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Sample records for model reaction studies

  1. A model study of sequential enzyme reactions and electrostatic channeling.

    Science.gov (United States)

    Eun, Changsun; Kekenes-Huskey, Peter M; Metzger, Vincent T; McCammon, J Andrew

    2014-03-14

    We study models of two sequential enzyme-catalyzed reactions as a basic functional building block for coupled biochemical networks. We investigate the influence of enzyme distributions and long-range molecular interactions on reaction kinetics, which have been exploited in biological systems to maximize metabolic efficiency and signaling effects. Specifically, we examine how the maximal rate of product generation in a series of sequential reactions is dependent on the enzyme distribution and the electrostatic composition of its participant enzymes and substrates. We find that close proximity between enzymes does not guarantee optimal reaction rates, as the benefit of decreasing enzyme separation is countered by the volume excluded by adjacent enzymes. We further quantify the extent to which the electrostatic potential increases the efficiency of transferring substrate between enzymes, which supports the existence of electrostatic channeling in nature. Here, a major finding is that the role of attractive electrostatic interactions in confining intermediate substrates in the vicinity of the enzymes can contribute more to net reactive throughput than the directional properties of the electrostatic fields. These findings shed light on the interplay of long-range interactions and enzyme distributions in coupled enzyme-catalyzed reactions, and their influence on signaling in biological systems.

  2. KINETIC MODELS STUDY OF HYDRODESULPHURIZATION VACUUM DISTILLATE REACTION

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    AbdulMunem A. Karim

    2013-05-01

    Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

  3. A computational study of pyrolysis reactions of lignin model compounds

    Science.gov (United States)

    Thomas Elder

    2010-01-01

    Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

  4. A discrete model to study reaction-diffusion-mechanics systems.

    Science.gov (United States)

    Weise, Louis D; Nash, Martyn P; Panfilov, Alexander V

    2011-01-01

    This article introduces a discrete reaction-diffusion-mechanics (dRDM) model to study the effects of deformation on reaction-diffusion (RD) processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material). Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  5. A discrete model to study reaction-diffusion-mechanics systems.

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    Louis D Weise

    Full Text Available This article introduces a discrete reaction-diffusion-mechanics (dRDM model to study the effects of deformation on reaction-diffusion (RD processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material. Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  6. a Model Study of Complex Behavior in the Belousov - Reaction.

    Science.gov (United States)

    Lindberg, David Mark

    1988-12-01

    We have studied the complex oscillatory behavior in a model of the Belousov-Zhabotinskii (BZ) reaction in a continuously-fed stirred tank reactor (CSTR). The model consisted of a set of nonlinear ordinary differential equations derived from a reduced mechanism of the chemical system. These equations were integrated numerically on a computer, which yielded the concentrations of the constituent chemicals as functions of time. In addition, solutions were tracked as functions of a single parameter, the stability of the solutions was determined, and bifurcations of the solutions were located and studied. The intent of this study was to use this BZ model to explore further a region of complex oscillatory behavior found in experimental investigations, the most thorough of which revealed an alternating periodic-chaotic (P-C) sequence of states. A P-C sequence was discovered in the model which showed the same qualitative features as the experimental sequence. In order to better understand the P-C sequence, a detailed study was conducted in the vicinity of the P-C sequence, with two experimentally accessible parameters as control variables. This study mapped out the bifurcation sets, and included examination of the dynamics of the stable periodic, unstable periodic, and chaotic oscillatory motion. Observations made from the model results revealed a rough symmetry which suggests a new way of looking at the P-C sequence. Other nonlinear phenomena uncovered in the model were boundary and interior crises, several codimension-two bifurcations, and similarities in the shapes of areas of stability for periodic orbits in two-parameter space. Each earlier model study of this complex region involved only a limited one-parameter scan and had limited success in producing agreement with experiments. In contrast, for those regions of complex behavior that have been studied experimentally, the observations agree qualitatively with our model results. Several new predictions of the model

  7. Study of n-Butyl Acrylate Self-Initiation Reaction Experimentally and via Macroscopic Mechanistic Modeling

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    Ahmad Arabi Shamsabadi

    2016-04-01

    Full Text Available This paper presents an experimental study of the self-initiation reaction of n-butyl acrylate (n-BA in free-radical polymerization. For the first time, the frequency factor and activation energy of the monomer self-initiation reaction are estimated from measurements of n-BA conversion in free-radical homo-polymerization initiated only by the monomer. The estimation was carried out using a macroscopic mechanistic mathematical model of the reactor. In addition to already-known reactions that contribute to the polymerization, the model considers a n-BA self-initiation reaction mechanism that is based on our previous electronic-level first-principles theoretical study of the self-initiation reaction. Reaction rate equations are derived using the method of moments. The reaction-rate parameter estimates obtained from conversion measurements agree well with estimates obtained via our purely-theoretical quantum chemical calculations.

  8. MODEL STUDIES OF MODE-SPECIFICITY IN UNIMOLECULAR REACTION DYNAMICS

    Energy Technology Data Exchange (ETDEWEB)

    Waite, Boyd A.; Miller, William H.

    1980-06-01

    Essentially exact quantum mechanical calculations are carried out to determine the energies and lifetimes of the quasi-bound states for a system of two (non~linearly) coupled oscillators (one of which is harmonic, the other being able to dissociate). For weak coupling the system displays mode-specificity, i.e., the unimolecular rate constants are not a monotonic function of the total energy, but increased coupling and frequency degeneracy tends to destroy mode-specificity. A somewhat surprising result is that for a given coupling the degree of modespecificity is roughly independent of the energy, in marked contrast to the fact that there is an energetic threshold for the onset of "stochastic trajectories" of the corresponding classical system; i.e., there seems to be no relation between statistical/mode-specific behavior of the unimolecular rate constants and stochastic/regular classical trajectories. In order to be able to treat more physically relevant models--i.e., those with more than two degrees of freedom--a semiclassical model is constructed and seen to be able to reproduce the accurate quantum mechanical rates reasonably well.

  9. Geochemical modeling of diagenetic reactions in Snorre Field reservoir sandstones: a comparative study of computer codes

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    Marcos Antonio Klunk

    Full Text Available ABSTRACTDiagenetic reactions, characterized by the dissolution and precipitation of minerals at low temperatures, control the quality of sedimentary rocks as hydrocarbon reservoirs. Geochemical modeling, a tool used to understand diagenetic processes, is performed through computer codes based on thermodynamic and kinetic parameters. In a comparative study, we reproduced the diagenetic reactions observed in Snorre Field reservoir sandstones, Norwegian North Sea. These reactions had been previously modeled in the literature using DISSOL-THERMAL code. In this study, we modeled the diagenetic reactions in the reservoirs using Geochemist's Workbench (GWB and TOUGHREACT software, based on a convective-diffusive-reactive model and on the thermodynamic and kinetic parameters compiled for each reaction. TOUGHREACT and DISSOL-THERMAL modeling showed dissolution of quartz, K-feldspar and plagioclase in a similar temperature range from 25 to 80°C. In contrast, GWB modeling showed dissolution of albite, plagioclase and illite, as well as precipitation of quartz, K-feldspar and kaolinite in the same temperature range. The modeling generated by the different software for temperatures of 100, 120 and 140°C showed similarly the dissolution of quartz, K-feldspar, plagioclase and kaolinite, but differed in the precipitation of albite and illite. At temperatures of 150 and 160°C, GWB and TOUGHREACT produced different results from the DISSOL-THERMAL, except for the dissolution of quartz, plagioclase and kaolinite. The comparative study allows choosing the numerical modeling software whose results are closer to the diagenetic reactions observed in the petrographic analysis of the modeled reservoirs.

  10. Importance of cytochromes in cyclization reactions: quantum chemical study on a model reaction of proguanil to cycloguanil.

    Science.gov (United States)

    Arfeen, Minhajul; Patel, Dhilon S; Abbat, Sheenu; Taxak, Nikhil; Bharatam, Prasad V

    2014-10-30

    Proguanil, an anti-malarial prodrug, undergoes cytochrome P450 catalyzed biotransformation to the pharmacologically active triazine metabolite (cycloguanil), which inhibits plasmodial dihydrofolate reductase. This cyclization is catalyzed by CYP2C19 and many anti-malarial lead compounds are being designed and synthesized to exploit this pathway. Quantum chemical calculations were performed using the model species (Cpd I for active species of cytochrome and N4-isopropyl-N6-methylbiguanide for proguanil) to elucidate the mechanism of the cyclization pathway. The overall reaction involves the loss of a water molecule, and is exothermic by approximately 55 kcal/mol, and involves a barrier of approximately 17 kcal/mol. The plausible reaction pathway involves the initial H-radical abstraction from the isopropyl group by Cpd I, followed by two alternative paths- (i) oxygen rebound to provide hydroxyl derivative and (ii) loss of additional H-radical to yield 1,3,5-triazatriene, which undergoes cyclization. This study helped in understanding the role of the active species of cytochromes in this important cyclization reaction. Copyright © 2014 Wiley Periodicals, Inc.

  11. Kinetic study of CO2 reaction with CaO by a modified random pore model

    Directory of Open Access Journals (Sweden)

    Nouri S.M.M.

    2016-03-01

    Full Text Available In this work, a modified random pore model was developed to study the kinetics of the carbonation reaction of CaO. Pore size distributions of the CaO pellets were measured by nitrogen adsorption and mercury porosimetry methods. The experiments were carried out in a thermogravimeter at different isothermal temperatures and CO2 partial pressures. A fractional concentration dependency function showed the best accuracy for predicting the intrinsic rate of reaction. The activation energy was determined as 11 kcal/mole between 550–700°C. The effect of product layer formation was also taken into account by using the variable product layer diffusivity. Also, the model was successfully predicted the natural lime carbonation reaction data extracted from the literature.

  12. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

    Science.gov (United States)

    Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Arias, T. A.; Hennig, Richard G.

    2014-02-01

    Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the SN2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the SN2 reaction.

  13. Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

    Energy Technology Data Exchange (ETDEWEB)

    Grunes, Jeffrey Benjamin

    2004-05-15

    In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al{sub 2}O{sub 3}) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum nanoparticles. The

  14. Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

    Energy Technology Data Exchange (ETDEWEB)

    Grunes, Jeffrey Benjamin [Univ. of California, Berkeley, CA (United States)

    2004-05-01

    In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al2O3) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum

  15. Neutron-induced reactions on AlF{sub 3} studied using the optical model

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Chun-Wang, E-mail: machunwang@126.com [Institute of Particle and Nuclear Physics, Henan Normal University, Xinxiang 453007 (China); Lv, Cui-Juan [Institute of Particle and Nuclear Physics, Henan Normal University, Xinxiang 453007 (China); Zhang, Guo-Qiang; Wang, Hong-Wei [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Zuo, Jia-Xu [Department of Nuclear and Radiation Safety Research, Nuclear and Radiation Safety Center (MEP), Beijing 100082 (China)

    2015-08-01

    Neutron-induced reactions on {sup 27}Al and {sup 19}F nuclei are investigated using the optical model implemented in the TALYS 1.4 toolkit. Incident neutron energies in a wide range from 0.1 keV to 30 MeV are calculated. The cross sections for the main channels (n, np), (n, p), (n, α), (n, 2n), and (n, γ) and the total reaction cross section (n, tot) of the reactions are obtained. When the default parameters in TALYS 1.4 are adopted, the calculated results agree with the measured results. Based on the calculated results for the n + {sup 27}Al and n + {sup 19}F reactions, the results of the n + {sup 27}Al{sup 19}F reactions are predicted. These results are useful both for the design of thorium-based molten salt reactors and for neutron activation analysis techniques.

