of the apparatus and a lumped kinetic model is adopted to take into account the high heterogeneity of the ASR material. The key elements for the simulation are the inlet solid temperature and the outlet gas temperature. The problem is modelled by a system of first-order boundary-value ordinary differential equations and it is solved by means of a relaxation technique owing to the nonlinearities contained in the chemical kinetic expression. (author)
Reproducing Phenomenology of Peroxidation Kinetics via Model Optimization
Ruslanov, Anatole D.; Bashylau, Anton V.
2010-06-01
We studied mathematical modeling of lipid peroxidation using a biochemical model system of iron (II)-ascorbate-dependent lipid peroxidation of rat hepatocyte mitochondrial fractions. We found that antioxidants extracted from plants demonstrate a high intensity of peroxidation inhibition. We simplified the system of differential equations that describes the kinetics of the mathematical model to a first order equation, which can be solved analytically. Moreover, we endeavor to algorithmically and heuristically recreate the processes and construct an environment that closely resembles the corresponding natural system. Our results demonstrate that it is possible to theoretically predict both the kinetics of oxidation and the intensity of inhibition without resorting to analytical and biochemical research, which is important for cost-effective discovery and development of medical agents with antioxidant action from the medicinal plants.
Kinetic modeling of the Townsend breakdown in argon
Energy Technology Data Exchange (ETDEWEB)
Macheret, S. O.; Shneider, M. N. [Department of Mechanical and Aerospace Engineering, Princeton University, D-414 Engineering Quadrangle, Princeton, New Jersey 08544 (United States)
2013-10-15
Kinetic modeling of the Townsend breakdown in argon was performed in the “forward-back” approximation. The kinetic model was found to adequately describe the left branch of the Paschen curve, and the important role of ionization by fast ions and atoms near the cathode, as well as the increase in secondary emission coefficient in strong electric fields described in the literature, was confirmed. The modeling also showed that the electron energy distribution function develops a beam of high-energy electrons and that the runaway effect, i.e., the monotonic increase of the mean electron energy with the distance from the cathode, occurs at the left branch of the Paschen curve.
Energy Technology Data Exchange (ETDEWEB)
Handy, B.J.; Greene, J.C. [NNC Solutions Ltd, Warrington (United Kingdom)
2004-09-01
NNC limited provides an ion exchange resin technology facility, which includes a resin testing service. A range of ion exchange resin properties is measured and this includes ion exchange capacity, resin bead particle sizes and anion kinetic performance in terms of mass transfer coefficients. It has long been considered by the authors that the experimental data for resins taken from operating condensate polishing plant (CPP) could be used to predict the expected plant performance. This has now been realised with the development of a mathematical model which predicts CPP behaviour using appropriate experimentally derived parameters and plant design data. Modelling methods for the separate anion and cation components of a mixed bed were initially developed before the mixed bed as a whole was addressed. Initially, an analytical approach was adopted, which proved successful for simple cases. For more complex examples a numerical approach was developed and found to be more suitable. The paper describes the development of anion and cation bed models, and a mixed bed model. In the latter model, the anion and cation components modelled earlier are combined, and used to model simultaneously typical concentrations of ammonia, sodium, chloride and sulphate. Examples of operation are given, and observations and points of interest are discussed with respect to the calculated concentration profiles. The experimental behaviour of a number of resin samples taken from operating plant was examined in a purpose-built ultrapure water recirculation loop equipped with a range of analytical instruments. This has permitted the observed experimental results to be compared with model predictions. The next stage of the model development is to identify plants suitable for testing the model against real plant performance and the authors are now seeking to identify plant managers interested in collaborating in this venture. (orig.)
New hybrid model of proton exchange membrane fuel cell
Institute of Scientific and Technical Information of China (English)
WANG Rui-min; CAO Guang-yi; ZHU Xin-jian
2007-01-01
Model and simulation are good tools for design optimization of fuel cell systems. This paper proposes a new hybrid model of proton exchange membrane fuel cell (PEMFC). The hybrid model includes physical component and black-box component. The physical component represents the well-known part of PEMFC, while artificial neural network (ANN) component estimates the poorly known part of PEMFC. The ANN model can compensate the performance of the physical model. This hybrid model is implemented on Matlab/Simulink software. The hybrid model shows better accuracy than that of the physical model and ANN model. Simulation results suggest that the hybrid model can be used as a suitable and accurate model for PEMFC.
Schokker, E.P.
1997-01-01
The kinetics of heat inactivation of the extracellular proteinase from Pseudomonas fluorescens 22F was studied. It was established, by making use of kinetic modelling, that heat inactivation in the temperature range 35 - 70 °C was most likely caused by intermolecular autoproteolysis, where unfolded
Ordering kinetics in model systems with inhibited interfacial adsorption
DEFF Research Database (Denmark)
Willart, J.-F.; Mouritsen, Ole G.; Naudts, J.
1992-01-01
The ordering kinetics in two-dimensional Ising-like spin moels with inhibited interfacial adsorption are studied by computer-simulation calculations. The inhibited interfacial adsorption is modeled by a particular interfacial adsorption condition on the structure of the domain wall between...... neighboring domains. This condition can be either hard, as modeled by a singularity in the domain-boundary potential, or soft, as modeled by a version of the Blume-Capel model. The results show that the effect of the steric hindrance, be it hard or soft, is only manifested in the amplitude, A...
An autocatalytic kinetic model for describing microbial growth during fermentation.
Ibarz, Albert; Augusto, Pedro E D
2015-01-01
The mathematical modelling of the behaviour of microbial growth is widely desired in order to control, predict and design food and bioproduct processing, stability and safety. This work develops and proposes a new semi-empirical mathematical model, based on an autocatalytic kinetic, to describe the microbial growth through its biomass concentration. The proposed model was successfully validated using 15 microbial growth patterns, covering the three most important types of microorganisms in food and biotechnological processing (bacteria, yeasts and moulds). Its main advantages and limitations are discussed, as well as the interpretation of its parameters. It is shown that the new model can be used to describe the behaviour of microbial growth.
TESTING MONETARY EXCHANGE RATE MODELS WITH PANEL COINTEGRATION TESTS
Directory of Open Access Journals (Sweden)
Szabo Andrea
2015-07-01
Full Text Available The monetary exchange rate models explain the long run behaviour of the nominal exchange rate. Their central assertion is that there is a long run equilibrium relationship between the nominal exchange rate and monetary macro-fundamentals. Although these models are essential tools of international macroeconomics, their empirical validity is ambiguous. Previously, time series testing was prevalent in the literature, but it did not bring convincing results. The power of the unit root and the cointegration tests are too low to reject the null hypothesis of no cointegration between the variables. This power can be enhanced by arranging our data in a panel data set, which allows us to analyse several time series simultaneously and enables us to increase the number of observations. We conducted a weak empirical test of the monetary exchange rate models by testing the existence of cointegration between the variables in three panels. We investigated 6, 10 and 15 OECD countries during the following periods: 1976Q1-2011Q4, 1985Q1-2011Q4 and 1996Q1-2011Q4. We tested the reduced form of the monetary exchange rate models in three specifications; we have two restricted models and an unrestricted model. Since cointegration can only be interpreted among non-stationary processes, we investigate the order of the integration of our variables with IPS, Fisher-ADF, Fisher-PP panel unit root tests and the Hadri panel stationary test. All the variables can be unit root processes; therefore we analyze the cointegration with the Pedroni and Kao panel cointegration test. The restricted models performed better than the unrestricted one and we obtained the best results with the 1985Q1-2011Q4 panel. The Kao test rejects the null hypotheses – there is no cointegration between the variables – in all the specifications and all the panels, but the Pedroni test does not show such a positive picture. Hence we found only moderate support for the monetary exchange rate models.
Kinetic bottlenecks to chemical exchange rates for deep-sea animals – Part 1: Oxygen
Directory of Open Access Journals (Sweden)
E. T. Peltzer
2012-10-01
Full Text Available Ocean warming will reduce dissolved oxygen concentrations which can pose challenges to marine life. Oxygen limits are traditionally reported simply as a static concentration thresholds with no temperature, pressure or flow rate dependency. Here we treat the oceanic oxygen supply potential for heterotrophic consumption as a dynamic molecular exchange problem analogous to familiar gas exchange processes at the sea surface. A combination of the purely physico-chemical oceanic properties temperature, hydrostatic pressure, and oxygen concentration defines the ability of the ocean to supply oxygen to any given animal. This general oceanic oxygen supply potential is modulated by animal specific properties such as the diffusive boundary layer thickness to define and limit maximal oxygen supply rates. Here we combine all these properties into formal, mechanistic equations defining novel oceanic properties that subsume various relevant classical oceanographic parameters to better visualize, map, comprehend, and predict the impact of ocean deoxygenation on aerobic life. By explicitly including temperature and hydrostatic pressure into our quantities, various ocean regions ranging from the cold deep-sea to warm, coastal seas can be compared. We define purely physico-chemical quantities to describe the oceanic oxygen supply potential, but also quantities that contain organism-specific properties which in a most generalized way describe general concepts and dependencies. We apply these novel quantities to example oceanic profiles around the world and find that temperature and pressure dependencies of diffusion and partial pressure create zones of greatest physical constriction on oxygen supply typically at around 1000 m depth, which coincides with oxygen concentration minimum zones. In these zones, which comprise the bulk of the world ocean, ocean warming and deoxygenation have a clear negative effect for aerobic life. In some shallow and warm waters the
Modelling on corrosion inhibitor kinetics in carbon steel pipe used in oil industry
Hasmi, A. N.; Nuraini, N.; Wahyuningrum, D.; Sumarti, N.; Bunjali, B.
2014-02-01
A model to explain the kinetics of corrosion inhibitor is proposed here. The model is based on Transition State Theory. Our model has many similarities with Michelis-Menten Kinetics. The kinetics difference between uninhibited corrosion and inhibited corrosion is presented. Our model showed the inhibitor could suppress the corrosion rate.
Konev, D. V.; Fertikov, V. V.; Kravchenko, T. A.; Kalinichev, A. I.
2008-08-01
The inverse kinetic problem of reducing sorption of molecular oxygen by a copper-containing electron-ion exchanger was formulated and solved taking into account the influence of the size of ultradisperse metal particles on the total rate of the process. These results were used to determine the inside diffusion coefficient of oxygen and rate constants for its interaction with disperse copper from the experimental kinetic curves. The diffusion coefficient obtained was compared with the result of an independent experiment. The kinetic parameters found were used to perform a theoretical analysis of the contributions of various factors influencing the rate of the process under consideration. The reason for the experimentally observed acceleration of the reducing sorption of oxygen by a high-dispersity electron-ion exchanger sample was shown to be an increase in the surface area of metal because of a decrease in the size of its particles and a comparatively high copper content in the surface layer of grains.
Stepwise kinetic equilibrium models of quantitative polymerase chain reaction
Directory of Open Access Journals (Sweden)
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
Kinetic models of gene expression including non-coding RNAs
Zhdanov, Vladimir P.
2011-03-01
In cells, genes are transcribed into mRNAs, and the latter are translated into proteins. Due to the feedbacks between these processes, the kinetics of gene expression may be complex even in the simplest genetic networks. The corresponding models have already been reviewed in the literature. A new avenue in this field is related to the recognition that the conventional scenario of gene expression is fully applicable only to prokaryotes whose genomes consist of tightly packed protein-coding sequences. In eukaryotic cells, in contrast, such sequences are relatively rare, and the rest of the genome includes numerous transcript units representing non-coding RNAs (ncRNAs). During the past decade, it has become clear that such RNAs play a crucial role in gene expression and accordingly influence a multitude of cellular processes both in the normal state and during diseases. The numerous biological functions of ncRNAs are based primarily on their abilities to silence genes via pairing with a target mRNA and subsequently preventing its translation or facilitating degradation of the mRNA-ncRNA complex. Many other abilities of ncRNAs have been discovered as well. Our review is focused on the available kinetic models describing the mRNA, ncRNA and protein interplay. In particular, we systematically present the simplest models without kinetic feedbacks, models containing feedbacks and predicting bistability and oscillations in simple genetic networks, and models describing the effect of ncRNAs on complex genetic networks. Mathematically, the presentation is based primarily on temporal mean-field kinetic equations. The stochastic and spatio-temporal effects are also briefly discussed.
Modeling organic micro pollutant degradation kinetics during sewage sludge composting.
Sadef, Yumna; Poulsen, Tjalfe Gorm; Bester, Kai
2014-11-01
Degradation of 13 different organic micro-pollutants in sewage sludge during aerobic composting at 5 different temperatures over a 52 day period was investigated. Adequacy of two kinetic models: a single first order, and a dual first order expression (using an early (first 7 days) and a late-time (last 45 days) degradation coefficient), for describing micro-pollutant degradation, and kinetic constant dependency on composting temperature were evaluated. The results showed that both models provide relatively good descriptions of the degradation process, with the dual first order model being most accurate. The single first order degradation coefficient was 0.025 d(-1) on average across all compounds and temperatures. At early times, degradation was about three times faster than at later times. Average values of the early and late time degradation coefficients for the dual first order model were 0.066 d(-1) and 0.022 d(-1), respectively. On average 30% of the initial micro-pollutant mass present in the compost was degraded rapidly during the early stages of the composting process. Single first order and late time dual first order kinetic constants were strongly dependent on composting temperature with maximum values at temperatures of 35-65°C. In contrast the early time degradation coefficients were relatively independent of composting temperature.
Categorization of exchange fluxes explains the four relational models
Favre, Maroussia
2013-01-01
The theory of Relational Models (RMs) posits four elementary models of relationships governing all human interactions, singly or in combination: Communal Sharing, Authority Ranking, Equality Matching, and Market Pricing. By considering two agents that can act in one out of three ways towards one another: give resource A, give resource B, or give nothing, we find four discrete categories of exchange fluxes that map unequivocally to the four RMs. This categorization shows that the RMs form an exhaustive set of all possible elementary exchanges. Hence, the fluxes categorization answers why there are just four RMs and explains their discreteness. By considering the costs associated with extracting resources, storing them and implementing each flux category, we are able to propose conditions under which each RM should evolve. We also logically deduce the singular nature of the Authority Ranking model. Our propositions are compatible with anthropological, ethnological and historical observations and can be tested a...
ECONOMETRIC APPROACH TO DIFFERENCE EQUATIONS MODELING OF EXCHANGE RATES CHANGES
Directory of Open Access Journals (Sweden)
Josip Arnerić
2010-12-01
Full Text Available Time series models that are commonly used in econometric modeling are autoregressive stochastic linear models (AR and models of moving averages (MA. Mentioned models by their structure are actually stochastic difference equations. Therefore, the objective of this paper is to estimate difference equations containing stochastic (random component. Estimated models of time series will be used to forecast observed data in the future. Namely, solutions of difference equations are closely related to conditions of stationary time series models. Based on the fact that volatility is time varying in high frequency data and that periods of high volatility tend to cluster, the most successful and popular models in modeling time varying volatility are GARCH type models and their variants. However, GARCH models will not be analyzed because the purpose of this research is to predict the value of the exchange rate in the levels within conditional mean equation and to determine whether the observed variable has a stable or explosive time path. Based on the estimated difference equation it will be examined whether Croatia is implementing a stable policy of exchange rates.
Wealth concentration in a biased asset-exchange model
Devitt-Lee, Adrian
Economic inequality is a significant and dynamic problem throughout the world. Asset-exchange models have been used to model macroeconomic systems based on microeconomic assumptions about how agents exchange wealth in an economy. Previous studies of a certain asset-exchange model, called the Yard-Sale model, have found that trade alone promotes the condensation of wealth to a single individual in an economy [Chakraborti, 2002, Moukarzel et al., 2007, Boghosian, 2014b]. A later study found that a slight modification of the Yard-Sale model seems to allow for the coexistence of both "condensed wealth" and a normal population in an economy [Boghosian et al., 2016a]. This work formalizes the notion of wealth condensation in a macroeconomic system. This can be done by extending Schwartz's theory of distributions to allow for objects which increase at most linearly at infinity, or by considering condensed wealth to be a nonstandard phenomenon, and describing it as such. Numerical simulations indicate that this continuous description of wealth concentration is a valid approximation of wealth concentration in discrete systems with as few as 256 agents. We then study the properties of the steady-state distribution of wealth in such a system, and mention the fit of our system to the distribution of wealth in the United States in 2016.
Closed Loop Brain Model of Neocortical Information Based Exchange
Directory of Open Access Journals (Sweden)
James eKozloski
2016-01-01
Full Text Available Here we describe an information based exchange' model of brain function that ascribes to neocortex, basal ganglia, and thalamus distinct network functions. The model allows us to analyze whole brain system set point measures, such as the rate and heterogeneity of transitions in striatum and neocortex, in the context of neuromodulation and other perturbations. Our closed-loop model is grounded in neuroanatomical observations, proposing a novel Grand Loop through neocortex, and invokes different forms of plasticity at specific tissue interfaces and their principle cell synapses to achieve these transitions. By implementing a system for maximum information based exchange of action potentials between modeled neocortical areas, we observe changes to these measures in simulation. We hypothesize that similar dynamic set points and modulations exist in the brain's resting state activity, and that different modifications to information based exchange may shift the risk profile of different component tissues, resulting in different neurodegenerative diseases. This model is targeted for further development using IBM's Neural Tissue Simulator, which allows scalable elaboration of networks, tissues, and their neural and synaptic components towards ever greater complexity and biological realism.
A robust methodology for kinetic model parameter estimation for biocatalytic reactions
DEFF Research Database (Denmark)
Al-Haque, Naweed; Andrade Santacoloma, Paloma de Gracia; Lima Afonso Neto, Watson;
2012-01-01
Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several...
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
A kinetic model for the first stage of pygas upgrading
Directory of Open Access Journals (Sweden)
J. L. de Medeiros
2007-03-01
Full Text Available Pyrolysis gasoline - PYGAS - is an intermediate boiling product of naphtha steam cracking with a high octane number and high aromatic/unsaturated contents. Due to stabilization concerns, PYGAS must be hydrotreated in two stages. The first stage uses a mild trickle-bed conversion for removing extremely reactive species (styrene, dienes and olefins prior to the more severe second stage where sulfured and remaining olefins are hydrogenated in gas phase. This work addresses the reaction network and two-phase kinetic model for the first stage of PYGAS upgrading. Nonlinear estimation was used for model tuning with kinetic data obtained in bench-scale trickle-bed hydrogenation with a commercial Pd/Al2O3 catalyst. On-line sampling experiments were designed to study the influence of variables - temperature and spatial velocity - on the conversion of styrene, dienes and olefins.
Stochastic kinetic models: Dynamic independence, modularity and graphs
Bowsher, Clive G
2010-01-01
The dynamic properties and independence structure of stochastic kinetic models (SKMs) are analyzed. An SKM is a highly multivariate jump process used to model chemical reaction networks, particularly those in biochemical and cellular systems. We identify SKM subprocesses with the corresponding counting processes and propose a directed, cyclic graph (the kinetic independence graph or KIG) that encodes the local independence structure of their conditional intensities. Given a partition $[A,D,B]$ of the vertices, the graphical separation $A\\perp B|D$ in the undirected KIG has an intuitive chemical interpretation and implies that $A$ is locally independent of $B$ given $A\\cup D$. It is proved that this separation also results in global independence of the internal histories of $A$ and $B$ conditional on a history of the jumps in $D$ which, under conditions we derive, corresponds to the internal history of $D$. The results enable mathematical definition of a modularization of an SKM using its implied dynamics. Gra...
Kinetics approach to modeling of polymer additive degradation in lubricants
Institute of Scientific and Technical Information of China (English)
llyaI.KUDISH; RubenG.AIRAPETYAN; Michael; J.; COVITCH
2001-01-01
A kinetics problem for a degrading polymer additive dissolved in a base stock is studied.The polymer degradation may be caused by the combination of such lubricant flow parameters aspressure, elongational strain rate, and temperature as well as lubricant viscosity and the polymercharacteristics (dissociation energy, bead radius, bond length, etc.). A fundamental approach tothe problem of modeling mechanically induced polymer degradation is proposed. The polymerdegradation is modeled on the basis of a kinetic equation for the density of the statistical distribu-tion of polymer molecules as a function of their molecular weight. The integrodifferential kineticequation for polymer degradation is solved numerically. The effects of pressure, elongational strainrate, temperature, and lubricant viscosity on the process of lubricant degradation are considered.The increase of pressure promotes fast degradation while the increase of temperature delaysdegradation. A comparison of a numerically calculated molecular weight distribution with an ex-perimental one obtained in bench tests showed that they are in excellent agreement with eachother.