  16. Reaction Networks as a Language for Systemic Modeling: On the Study of Structural Changes

    Directory of Open Access Journals (Sweden)

    Tomas Veloz

    2017-03-01

    Full Text Available Reaction Networks have been recently proposed as a framework for systems modeling due to its capability to describe many entities interacting in contextual ways and leading to the emergence of meta-structures. Since systems can be subjected to structural changes that not only alter their inner functioning, but also their underlying ontological features, a crucial issue is how to address these structural changes within a formal representational framework. When modeling systems using reaction networks, we find that three fundamentally different types of structural change are possible. The first corresponds to the usual notion of perturbation in dynamical systems, i.e., change in system’s state. The second corresponds to behavioral changes, i.e., changes not in the state of the system but on the properties of its behavioral rules. The third corresponds to radical structural changes, i.e., changes in the state-set structure and/or in reaction-set structure. In this article, we describe in detail the three types of structural changes that can occur in a reaction network, and how these changes relate to changes in the systems observable within this reaction network. In particular, we develop a decomposition theorem to partition a reaction network as a collection of dynamically independent modules, and show how such decomposition allows for precisely identifying the parts of the reaction network that are affected by a structural change.

  17. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    Science.gov (United States)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  18. Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)

    2006-05-20

    In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

  19. Theoretical kinetics studies of two model reactions in biodiesel and diesel combustion

    Science.gov (United States)

    Sha, Yuan

    We use 1-methylallyl radical (CH3CH=CH-CH2· ↔ CH3C·H-CH=CH2·) as a model of allylic radicals generated during combustion of unsaturated diesel fuel molecules. The chemically activated isomerization of 1-methylallyl generated in the highly exothermic (˜35 kcal/mol) OH + trans-2-butene reaction was considered by using RRKM/Master Equation calculations from 0.01 to 100 atm and from 300 to 700 K. Density functional theory (DFT) with the M05-2X, M06-2X and B3LYP functionals are used for structures, energies, vibrational frequencies, anharmonic constants, and the torsional potentials of methyl rotations. The cis:trans ratio formed upon quenching the radicals were, as might be expected, dependent on the functional, but, were even more sensitive when an vibrations were treated as anharmonic. The fraction of cis- 1-methylallyl is significant, if not dominant at 300 -700 K and 0.01 -10 atm. Sensitivity studies were carried out to determine the dependence of the cis:trans ratio on the extent of chemical activation, treatment of the K-rotor as active or inactive, and the rate of collisional energy transfer. All these parameters significantly influence the cis:trans ratio. The 1,5 H-migration reaction of 3-hydroperoxy-1-propylperoxy radical (HOOCH2CH2CH2OO·) is a important as a model of a critical propagation step in diesel autoignition from alkanes or molecules with long alkyl tails. Its product may be the meta-stable alpha,gamma-dihydroperoxypropyl radical or, if unstable, OH + 3-hydroperoxypropanal. To study the possibly different tunneling effects of the two possible products, the quantum mechanical rate constants, including tunneling, are directly determined using semi-classical transition state theory (SCTST) at 200 K to 1700 K. Small-curvature tunneling (SCT) is to compute tunneling corrections to classical rate constants. The two reactions do not have obvious tunneling differences at above 700 K. Below 700 K, SCTST tunneling corrections are significantly higher

  20. Kinetic modelling of hydro-treatment reactions by study of different chemical groups; Modelisation cinetique des reactions d`hydrotraitement par regroupement en familles chimiques

    Energy Technology Data Exchange (ETDEWEB)

    Bonnardot, J.

    1998-11-19

    Hydro-treatment of petroleum shortcuts permits elimination of unwanted components in order to increase combustion in engine and to decrease atmospheric pollution. Hydro-desulfurization (HDS), Hydro-denitrogenation (HDN) and Hydrogenation of aromatics (HDA) of a LCO (Light Cycle Oil)-Type gas oil have been studied using a new pilot at a fixed temperature with a NiMo/Al{sub 2}O{sub 3} catalyst. A hydrodynamic study showed that reactions occurring in the up-flow fixed bed reactor that has been used during the experiments, were governed exclusively by chemical reaction rates and not by diffusion. Through detailed chemical analysis, height chemical groups have been considered: three aromatics groups, one sulfided group, one nitrogenized and NH{sub 3}, H{sub 2}S, H{sub 2}. Two Langmuir-Hinshelwood-type kinetic models with either one or two types of sites have been established. The model with two types of site - one site of hydrogenation and one site of hydrogenolysis - showed a better fit in the modeling of the experimental results. This model enables to forecast the influence of partial pressure of H{sub 2}S and partial pressure of H{sub 2} on hydro-treatment reactions of a LCO-type gas oil. (author) 119 refs.

  1. Studying Nuclear Level Densities of 238U in the Nuclear Reactions within the Macroscopic Nuclear Models

    Science.gov (United States)

    Razavi, Rohallah; Rahmatinejad, Azam; Kakavand, Tayeb; Taheri, Fariba; Aghajani, Maghsood; Khooy, Asghar

    2016-02-01

    In this work the nuclear level density parameters of 238U have been extracted in the back-shifted Fermi gas model (BSFGM), as well as the constant temperature model (CTM), through fitting with the recent experimental data on nuclear level densities measured by the Oslo group. The excitation functions for 238U(p,2nα)233Pa, and 238U(p,4n)235Np reactions and the fragment yields for the fragments of the 238U(p,f) reaction have been calculated using obtained level density parameters. The results are compared to their corresponding experimental values. It was found that the extracted excitation functions and the fragment yields in the CTM coincide well with the experimental values in the low-energy region. This finding is according to the claim made by the Oslo group that the extracted level densities of 238U show a constant temperature behaviour.

  2. A comprehensive study of back-reaction and effective acceleration in generic LTB dust models

    CERN Document Server

    Sussman, Roberto A

    2011-01-01

    We provide a thorough examination of the conditions for the existence of back-reaction and an "effective" acceleration (in the context of Buchert's averaging formalism) in regular generic spherically symmetric Lemaitre-Tolman-Bondi (LTB) dust models. By considering arbitrary spherical comoving domains, we verify rigorously the fulfillment of these conditions expressed in terms of suitable scalar variables that are evaluated at the domains' boundaries. Effective deceleration necessarily occurs in all domains in: (a) the asymptotic radial range of models converging to a FLRW background, (b) the asymptotic time range of non-vacuum hyperbolic models, (c) LTB self-similar solutions and (d) near a simultaneous big bang. Accelerating domains are proven to exist in the following scenarios: (i) central vacuum regions, (ii) central (non-vacuum) density voids, (iii) the intermediate radial range of models converging to a FLRW background, (iv) the asymptotic radial range of models converging to a Minkowski vacuum and (v)...

  3. Reaction mechanism of ethylene glycol decomposition on Pt model catalysts: A density functional theory study

    Science.gov (United States)

    Lv, Cun-Qin; Yang, Bo; Pang, Xian-Yong; Wang, Gui-Chang

    2016-12-01

    Understanding and controlling bond beak sequence is important in catalytic processes. The DFT-GGA method combined with slab model was performed to study the ethylene glycol decomposition on various Pt model catalysts such as close-packed Pt(111), stepped Pt(211) and a more open one, Pt(100). Calculation results show that the adsorption energies of ethylene glycol and other decomposition species depend on the coordination number of surface atom, that is, low coordination number correspond to high adsorption energy. Moreover, it was found that final products of ethylene glycol decomposition are CO and H2 on all model catalysts, but the reaction mechanism varies: On Pt(111), the first step is Osbnd H bond scission, followed by Csbnd H bond cleavage, namely C2H6O2 → HOCH2CH2O + H → HOCH2CHO + 2H→ HOCH2CO +3H → OCH2CO + 4H → OCHCO + 5H → CO + HCO + 5H → 2CO + 6H→ 2CO + 3H2; On Pt(211) and Pt(100), however, it is a second Osbnd H bond cleavage that follows the initial Osbnd H bond scission, that is, C2H6O2 → HOCH2CH2O + H → OCH2CH2O + 2H → OCHCH2O + 3H → OCHCHO + 4H → 2HCO + 4H → 2CO + 6H → 2CO + 3H2 on Pt(211), and C2H6O2 →HOCH2CH2O+ H → OCH2CH2O + 2H→OCHCH2O+3H→OCCH2O+4H→CO+H2CO+4H→CO+HCO+5H→2CO+6H→2CO+3H2 on Pt(100) For the catalytic order of ethylene glycol to form H2, it may be determined based on the rate-controlling step, and it is Pt(111) > Pt(211) > Pt(100).

  4. Experimental and Modeling Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor

    OpenAIRE

    Hacarlioglu, Pelin

    2007-01-01

    This dissertation describes the preparation of a novel inorganic membrane for hydrogen permeation and its application in a membrane reactor for the study of the methane steam reforming reaction. The investigations include both experimental studies of the membrane permeation mechanism and theoretical modeling of mass transfer through the membrane and simulation of the membrane reactor with 1-D and 2-D models. A hydrothermally stable and hydrogen selective membrane composed of silica and a...

  5. An In Vitro Model for Studying Neutrophil Activation During Cardiopulmonary Bypass by Using a Polymerase Chain Reaction Thermocycler

    NARCIS (Netherlands)

    Tang, Min; Zhao, Xiao-Gang; Gu, Y. John; Chen, Chang-Zhi

    2010-01-01

    The accurate temperature control of a polymerase chain reaction (PCR) thermocycler was exploited in developing an in vitro model to study neutrophil activation during cardiopulmonary bypass. Neutrophils from 12 volunteers underwent temperature changes in a PCR thermocycler (37 degrees C for 30 minut

  6. An In Vitro Model for Studying Neutrophil Activation During Cardiopulmonary Bypass by Using a Polymerase Chain Reaction Thermocycler

    NARCIS (Netherlands)

    Tang, Min; Zhao, Xiao-Gang; Gu, Y. John; Chen, Chang-Zhi

    The accurate temperature control of a polymerase chain reaction (PCR) thermocycler was exploited in developing an in vitro model to study neutrophil activation during cardiopulmonary bypass. Neutrophils from 12 volunteers underwent temperature changes in a PCR thermocycler (37 degrees C for 30

  7. Identifiability of parameters and behaviour of MCMC chains: a case study using the reaction norm model.

    Science.gov (United States)