Kinetic model of metabolic network for xiamenmycin biosynthetic optimisation.
Xu, Min-juan; Chen, Yong-cong; Xu, Jun; Ao, Ping; Zhu, Xiao-mei
2016-02-01
Xiamenmycins, a series of prenylated benzopyran compounds with anti-fibrotic bioactivities, were isolated from a mangrove-derived Streptomyces xiamenensis. To fulfil the requirements of pharmaceutical investigations, a high production of xiamenmycin is needed. In this study, the authors present a kinetic metabolic model to evaluate fluxes in an engineered Streptomyces lividans with xiamenmycin-oriented genetic modification based on generic enzymatic rate equations and stability constraints. Lyapunov function was used for a viability optimisation. From their kinetic model, the flux distributions for the engineered S. lividans fed on glucose and glycerol as carbon sources were calculated. They found that if the bacterium can utilise glucose simultaneously with glycerol, xiamenmycin production can be enhanced by 40% theoretically, while maintaining the same growth rate. Glycerol may increase the flux for phosphoenolpyruvate synthesis without interfering citric acid cycle. They therefore believe this study demonstrates a possible new direction for bioengineering of S. lividans.
Kinetic modeling and exploratory numerical simulation of chloroplastic starch degradation
Directory of Open Access Journals (Sweden)
Nag Ambarish
2011-06-01
Full Text Available Abstract Background Higher plants and algae are able to fix atmospheric carbon dioxide through photosynthesis and store this fixed carbon in large quantities as starch, which can be hydrolyzed into sugars serving as feedstock for fermentation to biofuels and precursors. Rational engineering of carbon flow in plant cells requires a greater understanding of how starch breakdown fluxes respond to variations in enzyme concentrations, kinetic parameters, and metabolite concentrations. We have therefore developed and simulated a detailed kinetic ordinary differential equation model of the degradation pathways for starch synthesized in plants and green algae, which to our knowledge is the most complete such model reported to date. Results Simulation with 9 internal metabolites and 8 external metabolites, the concentrations of the latter fixed at reasonable biochemical values, leads to a single reference solution showing β-amylase activity to be the rate-limiting step in carbon flow from starch degradation. Additionally, the response coefficients for stromal glucose to the glucose transporter kcat and KM are substantial, whereas those for cytosolic glucose are not, consistent with a kinetic bottleneck due to transport. Response coefficient norms show stromal maltopentaose and cytosolic glucosylated arabinogalactan to be the most and least globally sensitive metabolites, respectively, and β-amylase kcat and KM for starch to be the kinetic parameters with the largest aggregate effect on metabolite concentrations as a whole. The latter kinetic parameters, together with those for glucose transport, have the greatest effect on stromal glucose, which is a precursor for biofuel synthetic pathways. Exploration of the steady-state solution space with respect to concentrations of 6 external metabolites and 8 dynamic metabolite concentrations show that stromal metabolism is strongly coupled to starch levels, and that transport between compartments serves to
Kinetic bottlenecks to chemical exchange rates for deep-sea animals II: Carbon dioxide
Hofmann, A. F.; Peltzer, E. T.; Brewer, P. G.
2012-11-01
Increased ocean acidification from fossil fuel CO2 invasion, from temperature-driven changes in respiration, and from possible leakage from sub-seabed geologic CO2 disposal has aroused concern over the impacts of elevated CO2 concentrations on marine life. Discussion of these impacts has so far focused only on changes in the oceanic bulk fluid properties (ΔpH, Δ[∑CO2] etc.) as the critical variable and with a major focus on carbonate shell dissolution. Here we describe the rate problem for animals that must export CO2 at about the same rate at which O2 is consumed. We analyze the basic properties controlling CO2 export within the diffusive boundary layer around marine animals in an ocean changing in temperature (T) and CO2 concentration in order to compare the challenges posed by O2 uptake under stress with the equivalent problem of CO2 expulsion. The problem is more complex than that for a non-reactive gas since, as with gas exchange of CO2 at the air-sea interface, the influence of the ensemble of reactions within the CO2-HCO3--CO32- acid-base system needs to be considered. These reactions significantly facilitate CO2 efflux compared to O2 intake at equal temperature, pressure and flow rate under typical oceanic concentrations.The effect of these reactions can be described by an enhancement factor. For organisms, this means mechanically increasing flow over their surface to thin the boundary layer as is required to alleviate O2 stress seems not necessary to facilitate CO2 efflux. Nevertheless the elevated pCO2 cost most likely is non-zero. Regionally as with O2 the combination of T, P, and pH/pCO2 creates a zone of maximum CO2 stress at around 1000 m depth. But the net result is that, for the problem of gas exchange with the bulk ocean, the combination of an increasing T combined with declining O2 poses a greater challenge to marine life than does increasing CO2. The relationships developed here allow a more accurate prediction of the impacts on marine life
Controllability in hybrid kinetic equations modeling nonequilibrium multicellular systems.
Bianca, Carlo
2013-01-01
This paper is concerned with the derivation of hybrid kinetic partial integrodifferential equations that can be proposed for the mathematical modeling of multicellular systems subjected to external force fields and characterized by nonconservative interactions. In order to prevent an uncontrolled time evolution of the moments of the solution, a control operator is introduced which is based on the Gaussian thermostat. Specifically, the analysis shows that the moments are solution of a Riccati-type differential equation.
Ebrahimi, Shelir; Roberts, Deborah J
2016-01-01
Nitrate contamination is one of the largest issues facing communities worldwide. One of the most common methods for nitrate removal from water is ion exchange using nitrate selective resin. Although these resins have a great capacity for nitrate removal, they are considered non regenerable. The sustainability of nitrate-contaminated water treatment processes can be achieved by regenerating the exhausted resin several times rather than replacing and incineration of exhausted resin. The use of multi-cycle exhaustion/bioregeneration of resin enclosed in a membrane has been shown to be an effective and innovative regeneration method. In this research, the mechanisms for bioregeneration of resin were studied and a mathematical model which incorporated physical desorption process with biological removal kinetics was developed. Regardless of the salt concentration of the solution, this specific resin is a pore-diffusion controlled process (XδD ¯CDr0(5+2α)3) shows that the bioregeneration process is controlled by reaction kinetics and is governed by biological removal of nitrate. The model was validated by comparison to experimental data; the average of R-squared values for cycle 1 to 5 of regeneration was 0.94 ± 0.06 which shows that the developed model predicted the experimental results very well. The model sensitivity for different parameters was evaluated and a model bioreactor design for bioregeneration of highly selective resins was also presented.
A model for recovery kinetics of aluminum after large strain
DEFF Research Database (Denmark)
Yu, Tianbo; Hansen, Niels
2012-01-01
A model is suggested to analyze recovery kinetics of heavily deformed aluminum. The model is based on the hardness of isothermal annealed samples before recrystallization takes place, and it can be extrapolated to longer annealing times to factor out the recrystallization component of the hardness...... for conditions where recovery and recrystallization overlap. The model is applied to the isothermal recovery at temperatures between 140 and 220°C of commercial purity aluminum deformed to true strain 5.5. EBSD measurements have been carried out to detect the onset of discontinuous recrystallization. Furthermore...
Desorption isotherms and mathematical modeling of thin layer drying kinetics of tomato
Belghith, Amira; Azzouz, Soufien; ElCafsi, Afif
2016-03-01
In recent years, there is an increased demand on the international market of dried fruits and vegetables with significant added value. Due to its important production, consumption and nutrient intake, drying of tomato has become a subject of extended and varied research works. The present work is focused on the drying behavior of thin-layer tomato and its mathematical modeling in order to optimize the drying processes. The moisture desorption isotherms of raw tomato were determined at four temperature levels namely 45, 50, 60 and 65 °C using the static gravimetric method. The experimental data obtained were modeled by five equations and the (GAB) model was found to be the best-describing these isotherms. The drying kinetics were experimentally investigated at 45, 55 and 65 °C and performed at air velocities of 0.5 and 2 m/s. In order to investigate the effect of the exchange surface on drying time, samples were dried into two different shapes: tomato halves and tomato quarters. The impact of various drying parameters was also studied (temperature, air velocity and air humidity). The drying curves showed only the preheating period and the falling drying rate period. In this study, attention was paid to the modeling of experimental thin-layer drying kinetics. The experimental results were fitted with four different models.
Schmoeger, Elisabeth; Wellhoefer, Martin; Dürauer, Astrid; Jungbauer, Alois; Hahn, Rainer
2010-09-17
Matrix-assisted refolding is an excellent technique for performing refolding of recombinant proteins at high concentration because aggregation during refolding is partially suppressed. The autoprotease N(pro) and its engineered mutant EDDIE can be efficiently refolded on cation-exchangers. In the current work, denatured fusion proteins were loaded at different column saturations (5 and 50 mg mL(-1) gel), and refolding and self-cleavage were initiated during elution. The contact time of the protein with the matrix significantly influenced the refolding rate and yield. On POROS 50 HS, the refolding rate was comparable to a batch refolding process, but yield was substantially higher; at a protein concentration of 1.55 mg mL(-1), an almost complete conversion was observed. With Capto S, the rate of self-cleavage increased by a factor of 20 while yield was slightly reduced. Processing the autoprotease fusion protein on Capto S at a high protein loading of 50 mg mL(-1) gel and short contact time (0.5h) yielded the highest productivity.
Computation Molecular Kinetics Model of HZE Induced Cell Cycle Arrest
Cucinotta, Francis A.; Ren, Lei
2004-01-01
Cell culture models play an important role in understanding the biological effectiveness of space radiation. High energy and charge (HZE) ions produce prolonged cell cycle arrests at the G1/S and G2/M transition points in the cell cycle. A detailed description of these phenomena is needed to integrate knowledge of the expression of DNA damage in surviving cells, including the determination of relative effectiveness factors between different types of radiation that produce differential types of DNA damage and arrest durations. We have developed a hierarchical kinetics model that tracks the distribution of cells in various cell phase compartments (early G1, late G1, S, G2, and M), however with transition rates that are controlled by rate-limiting steps in the kinetics of cyclin-cdk's interactions with their families of transcription factors and inhibitor molecules. The coupling of damaged DNA molecules to the downstream cyclin-cdk inhibitors is achieved through a description of the DNA-PK and ATM signaling pathways. For HZE irradiations we describe preliminary results, which introduce simulation of the stochastic nature of the number of direct particle traversals per cell in the modulation of cyclin-cdk and cell cycle population kinetics. Comparison of the model to data for fibroblast cells irradiated photons or HZE ions are described.
Kinetics and specificity of nickel hypersensitivity in the murine model.
Siller, G M; Seymour, G J
1994-01-01
Nickel contact dermatitis appears to be almost exclusively a disease of females despite the increasing exposure of males to nickel. Successful murine models of nickel allergic contact dermatitis have been described. The purpose of this study is to investigate the kinetics and specificity of the response in this model and to examine if any differences exist between male and female. Mice were sensitised epicutaneously with nickel sulphate in aqueous solution of varying concentration, volume and duration of application. Following intradermal challenge, dose dependent response kinetics which approximated linearity were demonstrated upto the point of toxicity. Sensitised mice were challenged with Cobaltous chloride, Chromic chloride and Cupric sulphate and demonstrated no evidence of cross sensitivity to cobalt or chrome. Copper produced an irritant response making interpretation difficult. Earlier and stronger responses were observed in female mice, however these differences fell short of statistical significance. The results of the present study therefore establishes a reliable model for nickel hypersensitivity, that demonstrates both specificity and dose dependent kinetics without significant sex differences.
Kinetic model on coke oven gas with steam reforming
Institute of Scientific and Technical Information of China (English)
ZHANG Jia-yuan; ZHOU Jie-min; YAN Hong-jie
2008-01-01
The effects of factors such as the molar ratio of H2O to CH4 (n(H2O)/n(CH4)), methane conversion temperature and time on methane conversion rate were investigated to build kinetic model for reforming of coke-oven gas with steam. The results of experiments show that the optimal conditions for methane conversion are that the molar ratio of H2O to CH4 varies from 1.1 to 1.3and the conversion temperature varies from 1 223 to 1 273 K. The methane conversion rate is more than 95% when the molar ratio ofH2O to CH4 is 1.2, the conversion temperature is above 1 223 K and the conversion time is longer than 0.75 s. Kinetic model of methane conversion was proposed. All results demonstrate that the calculated values by the kinetic model accord with the experimental data well, and the error is less than 1.5%.
Simulation of DME synthesis from coal syngas by kinetics model
Energy Technology Data Exchange (ETDEWEB)
Shim, H.M.; Lee, S.J.; Yoo, Y.D.; Yun, Y.S.; Kim, H.T. [Ajou University, Suwon (Republic of Korea)
2009-05-15
DME (Dimethyl Ether) has emerged as a clean alternative fuel for diesel. In this study it is developed a simulation model through a kinetics model of the ASPEN plus simulator, performed to detect operating characteristics of DME direct synthesis. An overall DME synthesis process is referenced by experimental data of 3 ton/day (TPD) coal gasification pilot plant located at IAE in Korea. Supplying condition of DME synthesis model is equivalently set to 80 N/m{sup 3} of syngas which is derived from a coal gasification plant. In the simulation it is assumed that the overall DME synthesis process proceeds with steady state, vapor-solid reaction with DME catalyst. The physical properties of reactants are governed by Soave-Redlich-Kwong (SRK) EOS in this model. A reaction model of DME synthesis is considered that is applied with the LHHW (Langmuir-Hinshelwood Hougen Watson) equation as an adsorption-desorption model on the surface of the DME catalyst. After adjusting the kinetics of the DME synthesis reaction among reactants with experimental data, the kinetics of the governing reactions inner DME reactor are modified and coupled with the entire DME synthesis reaction. For validating simulation results of the DME synthesis model, the obtained simulation results are compared with experimental results: conversion ratio, DME yield and DME production rate. Then, a sensitivity analysis is performed by effects of operating variables such as pressure, temperature of the reactor, void fraction of catalyst and H{sub 2}/CO ratio of supplied syngas with modified model. According to simulation results, optimum operating conditions of DME reactor are obtained in the range of 265-275{sup o}C and 60 kg/cm{sup 2}. And DME production rate has a maximum value in the range of 1-1.5 of H{sub 2}/CO ratio in the syngas composition.
Performance analysis of a medical record exchanges model.
Huang, Ean-Wen; Liou, Der-Ming
2007-03-01
Electronic medical record exchange among hospitals can provide more information for physician diagnosis and reduce costs from duplicate examinations. In this paper, we proposed and implemented a medical record exchange model. According to our study, exchange interface servers (EISs) are designed for hospitals to manage the information communication through the intra and interhospital networks linked with a medical records database. An index service center can be given responsibility for managing the EIS and publishing the addresses and public keys. The prototype system has been implemented to generate, parse, and transfer the health level seven query messages. Moreover, the system can encrypt and decrypt a message using the public-key encryption algorithm. The queuing theory is applied to evaluate the performance of our proposed model. We estimated the service time for each queue of the CPU, database, and network, and measured the response time and possible bottlenecks of the model. The capacity of the model is estimated to process the medical records of about 4000 patients/h in the 1-MB network backbone environments, which comprises about the 4% of the total outpatients in Taiwan.
Kinetic Modeling of Sunflower Grain Filling and Fatty Acid Biosynthesis
Durruty, Ignacio; Aguirrezábal, Luis A. N.; Echarte, María M.
2016-01-01
Grain growth and oil biosynthesis are complex processes that involve various enzymes placed in different sub-cellular compartments of the grain. In order to understand the mechanisms controlling grain weight and composition, we need mathematical models capable of simulating the dynamic behavior of the main components of the grain during the grain filling stage. In this paper, we present a non-structured mechanistic kinetic model developed for sunflower grains. The model was first calibrated for sunflower hybrid ACA855. The calibrated model was able to predict the theoretical amount of carbohydrate equivalents allocated to the grain, grain growth and the dynamics of the oil and non-oil fraction, while considering maintenance requirements and leaf senescence. Incorporating into the model the serial-parallel nature of fatty acid biosynthesis permitted a good representation of the kinetics of palmitic, stearic, oleic, and linoleic acids production. A sensitivity analysis showed that the relative influence of input parameters changed along grain development. Grain growth was mostly affected by the specific growth parameter (μ′) while fatty acid composition strongly depended on their own maximum specific rate parameters. The model was successfully applied to two additional hybrids (MG2 and DK3820). The proposed model can be the first building block toward the development of a more sophisticated model, capable of predicting the effects of environmental conditions on grain weight and composition, in a comprehensive and quantitative way. PMID:27242809
Kinetic models for fermentative hydrogen production: A review
Energy Technology Data Exchange (ETDEWEB)
Wang, Jianlong; Wan, Wei [Laboratory of Environmental Technology, INET, Tsinghua University, Beijing 100084 (China)
2009-05-15
The kinetic models were developed and applied for fermentative hydrogen production. They were used to describe the progress of a batch fermentative hydrogen production process, to investigate the effects of substrate concentration, inhibitor concentration, temperatures, pH, and dilution rates on the process of fermentative hydrogen production, and to establish the relationship among the substrate degradation rate, the hydrogen-producing bacteria growth rate and the product formation rate. This review showed that the modified Gompertz model was widely used to describe the progress of a batch fermentative hydrogen production process, while the Monod model was widely used to describe the effects of substrate concentration on the rates of substrate degradation, hydrogen-producing bacteria growth and hydrogen production. Arrhenius model was used a lot to describe the effects of temperature on fermentative hydrogen production, while modified Han-Levenspiel model was used to describe the effects of inhibitor concentration on fermentative hydrogen production. The Andrew model was used to describe the effects of H{sup +} concentration on the specific hydrogen production rate, while the Luedeking-Piret model and its modified form were widely used to describe the relationship between the hydrogen-producing bacteria growth rate and the product formation rate. Finally, some suggestions for future work with these kinetic models were proposed. (author)
Montigny, Cédric; Dieudonné, Thibaud; Orlowski, Stéphane; Vázquez-Ibar, José Luis; Gauron, Carole; Georgin, Dominique; Lund, Sten; le Maire, Marc; Møller, Jesper V.; Champeil, Philippe
2017-01-01
Membrane proteins are largely dependent for their function on the phospholipids present in their immediate environment, and when they are solubilized by detergent for further study, residual phospholipids are critical, too. Here, brominated phosphatidylcholine, a phospholipid which behaves as an unsaturated phosphatidylcholine, was used to reveal the kinetics of phospholipid exchange or transfer from detergent mixed micelles to the environment of a detergent-solubilized membrane protein, the paradigmatic P-type ATPase SERCA1a, in which Trp residues can experience fluorescence quenching by bromine atoms present on phospholipid alkyl chains in their immediate environment. Using dodecylmaltoside as the detergent, exchange of (brominated) phospholipid was found to be much slower than exchange of detergent under the same conditions, and also much slower than membrane solubilization, the latter being evidenced by light scattering changes. The kinetics of this exchange was strongly dependent on temperature. It was also dependent on the total concentration of the mixed micelles, revealing the major role for such exchange of the collision of detergent micelles with the detergent-solubilized protein. Back-transfer of the brominated phospholipid from the solubilized protein to the detergent micelle was much faster if lipid-free DDM micelles instead of mixed micelles were added for triggering dissociation of brominated phosphatidylcholine from the solubilized protein, or in the additional presence of C12E8 detergent during exchange, also emphasizing the role of the chemical nature of the micelle/protein interface. This protocol using brominated lipids appears to be valuable for revealing the possibly slow kinetics of phospholipid transfer to or from detergent-solubilized membrane proteins. Independently, continuous recording of the activity of the protein can also be used in some cases to correlate changes in activity with the exchange of a specific phospholipid, as shown here
Vector Meson Electro-production in Pomeron Exchange Model
Institute of Scientific and Technical Information of China (English)
MA Wei-Xing; LIU Bao-Rong; ZHOU Li-Juan; TAN Zhen-Qiang; HE Xiao-Rong; GU Yun-Ting
2005-01-01
Based on Pomeron exchange model, elastic production of vector meson in electro-proton interaction is investigated with both linear and non-linear Pomeron trajectory. A numerical calculation for J/ψ production is performed. The effect of the energy scale so and photon virtuality Q2 on differential cross section are also predicted. Agood agreement with experimental data is obtained. Our conclusions are that the Pomeron exchange model is a successful description of J/ψ electro-production, the dependence of the differential cross sections on Q2 is negligible, the linear trajectory is a good approximation to non-linearity of the Pomeron trajectory, and the value of the energy scale parameter so is dependent on the momentum transfer, namely its effect is moderate at low momentum transfer but it causes no difference at high momentum transfer | t |≥ 1.25 GeV2.
Kinetic bottlenecks to chemical exchange rates for deep-sea animals II: Carbon dioxide
Directory of Open Access Journals (Sweden)
A. F. Hofmann
2012-11-01
Full Text Available Increased ocean acidification from fossil fuel CO_{2} invasion, from temperature-driven changes in respiration, and from possible leakage from sub-seabed geologic CO_{2} disposal has aroused concern over the impacts of elevated CO_{2} concentrations on marine life. Discussion of these impacts has so far focused only on changes in the oceanic bulk fluid properties (ΔpH, Δ[∑CO_{2}] etc. as the critical variable and with a major focus on carbonate shell dissolution. Here we describe the rate problem for animals that must export CO_{2} at about the same rate at which O_{2} is consumed. We analyze the basic properties controlling CO_{2} export within the diffusive boundary layer around marine animals in an ocean changing in temperature (T and CO_{2} concentration in order to compare the challenges posed by O_{2} uptake under stress with the equivalent problem of CO_{2} expulsion. The problem is more complex than that for a non-reactive gas since, as with gas exchange of CO_{2} at the air-sea interface, the influence of the ensemble of reactions within the CO_{2}-HCO_{3}^{–}-CO_{3}^{2–} acid-base system needs to be considered. These reactions significantly facilitate CO_{2} efflux compared to O_{2} intake at equal temperature, pressure and flow rate under typical oceanic concentrations.The effect of these reactions can be described by an enhancement factor. For organisms, this means mechanically increasing flow over their surface to thin the boundary layer as is required to alleviate O_{2} stress seems not necessary to facilitate CO_{2} efflux. Nevertheless the elevated pCO_{2} cost most likely is non-zero. Regionally as with O_{2} the combination of T, P, and pH/pCO_{2} creates a zone of maximum CO_{2} stress at around
Weiss, Michael; Krejcie, Tom C; Avram, Michael J
2007-04-01
A pharmacokinetic model was developed to estimate physiologically meaningful parameters of distribution kinetics from plasma concentration-time data. The model is based on simultaneously measured disposition curves of drug and vascular marker. Employing residence time distribution theory, a recirculatory model with two subsystems, the pulmonary and systemic circulation, was constructed. In addition to intravascular mixing, the axially distributed model of the systemic circulation accounts for transcapillary transport of solutes, quantified by permeability-surface area product (PS) and diffusional equilibration time. Parameters of ICG, inulin, and antipyrine were estimated from disposition data obtained in awake dogs under control conditions and during an isoproterenol infusion or moderate hypovolemia. Results suggest that distribution kinetics is (1) governed by extravascular diffusion and (2) its dependency on cardiac output decreases with increasing diffusional resistance. Hemorrhage decreased the effective PS of inulin. In conclusion, this novel mechanistic model effectively described both the permeability-limited distribution of inulin into interstitial fluid and the flow-limited distribution of antipyrine into total body water and might be useful for other drugs.
Kinetic models for nucleocytoplasmic transport of messenger RNA.
Schröder, H C; Müller, W E; Agutter, P S
1995-05-21
Much is known about the mechanism by which mRNAs cross the nuclear envelope (the translocation stage of nucleocytoplasmic transport), but far less is known about the preceding (intranuclear migration/release) and succeeding (cytoplasmic binding) stages. Therefore, existing information suffices for articulating detailed kinetic models of translocation, but not models for the overall mRNA transport process. In this paper, we show that simple kinetic models of translocation can (i) accommodate data about nucleocytoplasmic distributions of endogenous transcripts; (ii) predict the overall effects on these distributions of effectors such as insulin and epidermal growth factor; (iii) throw some light on the mechanism(s) of action of the HIV-1 protein Rev and produce experimentally testable predictions about this mechanism; and (iv) account for the action of influenza virus NS1 protein. However, the simplest forms of translocation models apparently fail to account for some properties of viral regulators such as HIV Rev and adenovirus E1B-E4 complex. To elucidate these topics, less narrowly focused models of mRNA transport are required, describing intranuclear binding/release as well as translocation. On the basis of our examination of translocation models, we suggest some criteria that the requisite broadly based models must satisfy.
Generalized Bogoliubov Polariton Model: An Application to Stock Exchange Market
Thuy Anh, Chu; Anh, Truong Thi Ngoc; Lan, Nguyen Tri; Viet, Nguyen Ai
2016-06-01
A generalized Bogoliubov method for investigation non-simple and complex systems was developed. We take two branch polariton Hamiltonian model in second quantization representation and replace the energies of quasi-particles by two distribution functions of research objects. Application to stock exchange market was taken as an example, where the changing the form of return distribution functions from Boltzmann-like to Gaussian-like was studied.
Exchange bias of patterned systems: Model and numerical simulation
Energy Technology Data Exchange (ETDEWEB)
Garcia, Griselda [Facultad de Fisica, P. Universidad Catolica de Chile, Casilla 306, Santiago 7820436 (Chile); Centro para el Desarrollo de la Nanociencia y la Nanotecnologia, CEDENNA, Avda. Ecuador 3493, Santiago (Chile); Kiwi, Miguel, E-mail: mkiwi@puc.c [Facultad de Fisica, P. Universidad Catolica de Chile, Casilla 306, Santiago 7820436 (Chile); Centro para el Desarrollo de la Nanociencia y la Nanotecnologia, CEDENNA, Avda. Ecuador 3493, Santiago (Chile); Mejia-Lopez, Jose; Ramirez, Ricardo [Facultad de Fisica, P. Universidad Catolica de Chile, Casilla 306, Santiago 7820436 (Chile); Centro para el Desarrollo de la Nanociencia y la Nanotecnologia, CEDENNA, Avda. Ecuador 3493, Santiago (Chile)
2010-11-15
The magnitude of the exchange bias field of patterned systems exhibits a notable increase in relation to the usual bilayer systems, where a continuous ferromagnetic film is deposited on an antiferromagnet insulator. Here we develop a model, and implement a Monte Carlo calculation, to interpret the experimental observations which is consistent with experimental results, on the basis of assuming a small fraction of spins pinned ferromagnetically in the antiferromagnetic interface layer.
Study on kinetic model of microwave thermocatalytic treatment of biomass tar model compound.
Anis, Samsudin; Zainal, Z A
2014-01-01
Kinetic model parameters for toluene conversion under microwave thermocatalytic treatment were evaluated. The kinetic rate constants were determined using integral method based on experimental data and coupled with Arrhenius equation for obtaining the activation energies and pre-exponential factors. The model provides a good agreement with the experimental data. The kinetic model was also validated with standard error of 3% on average. The extrapolation of the model showed a reasonable trend to predict toluene conversion and product yield both in thermal and catalytic treatments. Under microwave irradiation, activation energy of toluene conversion was lower in the range of 3-27 kJ mol(-1) compared to those of conventional heating reported in the literatures. The overall reaction rate was six times higher compared to conventional heating. As a whole, the kinetic model works better for tar model removal in the absence of gas reforming within a level of reliability demonstrated in this study.
Directory of Open Access Journals (Sweden)
Yukinobu Arata
2016-08-01
Full Text Available Cell polarity arises through the spatial segregation of polarity regulators. PAR proteins are polarity regulators that localize asymmetrically to two opposing cortical domains. However, it is unclear how the spatially segregated PAR proteins interact to maintain their mutually exclusive partitioning. Here, single-molecule detection analysis in Caenorhabditis elegans embryos reveals that cortical PAR-2 diffuses only short distances, and, as a result, most PAR-2 molecules associate and dissociate from the cortex without crossing into the opposing domain. Our results show that cortical PAR-2 asymmetry is maintained by the local exchange reactions that occur at the cortical-cytoplasmic boundary. Additionally, we demonstrate that local exchange reactions are sufficient to maintain cortical asymmetry in a parameter-free mathematical model. These findings suggest that anterior and posterior PAR proteins primarily interact through the cytoplasmic pool and not via cortical diffusion.
Arata, Yukinobu; Hiroshima, Michio; Pack, Chan-Gi; Ramanujam, Ravikrishna; Motegi, Fumio; Nakazato, Kenichi; Shindo, Yuki; Wiseman, Paul W; Sawa, Hitoshi; Kobayashi, Tetsuya J; Brandão, Hugo B; Shibata, Tatsuo; Sako, Yasushi
2016-08-23
Cell polarity arises through the spatial segregation of polarity regulators. PAR proteins are polarity regulators that localize asymmetrically to two opposing cortical domains. However, it is unclear how the spatially segregated PAR proteins interact to maintain their mutually exclusive partitioning. Here, single-molecule detection analysis in Caenorhabditis elegans embryos reveals that cortical PAR-2 diffuses only short distances, and, as a result, most PAR-2 molecules associate and dissociate from the cortex without crossing into the opposing domain. Our results show that cortical PAR-2 asymmetry is maintained by the local exchange reactions that occur at the cortical-cytoplasmic boundary. Additionally, we demonstrate that local exchange reactions are sufficient to maintain cortical asymmetry in a parameter-free mathematical model. These findings suggest that anterior and posterior PAR proteins primarily interact through the cytoplasmic pool and not via cortical diffusion.
Bednarek, Tomasz; Tsotridis, Georgios
2017-03-01
The objective of the current study is to highlight possible limitations and difficulties associated with Computational Fluid Dynamics in PEM single fuel cell modelling. It is shown that an appropriate convergence methodology should be applied for steady-state solutions, due to inherent numerical instabilities. A single channel fuel cell model has been taken as numerical example. Results are evaluated for quantitative as well qualitative points of view. The contribution to the polarization curve of the different fuel cell components such as bi-polar plates, gas diffusion layers, catalyst layers and membrane was investigated via their effects on the overpotentials. Furthermore, the potential losses corresponding to reaction kinetics, due to ohmic and mas transport limitations and the effect of the exchange current density and open circuit voltage, were also investigated. It is highlighted that the lack of reliable and robust input data is one of the issues for obtaining accurate results.
Kinetic Model of Resin－Catalyzed Decomposition of Acetone Cyanohydrin in Organic Solvent
Institute of Scientific and Technical Information of China (English)
章亭洲; 杨立荣; 朱自强; 吴坚平
2003-01-01
Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the compatibility of biocatalysts with chemical catalysts and the successive operation in the bioreactor, anion exchange resin (D301) was used as catalyst for this reaction. External diffusion limitation was excluded by raising rotational speed to higher than 190r·min-1 in both solvents. Internal diffusion limitation was verified to be insignificant in this reaction system. The effect of acetone cyanohydrin concentration on the reaction was also investigated. An intrinsic kinetic model was proposed when the mass transfer limitation was excluded, and the average deviation of the model is 10.5%.
Integrated stoichiometric, thermodynamic and kinetic modelling of steady state metabolism.
Fleming, R M T; Thiele, I; Provan, G; Nasheuer, H P
2010-06-07
The quantitative analysis of biochemical reactions and metabolites is at frontier of biological sciences. The recent availability of high-throughput technology data sets in biology has paved the way for new modelling approaches at various levels of complexity including the metabolome of a cell or an organism. Understanding the metabolism of a single cell and multi-cell organism will provide the knowledge for the rational design of growth conditions to produce commercially valuable reagents in biotechnology. Here, we demonstrate how equations representing steady state mass conservation, energy conservation, the second law of thermodynamics, and reversible enzyme kinetics can be formulated as a single system of linear equalities and inequalities, in addition to linear equalities on exponential variables. Even though the feasible set is non-convex, the reformulation is exact and amenable to large-scale numerical analysis, a prerequisite for computationally feasible genome scale modelling. Integrating flux, concentration and kinetic variables in a unified constraint-based formulation is aimed at increasing the quantitative predictive capacity of flux balance analysis. Incorporation of experimental and theoretical bounds on thermodynamic and kinetic variables ensures that the predicted steady state fluxes are both thermodynamically and biochemically feasible. The resulting in silico predictions are tested against fluxomic data for central metabolism in Escherichia coli and compare favourably with in silico prediction by flux balance analysis.
Clinical studies of bone metabolism using a simple model of calcium tracer kinetics
Energy Technology Data Exchange (ETDEWEB)
Roncari, G.
1981-08-01
Bone metabolism studies were performed in 44 subjects with and without bone disease using a calcium tracer kinetics model, the central feature of which is an expanding exchangeable calcium pool. In normal subjects the accretion rate and the exchangeable calcium pool ranged from 1.49 to 8.45 (mean 3.9 +- 2.05) mg.d/sup -1/kg/sup -1/ and from 60 to 131 (mean 81.25 +- 18.11) mg.kg/sup -1/, respectively. The patients with osteogenesis imperfecta, Pierre Marie's disease and one out of two cases of hypoparathyroidism had values which fell within the normal range. Both the accretion rate and the exchangeable calcium pool were significantly elevated in patients with Paget's disease and with hyperparathyroidism. Uremic patients with generalizated bone lesions had accretion rates or both parameters elevated. As far as patients with successful renal transplant are concerned, the results suggest that this method is a very poor means for detecting bone disorders with only focal lesions. In contrast, the method can be very useful when persistent renal osteodystrophy or secondary hyperparathyroidism are suspected.
Alkaline Hydrolysis Kinetics Modeling of Bagasse Pentosan Dissolution
Directory of Open Access Journals (Sweden)
Yuxin Liu
2013-11-01
Full Text Available The main pentosan components of sugarcane bagasse, which can be subjected to alkaline hydrolysis, are xylose, arabinose, glucose, and galactose. The pentosan reaction mechanism was considered for alkali-treated bagasse with variation of temperature and time. The kinetics of pentosan degradation were studied concurrently at temperatures of 50 °C, 70 °C, and 90 °C, with a solid-liquid mass ratio of 1:15, a stirring speed of 500 revolutions/min, and different holding times for bagasse alkali pre-extraction. With respect to residual pentosan content and the losses of raw material, the hydrolysis rates of alkali pre-extraction and pentosan degradation reactions of bagasse all followed pseudo-first-order kinetic models. Finally, the main degradation activation energy was determined to be 20.86 KJ/mol, and the residual degradation activation energy was 28.75 KJ/mol according to the Arrhenius equation.
Kinetic modeling of ethylbenzene dehydrogenation over hydrotalcite catalysts
Atanda, Luqman
2011-07-01
Kinetics of ethylbenzene dehydrogenation to styrene was investigated over a series of quaternary mixed oxides of Mg3Fe0.25Me0.25Al0.5 (Me=Co, Mn and Ni) catalysts prepared by calcination of hydrotalcite-like compounds and compared with commercial catalyst. The study was carried out in the absence of steam using a riser simulator at 400, 450, 500 and 550°C for reaction times of 5, 10, 15 and 20s. Mg3Fe0.25Mn0.25Al0.5 afforded the highest ethylbenzene conversion of 19.7% at 550°C. Kinetic parameters for the dehydrogenation process were determined using the catalyst deactivation function based on reactant conversion model. The apparent activation energies for styrene production were found to decrease as follows: E1-Ni>E1-Co>E1-Mn. © 2011 Elsevier B.V.
Kinetic modelling and mechanism of dye adsorption on unburned carbon
Energy Technology Data Exchange (ETDEWEB)
Wang, S.B.; Li, H.T. [Curtin University of Technology, Perth, WA (Australia). Dept. of Chemical Engineering
2007-07-01
Textile dyeing processes are among the most environmentally unfriendly industrial processes by producing coloured wastewaters. The adsorption method using unburned carbon from coal combustion residue was studied for the decolourisation of typical acidic and basic dyes. It was discovered that the unburned carbon showed high adsorption capacity at 1.97 x 10{sup -4} and 5.27 x 10{sup -4} mol/g for Basic Violet 3 and Acid Black 1, respectively. The solution pH, particle size and temperature significantly influenced the adsorption capacity. Higher solution pH favoured the adsorption of basic dye while reduced the adsorption of acid dye. The adsorption of dye increased with increasing temperature but decreased with increasing particle size. Sorption kinetic data indicated that the adsorption kinetics followed the pseudo-second-order model. The adsorption mechanism consisted of two processes, external diffusion and intraparticle diffusion, and the external diffusion was the dominating process.
An enhanced Brinson model with modified kinetics for martensite transformation
Energy Technology Data Exchange (ETDEWEB)
Kim, Young-Jin; Lee, Jung Ju [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of); Jeong, Ju-Won [Korea Aerospace Research Institute, Daejeon (Korea, Republic of); Lim, Jae Hyuk [Chonbuk National University, Jeonju (Korea, Republic of)
2017-03-15
We propose an enhanced Brinson model with modified kinetics for martensite transformation. Two additional material constants are considered to follow the stress-temperature diagram above austenite start temperature (As) along with treatment to keep the continuity of the martensite volume fraction and the path dependency of the phase transformation. To demonstrate the performance of the proposed model, we implement this algorithm into ABAQUS user subroutine, then conduct several numerical simulations and compare their results with SMA wire experiments as well as those of three-dimensional SMA constitutive models. From the results, it turns out that the proposed model is as accurate as the three-dimensional models and shows better accuracy over original Brinson model in terms of recovery stress.
LIQUID-PHASE ADSORPTION KINETICS OF ISOMALTOTRIOSE ON Ca2+ EXCHANGE RESIN
Institute of Scientific and Technical Information of China (English)
LI Xiang; GUO Haifu
2006-01-01
The adsorption of isomaltotriose from aqueous solution on Ca2+ resin was investigated.The adsorption isotherm and the rate curve were determined. The pseudo-first-order model,pseudo-second-order model and the intraparticle diffusion model were used to predict the rate constants of adsorption. The activation energy of adsorption has been also evaluated using the pseudo-second-order rate constants. The results showed that the adsorption of isomaltotriose onto Ca2+ resin is an exothermically activated process. The adsorption isotherm can be described by Langmuir equation. The pseudo-second-order model can fit well to the adsorption rate curve of isomaltotriose onto Ca2+ resin. It suggests that the adsorption of isomoltotriose onto Ca2+ resin involve chemical adsorption.
Modeling the turbulent kinetic energy equation for compressible, homogeneous turbulence
Aupoix, B.; Blaisdell, G. A.; Reynolds, William C.; Zeman, Otto
1990-01-01
The turbulent kinetic energy transport equation, which is the basis of turbulence models, is investigated for homogeneous, compressible turbulence using direct numerical simulations performed at CTR. It is shown that the partition between dilatational and solenoidal modes is very sensitive to initial conditions for isotropic decaying turbulence but not for sheared flows. The importance of the dilatational dissipation and of the pressure-dilatation term is evidenced from simulations and a transport equation is proposed to evaluate the pressure-dilatation term evolution. This transport equation seems to work well for sheared flows but does not account for initial condition sensitivity in isotropic decay. An improved model is proposed.
Web-based kinetic modelling using JWS Online.
Olivier, Brett G; Snoep, Jacky L
2004-09-01
JWS Online is a repository of kinetic models, describing biological systems, which can be interactively run and interrogated over the Internet. It is implemented using a client-server strategy where the clients, in the form of web browser based Java applets, act as a graphical interface to the model servers, which perform the required numerical computations. The JWS Online website is publicly accessible at http://jjj.biochem.sun.ac.za/ with mirrors at http://www.jjj.bio.vu.nl/ and http://jjj.vbi.vt.edu/
Kinetic model for microbial growth and desulphurisation with Enterobacter sp.