    Shariati, M M; Korsgaard, I R; Sorensen, D

    2009-04-01

    Markov chain Monte Carlo (MCMC) enables fitting complex hierarchical models that may adequately reflect the process of data generation. Some of these models may contain more parameters than can be uniquely inferred from the distribution of the data, causing non-identifiability. The reaction norm model with unknown covariates (RNUC) is a model in which unknown environmental effects can be inferred jointly with the remaining parameters. The problem of identifiability of parameters at the level of the likelihood and the associated behaviour of MCMC chains were discussed using the RNUC as an example. It was shown theoretically that when environmental effects (covariates) are considered as random effects, estimable functions of the fixed effects, (co)variance components and genetic effects are identifiable as well as the environmental effects. When the environmental effects are treated as fixed and there are other fixed factors in the model, the contrasts involving environmental effects, the variance of environmental sensitivities (genetic slopes) and the residual variance are the only identifiable parameters. These different identifiability scenarios were generated by changing the formulation of the model and the structure of the data and the models were then implemented via MCMC. The output of MCMC sampling schemes was interpreted in the light of the theoretical findings. The erratic behaviour of the MCMC chains was shown to be associated with identifiability problems in the likelihood, despite propriety of posterior distributions, achieved by arbitrarily chosen uniform (bounded) priors. In some cases, very long chains were needed before the pattern of behaviour of the chain may signal the existence of problems. The paper serves as a warning concerning the implementation of complex models where identifiability problems can be difficult to detect a priori. We conclude that it would be good practice to experiment with a proposed model and to understand its features

  8. A computational study of ultrafast acid dissociation and acid-base neutralization reactions. I. The model.

    Science.gov (United States)

    Maurer, Patrick; Thomas, Vibin; Rivard, Ugo; Iftimie, Radu

    2010-07-28

    Ultrafast, time-resolved investigations of acid-base neutralization reactions have recently been performed using systems containing the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) and various Bronsted bases. Two conflicting neutralization mechanisms have been formulated by Mohammed et al. [Science 310, 83 (2005)] and Siwick et al. [J. Am. Chem. Soc. 129, 13412 (2007)] for the same acid-base system. Herein an ab initio molecular dynamics based computational model is formulated, which is able to investigate the validity of the proposed mechanisms in the general context of ground-state acid-base neutralization reactions. Our approach consists of using 2,4,6-tricyanophenol (exp. pKa congruent with 1) as a model for excited-state HPTS( *) (pKa congruent with 1.4) and carboxylate ions for the accepting base. We employ our recently proposed dipole-field/quantum mechanics (QM) treatment [P. Maurer and R. Iftimie, J. Chem. Phys. 132, 074112 (2010)] of the proton donor and acceptor molecules. This approach allows one to tune the free energy of neutralization to any desired value as well as model initial nonequilibrium hydration effects caused by a sudden increase in acidity, making it possible to achieve a more realistic comparison with experimental data than could be obtained via a full-QM treatment of the entire system. It is demonstrated that the dipole-field/QM model reproduces correctly key properties of the 2,4,6-tricyanophenol acid molecule including gas-phase proton dissociation energies and dipole moments, and condensed-phase hydration structure and pKa values.

  9. The effect of a number of selective points in modeling of polymerization reacting Monte Carlo method: studying the initiation reaction

    CERN Document Server

    Sadi, M; Dabir, B

    2003-01-01

    Monte Carlo Method is one of the most powerful techniques to model different processes, such as polymerization reactions. By this method, without any need to solve moment equations, a very detailed information on the structure and properties of polymers are obtained. The number of algorithm repetitions (selected volumes of reactor for modelling which represent the number of initial molecules) is very important in this method. In Monte Carlo method calculations are based on the random number of generations and reaction probability determinations. so the number of algorithm repetition is very important. In this paper, the initiation reaction was considered alone and the importance of number of initiator molecules on the result were studied. It can be concluded that Monte Carlo method will not give accurate results if the number of molecules is not satisfied to be big enough, because in that case , selected volume would not be representative of the whole system.

  10. Reduction of chemical reaction models

    Science.gov (United States)

    Frenklach, Michael

    1991-01-01

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

  11. Chemical-reaction model for Mexican wave

    Science.gov (United States)

    Nagatani, Takashi

    2003-05-01

    We present a chemical-reaction model to describe the Mexican wave ( La Ola) in football stadia. The spectator's action is described in terms of chemical reactions. The model is governed by three reaction rates k 1, k 2, and k3. We study the nonlinear waves on one- and two-dimensional lattices. The Mexican wave is formulated as a clockwise forwardly propagating wave. Waves are growing or disappear, depending on the values of reaction rates. In the specific case of k1= k2= k3=1, the nonlinear-wave equation produces a propagating pulse like soliton.

  12. The potential of model studies for the understanding of catalyst poisoning and temperature effects in polymer electrolyte fuel cell reactions

    Science.gov (United States)

    Behm, R. J.; Jusys, Z.

    In this contribution we demonstrate the potential of model studies for the understanding of electrocatalytic reactions in low-temperature polymer electrolyte fuel cells (PEFCs) operated by H 2-rich anode feed gas, in particular of the role of temperature effects and catalyst poisoning. Reviewing previous work from our laboratory and, for better comparison, focussing on carbon-supported Pt catalysts, the important role of using fuel cell relevant reaction and mass transport conditions will be outlined. The latter conditions include continuous reaction, elevated temperatures, realistic supported catalyst materials and controlled mass transport. The data show the importance of combining electrochemical techniques such as rotating disc electrode (RDE), wall-jet and flow cell measurements, and on-line differential electrochemical mass spectrometry (DEMS) under controlled mass transport conditions.

  13. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  14. Theoretical Studies of Reaction Surfaces

    Science.gov (United States)

    2007-11-02

    Similar levels of agreement are being found in studies of water clusters12 , the Menshutkin reaction 13 (ion separation reaction ), a prototypical SN2 ...of both reactants and products. These analyses reveal that Bery pseudorotation occurs repeatedly during the side attack, whereas the SN2 reaction H...31 Aug 97 4. TITLE AND SUBTITLE 5. FUNDING NUMBERS AASERT93 THEORETICAL STUDIES OF REACTION SURFACES F49620-93-1-0556 3484/XS 6. AUTHOR(S) 61103D DR

  15. Heterogeneous reactions of NO2 and HNO3 on oxides and mineral dust: A combined laboratory and modeling study

    Science.gov (United States)

    Underwood, G. M.; Song, C. H.; Phadnis, M.; Carmichael, G. R.; Grassian, V. H.

    2001-08-01

    This study combines laboratory measurements and modeling analysis to quantify the role of heterogeneous reactions of gaseous nitrogen dioxide and nitric acid on mineral oxide and mineral dust particles in tropospheric ozone formation. At least two types of heterogeneous reactions occur on the surface of these particles. Upon initial exposure of the oxide to NO2 there is a loss of NO2 from the gas phase by adsorption on the particle surface, i.e., NO2(g) → NO2(a). As the reaction proceeds, a reduction of gaseous NO2 to NO, NO2 (g) → NO (g) is found to occur. Initial uptake coefficients γ0 for NO2 on the surface of these particles have been measured at 298 K using a Knudsen cell reactor coupled to a mass spectrometer. For the oxides studied, α,γ-Al2O3, α,γ-Fe2O3, TiO2, SiO2, CaO, and MgO, γ0 ranges from dry surfaces are just below the lower limit to have an impact on the photochemical oxidant cycle, while the heterogeneous reactivity of HNO3 is sufficiently large to have an effect. Under conditions of high mineral dust mass loadings and/or smaller size distributions the importance of these reactions (both NO2 and HNO3) is expected to increase.

  16. Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

    NARCIS (Netherlands)

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions durin

  17. Kinetic Models Study of Hydrogenation of Aromatic Hydrocarbons in Vacuum Gas Oil and Basrah Crude Oil Reaction

    Directory of Open Access Journals (Sweden)

    Muzher M. Ibraheem

    2013-05-01

    Full Text Available             The aim of this research is to study the kinetic reaction models for catalytic hydrogenation of aromatic content for Basrah crude oil (BCO and vacuum gas oil (VGO derived from Kirkuk crude oil which has the boiling point rang of (611-833K.            This work is performed using a hydrodesulphurization (HDS pilot plant unit located in AL-Basil Company. A commercial (HDS catalyst cobalt-molybdenum (Co-Mo supported in alumina (γ-Al2O3 is used in this work. The feed is supplied by North Refinery Company in Baiji. The reaction temperatures range is (600-675 K over liquid hourly space velocity (LHSV range of (0.7-2hr-1 and hydrogen pressure is 3 MPa with H2/oil ratio of 300 of Basrah Crude oil (BCO, while the corresponding conditions for vacuum gas oil (VGO are (583-643 K, (1.5-3.75 hr-1, 3.5 MPa and 250  respectively .            The results showed that the reaction kinetics is of second order for both types of feed. Activation energies are found to be 30.396, 38.479 kJ/mole for Basrah Crude Oil (BCO and Vacuum Gas Oil (VGO respectively.

  18. A Field Study of Participant Reactions to a Developmental Assessment Centre: Testing an organisational justice model

    Directory of Open Access Journals (Sweden)

    Michael M Harris

    2008-06-01

    Full Text Available Although assessment centres are being increasingly employed for developmental purposes, there has been a dearth of research regarding them. We investigated an organisational justice theory model suggested by Cohen-Charash and Spector (2001 in this relatively novel context. The model included antecedents (e.g., perceived validity, organisational justice perceptions (i.e., distributive justice and procedural justice, and one outcome (i.e., feedback utility perceptions. Most of our hypotheses were supported, suggesting much evidence for this model. The predicted effect for perceived fakability was not supported. Contrary to our hypothesis, distributive justice perceptions were at least as important as procedural justice perceptions in predicting feedback utility perceptions. A direct test of the effect of context on organisational justice theory is recommended.

  19. Progress in microscopic direct reaction modeling of nucleon induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dupuis, M.; Bauge, E.; Hilaire, S.; Lechaftois, F.; Peru, S.; Pillet, N.; Robin, C. [CEA, DAM, DIF, Arpajon (France)

    2015-12-15

    A microscopic nuclear reaction model is applied to neutron elastic and direct inelastic scatterings, and pre-equilibrium reaction. The JLM folding model is used with nuclear structure information calculated within the quasi-particle random phase approximation implemented with the Gogny D1S interaction. The folding model for direct inelastic scattering is extended to include rearrangement corrections stemming from both isoscalar and isovector density variations occurring during a transition. The quality of the predicted (n,n), (n,n{sup '}), (n,xn) and (n,n{sup '}γ) cross sections, as well as the generality of the present microscopic approach, shows that it is a powerful tool that can help improving nuclear reactions data quality. Short- and long-term perspectives are drawn to extend the present approach to more systems, to include missing reactions mechanisms, and to consistently treat both structure and reaction problems. (orig.)

  20. A Reaction-Based River/Stream Water Quality Model: Reaction Network Decomposition and Model Application

    Directory of Open Access Journals (Sweden)

    Fan Zhang

    2012-01-01

    Full Text Available This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equilibrium reactions to decouple equilibrium and kinetic reactions. This approach minimizes the number of partial differential advective-dispersive transport equations and enables robust numerical integration. Complete matrix decomposition by further pivoting on linearly independent kinetic reactions allows some rate equations to be formulated individually and explicitly enforces conservation of component species when component transport equations are solved. The methodology is demonstrated for a case study involving eutrophication reactions in the Des Moines River in Iowa, USA and for two hypothetical examples to illustrate the ability of the model to simulate sediment and chemical transport with both mobile and immobile water phases and with complex reaction networks involving both kinetic and equilibrium reactions.