Liu, Long; Guo, Zhiguo; Lu, Jianjiang; Xu, Xiaolin
2015-02-01
Biodesulphurisation was investigated by using Enterobacter sp. D4, which can selectively desulphurise and convert dibenzothiophene into 2-hydroxybiphenyl (2-HBP). The experimental values of growth, substrate consumption and product generation were obtained at 95 % confidence level of the fitted values using three models: Hinshelwood equation, Luedeking-Piret and Luedeking-Piret-like equations. The average error values between experimental values and fitted values were less than 10 %. These kinetic models describe all the experimental data with good statistical parameters. The production of 2-HBP in Enterobacter sp. was by "coupled growth".
Small velocity and finite temperature variations in kinetic relaxation models
Markowich, Peter
2010-01-01
A small Knuden number analysis of a kinetic equation in the diffusive scaling is performed. The collision kernel is of BGK type with a general local Gibbs state. Assuming that the flow velocity is of the order of the Knudsen number, a Hilbert expansion yields a macroscopic model with finite temperature variations, whose complexity lies in between the hydrodynamic and the energy-transport equations. Its mathematical structure is explored and macroscopic models for specific examples of the global Gibbs state are presented. © American Institute of Mathematical Sciences.
Numerical Comparison of Solutions of Kinetic Model Equations
Directory of Open Access Journals (Sweden)
A. A. Frolova
2015-01-01
Full Text Available The collision integral approximation by different model equations has created a whole new trend in the theory of rarefied gas. One widely used model is the Shakhov model (S-model obtained by expansion of inverse collisions integral in a series of Hermite polynomials up to the third order. Using the same expansion with another value of free parameters leads to a linearized ellipsoidal statistical model (ESL.Both model equations (S and ESL have the same properties, as they give the correct relaxation of non-equilibrium stress tensor components and heat flux vector, the correct Prandtl number at the transition to the hydrodynamic regime and do not guarantee the positivity of the distribution function.The article presents numerical comparison of solutions of Shakhov equation, ESL- model and full Boltzmann equation in the four Riemann problems for molecules of hard spheres.We have considered the expansion of two gas flows, contact discontinuity, the problem of the gas counter-flows and the problem of the shock wave structure. For the numerical solution of the kinetic equations the method of discrete ordinates is used.The comparison shows that solution has a weak sensitivity to the form of collision operator in the problem of expansions of two gas flows and results obtained by the model and the kinetic Boltzmann equations coincide.In the problem of the contact discontinuity the solution of model equations differs from full kinetic solutions at the point of the initial discontinuity. The non-equilibrium stress tensor has the maximum errors, the error of the heat flux is much smaller, and the ESL - model gives the exact value of the extremum of heat flux.In the problems of gas counter-flows and shock wave structure the model equations give significant distortion profiles of heat flux and non-equilibrium stress tensor components in front of the shock waves. This behavior is due to fact that in the models under consideration there is no dependency of the
Modeling Heavy Metal Sorption Kinetics Using Fractional Calculus
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V. C. Friesen
2015-01-01
Full Text Available Heavy metals are commonly regarded as environmentally aggressive and hazardous to human health. Among the different metals, lead plays an important economic role due to its large use in the automotive industry, being an essential component of batteries. Different approaches have been reported in the literature aimed at lead removal, and among them a very successful one considers the use of water hyacinths for sorption-based operation. The modeling of the metal sorption kinetics is a fundamental step towards in-depth studies and proper separation equipment design and optimization. Fractional calculus represents a novel approach and a growing research field for process modeling, which is based on the successful use of derivatives of arbitrary order. This paper reports the modeling of the kinetics of lead sorption by water hyacinths (Eichhornia crassipes using a fractional calculus. A general procedure on error analysis is also employed to prove the actual fractional nature of the proposed model by the use of parametric variance analysis, which was carried out using two different approaches (with the complete Hessian matrix and with a simplified Hessian matrix. The joint parameter confidence regions were generated, allowing to successfully show the fractional nature of the model and the sorption process.
Wealth distribution of simple exchange models coupled with extremal dynamics
Bagatella-Flores, N.; Rodríguez-Achach, M.; Coronel-Brizio, H. F.; Hernández-Montoya, A. R.
2015-01-01
Punctuated Equilibrium (PE) states that after long periods of evolutionary quiescence, species evolution can take place in short time intervals, where sudden differentiation makes new species emerge and some species extinct. In this paper, we introduce and study the effect of punctuated equilibrium on two different asset exchange models: the yard sale model (YS, winner gets a random fraction of a poorer player's wealth) and the theft and fraud model (TF, winner gets a random fraction of the loser's wealth). The resulting wealth distribution is characterized using the Gini index. In order to do this, we consider PE as a perturbation with probability ρ of being applied. We compare the resulting values of the Gini index at different increasing values of ρ in both models. We found that in the case of the TF model, the Gini index reduces as the perturbation ρ increases, not showing dependence with the agents number. While for YS we observe a phase transition which happens around ρc = 0.79. For perturbations ρ increases (an extreme wealth condensation state), whereas for perturbations greater than or equal to ρc the Gini index becomes different to one, avoiding the system reaches this extreme state. We show that both simple exchange models coupled with PE dynamics give more realistic results. In particular for YS, we observe a power low decay of wealth distribution.
Multilinear Model of Heat Exchanger with Hammerstein Structure
Directory of Open Access Journals (Sweden)
Dragan Pršić
2016-01-01
Full Text Available The multilinear model control design approach is based on the approximation of the nonlinear model of the system by a set of linear models. The paper presents the method of creation of a bank of linear models of the two-pass shell and tube heat exchanger. The nonlinear model is assumed to have a Hammerstein structure. The set of linear models is formed by decomposition of the nonlinear steady-state characteristic by using the modified Included Angle Dividing method. Two modifications of this method are proposed. The first one refers to the addition to the algorithm for decomposition, which reduces the number of linear segments. The second one refers to determination of the threshold value. The dependence between decomposition of the nonlinear characteristic and the linear dynamics of the closed-loop system is established. The decoupling process is more formal and it can be easily implemented by using software tools. Due to its simplicity, the method is particularly suitable in complex systems, such as heat exchanger networks.
Kinetic model of ductile iron solidification with experimental verification
Directory of Open Access Journals (Sweden)
W. Kapturkiewicz
2009-10-01
Full Text Available A solidification model for ductile iron, including Weibull formula for nodule count has been presented. From this model, the following can be determined: cooling curves, kinetics of austenite and eutectic nucleation, austenite and eutectic growth velocity, volume fraction, distribution of Si and P both in austenite and eutectic grain with distribution in casting section.In the developed model of nodular graphite iron casting solidification, the correctness of the mathematical model has been experimentally verified in the range of the most significant factors, which include temperature field, the value of maximum undercooling, and the graphite nodule count interrelated with the casting cross-section. Literature offers practically no data on so confronted process model and simulation program.
Langrangian model of nitrogen kinetics in the Chattahoochee river
Jobson, H.E.
1987-01-01
A Lagrangian reference frame is used to solve the convection-dispersion equation and interpret water-quality obtained from the Chattahoochee River. The model was calibrated using unsteady concentrations of organic nitrogen, ammonia, and nitrite plus nitrate obtained during June 1977 and verified using data obtained during August 1976. Reaction kinetics of the cascade type are shown to provide a reasonable description of the nitrogen-species processes in the Chattahoochee River. The conceptual model is easy to visualize in the physical sense and the output includes information that is not easily determined from an Eulerian approach, but which is very helpful in model calibration and data interpretation. For example, the model output allows one to determine which data are of most value in model calibration or verification.
Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling
Directory of Open Access Journals (Sweden)
A. S. Almeida
2008-06-01
Full Text Available A mathematical model for the free radical polymerization of styrene is developed to predict the steady-state and dynamic behavior of a continuous process. Special emphasis is given for the kinetic and thermodynamic models, where the most sensitive parameters were estimated using data from an industrial plant. The thermodynamic model is based on a cubic equation of state and a mixing rule applied to the low-pressure vapor-liquid equilibrium of polymeric solutions, suitable for modeling the auto-refrigerated polymerization reactors, which use the vaporization rate to remove the reaction heat from the exothermic reactions. The simulation results show the high predictive capability of the proposed model when compared with plant data for conversion, average molecular weights, polydispersity, melt flow index, and thermal properties for different polymer grades.
Kinetic equations modelling wealth redistribution: a comparison of approaches.
Düring, Bertram; Matthes, Daniel; Toscani, Giuseppe
2008-11-01
Kinetic equations modelling the redistribution of wealth in simple market economies is one of the major topics in the field of econophysics. We present a unifying approach to the qualitative study for a large variety of such models, which is based on a moment analysis in the related homogeneous Boltzmann equation, and on the use of suitable metrics for probability measures. In consequence, we are able to classify the most important feature of the steady wealth distribution, namely the fatness of the Pareto tail, and the dynamical stability of the latter in terms of the model parameters. Our results apply, e.g., to the market model with risky investments [S. Cordier, L. Pareschi, and G. Toscani, J. Stat. Phys. 120, 253 (2005)], and to the model with quenched saving propensities [A. Chatterjee, B. K. Chakrabarti, and S. S. Manna, Physica A 335, 155 (2004)]. Also, we present results from numerical experiments that confirm the theoretical predictions.
7-lump kinetic model for residual oil catalytic cracking
Institute of Scientific and Technical Information of China (English)
XU Ou-guan; SU Hong-ye; MU Sheng-jing; CHU Jian
2006-01-01
In this paper a novel 7-lump kinetic model is proposed to describe residual oil catalytic cracking, in which coke is lumped separately for accurate prediction. The reactor block is modeled as a combination of an ideal pipe flow reactor (PFR)and a continuously stirred tank reactor (CSTR). Unit factors are designed to correct the deviation between model predictions and practical plant data and tuned by modified Levenberg-Marquardt algorithm. The parameters estimated are reliable and good agreement between the model predictions and plant observations is observed. The model helps us get good insight into the performance of an industrial riser reactor that would be useful for optimization of residual oil catalytic cracking.
Kinetics of lime/bentonite pozzolanic reactions at 20 and 50 °C: Batch tests and modeling
Energy Technology Data Exchange (ETDEWEB)
De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr [Mines-ParisTech (Ecole des Mines de Paris), Centre de Géosciences, 35 Rue St-Honoré, 77305 Fontainebleau Cedex (France); Deneele, Dimitri [LUNAM, IFSTTAR, Institut Français des Sciences et des Technologies des Transports, de l' Aménagement et des Réseaux, BP 4129, route de Bouaye, 44332 Bouguenais (France); Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); Maubec, Nicolas [LUNAM, IFSTTAR, Institut Français des Sciences et des Technologies des Transports, de l' Aménagement et des Réseaux, BP 4129, route de Bouaye, 44332 Bouguenais (France)
2014-05-01
The effects of duration (1–100 days) and temperature (20 and 50 °C) were assessed from batch tests for Ca-bentonite mixed with 10 wt.% lime. The pozzolanic processes were monitored over time by {sup 29}Si NMR (Cement Concr. Res. 42, 2012), TGA-DTA, XRD and chemical analysis. Modeling considered kinetics and thermodynamics of mineralogical transformations and cation exchange. Kinetic laws were dependent on pH and temperature (Arrhenius energy). Lime hydration occurs within hours, modifying the bentonite exchangeable population and increasing the pH. These alkaline conditions initiate the pozzolanic reactions in a second stage. The rate-limiting step is the dissolution kinetics of the bentonite minerals, i.e. a relatively fast and total consumption of cristobalite in parallel to a long-term slower dissolution of montmorillonite. First C–S–H and then C–A–S–H are formed consequently. Temperature speeds up the pozzolanic reaction kinetics by a factor 5 from 20 to 50 °C, corresponding to an apparent activation energy of 40–50 kJ/mol.
Digital Repository Service at National Institute of Oceanography (India)
Vudamala, K.; Chakraborty, P.
river emptying into Cochin backwaters, Indian J. Mar. Sci. 15 (1986) 253–259. http://cat.inist.fr/?aModele=afficheN&cpsidt=8219806 (accessed September 4, 2015). [25] P.K. Krishnakumar, V.K. Pillai, Mercury Near a Caustic Soda plant at karwar,India, Mar...
Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark
Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.
2014-12-01
Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.
Kinetic modelling of cadmium and lead removal by aquatic mosses
Directory of Open Access Journals (Sweden)
R. J. E. Martins
2014-03-01
Full Text Available Because biosorption is a low cost and effective method for treating metal-bearing wastewaters, understanding the process kinetics is relevant for design purposes. In the present study, the performance of the aquatic moss Fontinalis antipyretica for removing cadmium and lead from simulated wastewaters has been evaluated. Five kinetic models (first-order, pseudo-first-order, Elovich, modified Ritchie second-order and pseudo-second-order were fitted to the experimental data and compared. Previously, the effect of parameters such as the initial solution pH, contact time, and initial metal ion concentration on biosorption was investigated. The initial pH of the solution was found to have an optimum value in the range of 4.0-6.0. The equilibrium sorption capacity of cadmium and lead by Fontinalis antipyretica increased with the initial metal concentration. For an initial metal concentration of 10 mg L-1, the uptake capacity of the moss, at equilibrium, is the same for both metals (4.8 mg g-1. Nevertheless, when the initial concentration increases up to 100 mg L-1, the uptake of Pb(II was higher than 78%. The pseudo-second order biosorption kinetics provided the better correlation with the experimental data (R² ≥ 0.999.
Kinetic model for astaxanthin aggregation in water-methanol mixtures
Giovannetti, Rita; Alibabaei, Leila; Pucciarelli, Filippo
2009-07-01
The aggregation of astaxanthin in hydrated methanol was kinetically studied in the temperature range from 10 °C to 50 °C, at different astaxanthin concentrations and solvent composition. A kinetic model for the formation and transformation of astaxanthin aggregated has been proposed. Spectrophotometric studies showed that monomeric astaxanthin decayed to H-aggregates that after-wards formed J-aggregates when water content was 50% and the temperature lower than 20 °C; at higher temperatures, very stable J-aggregates were formed directly. Monomer formed very stable H-aggregates when the water content was greater than 60%; in these conditions H-aggregates decayed into J-aggregates only when the temperature was at least 50 °C. Through these findings it was possible to establish that the aggregation reactions took place through a two steps consecutive reaction with first order kinetic constants and that the values of these depended on the solvent composition and temperature.
Kinetic modeling of primary and secondary oxygen atom fluxes at 1 AU
Balyukin, Igor; Katushkina, Olga; Alexashov, Dmitry; Izmodenov, Vladislav
2016-07-01
The first quantitative measurements of the interstellar heavy (oxygen and neon) neutral atoms obtained on the IBEX spacecraft were presented in Park et al. (ApJS, 2015). Qualitative analysis of these data shows that the secondary component of the interstellar oxygen atoms was also measured along with the primary interstellar atoms. This component is formed near the heliopause due to process of charge exchange of interstellar oxygen ions with hydrogen atoms and its existence in the heliosphere was previously predicted theoretically (Izmodenov et al, 1997, 1999, 2001). Quantitative analysis of fluxes of interstellar heavy neutral atoms is only possible with the help of a model which takes into account both filtration of the primary and origin of the secondary interstellar oxygen in the region of interaction of the solar wind with the local interstellar medium as well as a detailed simulation of the motion of interstellar atoms inside the heliosphere. This simulation must take into account the temporal and heliolatitudinal dependences of ionization, the process of charge exchange with the protons of the solar wind and the effect of the solar gravitational attraction. This paper presents the results of modeling interstellar oxygen and neon atoms in the heliospheric shock layer and inside the heliosphere based on a new three-dimensional kinetic-MHD model of the solar wind interaction with the local interstellar medium (Izmodenov and Alexashov, ApJS, 2015) and the comparison of this results with the data obtained on the IBEX spacecraft.
Fully kinetic model of breakdown during sheath expansion after interruption of vacuum arcs
Wang, Zhenxing; Wang, Haoran; Zhou, Zhipeng; Tian, Yunbo; Geng, Yingsan; Wang, Jianhua; Liu, Zhiyuan
2016-08-01
Research on sheath expansion is critical to the understanding of the dielectric recovery process in a vacuum interrupter after interruption of vacuum arcs. In this paper, we investigated how residual plasma affects breakdown in the sheath expansion period after the current zero. To simulate sheath expansion and breakdown, we developed a fully kinetic particle-in-cell Monte Carlo collision model with one spatial dimension and three velocity dimensions. The model accounted for various collisions, including ionization, excitation, elastic collisions, charge exchange, and momentum exchange, and we added an external circuit to the model to make the calculations self-consistent. The existence of metal vapor slowed the sheath expansion in the gap and caused high electric field formation in front of the cathode surface. The initial residual plasma, which was at sufficiently low density, seemed to have a limited impact on breakdown, and the metal vapor dominated the breakdown in this case. Additionally, the breakdown probability was sensitive to the initial plasma density if the value exceeded a specific threshold, and plasma at sufficiently high density could mean that breakdown would occur more easily. We found that if the simulation does not take the residual plasma into account, it could overestimate the critical value of the metal vapor density, which is always used to describe the boundary of breakdown after interruption of vacuum arcs. We discussed the breakdown mechanism in sheath expansion, and the breakdown is determined by a combination of metal vapor, residual plasma, and the electric field in front of the cathode surface.
Kinetic Model for 1D aggregation of yeast ``prions''
Kunes, Kay; Cox, Daniel; Singh, Rajiv
2004-03-01
Mammalian prion proteins (PrP) are of public health interest because of mad cow and chronic wasting diseases. Yeast have proteins which can undergo similar reconformation and aggregation processes to PrP; yeast forms are simpler to experimentally study and model. Recent in vitro studies of the SUP35 protein(1), showed long aggregates and pure exponential growth of the misfolded form. To explain this data, we have extended a previous model of aggregation kinetics(2). The model assumes reconformation only upon aggregation, and includes aggregate fissioning and an initial nucleation barrier. We find for sufficiently small nucleation rates or seeding by small dimer concentrations that we can achieve the requisite exponential growth and long aggregates. We will compare to a more realistic stochastic kinetics model and present prelimary attempts to describe recent experiments on SUP35 strains. *-Supported by U.S. Army Congressionally Mandated Research Fund. 1) P. Chien and J.S. Weissman, Nature 410, 223 (2001); http://online.kitp.ucsb.edu/online/bionet03/collins/. 2) J. Masel, V.A.> Jansen, M.A. Nowak, Biophys. Chem. 77, 139 (1999).
Kinetic models for the VASIMR thruster helicon plasma source
Batishchev, Oleg; Molvig, Kim
2001-10-01
Helicon gas discharge [1] is widely used by industry because of its remarkable efficiency [2]. High energy and fuel efficiencies make it very attractive for space electrical propulsion applications. For example, helicon plasma source is used in the high specific impulse VASIMR [3] plasma thruster, including experimental prototypes VX-3 and upgraded VX-10 [4] configurations, which operate with hydrogen (deuterium) and helium plasmas. We have developed a set of models for the VASIMR helicon discharge. Firstly, we use zero-dimensional energy and mass balance equations to characterize partially ionized gas condition/composition. Next, we couple it to one-dimensional hybrid model [6] for gas flow in the quartz tube of the helicon. We compare hybrid model results to a purely kinetic simulation of propellant flow in gas feed + helicon source subsystem. Some of the experimental data [3-4] are explained. Lastly, we discuss full-scale kinetic modeling of coupled gas and plasmas [5-6] in the helicon discharge. [1] M.A.Lieberman, A.J.Lihtenberg, 'Principles of ..', Wiley, 1994; [2] F.F.Chen, Plas. Phys. Contr. Fus. 33, 339, 1991; [3] F.Chang-Diaz et al, Bull. APS 45 (7) 129, 2000; [4] J.Squire et al., Bull. APS 45 (7) 130, 2000; [5] O.Batishchev et al, J. Plasma Phys. 61, part II, 347, 1999; [6] O.Batishchev, K.Molvig, AIAA technical paper 2000-3754, -14p, 2001.
Kinetic modelling of cytochrome c adsorption on SBA-15.