  1. Modelling Chemical Reasoning to Predict Reactions

    CERN Document Server

    Segler, Marwin H S

    2016-01-01

    The ability to reason beyond established knowledge allows Organic Chemists to solve synthetic problems and to invent novel transformations. Here, we propose a model which mimics chemical reasoning and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180,000 randomly selected binary reactions. We show that our data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-) discovering novel transformations (even including transition-metal catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph, and because each single reaction prediction is typically ac...

  2. Reaction-diffusion pulses: a combustion model

    Energy Technology Data Exchange (ETDEWEB)

    Campos, Daniel [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Llebot, Josep Enric [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Fort, Joaquim [Dept. de FIsica, Univ. de Girona, Campus de Montilivi, 17071 Girona, Catalonia (Spain)

    2004-07-02

    We focus on a reaction-diffusion approach proposed recently for experiments on combustion processes, where the heat released by combustion follows first-order reaction kinetics. This case allows us to perform an exhaustive analytical study. Specifically, we obtain the exact expressions for the speed of the thermal pulses, their maximum temperature and the condition of self-sustenance. Finally, we propose two generalizations of the model, namely, the case of several reactants burning together, and that of time-delayed heat conduction. We find an excellent agreement between our analytical results and simulations.

  3. Quark model study of the π N →π N reactions up to the N (1440 ) resonance region

    Science.gov (United States)

    Wang, Kai-Lei; Xiao, Li-Ye; Zhong, Xian-Hui

    2017-05-01

    A combined analysis of the reactions π+p →π+p , π-p →π-p , and π-p →π0n is carried out with a chiral quark model. The observations are reasonably described from the Δ (1232 ) resonance region up to the N (1440 ) resonance region. Besides the Δ (1232 ) P33 , a confirmed role of N (1440 ) P11 is found in the polarizations of the π-p →π-p and π-p →π0n reactions. It is found that the N (1440 )N π and Δ (1232 )N π couplings are about 1.7 and 4.8 times larger than the expectations from the simple quark model, respectively, which may suggest the unusual property of N (1440 ) P11 and deficiency of the simple quark model in the description of N (1440 ) P11 and Δ (1232 ) P33 . The t - and u -channel backgrounds have notable contributions to the π+p →π+p reaction, while in the π-p →π-p ,π0n reactions, the s -channel nucleon and t - and u -channel backgrounds play crucial roles.

  4. Investigation and Modelling of Diesel Hydrotreating Reactions

    DEFF Research Database (Denmark)

    Boesen, Rasmus Risum

    This project consists of a series of studies, that are related to hydrotreating of diesel. Hy- drotreating is an important refinery process, in which the oil stream is upgraded to meet the required environmental specifications and physical properties. Although hydrotreating is a ma- ture technology...... on a commercial CoMo catalyst, and a simple kinetic model is presented. Hydrogenation of fused aromatic rings are known to be fast, and it is possible, that the reaction rates are limited by either internal or external mass transfer. An experiment conducted at industrial temperatures and pressure, using...... kinetic models. Hydrogenation reactions are quite fast, and in order to avoid mass transfer limitations, and only measure intrinsic rates, experiments are often conducted, at conditions that are milder than in industrial units. A reactor model for a Robinson-Mahoney reactor that takes mass transfer...

  5. Studying nuclear level densities of {sup 238}U in the nuclear reactions within the macroscopic nuclear models

    Energy Technology Data Exchange (ETDEWEB)

    Razavi, Rohallah; Aghajani, Maghsood; Khooy, Asghar [Imam Hossein Comprehensive Univ., Tehran (Iran, Islamic Republic of). Dept. of Physics; Rahmatinejad, Azam; Taheri, Fariba [Univ. of Zanjan (Iran, Islamic Republic of). Dept. of Physics; Kakavand, Tayeb [Imam Khomeini International Univ., Qazvin (Iran, Islamic Republic of). Dept. of Physics

    2016-05-01

    In this work the nuclear level density parameters of {sup 238}U have been extracted in the back-shifted Fermi gas model (BSFGM), as well as the constant temperature model (CTM), through fitting with the recent experimental data on nuclear level densities measured by the Oslo group. The excitation functions for {sup 238}U(p,2nα){sup 233}Pa, and {sup 238}U(p,4n){sup 235}Np reactions and the fragment yields for the fragments of the {sup 238}U(p,f) reaction have been calculated using obtained level density parameters. The results are compared to their corresponding experimental values. It was found that the extracted excitation functions and the fragment yields in the CTM coincide well with the experimental values in the low-energy region. This finding is according to the claim made by the Oslo group that the extracted level densities of {sup 238}U show a constant temperature behaviour.

  6. Influence of a dexamethasone-eluting covered stent on tissue reaction: an experimental study in a canine bronchial model

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Ji Hoon; Song, Ho-Young; Choi, Gi Bok; Kim, Tae-Hyung; Suh, Ji-Yeon [University of Ulsan College of Medicine, Department of Radiology, Asan Medical Center, Seoul (Korea); Seo, Tae-Seok [Gachon Medical School, Department of Radiology, Gil Medical Center, Inchon (Korea); Yuk, Soon Hong [Hannam University, Department of Polymer Science and Engineering, College of Engineering, Daejeon (Korea); Kim, Young-Hwa [Soonchunhyang University Chonan Hospital, Department of Radiology, Chonan (Korea); Cho, Yong-Mee [University of Ulsan College of Medicine, Department of Pathology, Asan Medical Center, Seoul (Korea)

    2005-06-01

    This study was designed to evaluate the feasibility and efficacy of a dexamethasone (DXM)-eluting, covered, self-expanding metallic stent to reduce tissue reaction following stent placement in a canine bronchial model. We placed a DXM-eluting, polyurethane-covered, self-expanding metallic stent (drug stent, DS) and a polyurethane-covered, self-expanding metallic stent (control stent, CS) alternately in each left main bronchus and left lower lobe bronchus in 12 dogs. The stents were 20 mm in diameter and length when fully expanded. The dose of DXM was approximately 36.7 mg in each DS, but was absent in the CS. The dogs were euthanased 1 week (n=4), 2 weeks (n=4) or 4 weeks (n=4) after stent placement. Histologic findings, such as epithelial erosion/ulcer or granulation tissue thickness, were obtained from the mid-portion of the bronchus, where the stent had been placed, and evaluated between DS and CS. There were no procedure-related complications or malpositioning of any of the bronchial stents. Stent migration was detected in one dog just before euthanasia 1 week following stent placement. Stent patency was maintained until euthanasia in all dogs. Epithelial erosion/ulcer (%) was significantly less in the DS (mean{+-}standard deviation, 46.88{+-}23.75) than in the CS (73.75{+-}14.08) (P=0.026) for all time-points. There was a decrease in epithelial erosion/ulcer as the follow-up period increased in both DS and CS. The granulation tissue thickness (mm) was less in DS (2.63{+-}2.05) than in CS (3.49{+-}2.95), although the difference was not significant (P=0.751) for all time-points. There was a tendency toward an increase in granulation tissue thickness and chronic lymphocytic infiltration as the follow-up period increased in both DS and CS. In conclusion, DXM-eluting, covered, self-expanding metallic stent seems to be effective in reducing tissue reaction secondary to stent placement in a canine bronchial model. (orig.)

  7. Estimating reaction constants by ab initio molecular modeling: a study on the oxidation of phenol to catechol and hydroquinone in advanced oxidation processes

    Directory of Open Access Journals (Sweden)

    B. Ramos

    2012-03-01

    Full Text Available Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

  8. A study of kinetic modelling and reaction pathway of 2,4-dichlorophenol transformation by photo-fenton-like oxidation.

    Science.gov (United States)

    Chu, W; Kwan, C Y; Chan, K H; Kam, S K

    2005-05-20

    The degradation of 2,4-dichlorophenol (2,4-DCP) by the photo-Fenton-like (Fe3+/H2O2/UVC) process under various reaction conditions was investigated. It was interesting to find that the reaction kinetics of 2,4-DCP in Fe3+/H2O2/UVC systems varied depending on the initial [Fe3+] concentration. A pseudo first-order kinetic and a non-conventional kinetic were discovered at low and higher [Fe3+] concentrations, respectively. A model was used to simulate the non-conventional kinetic process, where two character parameters (the initial decay rate and the final decay fraction) were found to be critical in determining the process. The two parameters successfully quantify the photo-Fenton-like oxidation under different concentrations of [Fe3+] and [H2O2] and the corresponding ratios of Fe(III)/H2O2. The reaction intermediates were identified by an LC/MS analysis and a reaction mechanism was proposed.

  9. Exhaustive study of the noise-induced phase transition in a stochastic model of self-catalyzed reactions

    Science.gov (United States)

    Pham, T. M.; Virchenko, Yu. P.

    2016-08-01

    We completely investigate the stationary distribution density in the space of relative concentrations for the three-parameter stochastic Horsthemke-Lefever model of a binary self-catalyzed cyclic chemical reaction with perturbations produced by thermal fluctuations of reagents taken into account. This model is a stationary diffusion random process generated by a stochastic equation with the Stratonovich differential, whose marginal distribution density admits a bifurcation restructuring from the unimodal to the bimodal phase with increasing noise intensity, which is interpreted physically as a dynamical phase transition induced by fluctuations in the system.

  10. Recovery Act: An Integrated Experimental and Numerical Study: Developing a Reaction Transport Model that Couples Chemical Reactions of Mineral Dissolution/Precipitation with Spatial and Temporal Flow Variations.

    Energy Technology Data Exchange (ETDEWEB)

    Saar, Martin O. [ETH Zurich (Switzerland); Univ. of Minnesota, Minneapolis, MN (United States); Seyfried, Jr., William E. [Univ. of Minnesota, Minneapolis, MN (United States); Longmire, Ellen K. [Univ. of Minnesota, Minneapolis, MN (United States)

    2016-06-24

    A total of 12 publications and 23 abstracts were produced as a result of this study. In particular, the compilation of a thermodynamic database utilizing consistent, current thermodynamic data is a major step toward accurately modeling multi-phase fluid interactions with solids. Existing databases designed for aqueous fluids did not mesh well with existing solid phase databases. Addition of a second liquid phase (CO2) magnifies the inconsistencies between aqueous and solid thermodynamic databases. Overall, the combination of high temperature and pressure lab studies (task 1), using a purpose built apparatus, and solid characterization (task 2), using XRCT and more developed technologies, allowed observation of dissolution and precipitation processes under CO2 reservoir conditions. These observations were combined with results from PIV experiments on multi-phase fluids (task 3) in typical flow path geometries. The results of the tasks 1, 2, and 3 were compiled and integrated into numerical models utilizing Lattice-Boltzmann simulations (task 4) to realistically model the physical processes and were ultimately folded into TOUGH2 code for reservoir scale modeling (task 5). Compilation of the thermodynamic database assisted comparisons to PIV experiments (Task 3) and greatly improved Lattice Boltzmann (Task 4) and TOUGH2 simulations (Task 5). PIV (Task 3) and experimental apparatus (Task 1) have identified problem areas in TOUGHREACT code. Additional lab experiments and coding work has been integrated into an improved numerical modeling code.

  11. Modelling Chemical Reasoning to Predict Reactions

    OpenAIRE

    Segler, Marwin H. S.; Waller, Mark P.

    2016-01-01

    The ability to reason beyond established knowledge allows Organic Chemists to solve synthetic problems and to invent novel transformations. Here, we propose a model which mimics chemical reasoning and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outpe...

  12. A topological study of the decomposition of 6,7,8-trioxabicyclo[3.2.2]nonane induced by Fe(II): modeling the artemisinin reaction with heme.

    Science.gov (United States)

    Moles, Pamela; Oliva, Mónica; Sánchez-González, Angel; Safont, Vicent S

    2010-01-21

    We report a theoretical study on the electronic and topological aspects of the reaction of dihydrated Fe(OH)(2) with 6,7,8-trioxabicyclo[3.2.2]nonane, as a model for the reaction of heme with artemisinin. A comparison is made with the reaction of dihydrated ferrous hydroxide with O(2), as a model for the heme interaction with oxygen. We found that dihydrated Fe(OH)(2) reacts more efficiently with the artemisinin model than with O(2). This result suggests that artemisinin instead of molecular oxygen would interact with heme, disrupting its detoxification process by avoiding the initial heme to hemin oxidation, and killing in this way the malaria parasite. The ELF and AIM theories provide support for such a conclusion, which further clarifies our understanding on how artemisinin acts as an antimalarial agent.

  13. Kinetic analysis of the phenyl-shift reaction in $\\beta$-O-4 lignin model compounds: A computational study.

    Energy Technology Data Exchange (ETDEWEB)

    Beste, Ariana [ORNL; Buchanan III, A C [ORNL

    2011-01-01

    The phenyl-shift reaction in $\\beta$-phenethyl phenyl ether ($\\beta - \\rm PhCH_2CH_2OPh$, $\\beta$-PPE) is an integral step in the pyrolysis of PPE, which is a model compound for the $\\beta$-O-4 linkage in lignin. We investigated the influence of natural occurring substituents (hydroxy, methoxy) on the reaction rate by calculating relative rate constant using density functional theory in combination with transition state theory, including anharmonic correction for low-frequency modes. The phenyl-shift reaction proceeds through an intermediate and the overall rate constants were computed invoking the steady-state approximation (its validity was confirmed). Substituents on the phenethyl group have only little influence on the rate constants. If a methoxy substituent is located in para position of the phenyl ring adjacent to the ether oxygen, the energies of the intermediate and second transition state are lowered, but the overall rate constant is not significantly altered. This is a consequence of the dominating first transition from pre-complex to intermediate in the overall rate constant. {\\it O}- and di-{\\it o}-methoxy substituents accelerate the phenyl-migration rate compared to $\\beta$-PPE.

  14. Constraints on the α + nucleus optical-model potential via α-induced reaction studies on 108Cd

    Science.gov (United States)

    Scholz, P.; Heim, F.; Mayer, J.; Münker, C.; Netterdon, L.; Wombacher, F.; Zilges, A.

    2016-10-01

    A big part in understanding the nucleosynthesis of heavy nuclei is a proper description of the effective interaction between an α-particle and a target nucleus. Information about the so-called α +nucleus optical-model potential is achieved by precise cross-section measurements at sub-Coulomb energies aiming to constrain the theoretical models for the nuclear physics input-parameters. The cross sections of the 108Cd(α , γ) and 108Cd(α , n) reaction have been measured for the first time close to the astrophysically relevant energy region via the in-beam method at the high-efficiency γ-ray spectrometer HORUS and via the activation technique at the Cologne Clover Counting Setup at the Institute for Nuclear Physics in Cologne, Germany. Comparisons between experimental results and theoretical predictions calculated in the scope of the Hauser-Feshbach statistical model confirm the need for a exponentially decreasing imaginary part of the potential. Moreover, it is shown that the results presented here together with already published data indicate that a systematic investigation of the real part of the potential could help to further improve the understanding of reactions involving α-particles.

  15. Constraints on the α+nucleus optical-model potential via α-induced reaction studies on 108Cd

    Directory of Open Access Journals (Sweden)

    P. Scholz

    2016-10-01

    Full Text Available A big part in understanding the nucleosynthesis of heavy nuclei is a proper description of the effective interaction between an α-particle and a target nucleus. Information about the so-called α+nucleus optical-model potential is achieved by precise cross-section measurements at sub-Coulomb energies aiming to constrain the theoretical models for the nuclear physics input-parameters. The cross sections of the 108Cd(α,γ and 108Cd(α,n reaction have been measured for the first time close to the astrophysically relevant energy region via the in-beam method at the high-efficiency γ-ray spectrometer HORUS and via the activation technique at the Cologne Clover Counting Setup at the Institute for Nuclear Physics in Cologne, Germany. Comparisons between experimental results and theoretical predictions calculated in the scope of the Hauser–Feshbach statistical model confirm the need for a exponentially decreasing imaginary part of the potential. Moreover, it is shown that the results presented here together with already published data indicate that a systematic investigation of the real part of the potential could help to further improve the understanding of reactions involving α-particles.

  16. Thermal Studies of Ammonium Cyanide Reactions: A Model for Thermal Alteration of Prebiotic Compounds in Meteorite Parent Bodies

    Science.gov (United States)

    Hammer, P. G.; Locke, D. R.; Burton, A. S.; Callahan, M. P.

    2017-01-01

    Organic compounds in carbonaceous chondrites were likely transformed by a variety of parent body processes including thermal and aqueous processing. Here, we analyzed ammonium cyanide reactions that were heated at different temperatures and times by multiple analytical techniques. The goal of this study is to better understand the effect of hydrothermal alteration on cyanide chemistry, which is believed to be responsible for the abiotic synthesis of purine nucleobases and their structural analogs detected in carbonaceous chondrites.

  17. Modelling of simultaneous mass and heat transfer with chemical reaction using the Maxwell-Stefan theory—I. Model development and isothermal study

    NARCIS (Netherlands)

    Frank, M.J.W.; Kuipers, J.A.M.; Versteeg, G.F.; Swaaij, W.P.M. van

    1995-01-01

    A general applicable model has been developed which can predict mass and heat transfer fluxes through a vapour/gas-liquid interface in case a reversible chemical reaction with associated heat effect takes place in the liquid phase. In this model the Maxwell-Stefan theory has been used to describe th

  18. Connectionist and diffusion models of reaction time.

    Science.gov (United States)

    Ratcliff, R; Van Zandt, T; McKoon, G

    1999-04-01

    Two connectionist frameworks, GRAIN (J. L. McClelland, 1993) and brain-state-in-a-box (J. A. Anderson, 1991), and R. Ratcliff's (1978) diffusion model were evaluated using data from a signal detection task. Dependent variables included response probabilities, reaction times for correct and error responses, and shapes of reaction-time distributions. The diffusion model accounted for all aspects of the data, including error reaction times that had previously been a problem for all response-time models. The connectionist models accounted for many aspects of the data adequately, but each failed to a greater or lesser degree in important ways except for one model that was similar to the diffusion model. The findings advance the development of the diffusion model and show that the long tradition of reaction-time research and theory is a fertile domain for development and testing of connectionist assumptions about how decisions are generated over time.

  19. A Networks Approach to Modeling Enzymatic Reactions.

    Science.gov (United States)

    Imhof, P

    2016-01-01

    Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes.

  20. 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.

  1. A Full Disturbance Model for Reaction Wheels

    NARCIS (Netherlands)

    Le, M.P.; Ellenbroek, Marcellinus Hermannus Maria; Seiler, R; van Put, P.; Cottaar, E.J.E.

    2014-01-01

    Reaction wheels are rotating devices used for the attitude control of spacecraft. However, reaction wheels also generate undesired disturbances in the form of vibrations, which may have an adverse effect on the pointing accuracy and stability of spacecraft (optical) payloads. A disturbance model for

  2. Modeling of turbulent chemical reaction

    Science.gov (United States)

    Chen, J.-Y.

    1995-01-01

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

  3. Structural, kinetic, and theoretical studies on models of the zinc-containing phosphodiesterase active center: medium-dependent reaction mechanisms.

    Science.gov (United States)

    Selmeczi, Katalin; Michel, Carine; Milet, Anne; Gautier-Luneau, Isabelle; Philouze, Christian; Pierre, Jean-Louis; Schnieders, David; Rompel, Annette; Belle, Catherine

    2007-01-01

    Dinuclear zinc(II) complexes [Zn(2)(bpmp)(mu-OH)](ClO(4))(2) (1) and [Zn(2)(bpmp)(H(2)O)(2)](ClO(4))(3) (2) (H-BPMP=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) have been synthesized, structurally characterized, and pH-driven changes in metal coordination observed. The transesterification reaction of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) in the presence of the two complexes was studied both in a water/DMSO (70:30) mixture and in DMSO. Complex 2 was not reactive whereas for 1 considerable rate enhancement of the spontaneous hydrolysis reaction was observed. A detailed mechanistic investigation by kinetic studies, spectroscopic measurements ((1)H, (31)P NMR spectroscopy), and ESI-MS analysis in conjunction with ab initio calculations was performed on 1. Based on these results, two medium-dependent mechanisms are presented and an unusual bridging phosphate intermediate is proposed for the process in DMSO.

  4. A Kinetic Modeling study on the Oxidation of Primary Reference Fuel?Toluene Mixtures Including Cross Reactions between Aromatics and Aliphatics

    Energy Technology Data Exchange (ETDEWEB)

    Sakai, Y; Miyoshi, A; Koshi, M; Pitz, W J

    2008-01-09

    A detailed chemical kinetic model for the mixtures of Primary Reference Fuel (PRF: n-heptane and iso-octane) and toluene has been proposed. This model is divided into three parts; a PRF mechanism [T. Ogura et al., Energy & Fuels 21 (2007) 3233-3239], toluene sub-mechanism and cross reactions between PRF and toluene. Toluene sub-mechanism includes the low temperature kinetics relevant to engine conditions. A chemical kinetic mechanism proposed by Pitz et al. [Proc. the 2nd Joint Meeting of the U.S. Combust. Institute (2001)] was used as a starting model and modified by updating rate coefficients. Theoretical estimations of rate coefficients were performed for toluene and benzyl radical reactions important at low temperatures. Cross-reactions between alkane, alkene, and aromatics were also included in order to account for the acceleration by the addition of toluene into iso-octane recently found in the shock tube study of the ignition delay [Y. Sakai et al, SAE 2007-01-4014 (2007)]. Validations of the model were performed with existing shock tube and flow tube data. The model well predicts the ignition characteristics of toluene and PRF/Toluene mixtures under the wide range of temperatures (500-1700 K) and pressures (2-50 atm). It is found that reactions of benzyl radical with oxygen molecule determine the reactivity of toluene at low temperature. Although the effect of toluene addition to iso-octane is not fully resolved, the reactions of alkene with benzyl radical have the possibility to account for the kinetic interactions between PRF and toluene.

  5. Charge-transfer reaction of 1,4-benzoquinone with crizotinib: spectrophotometric study, computational molecular modeling and use in development of microwell assay for crizotinib.