Yokogawa, Yoshiyuki; Yamauchi, Rie; Saito, Akira; Yamato, Yuta; Toma, Takeshi
2017-01-01
The adsorption capacity of mesoporous silicate (MPS) materials as an adsorbent for protein adsorption from the aqueous phase and the mechanism of the adsorption processes by comparative analyses of the applicability of five kinetic transfer models, pseudo-first-order model, pseudo-second-order model, Elovich kinetic model, Bangham's equation model, and intraparticle diffusion model, were investigated. A mixture of tetraethyl orthosilicate (TEOS) and triblock copolymer as a template was stirred, hydrothermally treated to form the mesoporous SBA-15 structure, and heat-treated at 550°C to form the MPS material, SBA-15. The synthesized SBA-15 was immersed in a phosphate buffered saline (PBS) solution containing cytochrome c for 2, 48, and 120 hours at 4°C. The TEM observations of proteins on/in mesoporous SBA-15 revealed the protein behaviors. The holes of the MPS materials were observed to overlap those of the stained proteins for the first 2 hours of immersion. The stained proteins were observed between primary particles and partly inside the mesoporous channels in the MPS material when it had been immersed for 48 hours. For MPS when it had been immersed for 120 hours, stained proteins were observed in almost all meso-scale channels of MPS. The time profiles for adsorption of proteins can be described well by Bangham's equation model and the intraparticle diffusion model. The Bangham's equation model is based on the assumption that pore diffusion was the only rate controlling step during adsorption, whose contribution to the overall mechanism of cytochrome c adsorption on SBA-15 should not be neglected. The kinetic curves obtained from the experiment for cytochrome c adsorption on SBA-15 could show the three steps: the initial rapid increase of the adsorbed amount of cytochrome c, the second gradual increase, and the final equilibrium stage. These three adsorption steps can be interpreted well by the multi-linearity of the intraparticle diffusion model
Modeling inflation rates and exchange rates in Ghana: application of multivariate GARCH models.
Nortey, Ezekiel Nn; Ngoh, Delali D; Doku-Amponsah, Kwabena; Ofori-Boateng, Kenneth
2015-01-01
This paper was aimed at investigating the volatility and conditional relationship among inflation rates, exchange rates and interest rates as well as to construct a model using multivariate GARCH DCC and BEKK models using Ghana data from January 1990 to December 2013. The study revealed that the cumulative depreciation of the cedi to the US dollar from 1990 to 2013 is 7,010.2% and the yearly weighted depreciation of the cedi to the US dollar for the period is 20.4%. There was evidence that, the fact that inflation rate was stable, does not mean that exchange rates and interest rates are expected to be stable. Rather, when the cedi performs well on the forex, inflation rates and interest rates react positively and become stable in the long run. The BEKK model is robust to modelling and forecasting volatility of inflation rates, exchange rates and interest rates. The DCC model is robust to model the conditional and unconditional correlation among inflation rates, exchange rates and interest rates. The BEKK model, which forecasted high exchange rate volatility for the year 2014, is very robust for modelling the exchange rates in Ghana. The mean equation of the DCC model is also robust to forecast inflation rates in Ghana.
Investigation of kinetics model of dc reactive sputtering
Institute of Scientific and Technical Information of China (English)
朱圣龙; 王福会; 吴维叓
1996-01-01
A novel physical sputtering kinetics model for reactive sputtering is presented.Reactive gas gettering effects and interactions among the characteristic parameters have been taken into account in the model.The data derived from the model accorded fairly well with experimental results.The relationship between the values of initial oxide coverage on the target and the ready states was depicted in the model.This relationship gives reasons for the difference of the threshold of reactive gas fluxes (Q) from the metal sputtering region to the oxide sputtering region and in reverse direction.The discontinuities in oxide coverage on the target surface (θ) versus reactive gas fluxes (Q) are referred to as the effects of reactive gas partial pressure (p) upon the forming rates of oxide on the surfaces of target (V0).The diversity of the oxygen flux threshold results from the variance of the initial values of oxide coverage on target.
Study on Lumped Kinetic Model for FDFCC II. Validation and Prediction of Model
Institute of Scientific and Technical Information of China (English)
Wu Feiyue; Weng Huixin; Luo Shixian
2008-01-01
On the basis of formulating the 9-lump kinetic model for gasoline catalytic upgrading and the 12-lump kinetic model for heavy oil FCC, this paper is aimed at development of a combined kinetic model for a typical FDFCC process after analyzing the coupled relationship and combination of these two models. The model is also verified by using commercial data, the results of which showed that the model can better predict the product yields and their quality, with the relative errors between the main products of the unit and commercial data being less than five percent. Furthermore, the combined model is used to predict and optimize the operating conditions for gasoline riser and heavy oil riser in FDFCC. So this paper can offer some guidance for the processing of FDFCC and is instructive to model research and development of such multi-reactor process and combined process.
Adequacy indices for dialysis in acute renal failure: kinetic modeling.
Debowska, Malgorzata; Lindholm, Bengt; Waniewski, Jacek
2010-05-01
Many aspects of the management of renal replacement therapy in acute renal failure (ARF), including the appropriate assessment of dialysis adequacy, remain unresolved, because ARF patients often are not in a metabolic steady state. The aim of this study was to evaluate a system of adequacy indices for dialysis in ARF patients using urea and creatinine kinetic modeling. Kinetic modeling was performed for two different fictitious patients (A and B) with characteristics described by the average parameters for two patient groups and for two blood purification treatments: sustained low efficiency daily dialysis (SLEDD) in Patient A and continuous venovenous hemofiltration (CVVH) in Patient B, based on data from a clinical report. Urea and creatinine generation rates were estimated according to the clinical data on the solute concentrations in blood. Then, using estimated generation rates, two hypothetical treatments were simulated, CVVH in Patient A and SLEDD in Patient B. KT/V, fractional solute removal (FSR) and equivalent renal clearance (EKR) were calculated according to the definitions developed for metabolically unstable patients. CVVH appeared as being more effective than SLEDD because KT/V, FSR, and EKR were higher for CVVH than SLEDD in Patients A and B. Creatinine KT/V, FSR, and EKR were lower and well correlated to the respective indices for urea. Urea and creatinine generation rates were overestimated more than twice in Patient A and by 30-40% in Patient B if calculated assuming the metabolically stable state than if estimated by kinetic modeling. Adequacy indices and solute generation rates for ARF patients should be estimated using the definition for unsteady metabolic state. EKR and FSR were higher for urea and creatinine with CVVH than with SLEDD, because of higher K.T and minimized compartmental effects for CVVH.
Kinetics of solid state phase transformations: Measurement and modelling of some basic issues
Indian Academy of Sciences (India)
S Raju; E Mohandas
2010-01-01
A brief review of the issues involved in modelling of the solid state transformation kinetics is presented. The fact that apart from the standard thermodynamic parameters, certain path variables like heating or cooling rate can also exert a crucial influence on the kinetic outcome is stressed. The kinetic specialties that are intrinsic to phase changes proceeding under varying thermal history are enumerated. A simple and general modelling methodology for understanding the kinetics of non-isothermal transformations is outlined.
Tracer kinetic modelling in MRI: estimating perfusion and capillary permeability
Sourbron, S. P.; Buckley, D. L.
2012-01-01
The tracer-kinetic models developed in the early 1990s for dynamic contrast-enhanced MRI (DCE-MRI) have since become a standard in numerous applications. At the same time, the development of MRI hardware has led to increases in image quality and temporal resolution that reveal the limitations of the early models. This in turn has stimulated an interest in the development and application of a second generation of modelling approaches. They are designed to overcome these limitations and produce additional and more accurate information on tissue status. In particular, models of the second generation enable separate estimates of perfusion and capillary permeability rather than a single parameter Ktrans that represents a combination of the two. A variety of such models has been proposed in the literature, and development in the field has been constrained by a lack of transparency regarding terminology, notations and physiological assumptions. In this review, we provide an overview of these models in a manner that is both physically intuitive and mathematically rigourous. All are derived from common first principles, using concepts and notations from general tracer-kinetic theory. Explicit links to their historical origins are included to allow for a transfer of experience obtained in other fields (PET, SPECT, CT). A classification is presented that reveals the links between all models, and with the models of the first generation. Detailed formulae for all solutions are provided to facilitate implementation. Our aim is to encourage the application of these tools to DCE-MRI by offering researchers a clearer understanding of their assumptions and requirements.
A Photochemical Kinetic Model for Solid Dosage Forms.
Carvalho, Thiago C; La Cruz, Thomas E; Tabora, Jose E
2017-08-20
Photochemical kinetics models for pharmaceutical compounds in solution have been extensively investigated, but not in solid phase upon exposure to different light sources. The objective of this study was to develop a mathematical model to describe the solid state photodegradation of pharmaceutical powder materials under different area/volumetric scales and light exposure conditions. The model considered the previous formalism presented for photodegradation kinetics in solution phase with important elements applied to static powder material being irradiated with a polychromatic light source. The model also included the influence of optical phenomena (i.e. reflectance, scattering factors, etc.) by applying Beer-Lambert law to light attenuation, including effects of powder density. Drug substance and drug product intermediates (blends and tablet cores) were exposed to different light sources and intensities. The model reasonably predicted the photodegradation levels of powder beds of drug substance and drug product intermediates under white and yellow lights with intensities around 5 to 11 kLux. Importantly, the model estimates demonstrated that the reciprocity law for photoreactions was held. Further model evaluation showed that, due to light attenuation, the powder bed is in virtual darkness at cake depths greater than 500 μm. At 100 μm, the photodegradation of the investigated compound is expected to be close to 100% in 10 days under white fluorescent halophosphate light at 9.5 kLux. For tablets, defining the volume over exposed surface area ratio is more challenging. Nevertheless, the model can consider a bracket between worst and best cases to provide a reasonable photodegradation estimate. This tool can be significantly leveraged to simulate different light exposure scenarios while assessing photostability risk in order to define appropriate Control Strategy in manufacturing. Copyright © 2017. Published by Elsevier B.V.
Clinical exchange: one model to achieve culturally sensitive care.
Scholes, J; Moore, D
2000-03-01
This paper reports on a clinical exchange programme that formed part of a pre-registration European nursing degree run by three collaborating institutions in England, Holland and Spain. The course included: common and shared learning including two summer schools; and the development of a second language before the students went on a three-month clinical placement in one of the other base institutions' clinical environments. The aim of the course was to enable students to become culturally sensitive carers. This was achieved by developing a programme based on transcultural nursing principles in theory and practice. Data were gathered by interview, focus groups, and questionnaires from 79 exchange students, fostering the strategies of illuminative evaluation. The paper examines: how the aims of the course were met; the factors that inhibited the attainment of certain goals; and how the acquisition of a second language influenced the students' learning about nursing. A model is presented to illustrate the process of transformative learning from the exchange experience.
Shiraishi, Junya; Miyato, Naoaki; Matsunaga, Go
2016-01-01
It is found that new channels of energy exchange between macro- and microscopic dynamics exist in plasmas. They are induced by macroscopic plasma flow. This finding is based on the kinetic-magnetohydrodynamic (MHD) theory, which analyses interaction between macroscopic (MHD-scale) motion and microscopic (particle-scale) dynamics. The kinetic-MHD theory is extended to include effects of macroscopic plasma flow self-consistently. The extension is realised by generalising an energy exchange term due to wave-particle resonance, denoted by δ WK. The first extension is generalisation of the particle’s Lagrangian, and the second one stems from modification to the particle distribution function due to flow. These extensions lead to a generalised expression of δ WK, which affects the MHD stability of plasmas. PMID:27160346
Model-free kinetics applied to sugarcane bagasse combustion
Energy Technology Data Exchange (ETDEWEB)
Ramajo-Escalera, B.; Espina, A.; Garcia, J.R. [Department of Organic and Inorganic Chemistry, University of Oviedo, 33006 Oviedo (Spain); Sosa-Arnao, J.H. [Mechanical Engineering Faculty, State University of Campinas (UNICAMP), P.O. Box 6122, 13083-970 Campinas, SP (Brazil); Nebra, S.A. [Interdisciplinary Center of Energy Planning, State University of Campinas (UNICAMP), R. Shigeo Mori 2013, 13083-770 Campinas, SP (Brazil)
2006-09-15
Vyazovkin's model-free kinetic algorithms were applied to determine conversion, isoconversion and apparent activation energy to both dehydration and combustion of sugarcane bagasse. Three different steps were detected with apparent activation energies of 76.1+/-1.7, 333.3+/-15.0 and 220.1+/-4.0kJ/mol in the conversion range of 2-5%, 15-60% and 70-90%, respectively. The first step is associated with the endothermic process of drying and release of water. The others correspond to the combustion (and carbonization) of organic matter (mainly cellulose, hemicellulose and lignin) and the combustion of the products of pyrolysis. (author)
Fluctuation dissipation ratio in the one dimensional kinetic Ising model
Lippiello, E.; Zannetti, M.
2000-01-01
The exact relation between the response function $R(t,t^{\\prime})$ and the two time correlation function $C(t,t^{\\prime})$ is derived analytically in the one dimensional kinetic Ising model subjected to a temperature quench. The fluctuation dissipation ratio $X(t,t^{\\prime})$ is found to depend on time through $C(t,t^{\\prime})$ in the time region where scaling $C(t,t^{\\prime}) = f(t/t^{\\prime})$ holds. The crossover from the nontrivial form $X(C(t,t^{\\prime}))$ to $X(t,t^{\\prime}) \\equiv 1$ t...
Large Scale Simulations of the Kinetic Ising Model
Münkel, Christian
We present Monte Carlo simulation results for the dynamical critical exponent z of the two- and three-dimensional kinetic Ising model. The z-values were calculated from the magnetization relaxation from an ordered state into the equilibrium state at Tc for very large systems with up to (169984)2 and (3072)3 spins. To our knowledge, these are the largest Ising-systems simulated todate. We also report the successful simulation of very large lattices on a massively parallel MIMD computer with high speedups of approximately 1000 and an efficiency of about 0.93.
Kinetic Relations for a Lattice Model of Phase Transitions
Schwetlick, Hartmut; Zimmer, Johannes
2012-11-01
The aim of this article is to analyse travelling waves for a lattice model of phase transitions, specifically the Fermi-Pasta-Ulam chain with piecewise quadratic interaction potential. First, for fixed, sufficiently large subsonic wave speeds, we rigorously prove the existence of a family of travelling wave solutions. Second, it is shown that this family of solutions gives rise to a kinetic relation which depends on the jump in the oscillatory energy in the solution tails. Third, our constructive approach provides a very good approximate travelling wave solution.
A generic 3D kinetic model of gene expression
Zhdanov, Vladimir
2012-04-01
Recent experiments show that mRNAs and proteins can be localized both in prokaryotic and eukaryotic cells. To describe such situations, I present a 3D mean-field kinetic model aimed primarily at gene expression in prokaryotic cells, including the formation of mRNA, its translation into protein, and slow diffusion of these species. Under steady-state conditions, the mRNA and protein spatial distribution is described by simple exponential functions. The protein concentration near the gene transcribed into mRNA is shown to depend on the protein and mRNA diffusion coefficients and degradation rate constants.
Kinetic mixing effect in the 3 -3 -1 -1 model
Dong, P. V.; Si, D. T.
2016-06-01
We show that the mixing effect of the neutral gauge bosons in the 3 -3 -1 -1 model comes from two sources. The first one is due to the 3 -3 -1 -1 gauge symmetry breaking as usual, whereas the second one results from the kinetic mixing between the gauge bosons of U (1 )X and U (1 )N groups, which are used to determine the electric charge and baryon minus lepton numbers, respectively. Such mixings modify the ρ -parameter and the known couplings of Z with fermions. The constraints that arise from flavor-changing neutral currents due to the gauge boson mixings and nonuniversal fermion generations are also given.
Warped Higgsless Models with IR-Brane Kinetic Terms
Davoudiasl, H; Lillie, Benjamin Huntington; Rizzo, T G
2004-01-01
We examine a warped Higgsless $SU(2)_L\\times SU(2)_R\\times U(1)_{B-L}$ model in 5--$d$ with IR(TeV)--brane kinetic terms. It is shown that adding a brane term for the $U(1)_{B-L}$ gauge field does not affect the scale ($\\sim 2-3$ TeV) where perturbative unitarity in $W_L^+ W_L^- \\to W_L^+ W_L^-$ is violated. This term could, however, enhance the agreement of the model with the precision electroweak data. In contrast, the inclusion of a kinetic term corresponding to the $SU(2)_D$ custodial symmetry of the theory delays the unitarity violation in $W_L^\\pm$ scattering to energy scales of $\\sim 6-7$ TeV for a significant fraction of the parameter space. This is about a factor of 4 improvement compared to the corresponding scale of unitarity violation in the Standard Model without a Higgs. We also show that null searches for extra gauge bosons at the Tevatron and for contact interactions at LEP II place non-trivial bounds on the size of the IR-brane terms.
Kinetic modeling of 3D equilibria in a tokamak
Albert, C. G.; Heyn, M. F.; Kasilov, S. V.; Kernbichler, W.; Martitsch, A. F.; Runov, A. M.
2016-11-01
External resonant magnetic perturbations (RMPs) can modify the magnetic topology in a tokamak. In this case the magnetic field cannot generally be described by ideal MHD equilibrium equations in the vicinity of resonant magnetic surfaces where parallel and perpendicular relaxation timescales are comparable. Usually, resistive MHD models are used to describe these regions. In the present work, a kinetic model is used for this purpose. Within this model, plasma response, current and charge density are computed with help of a Monte Carlo method, where guiding center orbit equations are solved using a semianalytical geometrical integrator. Besides its higher efficiency in comparison to usual integrators this method is not sensitive to noise in field quantities. The computed charges and currents are used to calculate the electromagnetic field with help of a finite element solver. A preconditioned iterative scheme is applied to search for a self-consistent solution. The discussed method is aimed at the nonlinear kinetic description of RMPs in experiments on Edge Localized Mode (ELM) mitigation by external perturbation coil systems without simplification of the device geometry.
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
Kinetic modeling of ethane pyrolysis at high conversion.
Xu, Chen; Al Shoaibi, Ahmed Sultan; Wang, Chenguang; Carstensen, Hans-Heinrich; Dean, Anthony M
2011-09-29
The primary objective of this study is to develop an improved first-principle-based mechanism that describes the molecular weight growth kinetics observed during ethane pyrolysis. A proper characterization of the kinetics of ethane pyrolysis is a prerequisite for any analysis of hydrocarbon pyrolysis and oxidation. Flow reactor experiments were performed with ~50/50 ethane/nitrogen mixtures with temperatures ranging from 550 to 850 °C at an absolute pressure of ~0.8 atm and a residence time of ~5 s. These conditions result in ethane conversions ranging from virtually no reaction to ~90%. Comparisons of predictions using our original mechanism to these data yielded very satisfactory results in terms of the temperature dependence of ethane conversion and prediction of the major products ethylene and hydrogen. However, there were discrepancies in some of the minor species concentrations that are involved in the molecular weight growth kinetics. We performed a series of CBS-QB3 analyses for the C(3)H(7), C(4)H(7), and C(4)H(9) potential energy surfaces to better characterize the radical addition reactions that lead to molecular weight growth. We also extended a published C(6)H(9) PES to include addition of vinyl to butadiene. The results were then used to calculate pressure-dependent rate constants for the multiple reaction pathways of these addition reactions. Inclusion of the unadjusted rate constants resulting from these analyses in the mechanism significantly improved the description of several of the species involved in molecular weight growth kinetics. We compare the predictions of this improved model to those obtained with a consensus model recently published as well as to ethane steam cracking data. We find that a particularly important reaction is that of vinyl addition to butadiene. Another important observation is that several radical addition reactions are partially equilibrated. Not only does this mean that reliable thermodynamic parameters are essential
Kinetic and Stochastic Models of 1D yeast ``prions"
Kunes, Kay
2005-03-01
Mammalian prion proteins (PrP) are of public health interest because of mad cow and chronic wasting diseases. Yeasts have proteins, which can undergo similar reconformation and aggregation processes to PrP; yeast ``prions" are simpler to experimentally study and model. Recent in vitro studies of the SUP35 protein (1), showed long aggregates and pure exponential growth of the misfolded form. To explain this data, we have extended a previous model of aggregation kinetics along with our own stochastic approach (2). Both models assume reconformation only upon aggregation, and include aggregate fissioning and an initial nucleation barrier. We find for sufficiently small nucleation rates or seeding by small dimer concentrations that we can achieve the requisite exponential growth and long aggregates.