    Science.gov (United States)

    Darwish, Ibrahim A; Alshehri, Jamilah M; Alzoman, Nourah Z; Khalil, Nasr Y; Abdel-Rahman, Hamdy M

    2014-10-15

    The reaction of 1,4-benzoquinone (BQ) with crizotinib (CZT); a novel drug used for treatment of non-small cell lung cancer) was investigated in different solvents of varying dielectric constants and polarity indexes. The reaction resulted in the formation of a red-colored product. Spectrophotometric investigations confirmed that the reaction proceeded through charge-transfer (CT) complex formation. The molar absorptivity of the complex was found to be linearly correlated with the dielectric constant and polarity index of the solvent; the correlation coefficients were 0.9425 and 0.8340, respectively. The stoichiometric ratio of BQ:CZT was found to be 2:1 and the association constant of the complex was found to be 0.26×10(3)lmol(-1). The kinetics of the reaction was studied; the order of the reaction, rate and rate constant were determined. Computational molecular modeling for the complex between BQ and CZT was conducted, the sites of interaction on CZT molecule were determined, and the mechanism of the reaction was postulated. The reaction was employed as a basis in the development of a novel 96-microwell assay for CZT. The assay limits of detection and quantitation were 5.2 and 15.6μgml(-1), respectively. The assay was validated as per the guidelines of the International Conference on Harmonization (ICH) and successfully applied to the analysis of CZT in its bulk and capsules with good accuracy and precision. The assay has high throughput and consumes minimum volume of organic solvent thus it reduces the exposures of the analysts to the toxic effects of organic solvents, and significantly reduces the analysis cost. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. High-temperature shock tube and modeling studies on the reactions of methanol with D-atoms and CH3-radicals.

    Science.gov (United States)

    Peukert, S L; Michael, J V

    2013-10-10

    The shock tube technique has been used to study the hydrogen abstraction reactions D + CH3OH → CH2O + H + HD (A) and CH3 + CH3OH → CH2O + H + CH4 (B). For reaction A, the experiments span a T-range of 1016 K ≤ T ≤ 1325 K, at pressures 0.25 bar ≤ P ≤ 0.46 bar. The experiments on reaction B, CH3 + CH3OH, cover a T-range of 1138 K ≤ T ≤ 1270 K, at pressures around 0.40 bar. Reflected shock tube experiments, monitoring the depletion of D-atoms by applying D-atom atomic resonance absorption spectrometry (ARAS), were performed on reaction A using gas mixtures of C2D5I and CH3OH in Kr bath gas. C2D5I was used as precursor for D-atoms. For reaction B, reflected shock tube experiments monitoring H-atom formation with H-ARAS, were carried out using gas mixtures of diacetyl ((CH3CO)2) and CH3OH in Kr bath gas. (CH3CO)2 was used as the source of CH3-radicals. Detailed reaction models were assembled to fit the D-atom and H-atom time profiles in order to obtain experimental rate constants for reactions A and B. Total rate constants from the present experiments on D + CH3OH and CH3 + CH3OH can be represented by the Arrhenius equations kA(T) = 1.51 × 10(-10) exp(-3843 K/T) cm(3) molecules(-1) s(-1) (1016 K ≤ T ≤ 1325 K) and kB(T) = 9.62 × 10(-12) exp(-7477 K/T) cm(3) molecules(-1) s(-1) (1138 K ≤ T ≤ 1270 K). The experimentally obtained rate constants were compared with available rate data from the literature. The results from quantum chemical studies on reaction A were found to be in good agreement with the present results. The present work represents the first direct experimental study on these bimolecular reactions at combustion temperatures and is important to the high-temperature oxidation of CH3OH.

  7. A Reaction-Based River/Stream Water Quality Model: Reaction Network Decomposition and Model Application

    OpenAIRE

    2012-01-01

    This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equil...

  8. Model studies of the iron-catalysed Haber-Weiss cycle and the ascorbate-driven Fenton reaction.

    Science.gov (United States)

    Burkitt, M J; Gilbert, B C

    1990-01-01

    Complementary hydroxylation assays and stopped-flow e.s.r. techniques have been employed in the investigation of the effect of various iron chelators (of chemical, biological and clinical importance) on hydroxyl-radical generation via the Haber-Weiss cycle and the ascorbate-driven Fenton reaction. Chelators have been identified which selectively promote or inhibit various reactions involved in hydroxyl-radical generation (for example, NTA and EDTA promote all the reactions of both the Haber-Weiss cycle and the ascorbate-driven Fenton reaction, whereas DTPA and phytate inhibit the recycling of iron in these reactions). The biological chelators succinate and citrate are shown to be relatively poor catalysts of the Haber-Weiss cycle, whereas they are found to be effective catalysts of .OH generation in the ascorbate-driven Fenton reaction. It is also suggested that continuous redox-cycling reactions between iron, oxygen and ascorbate may represent an important mechanism of cell death in biological systems.

  9. Isobaric yield ratio difference between the 140 $A$ MeV $^{58, 64}$Ni + $^{9}$Be reactions studied by antisymmetric molecular dynamics model

    CERN Document Server

    Qiao, C Y; Ma, C W; Zhang, Y L; Wang, S S

    2015-01-01

    \\item[Background] The isobaric yield ratio difference (IBD) method is found to be sensitive to the density difference of neutron-rich nucleus induced reaction around the Fermi energy. \\item[Purpose] An investigation is performed to study the IBD results in the transport model. \\item[Methods] The antisymmetric molecular dynamics (AMD) model plus the sequential decay model GEMINI are adopted to simulate the 140$A$ MeV $^{58, 64}$Ni + $^{9}$Be reactions. A relative small coalescence radius R$_c =$ 2.5 fm is used for the phase space at $t =$ 500 fm/c to form the hot fragment. Two limitations on the impact parameter ($b1 = 0 - 2$ fm and $b2 = 0 - 9$ fm) are used to study the effect of central collisions in IBD. \\item[Results] The isobaric yield ratios (IYRs) for the large--$A$ fragments are found to be suppressed in the symmetric reaction. The IBD results for fragments with neutron-excess $I = $ 0 and 1 are obtained. A small difference is found in the IBDs with the $b1$ and $b2$ limitations in the AMD simulated re...

  10. Molecular studies of model surfaces of metals from single crystals to nanoparticles under catalytic reaction conditions. Evolution from prenatal and postmortem studies of catalysts.

    Science.gov (United States)

    Somorjai, Gabor A; Aliaga, Cesar

    2010-11-02

    Molecular level studies of metal crystal and nanoparticle surfaces under catalytic reaction conditions at ambient pressures during turnover were made possible by the use of instruments developed at the University of California at Berkeley. Sum frequency generation vibrational spectroscopy (SFGVS), owing to its surface specificity and sensitivity, is able to identify the vibrational features of adsorbed monolayers of molecules. We identified reaction intermediates, different from reactants and products, under reaction conditions and for multipath reactions on metal single crystals and nanoparticles of varying size and shape. The high-pressure scanning tunneling microscope (HP-STM) revealed the dynamics of a catalytically active metallic surface by detecting the mobility of the adsorbed species during catalytic turnover. It also demonstrated the reversible and adsorbate-driven surface restructuring of platinum when exposed to molecules such as CO and ethylene. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) detected the reversible changes of surface composition in rhodium-palladium, platinum-palladium, and other bimetallic nanoparticles as the reactant atmosphere changed from oxidizing to reducing. It was found that metal nanoparticles of less than 2 nm in size are present in higher oxidation states, which alters and enhances their catalytic activity. The catalytic nanodiode (CND) confirmed that a catalytic reaction-induced current flow exists at oxide-metal interfaces, which correlates well with the reaction turnover.

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

    Science.gov (United States)

    Grove, David B.; Stollenwerk, Kenneth G.

    1987-01-01

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

  12. Modeling of Reaction Processes Controlled by Diffusion

    CERN Document Server

    Revelli, J

    2003-01-01

    Stochastic modeling is quite powerful in science and technology.The technics derived from this process have been used with great success in laser theory, biological systems and chemical reactions.Besides, they provide a theoretical framework for the analysis of experimental results on the field of particle's diffusion in ordered and disordered materials.In this work we analyze transport processes in one-dimensional fluctuating media, which are media that change their state in time.This fact induces changes in the movements of the particles giving rise to different phenomena and dynamics that will be described and analyzed in this work.We present some random walk models to describe these fluctuating media.These models include state transitions governed by different dynamical processes.We also analyze the trapping problem in a lattice by means of a simple model which predicts a resonance-like phenomenon.Also we study effective diffusion processes over surfaces due to random walks in the bulk.We consider differe...

  13. Curing Reaction Model of Epoxy Asphalt Binder

    Institute of Scientific and Technical Information of China (English)

    QIAN Zhendong; CHEN Leilei; WANG Yaqi; SHEN Jialin

    2012-01-01

    In order to understand the strength developing law of the epoxy asphalt mixture,a curing reaction model of the epoxy asphalt binder was proposed based upon the thermokinetic analysis.Given some assumptions,the model was developed by applying the Kissinger law as well as Arrhenius equation,and the differential scanning calorimetry was performed for estimating the model parameters.To monitor the strength development of the epoxy asphalt mixture,a strength test program was employed and then results were compared to those produced from the proposed model.The comparative evaluation shows that a good consistency exists between the outputs from test program and the proposed model,indicating that the proposed model can be used effectively for simulating the curing reaction process for the epoxy asphalt binder and predicting the strength development for the epoxy asphalt mixture.

  14. Polymerization as a Model Chain Reaction

    Science.gov (United States)

    Morton, Maurice

    1973-01-01

    Describes the features of the free radical, anionic, and cationic mechanisms of chain addition polymerization. Indicates that the nature of chain reactions can be best taught through the study of macromolecules. (CC)

  15. Nonlinear control of the Salnikov model reaction

    DEFF Research Database (Denmark)

    Recke, Bodil; Jørgensen, Sten Bay

    1999-01-01

    This paper explores different nonlinear control schemes, applied to a simple model reaction. The model is the Salnikov model, consisting of two ordinary differential equations. The control strategies investigated are I/O-linearisation, Exact linearisation, exact linearisation combined with LQR...... and Control Lyapunov Functions (CLF's). The results show that based on the lowest possible cost function and shortest settling time, the exact linearisation performs marginally better than the other methods....

  16. Kinetic studies of elementary chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

  17. Dynamical Model of Weak Pion Production Reactions

    CERN Document Server

    Sato, T; Lee, T S H

    2003-01-01

    The dynamical model of pion electroproduction has been extended to investigate the weak pion production reactions. The predicted cross sections of neutrino-induced pion production reactions are in good agreement with the existing data. We show that the renormalized(dressed) axial N-$\\Delta$ form factor contains large dynamical pion cloud effects and this renormalization effects are crucial in getting agreement with the data. We conclude that the N-$\\Delta$ transitions predicted by the constituent quark model are consistent with the existing neutrino induced pion production data in the $\\Delta$ region.

  18. Test Reactions to Study Efficiency of

    OpenAIRE

    Jasińska Magdalena

    2015-01-01

    Effects of mixing on the course of fast chemical reactions are relatively well understood, especially in homogeneous systems. This enables to design and operate chemical reactors with the goal to achieve a high yield of a desired product and use systems of complex reactions as a chemical probe (chemical test reactions) to identify progress of mixing and quality of mixture. Recently, a number of studies have focused on the application of chemical test reactions to identify energy efficiency of...

  19. QGSM development for spallation reactions modeling

    Directory of Open Access Journals (Sweden)

    Gudima K.K.

    2012-12-01

    Full Text Available The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.