The Origin of the RNA World a Kinetic Model
Wattis, J A D; Wattis, Jonathan A. D.; Coveney, Peter V.
1999-01-01
The aims of this paper are to propose, construct and analyse microscopic kinetic models for the emergence of long chains of RNA from monomeric beta-D-ribonucleotide precursors in prebiotic circumstances. Our theory starts out from similar but more general chemical assumptions to those of Eigen, namely that catalytic replication can lead to a large population of long chains. In particular, our models incorporate the possibility of (i) direct chain growth, (ii) template-assisted synthesis and (iii) catalysis by RNA replicase ribozymes, all with varying degrees of efficiency. However, in our models the reaction mechanisms are kept `open'; we do not assume the existence of closed hypercycles which sustain a population of long chains. Rather it is the feasibility of the initial emergence of a self-sustaining set of RNA chains from monomeric nucleotides which is our prime concern. We confront directly the central nonlinear features of the problem, which have often been overlooked in previous studies. Our detailed m...
MODELLING THE WORLD EXCHANGE RATES:DYNAMICS, VOLATILITY AND FORECASTING
Nwaobi, Godwin
2008-01-01
Indeed, the specification of equilibrium in the world economy depends on the exchange rate regime and thus, the early contributions to the postwar literature on exchange rate economics are to a large extent concerened with the role of speculation in foreign exchange markets. However, the world has known several exchange rate systems beginning with the fixed-gold standard, the adjustable-peg system, adjustable-parity system and the flexible exchange rate system. Yet, in 1997, when foreign exch...
Van den Bergh, J; Jakubowski, B; Burba, P
2001-09-13
The conditional metal availability and the kinetic stability of humic substance-metal species in humic-rich waters (e.g. bog water) was characterized by means of EDTA exchange. For this purpose a combined procedure consisting of time-controlled ligand exchange by EDTA, species differentiation by a fast single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods (e.g. AAS, ICP-OES, TXRF) was developed. The kinetics and the yield of the EDTA exchange served as operational parameters for assessing the kinetic stability and EDTA availability of HS-metal species, respectively. Considerable fractions of natural HS-metal species studied were shown to be EDTA-inert (e.g. 31% of the total Fe, 44% of the total Al) even after long reaction times (48 h), in contrast to artificial ones formed in solutions of isolated HS. Moreover, the conditional thermodynamic stability of HS-metal complexes formed by successive loading of an aquatic reference HS (HO14) with a number of heavy metal ions (e.g. Cr(III), Cu(II), Fe(III), Mn(II), Zn(II)) was also evaluated discriminating the free metal concentrations by means of TF-UF. In addition, from the loading isotherms obtained conditional complexation capacities could be derived for the studied HS exhibiting the order Fe(III)>Cu(II)>Cr(III)>Co(II)>Mn(II).
Energy Technology Data Exchange (ETDEWEB)
Aleman, S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hamm, L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Smith, F. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
2007-06-27
This report discusses the expected performance of spherical Resorcinol-Formaldehyde (RF) ion exchange resin for the removal of cesium from alkaline Hanford radioactive waste. Predictions of full scale column performance in a carousel mode are made for the Hot Commissioning, Envelope B, and Subsequent Operations waste compositions under nominal operating conditions and for perturbations from the nominal. Only the loading phase of the process cycle is addressed in this report. Pertinent bench-scale column tests, kinetic experiments, and batch equilibrium experiments are used to estimate model parameters and to benchmark the ion-exchange model. The methodology and application presented in this report reflect the expected behavior of spherical RF resin manufactured at the intermediate-scale (i.e., approximately 100 gallon batch size; batch 5E-370/641). It is generally believed that scale-up to production-scale in resin manufacturing will result in similarly behaving resin batches whose chemical selectivity is unaffected while total capacity per gram of resin may vary some. As such, the full-scale facility predictions provided within this report should provide reasonable estimates of production-scale column performance.
φ Electro-production in Pomeron Exchange Model
Institute of Scientific and Technical Information of China (English)
MA Wei-Xing; LIU Bao-Rong; ZHOU Li-Juan; TAN Zhen-Qiang; HE Xiao-Rong; GU Yun-Ting
2005-01-01
Based on the Pomeron exchange model, elastic production of φ meson in electron-proton interaction is investigated with both linear and non-linear Pomeron trajectories. The numerical calculations of the differential cross section for e + p → e' + p+ φ are performed. The theoretical predictions show that the dependence of the differentialcross section on virtual photon virtuality, Q2, is of moderation, the change of the energy scale parameter so causes moderate effect on the differential cross section, and the linear trajectory is a good approximation to non-linearity of the Pomeron trajectory, in particular, at small momentum transfer region | t |≤ 0.2 GeV2.
Upper D region chemical kinetic modeling of LORE relaxation times
Gordillo-Vázquez, F. J.; Luque, A.; Haldoupis, C.
2016-04-01
The recovery times of upper D region electron density elevations, caused by lightning-induced electromagnetic pulses (EMP), are modeled. The work was motivated from the need to understand a recently identified narrowband VLF perturbation named LOREs, an acronym for LOng Recovery Early VLF events. LOREs associate with long-living electron density perturbations in the upper D region ionosphere; they are generated by strong EMP radiated from large peak current intensities of ±CG (cloud to ground) lightning discharges, known also to be capable of producing elves. Relaxation model scenarios are considered first for a weak enhancement in electron density and then for a much stronger one caused by an intense lightning EMP acting as an impulsive ionization source. The full nonequilibrium kinetic modeling of the perturbed mesosphere in the 76 to 92 km range during LORE-occurring conditions predicts that the electron density relaxation time is controlled by electron attachment at lower altitudes, whereas above 79 km attachment is balanced totally by associative electron detachment so that electron loss at these higher altitudes is controlled mainly by electron recombination with hydrated positive clusters H+(H2O)n and secondarily by dissociative recombination with NO+ ions, a process which gradually dominates at altitudes >88 km. The calculated recovery times agree fairly well with LORE observations. In addition, a simplified (quasi-analytic) model build for the key charged species and chemical reactions is applied, which arrives at similar results with those of the full kinetic model. Finally, the modeled recovery estimates for lower altitudes, that is <79 km, are in good agreement with the observed short recovery times of typical early VLF events, which are known to be associated with sprites.
Kinetic model of sucrose accumulation in maturing sugarcane culm tissue.
Uys, Lafras; Botha, Frederik C; Hofmeyr, Jan-Hendrik S; Rohwer, Johann M
2007-01-01
Biochemically, it is not completely understood why or how commercial varieties of sugarcane (Saccharum officinarum) are able to accumulate sucrose in high concentrations. Such concentrations are obtained despite the presence of sucrose synthesis/breakdown cycles (futile cycling) in the culm of the storage parenchyma. Given the complexity of the process, kinetic modelling may help to elucidate the factors governing sucrose accumulation or direct the design of experimental optimisation strategies. This paper describes the extension of an existing model of sucrose accumulation (Rohwer, J.M., Botha, F.C., 2001. Analysis of sucrose accumulation in the sugar cane culm on the basis of in vitro kinetic data. Biochem. J. 358, 437-445) to account for isoforms of sucrose synthase and fructokinase, carbon partitioning towards fibre formation, and the glycolytic enzymes phosphofructokinase (PFK), pyrophosphate-dependent PFK and aldolase. Moreover, by including data on the maximal activity of the enzymes as measured in different internodes, a growth model was constructed that describes the metabolic behaviour as sugarcane parenchymal tissue matures from internodes 3-10. While there was some discrepancy between modelled and experimentally determined steady-state sucrose concentrations in the cytoplasm, steady-state fluxes showed a better fit. The model supports a hypothesis of vacuolar sucrose accumulation against a concentration gradient. A detailed metabolic control analysis of sucrose synthase showed that each isoform has a unique control profile. Fructose uptake by the cell and sucrose uptake by the vacuole had a negative control on the futile cycling of sucrose and a positive control on sucrose accumulation, while the control profile for neutral invertase was reversed. When the activities of these three enzymes were changed from their reference values, the effects on futile cycling and sucrose accumulation were amplified. The model can be run online at the JWS Online
Reduced Models in Chemical Kinetics via Nonlinear Data-Mining
Directory of Open Access Journals (Sweden)
Eliodoro Chiavazzo
2014-01-01
Full Text Available The adoption of detailed mechanisms for chemical kinetics often poses two types of severe challenges: First, the number of degrees of freedom is large; and second, the dynamics is characterized by widely disparate time scales. As a result, reactive flow solvers with detailed chemistry often become intractable even for large clusters of CPUs, especially when dealing with direct numerical simulation (DNS of turbulent combustion problems. This has motivated the development of several techniques for reducing the complexity of such kinetics models, where, eventually, only a few variables are considered in the development of the simplified model. Unfortunately, no generally applicable a priori recipe for selecting suitable parameterizations of the reduced model is available, and the choice of slow variables often relies upon intuition and experience. We present an automated approach to this task, consisting of three main steps. First, the low dimensional manifold of slow motions is (approximately sampled by brief simulations of the detailed model, starting from a rich enough ensemble of admissible initial conditions. Second, a global parametrization of the manifold is obtained through the Diffusion Map (DMAP approach, which has recently emerged as a powerful tool in data analysis/machine learning. Finally, a simplified model is constructed and solved on the fly in terms of the above reduced (slow variables. Clearly, closing this latter model requires nontrivial interpolation calculations, enabling restriction (mapping from the full ambient space to the reduced one and lifting (mapping from the reduced space to the ambient one. This is a key step in our approach, and a variety of interpolation schemes are reported and compared. The scope of the proposed procedure is presented and discussed by means of an illustrative combustion example.
Kinetic modeling can describe in vivo glycolysis in Entamoeba histolytica.
Saavedra, Emma; Marín-Hernández, Alvaro; Encalada, Rusely; Olivos, Alfonso; Mendoza-Hernández, Guillermo; Moreno-Sánchez, Rafael
2007-09-01
Glycolysis in the human parasite Entamoeba histolytica is characterized by the absence of cooperative modulation and the prevalence of pyrophosphate-dependent (over ATP-dependent) enzymes. To determine the flux-control distribution of glycolysis and understand its underlying control mechanisms, a kinetic model of the pathway was constructed by using the software gepasi. The model was based on the kinetic parameters determined in the purified recombinant enzymes, and the enzyme activities, and steady-state fluxes and metabolite concentrations determined in amoebal trophozoites. The model predicted, with a high degree of accuracy, the flux and metabolite concentrations found in trophozoites, but only when the pyrophosphate concentration was held constant; at variable pyrophosphate, the model was not able to completely account for the ATP production/consumption balance, indicating the importance of the pyrophosphate homeostasis for amoebal glycolysis. Control analysis by the model revealed that hexokinase exerted the highest flux control (73%), as a result of its low cellular activity and strong AMP inhibition. 3-Phosphoglycerate mutase also exhibited significant flux control (65%) whereas the other pathway enzymes showed little or no control. The control of the ATP concentration was also mainly exerted by ATP consuming processes and 3-phosphoglycerate mutase and hexokinase (in the producing block). The model also indicated that, in order to diminish the amoebal glycolytic flux by 50%, it was required to decrease hexokinase or 3-phosphoglycerate mutase by 24% and 55%, respectively, or by 18% for both enzymes. By contrast, to attain the same reduction in flux by inhibiting the pyrophosphate-dependent enzymes pyrophosphate-phosphofructokinase and pyruvate phosphate dikinase, they should be decreased > 70%. On the basis of metabolic control analysis, steps whose inhibition would have stronger negative effects on the energy metabolism of this parasite were identified
Common Data Model for Neuroscience Data and Data Model Exchange
Gardner, Daniel; Kevin H. Knuth; Abato, Michael; Erde, Steven M.; White, Thomas; DeBellis, Robert; Gardner, Esther P
2001-01-01
Objective: Generalizing the data models underlying two prototype neurophysiology databases, the authors describe and propose the Common Data Model (CDM) as a framework for federating a broad spectrum of disparate neuroscience information resources.
STOCHASTIC KINETIC MODELS: DYNAMIC INDEPENDENCE, MODULARITY AND GRAPHS.
Bowsher, Clive G
2010-08-01
The dynamic properties and independence structure of stochastic kinetic models (SKMs) are analyzed. An SKM is a highly multivariate jump process used to model chemical reaction networks, particularly those in biochemical and cellular systems. We identify SKM subprocesses with the corresponding counting processes and propose a directed, cyclic graph (the kinetic independence graph or KIG) that encodes the local independence structure of their conditional intensities. Given a partition [A, D, B] of the vertices, the graphical separation A ⊥ B|D in the undirected KIG has an intuitive chemical interpretation and implies that A is locally independent of B given A ∪ D. It is proved that this separation also results in global independence of the internal histories of A and B conditional on a history of the jumps in D which, under conditions we derive, corresponds to the internal history of D. The results enable mathematical definition of a modularization of an SKM using its implied dynamics. Graphical decomposition methods are developed for the identification and efficient computation of nested modularizations. Application to an SKM of the red blood cell advances understanding of this biochemical system.
Modeling the kinetics of carbon coagulation in explosives detonation
Ree, F. H.; Viecelli, J. A.; Glosli, J. N.
1998-05-01
A typical insensitive high explosive such as LX-17 has a large carbon content. The detonation behavior of these explosives is affected by a slow coagulation of carbon atoms by diffusion and their possible transformation from one chemical bonding type to another. We have used the Brenner bond order potential to compute the melting line of diamond at high pressure and high temperature by molecular dynamics and Monte Carlo simulations, with the goal to refine the potential for the study of the kinetics of the graphite diamond transition. The slow diffusion-controlled kinetics of carbon clusters has been examined by including a time-dependent surface correction to the Gibbs free energy of these clusters in the nonequilibrium CHEQ code. We also propose a new explosive burn model which incorporates a partial release of the heat of detonation in a fast reaction zone, followed by a diffusion-limited release of the remaining energy. Hydrodynamic applications of the new burn model to LX-17 show that computed expansion and compression results both agree closely with experimental data.
Rotational and divergent kinetic energy in the mesoscale model ALADIN
Directory of Open Access Journals (Sweden)
V. Blažica
2013-03-01
Full Text Available Kinetic energy spectra from the mesoscale numerical weather prediction (NWP model ALADIN with horizontal resolution 4.4 km are split into divergent and rotational components which are then compared at horizontal scales below 300 km and various vertical levels. It is shown that about 50% of kinetic energy in the free troposphere in ALADIN is divergent energy. The percentage increases towards 70% near the surface and in the upper troposphere towards 100 hPa. The maximal percentage of divergent energy is found at stratospheric levels around 100 hPa and at scales below 100 km which are not represented by the global models. At all levels, the divergent energy spectra are characterised by shallower slopes than the rotational energy spectra, and the difference increases as horizontal scales become larger. A very similar vertical distribution of divergent energy is obtained by using the standard ALADIN approach for the computation of spectra based on the extension zone and by applying detrending approach commonly used in mesoscale NWP community.
Energy Technology Data Exchange (ETDEWEB)
Jiang Liangbao; Guo Xintao; Li Xiaoyu; Li Lei; Zhang Guanli [Beijing Institute of Aeronautical Materials, Beijing 100095 (China); Yan Yue, E-mail: Yue.Yan@biam.ac.cn [Beijing Institute of Aeronautical Materials, Beijing 100095 (China)
2013-01-15
Highlights: Black-Right-Pointing-Pointer The difference between the diffusion characteristics of K{sup +}-Na{sup +} ions in float glass on the air and tin sides was first demonstrated. Black-Right-Pointing-Pointer The diffusion coefficient is more sensitive to temperature and time on the tin than on the air sides. Black-Right-Pointing-Pointer The activation energy on the tin side is about three times larger than that on the air side. - Abstract: The difference between the inter-diffusion kinetics of K{sup +}-Na{sup +} in the air and tin sides of an ion-exchanged float aluminosilicate glass was investigated as a function of the exchange temperature and time. The potassium concentration profiles of the ion-exchanged glass surface were experimentally measured by electron microprobe analysis, and the diffusion coefficient was calculated by the Boltzmann-Montano approach. On the tin side of the ion-exchanged glass, the diffusion of K{sup +}-Na{sup +} ions is hindered by tin. The diffusion coefficient is also more sensitive to temperature and time on the tin than on the air sides. The results would be useful in guiding the strengthening process of float glass by one step ion-exchange or two step ion-exchange to obtain engineered stress profile (ESP) glasses.
Modeling Multi-commodity Trade Information Exchange Methods
Traczyk, Tomasz
2012-01-01
Market mechanisms are entering into new fields of economy, in which some constraints of physical world, e.g. Kirchoffs Law in power grid, must be taken into account during trading. On such markets, some of commodities, like telecommunication bandwidth or electrical energy, appear to be non-storable, and must be exchanged in real-time. On the other hand, the markets tend to react at shortest possible time, so an idea to delegate some competency to autonomous software agents is very attractive. Multi-commodity mechanism addresses the aforementioned requirements. Modeling the relationships between the commodities allows to formulate new, more sophisticated models and mechanisms, which reflect decision situations in a better manner. Application of multi-commodity approach requires solving several issues related to data modeling, communication, semantics aspects of communication, reliability, etc. This book answers some of the questions and points out promising paths for implementation and development. Presented s...
Multiple-relaxation-time lattice Boltzmann kinetic model for combustion.
Xu, Aiguo; Lin, Chuandong; Zhang, Guangcai; Li, Yingjun
2015-04-01
To probe both the hydrodynamic nonequilibrium (HNE) and thermodynamic nonequilibrium (TNE) in the combustion process, a two-dimensional multiple-relaxation-time (MRT) version of lattice Boltzmann kinetic model (LBKM) for combustion phenomena is presented. The chemical energy released in the progress of combustion is dynamically coupled into the system by adding a chemical term to the LB kinetic equation. Aside from describing the evolutions of the conserved quantities, the density, momentum, and energy, which are what the Navier-Stokes model describes, the MRT-LBKM presents also a coarse-grained description on the evolutions of some nonconserved quantities. The current model works for both subsonic and supersonic flows with or without chemical reaction. In this model, both the specific-heat ratio and the Prandtl number are flexible, the TNE effects are naturally presented in each simulation step. The model is verified and validated via well-known benchmark tests. As an initial application, various nonequilibrium behaviors, including the complex interplays between various HNEs, between various TNEs, and between the HNE and TNE, around the detonation wave in the unsteady and steady one-dimensional detonation processes are preliminarily probed. It is found that the system viscosity (or heat conductivity) decreases the local TNE, but increases the global TNE around the detonation wave, that even locally, the system viscosity (or heat conductivity) results in two kinds of competing trends, to increase and to decrease the TNE effects. The physical reason is that the viscosity (or heat conductivity) takes part in both the thermodynamic and hydrodynamic responses.
Energy Technology Data Exchange (ETDEWEB)
Martin-Garin, A.; Garcia-Sanchez, L.; Coppin, F. [Institut de Radioprotection et de Surete Nucleaire (France); Krimissa, M. [Electricite de France (France)
2014-07-01
The understanding of radionuclides (RN) behaviour and subsequent fluxes in the soil/solution/plant system is still a challenging question for realistic short, medium or long term risk assessments. Several years of researches have been devoted to improve the modeling of radionuclides migration in soils and their transfer to other compartments of the biosphere (eg. plants), as well as to constitute databases of model parameters (eg. distribution coefficient (K{sub d})). These works contributed to define, and then to extend, the domain of applicability of radioecological models, but they also helped to identify gaps and ways to improve them. However, these improvements have not been fully taken into account. Within this framework, the evolution of RN chemical speciation in time (often described as aging) was specifically addressed, as it control RN retention properties and bioavailability. Regarding soluble and RN solid speciation in soils, such processes generally lead to a shift from low to high K{sub d} values. Common explanations consist in the transfer of sorbed RN to non-(or less) exchangeable solid species, or in the lixiviation of the most available radionuclide fraction, both decreasing the reversibly sorbed RN fraction. Kinetics studies have examined such changes in K{sub d} value with time and various models have been proposed to fit the different evolutions. Among them, an empirical three-box model is often used to describe the kinetics of RN sorption when RN mostly occurs in the soil solution as a free ion (eg. Cs and Sr). This model assumes that the radionuclide may be sorbed either as a labile fraction, defining an exchangeable K{sub d}-like liquid/solid distribution, or sorbed as a less or non-exchangeable fraction. The last is estimated through its corresponding sorption and desorption rate constants, which describes a pseudo-first order reaction. Modeling of sorption dynamic is a way to link K{sub d} values derived from field-contaminated soils to
A study of the kinetic energy generation with general circulation models
Chen, T.-C.; Lee, Y.-H.