  20. QGSM development for spallation reactions modeling

    Science.gov (United States)

    Baznat, M. I.; Chigrinov, S. E.; Gudima, K. K.

    2012-12-01

    The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM) for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.

  1. Kinetic modeling of reactions in Foods

    NARCIS (Netherlands)

    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

  2. Nuclear reaction studies: Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Thaler, R.M.

    1986-11-19

    A principal focus of recent research has been the three-body problem. A great deal of effort has been devoted to the creation of a computer program to calculate physical observables in the three body problem below 1 GeV. Successful results have been obtained for the triton. Additional work concerns scattering of K/sup +/ mesons from nuclei, antinucleon physics, relativistic nuclear physics and inclusive reactions. (DWL)

  3. DSMC modeling of flows with recombination reactions

    Science.gov (United States)

    Gimelshein, Sergey; Wysong, Ingrid

    2017-06-01

    An empirical microscopic recombination model is developed for the direct simulation Monte Carlo method that complements the extended weak vibrational bias model of dissociation. The model maintains the correct equilibrium reaction constant in a wide range of temperatures by using the collision theory to enforce the number of recombination events. It also strictly follows the detailed balance requirement for equilibrium gas. The model and its implementation are verified with oxygen and nitrogen heat bath relaxation and compared with available experimental data on atomic oxygen recombination in argon and molecular nitrogen.

  4. [Rudolf-Virchow Prize 1998. Award lecture. Toxoplasmosis: a model infection for studying systemic and intracerebral immune reactions].

    Science.gov (United States)

    Deckert-Schlüter, M

    1998-01-01

    Toxoplasmosis has gained particular attention in the AIDS era as the most common opportunistic encephalitis in HIV-infected patients. Since there are important parallels between the human and rodent infection, experimental murine toxoplasmosis is widely used to study the immune reactions to this protozoal parasite. Oral application of low-virulent Toxoplasma (T.) gondii cysts leads to a biphasic disease characterized by an acute, generalized phase followed by a chronic stage confined to the brain, where an encephalitis with persistence of the parasite develops. Immunity to T. gondii is T cell mediated, and there is increasing evidence for a critical role of cytokines for an effective immune response. In order to address the functional role of interferon (IFN)-gamma in toxoplasmosis, we took advantage of mice lacking the IFN-gamma-receptor. Inactivation of the IFN-gamma-receptor rendered mice highly susceptible to T. gondii, and they died of a fulminant acute toxoplasmosis. Among the various organs affected, hepatitis was severe enough to cause death. In contrast to wild type animals, IFN-gamma-receptor-deficient mice were unable to activate their macrophages as evidenced by a lack of major histocompatibility complex (MHC) class II antigen induction and the absence of an upregulation of tumor necrosis factor (TNF)-alpha and inducible nitric oxide synthase (iNOS) mRNA transcripts, two macrophage effector molecules. These observations prompted the investigation of TNF- and TNF-receptor-mediated effects in toxoplasmosis by use of mice deficient in either the TNF-receptor type 1 (TNFR1) and/or the TNF-receptor type 2 (TNFR2). The lethal outcome of T. gondii-infected TNFR1/2- and TNFR1-deficient mice, but not of TNFR2-deficient and wild type animals, illustrated the important role of TNF-alpha and TNFR1-mediated signalling, respectively, in this infection. Histopathology attributed death of TNFR1- and TNFR1/2-deficient mice to a severe, necrotizing encephalitis

  5. Reaction Wheel Disturbance Model Extraction Software - RWDMES

    Science.gov (United States)

    Blaurock, Carl

    2009-01-01

    The RWDMES is a tool for modeling the disturbances imparted on spacecraft by spinning reaction wheels. Reaction wheels are usually the largest disturbance source on a precision pointing spacecraft, and can be the dominating source of pointing error. Accurate knowledge of the disturbance environment is critical to accurate prediction of the pointing performance. In the past, it has been difficult to extract an accurate wheel disturbance model since the forcing mechanisms are difficult to model physically, and the forcing amplitudes are filtered by the dynamics of the reaction wheel. RWDMES captures the wheel-induced disturbances using a hybrid physical/empirical model that is extracted directly from measured forcing data. The empirical models capture the tonal forces that occur at harmonics of the spin rate, and the broadband forces that arise from random effects. The empirical forcing functions are filtered by a physical model of the wheel structure that includes spin-rate-dependent moments (gyroscopic terms). The resulting hybrid model creates a highly accurate prediction of wheel-induced forces. It accounts for variation in disturbance frequency, as well as the shifts in structural amplification by the whirl modes, as the spin rate changes. This software provides a point-and-click environment for producing accurate models with minimal user effort. Where conventional approaches may take weeks to produce a model of variable quality, RWDMES can create a demonstrably high accuracy model in two hours. The software consists of a graphical user interface (GUI) that enables the user to specify all analysis parameters, to evaluate analysis results and to iteratively refine the model. Underlying algorithms automatically extract disturbance harmonics, initialize and tune harmonic models, and initialize and tune broadband noise models. The component steps are described in the RWDMES user s guide and include: converting time domain data to waterfall PSDs (power spectral

  6. A study on sodium-concrete reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Jae Heum; Min, Byong Hun [Suwon University, Suwon (Korea, Republic of)

    1997-07-01

    A small sodium-concrete reaction facility was designed, manufactured and installed. this facility has been operated under inert gas(N{sub 2}) with different experimental variables such as sodium injection temperature, injection amount of sodium, aging period of concrete, sodium reservoir temperature. As a result, it was found that sodium injection temperature and injected amount of sodium has little effect on sodium-concrete reaction. However, sodium reservoir temperature and aging period of concrete has relatively high impact on sodium-concrete reaction. Sodium-concrete reaction model has also been developed and compared with experimental results. (Author) 51 refs., 16 tabs., 64 figs.

  7. Principle Generalized Net Model of a Human Stress Reaction

    Directory of Open Access Journals (Sweden)

    Anthony Shannon

    2008-04-01

    Full Text Available The present study was aimed at investigating the mechanism of a human stress reaction by means of Generalized Nets (GNs. A principle GN-model of the main structures, organs and systems of the human body taking part in the acute and chronic reaction of the organism to a stress stimulus is generated. A possible application of the GN-model of the human stress reaction for testing the effect of known or newly synthesized pharmacological products as well as of food supplements is discussed.

  8. Uncertainty study of nuclear model parameters for the n+ ^{56}Fe reactions in the fast neutron region below 20 MeV

    CERN Document Server

    Duan, Junfeng; Sjöstrand, Henrik; Alhassan, Erwin; Gustavsson, Cecilia; Österlund, Michael; Koning, Arjan; Rochman, Dimitri

    2013-01-01

    In this work, we study the uncertainty of nuclear model parameters for neutron induced ^{56}Fe reactions in fast neutron region by using the Total Monte Carlo method. We perform a large number of TALYS runs and compare the calculated results with the experimental data of the cross sections to obtain the uncertainties of the model parameters. Based on the derived uncertainties another 1000 TALYS runs have been performed to create random cross section files. For comparison with the experimental data we calculate a weighted \\chi^2 value for each random file as well as the ENDF/B-VII.1, JEFF3.1, JENDL4.0 and CENDL3.1 data libraries. Furthermore, we investigate the optical model parameters correlation obtained by way of this procedure.

  9. Study on the chemical reaction kinetics of detonation models%详细化学反应模型中温度修正项特性研究

    Institute of Scientific and Technical Information of China (English)

    刘云峰; 姜宗林

    2011-01-01

    本研究主要讨论了爆轰过程中混合气体比热比的变化、详细化学反应模型中温度修正项的函数表达形式、以及活化能对化学反应动力学特性的影响.通过对传统Arrhenius定律的分析完善,提出了具有温度指数修正的总包一步爆轰计算模型.采用几个常用的爆轰计算模型,对满足化学当量比的H2/Air混合气体,开展了爆轰特性的数值模拟对比研究.计算结果表明,新提出的爆轰计算模型能够得到的胞格尺度与实验值符合良好,首次实现了爆轰波胞格尺度的定量数值模拟.论文进一步建立了总包反应模型与详细化学反应模型之间的关系,讨论了详细化学反应模型中温度修正项的物理意义.%In this paper, the influences of specific heat ratio, the modification term in the detailed reaction kinetics, and the activation energy on the properties of chemical reaction kinetics of detonation models are studied. The results first demonstrate that the temperature power function to modify the chemical reaction rates of detailed chemical reaction kinetics should be replaced by a temperature exponential function, which is produced by the variation of specific heat ratio during the reaction process, physically. A new overall one-step detonation model with variable specific ratio and gas constant is proposed to improve the property of Arrhenius law. Two dimensional numerical simulations with this new model are conducted, and the detonation cell sizes are in agreement with experimental results quantitatively.

  10. A molecular orbital study of a model of the Mg2+ coordination complex of the self splicing reaction of ribosomal RNA

    Science.gov (United States)

    McCourt, M.; Shibata, M.; McIver, J. W.; Rein, R.

    1988-01-01

    Recent discoveries have established the fact that RNA is capable of acting as an enzyme. In this study two different types of molecular orbital calculations, INDO and ab initio, were used in an attempt to assess the structural/functional role of the Mg2+ hydrated complex in ribozyme reactions. Preliminary studies indicate that the reaction is multistep and that the Mg2+ complex exerts a stabilizing effect on the intermediate or midpoint of the reaction.

  11. Breakup reaction models for two- and three-cluster projectiles

    CERN Document Server

    Baye, D

    2010-01-01

    Breakup reactions are one of the main tools for the study of exotic nuclei, and in particular of their continuum. In order to get valuable information from measurements, a precise reaction model coupled to a fair description of the projectile is needed. We assume that the projectile initially possesses a cluster structure, which is revealed by the dissociation process. This structure is described by a few-body Hamiltonian involving effective forces between the clusters. Within this assumption, we review various reaction models. In semiclassical models, the projectile-target relative motion is described by a classical trajectory and the reaction properties are deduced by solving a time-dependent Schroedinger equation. We then describe the principle and variants of the eikonal approximation: the dynamical eikonal approximation, the standard eikonal approximation, and a corrected version avoiding Coulomb divergence. Finally, we present the continuum-discretized coupled-channel method (CDCC), in which the Schroed...

  12. Identifiability of parameters and behaviour of the MCMC chains: a case study using the reaction norm model

    DEFF Research Database (Denmark)

    Shariati, M M; Korsgaard, I R; Sorensen, D

    2009-01-01

    the formulation of the model and the structure of the data and the models were then implemented via MCMC. The output of MCMC sampling schemes was interpreted in the light of the theoretical findings. The erratic behaviour of the MCMC chains was shown to be associated with identifiability problems...

  13. Turing patterns in a reaction-diffusion model with the Degn-Harrison reaction scheme

    Science.gov (United States)

    Li, Shanbing; Wu, Jianhua; Dong, Yaying

    2015-09-01

    In this paper, we consider a reaction-diffusion model with Degn-Harrison reaction scheme. Some fundamental analytic properties of nonconstant positive solutions are first investigated. We next study the stability of constant steady-state solution to both ODE and PDE models. Our result also indicates that if either the size of the reactor or the effective diffusion rate is large enough, then the system does not admit nonconstant positive solutions. Finally, we establish the global structure of steady-state bifurcations from simple eigenvalues by bifurcation theory and the local structure of the steady-state bifurcations from double eigenvalues by the techniques of space decomposition and implicit function theorem.