1983-01-01
The history data of winter simulation by the GLAS climate model and the NCAR community climate model are used to examine the generation of atmospheric kinetic energy. The contrast between the geographic distributions of the generation of kinetic energy and divergence of kinetic energy flux shows that kinetic energy is generated in the upstream side of jets, transported to the downstream side and destroyed there. The contributions from the time-mean and transient modes to the counterbalance between generation of kinetic energy and divergence of kinetic energy flux are also investigated. It is observed that the kinetic energy generated by the time-mean mode is essentially redistributed by the time-mean flow, while that generated by the transient flow is mainly responsible for the maintenance of the kinetic energy of the entire atmospheric flow.
Study on Lumped Kinetic Model for FDFCC I. Establishment of Model
Institute of Scientific and Technical Information of China (English)
Wu Feiyue; Weng Huixin; Luo Shixian
2008-01-01
According to the process features and the reaction mechanism of FDFCC technology, its two reaction subsystems, one for heavy oil riser reactor, the other for gasoline riser reactor, were respectively studied. Correspondingly, a 12-lump kinetic model for heavy oil FCC and a 9-lump kinetic model for gasoline catalytic upgrading were presented. Based on this work, mathematical correlation of the lumps in the feeds and products involved in the reaction subsystems and those of the overall reaction system were analyzed in detail. Then, a combined kinetic model for FDFCC, which was based on the data recovered from a commercial unit, was put forward. The reaction performance embodied by the kinetic constants for the combined model of FDFCC was in accordance with catalytic cracking reaction mechanism. The model-calculated values were close to the data obtained in commercial scale. The model was easy to be applied in practice and could also provide some theoretical groundwork for further research on kinetic model for FDFCC.
Quantum kinetics and thermalization in a particle bath model.
Alamoudi, S M; Boyanovsky, D; de Vega, H J
1999-07-01
We study the dynamics of relaxation and thermalization in an exactly solvable model of a particle interacting with a harmonic oscillator bath. Our goal is to understand the effects of non-Markovian processes on the relaxational dynamics and to compare the exact evolution of the distribution function with approximate Markovian and non-Markovian quantum kinetics. There are two different cases that are studied in detail: (i) a quasiparticle (resonance) when the renormalized frequency of the particle is above the frequency threshold of the bath and (ii) a stable renormalized "particle" state below this threshold. The time evolution of the occupation number for the particle is evaluated exactly using different approaches that yield to complementary insights. The exact solution allows us to investigate the concept of the formation time of a quasiparticle and to study the difference between the relaxation of the distribution of bare particles and that of quasiparticles. For the case of quasiparticles, the exact occupation number asymptotically tends to a statistical equilibrium distribution that differs from a simple Bose-Einstein form as a result of off-shell processes whereas in the stable particle case, the distribution of particles does not thermalize with the bath. We derive a non-Markovian quantum kinetic equation which resums the perturbative series and includes off-shell effects. A Markovian approximation that includes off-shell contributions and the usual Boltzmann equation (energy conserving) are obtained from the quantum kinetic equation in the limit of wide separation of time scales upon different coarse-graining assumptions. The relaxational dynamics predicted by the non-Markovian, Markovian, and Boltzmann approximations are compared to the exact result. The Boltzmann approach is seen to fail in the case of wide resonances and when threshold and renormalization effects are important.
Developing a computational model of human hand kinetics using AVS
Energy Technology Data Exchange (ETDEWEB)
Abramowitz, Mark S. [State Univ. of New York, Binghamton, NY (United States)
1996-05-01
As part of an ongoing effort to develop a finite element model of the human hand at the Institute for Scientific Computing Research (ISCR), this project extended existing computational tools for analyzing and visualizing hand kinetics. These tools employ a commercial, scientific visualization package called AVS. FORTRAN and C code, originally written by David Giurintano of the Gillis W. Long Hansen`s Disease Center, was ported to a different computing platform, debugged, and documented. Usability features were added and the code was made more modular and readable. When the code is used to visualize bone movement and tendon paths for the thumb, graphical output is consistent with expected results. However, numerical values for forces and moments at the thumb joints do not yet appear to be accurate enough to be included in ISCR`s finite element model. Future work includes debugging the parts of the code that calculate forces and moments and verifying the correctness of these values.
A Global Modeling Framework for Plasma Kinetics: Development and Applications
Parsey, Guy Morland
The modern study of plasmas, and applications thereof, has developed synchronously with com- puter capabilities since the mid-1950s. Complexities inherent to these charged-particle, many- body, systems have resulted in the development of multiple simulation methods (particle-in-cell, fluid, global modeling, etc.) in order to both explain observed phenomena and predict outcomes of plasma applications. Recognizing that different algorithms are chosen to best address specific topics of interest, this thesis centers around the development of an open-source global model frame- work for the focused study of non-equilibrium plasma kinetics. After verification and validation of the framework, it was used to study two physical phenomena: plasma-assisted combustion and the recently proposed optically-pumped rare gas metastable laser. Global models permeate chemistry and plasma science, relying on spatial averaging to focus attention on the dynamics of reaction networks. Defined by a set of species continuity and energy conservation equations, the required data and constructed systems are conceptually similar across most applications, providing a light platform for exploratory and result-search parameter scan- ning. Unfortunately, it is common practice for custom code to be developed for each application-- an enormous duplication of effort which negatively affects the quality of the software produced. Presented herein, the Python-based Kinetic Global Modeling framework (KGMf) was designed to support all modeling phases: collection and analysis of reaction data, construction of an exportable system of model ODEs, and a platform for interactive evaluation and post-processing analysis. A symbolic ODE system is constructed for interactive manipulation and generation of a Jacobian, both of which are compiled as operation-optimized C-code. Plasma-assisted combustion and ignition (PAC/PAI) embody the modernization of burning fuel by opening up new avenues of control and optimization
Ab initio determination of kinetics for atomic layer deposition modeling
Remmers, Elizabeth M.
A first principles model is developed to describe the kinetics of atomic layer deposition (ALD) systems. This model requires no fitting parameters, as it is based on the reaction pathways, structures, and energetics obtained from quantum-chemical studies. Using transition state theory and partition functions from statistical mechanics, equilibrium constants and reaction rates can be calculated. Several tools were created in Python to aid in the calculation of these quantities, and this procedure was applied to two systems- zinc oxide deposition from diethyl zinc (DEZ) and water, and alumina deposition from trimethyl aluminum (TMA) and water. A Gauss-Jordan factorization is used to decompose the system dynamics, and the resulting systems of equations are solved numerically to obtain the temporal concentration profiles of these two deposition systems.
Kinetic modelling of runaway electrons in dynamic scenarios
Stahl, A; Papp, G; Landreman, M; Fülöp, T
2016-01-01
Improved understanding of runaway-electron formation and decay processes are of prime interest for the safe operation of large tokamaks, and the dynamics of the runaway electrons during dynamical scenarios such as disruptions are of particular concern. In this paper, we present kinetic modelling of scenarios with time-dependent plasma parameters; in particular, we investigate hot-tail runaway generation during a rapid drop in plasma temperature. With the goal of studying runaway-electron generation with a self-consistent electric-field evolution, we also discuss the implementation of a conservative collision operator and demonstrate its properties. An operator for avalanche runaway-electron generation, which takes the energy dependence of the scattering cross section and the runaway distribution into account, is investigated. We show that the simpler avalanche model of Rosenbluth & Putvinskii [Nucl. Fusion 37, 1355 (1997)] can give very inaccurate results for the avalanche growth rate (either lower or hig...
High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes
Energy Technology Data Exchange (ETDEWEB)
Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M
2011-03-01
Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.
Modelling world gold prices and USD foreign exchange relationship using multivariate GARCH model
Ping, Pung Yean; Ahmad, Maizah Hura Binti
2014-12-01
World gold price is a popular investment commodity. The series have often been modeled using univariate models. The objective of this paper is to show that there is a co-movement between gold price and USD foreign exchange rate. Using the effect of the USD foreign exchange rate on the gold price, a model that can be used to forecast future gold prices is developed. For this purpose, the current paper proposes a multivariate GARCH (Bivariate GARCH) model. Using daily prices of both series from 01.01.2000 to 05.05.2014, a causal relation between the two series understudied are found and a bivariate GARCH model is produced.
Parameter estimation for models of ligninolytic and cellulolytic enzyme kinetics
Energy Technology Data Exchange (ETDEWEB)
Wang, Gangsheng [ORNL; Post, Wilfred M [ORNL; Mayes, Melanie [ORNL; Frerichs, Joshua T [ORNL; Jagadamma, Sindhu [ORNL
2012-01-01
While soil enzymes have been explicitly included in the soil organic carbon (SOC) decomposition models, there is a serious lack of suitable data for model parameterization. This study provides well-documented enzymatic parameters for application in enzyme-driven SOC decomposition models from a compilation and analysis of published measurements. In particular, we developed appropriate kinetic parameters for five typical ligninolytic and cellulolytic enzymes ( -glucosidase, cellobiohydrolase, endo-glucanase, peroxidase, and phenol oxidase). The kinetic parameters included the maximum specific enzyme activity (Vmax) and half-saturation constant (Km) in the Michaelis-Menten equation. The activation energy (Ea) and the pH optimum and sensitivity (pHopt and pHsen) were also analyzed. pHsen was estimated by fitting an exponential-quadratic function. The Vmax values, often presented in different units under various measurement conditions, were converted into the same units at a reference temperature (20 C) and pHopt. Major conclusions are: (i) Both Vmax and Km were log-normal distributed, with no significant difference in Vmax exhibited between enzymes originating from bacteria or fungi. (ii) No significant difference in Vmax was found between cellulases and ligninases; however, there was significant difference in Km between them. (iii) Ligninases had higher Ea values and lower pHopt than cellulases; average ratio of pHsen to pHopt ranged 0.3 0.4 for the five enzymes, which means that an increase or decrease of 1.1 1.7 pH units from pHopt would reduce Vmax by 50%. (iv) Our analysis indicated that the Vmax values from lab measurements with purified enzymes were 1 2 orders of magnitude higher than those for use in SOC decomposition models under field conditions.
Comparison of moving boundary and finite-volume heat exchanger models in the modelica language
Adriano Desideri; Bertrand Dechesne; Jorrit Wronski; Martijn van den Broek; Sergei Gusev; Vincent Lemort; Sylvain Quoilin
2016-01-01
When modeling low capacity energy systems, such as a small size (5–150 kWel) organic Rankine cycle unit, the governing dynamics are mainly concentrated in the heat exchangers. As a consequence, the accuracy and simulation speed of the higher level system model mainly depend on the heat exchanger model formulation. In particular, the modeling of thermo-flow systems characterized by evaporation or condensation requires heat exchanger models capable of handling phase transitions. To this aim, th...
Kinetic modelling of central carbon metabolism in Escherichia coli.
Peskov, Kirill; Mogilevskaya, Ekaterina; Demin, Oleg
2012-09-01
In the present study, we developed a detailed kinetic model of Escherichia coli central carbon metabolism. The main model assumptions were based on the results of metabolic and regulatory reconstruction of the system and thorough model verification with experimental data. The development and verification of the model included several stages, which allowed us to take into account both in vitro and in vivo experimental data and avoid the ambiguity that frequently occurs in detailed models of biochemical pathways. The choice of the level of detail for the mathematical description of enzymatic reaction rates and the evaluation of parameter values were based on available published data. Validation of the complete model of the metabolic pathway describing specific physiological states was based on fluxomics and metabolomics data. In particular, we developed a model that describes aerobic growth of E. coli in continuous culture with a limiting concentration of glucose. Such modification of the model was used to integrate experimental metabolomics data obtained in steady-state conditions for wild-type E. coli and genetically modified strains, e.g. knockout of the pyruvate kinase gene (pykA). Following analysis of the model behaviour, and comparison of the coincidence between predicted and experimental data, it was possible to investigate the functional and regulatory properties of E. coli central carbon metabolism. For example, a novel metabolic regulatory mechanism for 6-phosphogluconate dehydrogenase inhibition by phosphoenolpyruvate was hypothesized, and the flux ratios between the reactions catalysed by enzyme isoforms were predicted. The mathematical model described here has been submitted to the JWS Online Cellular Systems Modelling Database and can be accessed at http://jjj.biochem.sun.ac.za/database/peskov/index.html © 2012 The Authors Journal compilation © 2012 FEBS.
Pyrolysis Kinetic Modelling of Wheat Straw from the Pannonian Region
Directory of Open Access Journals (Sweden)
Ivan Pešenjanski
2016-01-01
Full Text Available The pyrolysis/devolatilization is a basic step of thermochemical processes and requires fundamental characterization. In this paper, the kinetic model of pyrolysis is specified as a one-step global reaction. This type of reaction is used to describe the thermal degradation of wheat straw samples by measuring rates of mass loss of solid matter at a linear increase in temperature. The mentioned experiments were carried out using a derivatograph in an open-air environment. The influence of different factors was investigated, such as particle size, humidity levels, and the heating rate in the kinetics of devolatilization. As the measured values of mass loss and temperature functions transform in Arrhenius coordinates, the results are shown in the form of saddle curves. Such characteristics cannot be approximated with one equation in the form of Arrhenius law. For use in numerical applications, transformed functions can be approximated by linear regression for three separate intervals. Analysis of measurement resulting in granulation and moisture content variations shows that these factors have no significant influence. Tests of heating rate variations confirm the significance of this impact, especially in warmer regions. The influence of this factor should be more precisely investigated as a general variable, which should be the topic of further experiments.
A probabilistic model of a porous heat exchanger
Agrawal, O. P.; Lin, X. A.
1995-01-01
This paper presents a probabilistic one-dimensional finite element model for heat transfer processes in porous heat exchangers. The Galerkin approach is used to develop the finite element matrices. Some of the submatrices are asymmetric due to the presence of the flow term. The Neumann expansion is used to write the temperature distribution as a series of random variables, and the expectation operator is applied to obtain the mean and deviation statistics. To demonstrate the feasibility of the formulation, a one-dimensional model of heat transfer phenomenon in superfluid flow through a porous media is considered. Results of this formulation agree well with the Monte-Carlo simulations and the analytical solutions. Although the numerical experiments are confined to parametric random variables, a formulation is presented to account for the random spatial variations.
Meson Exchange Current (MEC) Models in Neutrino Interaction Generators
Katori, Teppei
2013-01-01
Understanding of the so-called 2 particle-2 hole (2p-2h) effect is an urgent program in neutrino interaction physics for current and future oscillation experiments. Such processes are believed to be responsible for the event excesses observed by recent neutrino experiments. The 2p-2h effect is dominated by the meson exchange current (MEC), and is accompanied by a 2-nucleon emission from the primary vertex, instead of a single nucleon emission from the charged-current quasi-elastic (CCQE) interaction. Current and future high resolution experiments can potentially nail down this effect. For this reason, there are world wide efforts to model and implement this process in neutrino interaction simulations. In these proceedings, I would like to describe how this channel is modeled in neutrino interaction generators.
Integration Strategies for Efficient Multizone Chemical Kinetics Models
Energy Technology Data Exchange (ETDEWEB)
McNenly, M J; Havstad, M A; Aceves, S M; Pitz, W J
2009-10-15
Three integration strategies are developed and tested for the stiff, ordinary differential equation (ODE) integrators used to solve the fully coupled multizone chemical kinetics model. Two of the strategies tested are found to provide more than an order of magnitude of improvement over the original, basic level of usage for the stiff ODE solver. One of the faster strategies uses a decoupled, or segregated, multizone model to generate an approximate Jacobian. This approach yields a 35-fold reduction in the computational cost for a 20 zone model. Using the same approximate Jacobian as a preconditioner for an iterative Krylov-type linear system solver, the second improved strategy achieves a 75-fold reduction in the computational cost for a 20 zone model. The faster strategies achieve their cost savings with no significant loss of accuracy. The pressure, temperature and major species mass fractions agree with the solution from the original integration approach to within six significant digits; and the radical mass fractions agree with the original solution to within four significant digits. The faster strategies effectively change the cost scaling of the multizone model from cubic to quadratic, with respect to the number of zones. As a consequence of the improved scaling, the 40 zone model offers more than a 250-fold cost savings over the basic calculation.
Directory of Open Access Journals (Sweden)
Budiyono
2014-04-01
Full Text Available Anaerobic treatment using anaerobic digestion can convert organic materials of vinasse into biogas. The purpose of this study was modeling kinetic of biogas production using modified Gompertz model and first order kinetic model at variation of initial pH. Substrates were consisted of two kinds of compositions, which were vinasse+rumen (VR and vinasse+rumen+urea (VRU. Initial pH in each substrate was 6, 7 and 8. Degradation process was done in 30 days using batch anaerobic digesters at room temperature. Both, at VR and VRU, initial pH of 7 generated the more total biogas than the others two (initial pH of 6 and 8. Biogas formed at substrate of VRU was more than that at substrate of VR. The best condition was substrate of VRU and initial pH of 7. At best condition, kinetic constants of biogas production model using modified Gompertz were ym (biogas production potential = 6.49 mL/g VS; U (maximum biogas production rate = 1.24 mL/g VS. day; &lambda (minimum time to produce biogas = 1.79 days. Whereas kinetic constants of biogas production model using first order kinetic were ym (biogas production potential = 6.78 mL/g VS; k (biogas production rate = 0.176 /day. The difference between the predicted and measured biogas yield (fitting error was higher with the first-order kinetic model (1.54-7.50% than with the modified Gompertz model (0.76-3.14%.
Kinetic modeling and sensitivity analysis of plasma-assisted combustion
Togai, Kuninori
Plasma-assisted combustion (PAC) is a promising combustion enhancement technique that shows great potential for applications to a number of different practical combustion systems. In this dissertation, the chemical kinetics associated with PAC are investigated numerically with a newly developed model that describes the chemical processes induced by plasma. To support the model development, experiments were performed using a plasma flow reactor in which the fuel oxidation proceeds with the aid of plasma discharges below and above the self-ignition thermal limit of the reactive mixtures. The mixtures used were heavily diluted with Ar in order to study the reactions with temperature-controlled environments by suppressing the temperature changes due to chemical reactions. The temperature of the reactor was varied from 420 K to 1250 K and the pressure was fixed at 1 atm. Simulations were performed for the conditions corresponding to the experiments and the results are compared against each other. Important reaction paths were identified through path flux and sensitivity analyses. Reaction systems studied in this work are oxidation of hydrogen, ethylene, and methane, as well as the kinetics of NOx in plasma. In the fuel oxidation studies, reaction schemes that control the fuel oxidation are analyzed and discussed. With all the fuels studied, the oxidation reactions were extended to lower temperatures with plasma discharges compared to the cases without plasma. The analyses showed that radicals produced by dissociation of the reactants in plasma plays an important role of initiating the reaction sequence. At low temperatures where the system exhibits a chain-terminating nature, reactions of HO2 were found to play important roles on overall fuel oxidation. The effectiveness of HO2 as a chain terminator was weakened in the ethylene oxidation system, because the reactions of C 2H4 + O that have low activation energies deflects the flux of O atoms away from HO2. For the
Adaptation of the microdosimetric kinetic model to hypoxia
Bopp, C.; Hirayama, R.; Inaniwa, T.; Kitagawa, A.; Matsufuji, N.; Noda, K.
2016-11-01
Ion beams present a potential advantage in terms of treatment of lesions with hypoxic regions. In order to use this potential, it is important to accurately model the cell survival of oxic as well as hypoxic cells. In this work, an adaptation of the microdosimetric kinetic (MK) model making it possible to account for cell hypoxia is presented. The adaptation relies on the modification of damage quantity (double strand breaks and more complex lesions) due to the radiation. Model parameters such as domain size and nucleus size are then adapted through a fitting procedure. We applied this approach to two cell lines, HSG and V79 for helium, carbon and neon ions. A similar behaviour of the parameters was found for the two cell lines, namely a reduction of the domain size and an increase in the sensitive nuclear volume of hypoxic cells compared to those of oxic cells. In terms of oxygen enhancement ratio (OER), the experimental data behaviour can be reproduced, including dependence on particle type at the same linear energy transfer (LET). Errors on the cell survival prediction are of the same order of magnitude than for the original MK model. Our adaptation makes it possible to account for hypoxia without modelling the OER as a function of the LET of the particles, but directly accounting for hypoxic cell survival data.
Non-Markovian Persistence at the PC point of a 1d non-equilibrium kinetic Ising model
Menyhard, N; Menyhard, Nora; Odor, Geza
1997-01-01
One-dimensional non-equilibrium kinetic Ising models evolving under the competing effect of spin flips at zero temperature and nearest neighbour spin exchanges exhibiting a parity-conserving (PC) phase transition on the level of kinks are investigated here numerically from the point of view of the underlying spin system. The dynamical persistency exponent $\\Theta$ and the exponent $lambda$ characterising the two-time autocorrelation function of the total magnetization under non-equilibrium conditions are reported. It is found that the PC transition has strong effect: the process becomes non-Markovian and the above exponents exhibit drastic changes as compared to the Glauber-Ising case.
Steady-state brain glucose transport kinetics re-evaluated with a four-state conformational model
Directory of Open Access Journals (Sweden)
João M N Duarte
2009-10-01
Full Text Available Glucose supply from blood to brain occurs through facilitative transporter proteins. A near linear relation between brain and plasma glucose has been experimentally determined and described by a reversible model of enzyme kinetics. A conformational four-state exchange model accounting for trans-acceleration and asymmetry of the carrier was included in a recently developed multi-compartmental model of glucose transport. Based on this model, we demonstrate that brain glucose (Gbrain as function of plasma glucose (Gplasma can be described by a single analytical equation namely comprising three kinetic compartments: blood, endothelial cells and brain. Transport was described by four parameters: apparent half saturation constant Kt, apparent maximum rate constant Tmax, glucose consumption rate CMRglc, and the iso-inhibition constant Kii that suggests Gbrain as inhibitor of the isomerisation of the unloaded carrier. Previous published data, where Gbrain was quantified as a function of plasma glucose by either biochemical methods or NMR spectroscopy, were used to determine the aforementioned kinetic parameters. Glucose transport was characterized by Kt ranging from 1.5 to 3.5 mM, Tmax/CMRglc from 4.6 to 5.6, and Kii from 51 to 149 mM. It was noteworthy that Kt was on the order of a few mM, as previously determined from the reversible model. The conformational four-state exchange model of glucose transport into the brain includes both efflux and transport inhibition by Gbrain, predicting that Gbrain eventually approaches a maximum concentration. However, since Kii largely exceeds Gplasma, iso-inhibition is unlikely to be of substantial importance for plasma glucose below 25 mM. As a consequence, the reversible model can account for most experimental observations under euglycaemia and moderate cases of hypo- and hyperglycaemia.
Approximate linear confidence and curvature of a kinetic model of dodecanedioic acid in humans.
Panunzi, Simona; De Gaetano, Andrea; Mingrone, Geltrude
2005-11-01
Dicarboxylic acids with an even number of carbon atoms have been proposed as an alternate energy substrate for enteral or parenteral nutrition in the acutely ill patient, due to their water solubility and their yielding TCA cycle intermediates upon beta-oxidation. In the present work, a nonlinear compartmental model of the kinetics of dodecanedioic acid is developed, and its parameters are estimated from time concentration experimental observations obtained from six healthy volunteers undergoing a per os administration of 3 g of the substance. Although the model is linear in the transfer of the free substance from plasma to the tissues, the exchange between gut and plasma compartments is represented as a saturable function. Albumin binding is then incorporated to obtain the final model in terms of the measured total concentrations. Estimates of the model's structural parameters were computed for each experimental subject, and the usual single-subject approximate confidence regions for the parameters were derived by inversion of the Hessian at the optimum. To verify the applicability of this approximation, the nonlinearity of the expectation surface at the optimum was measured by computing the normal (intrinsic) component of curvature. Because the model curvature was excessive in all subjects, the usual approximation could not be trusted to provide acceptable approximations to the parameter confidence regions. A suitable Monte Carlo simulation yielded empirical joint parameter distributions from which the approximate parameter variances could finally be obtained.
Kinetic effects of adriamycin and bleomycin on two osteosarcoma models.
Bell, D F; Bell, R S; Mankin, H J; Gebhardt, M C; Weltie, F; O'Brien, T
1988-01-01
Although chemotherapeutic drugs are frequently administered to patients with osteosarcoma, there has been little research into the effect of cytotoxic drugs on osteosarcoma cell biology. The effect of two drugs (Adriamycin and bleomycin) on cell cycle kinetics was investigated in vitro in an established line of human osteosarcoma cells and in vivo using the Dunn osteosarcoma model. The cell cycle changes were consistent with G2 arrest for both drugs in vivo and in vitro. The alteration in cell cycle distribution was correlated with inhibition of 3H-thymidine incorporation in vitro. In vivo, the greater change in cell cycle distribution caused by Adriamycin was reflected in the increased inhibition of tumor growth found with this drug.
Formulation and kinetic modeling of curcumin loaded intranasal mucoadhesive microemulsion
Directory of Open Access Journals (Sweden)
B Mikesh Patel
2012-01-01
Full Text Available It is a challenge to develop the optimum dosage form of poorly water-soluble drugs and to target them due to limited bioavailability, intra and inter subject variability. In this investigation, mucoadhesive microemulsion of curcumin was developed by water titration method taking biocompatible components for intranasal delivery and was characterized. Nasal ciliotoxicity studies were carried out using excised sheep nasal mucosa. in vitro release studies of formulations and PDS were performed. Labrafil M 1944 CS based microemulsion was transparent, stable and nasal non-ciliotoxic having particle size 12.32±0.81nm (PdI=0.223 and from kinetic modeling, the release was found to be Fickian diffusion for mucoadhesive microemulsion.
An Experimental and Kinetic Modeling Study of Methyl Decanoate Combustion
Energy Technology Data Exchange (ETDEWEB)
Sarathy, S M; Thomson, M J; Pitz, W J; Lu, T
2010-02-19
Biodiesel is typically a mixture of long chain fatty acid methyl esters for use in compression ignition engines. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This research study presents new combustion data for methyl decanoate in an opposed-flow diffusion flame. An improved detailed chemical kinetic model for methyl decanoate combustion is developed, which serves as the basis for deriving a skeletal mechanism via the direct relation graph method. The novel skeletal mechanism consists of 648 species and 2998 reactions. This mechanism well predicts the methyl decanoate opposed-flow diffusion flame data. The results from the flame simulations indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular weight oxygenated compounds such as carbon monoxide, formaldehyde, and ketene.
Testing a dissipative kinetic k-essence model
Cardenas, V H; Villanueva, J R
2015-01-01
In this work, we present a study of a purely kinetic k-essence model, characterized basically by a parameter $\\alpha$ in presence of a bulk dissipative term, whose relationship between viscous pressure $\\Pi$ and energy density $\\rho$ of the background follows a polytropic type law $\\Pi \\propto \\rho^{\\lambda+1/2}$, where $\\lambda$, in principle, is a parameter without restrictions. Analytical solutions for the energy density of the k-essence field are found in two specific cases: $\\lambda=1/2$ and $\\lambda=(1-\\alpha)/2\\alpha$, and then we show that these solutions posses the same functional form than the non-viscous counterpart. Finally, both approach are contrasted with observational data from type Ia supernova, and the most recent Hubble parameter measurements, and therefore, the best values for the parameters of the theory are founds.
Testing a dissipative kinetic k-essence model
Energy Technology Data Exchange (ETDEWEB)
Cardenas, Victor H.; Villanueva, J.R. [Universidad de Valparaiso, Instituto de Fisica y Astronomia, Valparaiso (Chile); Centro de Astrofisica de Valparaiso, Valparaiso (Chile); Cruz, Norman [Universidad de Santiago de Chile, Departamento de Fisica, Santiago (Chile)
2015-04-01
In thiswork,we present a study of a purely kinetic k-essence model, characterized basically by a parameter α in presence of a bulk dissipative term, whose relationship between viscous pressure Π and energy density ρ of the background follows a polytropic type law, Π ∝ ρ{sup λ+1/2}, where λ, in principle, is a parameter without restrictions. Analytical solutions for the energy density of the k-essence field are found in two specific cases: λ = 1/2 and λ = (1 - α)/2α, and then we show that these solutions possess the same functional form as the non-viscous counterpart. Finally, both approaches are contrasted with observational data from type Ia supernova, and the most recent Hubble parameter measurements, and therefore, the best values for the parameters of the theory are found. (orig.)
Thermal stability of n-dodecane : experiments and kinetic modelling
Herbinet, Olivier; Battin-Leclerc, Frédérique; Fournet, René
2007-01-01
The thermal decomposition of n-dodecane, a component of some jet fuels, has been studied in a jet-stirred reactor at temperatures from 793 to 1093 K, for residence times between 1 and 5 s and at atmospheric pressure. Thermal decomposition of hydrocarbon fuel prior the entrance in the combustion chamber is an envisaged way to cool the wall of hypersonic vehicles. The products of the reaction are mainly hydrogen, methane, ethane, 1,3-butadiene and 1-alkenes from ethylene to 1-undecene. For higher temperatures and residence times acetylene, allene, propyne, cyclopentene, 1,3-cyclopentadiene and aromatic compounds from benzene to pyrene through naphthalene have also been observed. A previous detailed kinetic model of the thermal decomposition of n-dodecane generated using EXGAS software has been improved and completed by a sub-mechanism explaining the formation and the consumption of aromatic compounds.
A Laboratory Exercise Using a Physical Model for Demonstrating Countercurrent Heat Exchange
Loudon, Catherine; Davis-Berg, Elizabeth C.; Botz, Jason T.
2012-01-01
A physical model was used in a laboratory exercise to teach students about countercurrent exchange mechanisms. Countercurrent exchange is the transport of heat or chemicals between fluids moving in opposite directions separated by a permeable barrier (such as blood within adjacent blood vessels flowing in opposite directions). Greater exchange of…
Conflict measures in cooperative exchange models of collective decision-making
van Assen, Marcel; Stokman, Frans; van Oosten, Reinier
2003-01-01
This study focuses on externalities of exchanges of voting positions in collective decision-making. Exchanges are represented by nonconstant two-person cooperative games. It is assumed that the rate of exchange is specified by the Raiffa-Kalai-Smorodinsky solution, and a model is specified to identi
A Laboratory Exercise Using a Physical Model for Demonstrating Countercurrent Heat Exchange
Loudon, Catherine; Davis-Berg, Elizabeth C.; Botz, Jason T.
2012-01-01
A physical model was used in a laboratory exercise to teach students about countercurrent exchange mechanisms. Countercurrent exchange is the transport of heat or chemicals between fluids moving in opposite directions separated by a permeable barrier (such as blood within adjacent blood vessels flowing in opposite directions). Greater exchange of…
Kinetic Model for a Spherical Rolling Robot with Soft Shell in a Beeline Motion
Directory of Open Access Journals (Sweden)
Sheng Zhang
2014-02-01
Full Text Available A simplified kinetic model called Spring Pendulum is developed for a spherical rolling robot with soft shell in order to meet the needs of attitude stabilization and controlling for the robot. The elasticity and plasticity of soft shell is represented by some uniform springs connected to the bracket in this model. The expression of the kinetic model is deduced from Newtonian mechanics principles. Testing data of the driving angle acquired from a prototype built by authors indicate that testing data curve accords to the theoretic kinetic characteristic curve, so the kinetic model is validated
Directory of Open Access Journals (Sweden)
Alina Żogała
2014-01-01
Originality/value: This paper presents state of art in the field of coal gasification modeling using kinetic and computational fluid dynamics approach. The paper also presents own comparative analysis (concerned with mathematical formulation, input data and parameters, basic assumptions, obtained results etc. of the most important models of underground coal gasification.
Generic phase coexistence in the totally asymmetric kinetic Ising model
Godrèche, Claude; Luck, Jean-Marc
2017-07-01
The physical analysis of generic phase coexistence in the North-East-Center Toom model was originally given by Bennett and Grinstein. The gist of their argument relies on the dynamics of interfaces and droplets. We revisit the same question for a specific totally asymmetric kinetic Ising model on the square lattice. This nonequilibrium model possesses the remarkable property that its stationary-state measure in the absence of a magnetic field coincides with that of the usual ferromagnetic Ising model. We use both analytical arguments and numerical simulations in order to make progress in the quantitative understanding of the phenomenon of generic phase coexistence. At zero temperature a mapping onto the TASEP allows an exact determination of the time-dependent shape of the ballistic interface sweeping a large square minority droplet of up or down spins. At finite temperature, measuring the mean lifetime of such a droplet allows an accurate measurement of its shrinking velocity v, which depends on temperature T and magnetic field h. In the absence of a magnetic field, v vanishes with an exponent Δ_v≈2.5+/-0.2 as the critical temperature T c is approached. At fixed temperature in the ordered phase, v vanishes at the phase-boundary fields +/- h_b(T) which mark the limits of the coexistence region. The latter fields vanish with an exponent Δ_h≈3.2+/-0.3 as T c is approached.
Detailed kinetic modeling study of n-pentanol oxidation
Heufer, Karl Alexander
2012-10-18
To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.
Scale-up and kinetic modeling for bioethanol production.
Imamoglu, Esra; Sukan, Fazilet Vardar
2013-09-01
Bioethanol was produced from acidic hydrolysate of rice hulls using recombinant Escherichia coli KO11. Two different issues (scale-up and kinetic modeling) were evaluated simultaneously and concomitantly for bioethanol production. During the step-wise scale-up process from 100 mL shaken flask to 10 L stirred-tank bioreactor, the constant Reynolds number and the constant impeller tip speed were evaluated as scale-up methodologies under laboratory conditions. It was determined that the volumetric bioethanol productivity was 88% higher in 10 L bioreactor in comparison to the value of 0.21 g L(-1) h(-1) in shaken flask. The modified Monod and Luedeking-Piret models provided an accurate approach for the modeling of the experimental data. Ethanol concentration reached the maximum level of 29.03 g/L, which was 5% higher than the value of model prediction in 10 L bioreactor. The findings of this research could contribute to the industrial scale productions especially from lignocellulosic raw materials.
Gompertz kinetics model of fast chemical neurotransmission currents.
Easton, Dexter M
2005-10-01
At a chemical synapse, transmitter molecules ejected from presynaptic terminal(s) bind reversibly with postsynaptic receptors and trigger an increase in channel conductance to specific ions. This paper describes a simple but accurate predictive model for the time course of the synaptic conductance transient, based on Gompertz kinetics. In the model, two simple exponential decay terms set the rates of development and decline of transmitter action. The first, r, triggering conductance activation, is surrogate for the decelerated rate of growth of conductance, G. The second, r', responsible for Y, deactivation of the conductance, is surrogate for the decelerated rate of decline of transmitter action. Therefore, the differential equation for the net conductance change, g, triggered by the transmitter is dg/dt=g(r-r'). The solution of that equation yields the product of G(t), representing activation, and Y(t), which defines the proportional decline (deactivation) of the current. The model fits, over their full-time course, published records of macroscopic ionic current associated with fast chemical transmission. The Gompertz model is a convenient and accurate method for routine analysis and comparison of records of synaptic current and putative transmitter time course. A Gompertz fit requiring only three independent rate constants plus initial current appears indistinguishable from a Markov fit using seven rate constants.
Construction of the simplest model to explain complex receptor activation kinetics
DEFF Research Database (Denmark)
Bywater, RP; Sorensen, A; Røgen, Peter;
2002-01-01
We study the mathematical solutions to the kinetic equations arising from various simple ligand-reactor models. Focusing on the prediction of the various models for the activity vs. concentration curve, we find that solutions to the kinetic equations arising from the so-called dimer model exibit...
Forecasting Stock Exchange Movements Using Artificial Neural Network Models and Hybrid Models
Güreşen, Erkam; Kayakutlu, Gülgün
Forecasting stock exchange rates is an important financial problem that is receiving increasing attention. During the last few years, a number of neural network models and hybrid models have been proposed for obtaining accurate prediction results, in an attempt to outperform the traditional linear and nonlinear approaches. This paper evaluates the effectiveness of neural network models; recurrent neural network (RNN), dynamic artificial neural network (DAN2) and the hybrid neural networks which use generalized autoregressive conditional heteroscedasticity (GARCH) and exponential generalized autoregressive conditional heteroscedasticity (EGARCH) to extract new input variables. The comparison for each model is done in two view points: MSE and MAD using real exchange daily rate values of Istanbul Stock Exchange (ISE) index XU10).
Self-Service Banking: Value Creation Models and Information Exchange
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Ragnvald Sannes
2001-01-01
Full Text Available This paper argues that most banks have failed to exploit the potential of self-service banking because they base their service design on an incomplete business model for self-service. A framework for evaluation of self-service banking concepts is developed on the basis of Stabell and Fjeldstad's three value configurations. The value network and the value shop are consistent with self-service banking while the value chain is inappropriate. The impact of the value configurations on information exchange and self-service functionality is discussed, and a framework for design of such services proposed. Current self-service banking practices are compared to the framework, and it is concluded that current practice matches the concept of a value network and not the value shop. However, current practices are only a partial implementation of a value network-based self-service banking concept.
Enterprise Networks for Competences Exchange: A Simulation Model
Remondino, Marco; Pironti, Marco; Pisano, Paola
A business process is a set of logically related tasks performed to achieve a defined business and related to improving organizational processes. Process innovation can happen at various levels: incrementally, redesign of existing processes, new processes. The knowledge behind process innovation can be shared, acquired, changed and increased by the enterprises inside a network. An enterprise can decide to exploit innovative processes it owns, thus potentially gaining competitive advantage, but risking, in turn, that other players could reach the same technological levels. Or it could decide to share it, in exchange for other competencies or money. These activities could be the basis for a network formation and/or impact the topology of an existing network. In this work an agent based model is introduced (E3), aiming to explore how a process innovation can facilitate network formation, affect its topology, induce new players to enter the market and spread onto the network by being shared or developed by new players.
Modelling system level health information exchange: an ontological approach.
McMurray, J; Zhu, L; McKillop, I; Chen, H
2015-01-01
Investment of resources to purposively improve the movement of information between health system providers is currently made with imperfect information. No inventories of system-level digital information flows currently exist, nor do measures of inter-organizational electronic information. exchange (HIE). Using Protégé 4, an open-source OWL Web ontology language editor and knowledge-based framework we formalized a model that decomposes inter-organizational electronic health information flow into derivative concepts such as diversity, breadth, volume, structure, standardization and connectivity. Self-reported data from a regional health system is used to measure HIE; the ontology identifies providers with low and high HIE, useful for planners, and using a related database is used to monitor data quality.
Kinetic market models with single commodity having price fluctuations
Chatterjee, A; Chakrabarti, Bikas K.; Chatterjee, Arnab
2006-01-01
We study here numerically the behavior of an ideal gas like model of markets having only one non-consumable commodity. We investigate the behavior of the steady-state distributions of money, commodity and total wealth, as the dynamics of trading or exchange of money and commodity proceeds, with local (in time) fluctuations in the price of the commodity. These distributions are studied in markets with agents having uniform and random saving factors. The self-organizing features in money distribution are similar to the cases without any commodity (or with consumable commodities), the commodity distribution shows an exponential decay. The wealth distribution shows interesting behavior: Gamma like distribution for uniform saving propensity and has the same power-law tail, as that of the money distribution for a market with agents having random saving propensity.