  14. Test Reactions to Study Efficiency of

    Directory of Open Access Journals (Sweden)

    Jasińska Magdalena

    2015-06-01

    Full Text Available Effects of mixing on the course of fast chemical reactions are relatively well understood, especially in homogeneous systems. This enables to design and operate chemical reactors with the goal to achieve a high yield of a desired product and use systems of complex reactions as a chemical probe (chemical test reactions to identify progress of mixing and quality of mixture. Recently, a number of studies have focused on the application of chemical test reactions to identify energy efficiency of mixing, being a convenient way of comparing mixers and reactors in terms of their mixing efficiency. This review offers a presentation of chemical test reactions available in the literature and methods of applications of test reactions to identify the energy efficiency of mixing. Also methods to assess the extent of micromixing by measuring product distribution or segregation index, and to determine the time constant for mixing are presented for single phase homogeneous systems and two-phase liquid-liquid systems.

  15. Analytical Study of Thermonuclear Reaction Probability Integrals

    CERN Document Server

    Chaudhry, M A; Mathai, A M

    2000-01-01

    An analytic study of the reaction probability integrals corresponding to the various forms of the slowly varying cross-section factor $S(E)$ is attempted. Exact expressions for reaction probability integrals are expressed in terms of the extended gamma functions.

  16. Characterizing ozone pollution in a petrochemical industrial area in Beijing, China: a case study using a chemical reaction model.

    Science.gov (United States)

    Wei, Wei; Lv, Zhaofeng; Cheng, Shuiyuan; Wang, Lili; Ji, Dongsheng; Zhou, Ying; Han, Lihui; Wang, Litao

    2015-06-01

    This study selected a petrochemical industrial complex in Beijing, China, to understand the characteristics of surface ozone (O3) in this industrial area through the on-site measurement campaign during the July-August of 2010 and 2011, and to reveal the response of local O3 to its precursors' emissions through the NCAR-Master Mechanism model (NCAR-MM) simulation. Measurement results showed that the O3 concentration in this industrial area was significantly higher, with the mean daily average of 124.6 μg/m(3) and mean daily maximum of 236.8 μg/m(3), which are, respectively, 90.9 and 50.6 % higher than those in Beijing urban area. Moreover, the diurnal O3 peak generally started up early in 11:00-12:00 and usually remained for 5-6 h, greatly different with the normal diurnal pattern of urban O3. Then, we used NCAR-MM to simulate the average diurnal variation of photochemical O3 in sunny days of August 2010 in both industrial and urban areas. A good agreement in O3 diurnal variation pattern and in O3 relative level was obtained for both areas. For example of O3 daily maximum, the calculated value in the industrial area was about 51 % higher than in the urban area, while measured value in the industrial area was approximately 60 % higher than in the urban area. Finally, the sensitivity analysis of photochemical O3 to its precursors was conducted based on a set of VOCs/NOx emissions cases. Simulation results implied that in the industrial area, the response of O3 to VOCs was negative and to NOx was positive under the current conditions, with the sensitivity coefficients of -0.16~-0.43 and +0.04~+0.06, respectively. By contrast, the urban area was within the VOCs-limitation regime, where ozone enhancement in response to increasing VOCs emissions and to decreasing NOx emission. So, we think that the VOCs emissions control for this petrochemical industrial complex will increase the potential risk of local ozone pollution aggravation, but will be helpful to inhibit the

  17. Reaction-contingency based bipartite Boolean modelling

    Science.gov (United States)

    2013-01-01

    Background Intracellular signalling systems are highly complex, rendering mathematical modelling of large signalling networks infeasible or impractical. Boolean modelling provides one feasible approach to whole-network modelling, but at the cost of dequantification and decontextualisation of activation. That is, these models cannot distinguish between different downstream roles played by the same component activated in different contexts. Results Here, we address this with a bipartite Boolean modelling approach. Briefly, we use a state oriented approach with separate update rules based on reactions and contingencies. This approach retains contextual activation information and distinguishes distinct signals passing through a single component. Furthermore, we integrate this approach in the rxncon framework to support automatic model generation and iterative model definition and validation. We benchmark this method with the previously mapped MAP kinase network in yeast, showing that minor adjustments suffice to produce a functional network description. Conclusions Taken together, we (i) present a bipartite Boolean modelling approach that retains contextual activation information, (ii) provide software support for automatic model generation, visualisation and simulation, and (iii) demonstrate its use for iterative model generation and validation. PMID:23835289

  18. Modeling Corrosion Reactions of Steel in a Dilute Carbonate Solution

    Science.gov (United States)

    Eliyan, Faysal Fayez; Alfantazi, Akram

    2016-02-01

    This research models the corrosion reactions of a high-strength steel in an aerated, dilute, carbonate solution during a single-cycle voltammetry. Based on a previous study (Eliyan et al. in J Mater Eng Perform 24(6):1-8, 2015) and a literature survey, the corrosion reactions of the cathodic reduction, anodic dissolution, and passivation, as well as the interfacial interactions and the chemistry of the corrosion products are illustrated in schematics. The paper provides a visual guide on the corrosion reactions for steel in carbonate solutions based on the available mechanistic details that were reported and are still being investigated in literature.

  19. A theoretical model of metal surface reactions

    Energy Technology Data Exchange (ETDEWEB)

    Shustorovich, E. (Eastman Kodak Co., Rochester, NY); Baetzold, R.C.; Muetterties, E.L.

    1983-03-31

    Metal surface reactions are modeled with a novel theoretical construct in which periodic trends can be scrutinized. The theoretical model is succinctly presented and a conspectus of periodic trends, based on the model, is explored. Periodic trends are discussed in the contexts of chemisorption bond energies, electron transfer between metal surface and adsorbate, stereochemical features of chemisorption states for closed-shell diatomic and linear X-CN or X-NC molecules, and hydrocarbon reactions. Hydrocarbon C-H bond-breaking processes are analyzed in terms of d-level occupancy, electron transfer, and stereochemistry of intermediates. Conceptually and computationally, the metal surface is characterized as a good electron donor: antibonding molecular orbitals of the adsorbate species appear to be significant contributors to the chemisorption bond and also play a decisive role in bond-breaking processes. No aspect of the model projections is inconsistent with the experimental data although the electronic characterization of some chemisorption states are counter to commonly held perceptions.

  20. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models.

    Science.gov (United States)

    Liberman, M A; Kiverin, A D; Ivanov, M F

    2012-05-01

    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation.

  1. Modelling of simultaneous mass and heat transfer with chemical reaction using the Maxwell-Stefan theory II. Non-isothermal study

    NARCIS (Netherlands)

    Frank, M.J.W.; Frank, M.J.W.; Kuipers, J.A.M.; Krishna, R.; van Swaaij, Willibrordus Petrus Maria

    1995-01-01

    In Part I a general applicable model has been developed which calculates mass and heat transfer fluxes through a vapour/gas-liquid interface in case a reversible chemical reaction with associated heat effect takes place in the liquid phase. In this model the Maxwell-Stefan theory has been used to

  2. Uncertainty quantification for quantum chemical models of complex reaction networks.

    Science.gov (United States)

    Proppe, Jonny; Husch, Tamara; Simm, Gregor N; Reiher, Markus

    2016-12-22

    For the quantitative understanding of complex chemical reaction mechanisms, it is, in general, necessary to accurately determine the corresponding free energy surface and to solve the resulting continuous-time reaction rate equations for a continuous state space. For a general (complex) reaction network, it is computationally hard to fulfill these two requirements. However, it is possible to approximately address these challenges in a physically consistent way. On the one hand, it may be sufficient to consider approximate free energies if a reliable uncertainty measure can be provided. On the other hand, a highly resolved time evolution may not be necessary to still determine quantitative fluxes in a reaction network if one is interested in specific time scales. In this paper, we present discrete-time kinetic simulations in discrete state space taking free energy uncertainties into account. The method builds upon thermo-chemical data obtained from electronic structure calculations in a condensed-phase model. Our kinetic approach supports the analysis of general reaction networks spanning multiple time scales, which is here demonstrated for the example of the formose reaction. An important application of our approach is the detection of regions in a reaction network which require further investigation, given the uncertainties introduced by both approximate electronic structure methods and kinetic models. Such cases can then be studied in greater detail with more sophisticated first-principles calculations and kinetic simulations.

  3. QSAR model reproducibility and applicability: a case study of rate constants of hydroxyl radical reaction models applied to polybrominated diphenyl ethers and (benzo-)triazoles.

    Science.gov (United States)

    Roy, Partha Pratim; Kovarich, Simona; Gramatica, Paola

    2011-08-01

    The crucial importance of the three central OECD principles for quantitative structure-activity relationship (QSAR) model validation is highlighted in a case study of tropospheric degradation of volatile organic compounds (VOCs) by OH, applied to two CADASTER chemical classes (PBDEs and (benzo-)triazoles). The application of any QSAR model to chemicals without experimental data largely depends on model reproducibility by the user. The reproducibility of an unambiguous algorithm (OECD Principle 2) is guaranteed by redeveloping MLR models based on both updated version of DRAGON software for molecular descriptors calculation and some freely available online descriptors. The Genetic Algorithm has confirmed its ability to always select the most informative descriptors independently on the input pool of variables. The ability of the GA-selected descriptors to model chemicals not used in model development is verified by three different splittings (random by response, K-ANN and K-means clustering), thus ensuring the external predictivity of the new models, independently of the training/prediction set composition (OECD Principle 5). The relevance of checking the structural applicability domain becomes very evident on comparing the predictions for CADASTER chemicals, using the new models proposed herein, with those obtained by EPI Suite. Copyright © 2011 Wiley Periodicals, Inc.

  4. Model studies using supercritical carbon dioxide fluid (SF CO{sub 2}) as a reaction medium for radiotracer synthesis and purification

    Energy Technology Data Exchange (ETDEWEB)

    Ferrieri, R.A.; Fowler, J.S.; Wolf, A.P. [Brookhaven National Lab., Upton, NY (United States)

    1994-05-01

    Supercritical fluids (SFs) have found widespread use in the analytical field as solvents for compound purification, and initial results on their use for radiotracer synthesis have been reported. SF`s possess the unique feature that their solvating strength can be altered drastically through small changes in pressure and temperature of the fluid within the supercritical regime. We have modified a SF chromatograph to allow us to investigate its use in radiotracer synthesis and purification. The solubility of several PET radiotracers was measured in SF CO{sub 2} at 5000 psi and 55{degrees}C and showed the following: raclopride, 68 {mu}g/mL{sup 2}; (L)-deprenyl, 85 {mu}g/mL; flumazenil, 61 {mu}g/mL; (-)cocaine, 108 {mu}g/mL; ritalin, 45 {mu}g/Ml; and cogentin, 250 {mu}g/mL. Analytical separations were achieved on 30 to 50 {mu}g amounts of (L)-deprenyl (3.9 min RT) and nor-deprenyl (4.7 min RT), as well as raclopride (10.8 min RT) and nor-raclopride (10.3 min RT) using 250 mm x 4.5 mm i.d. Ultracarb 5 ODS (30), and 75 mm x 4.5 mm i.d. silica columns, respectively, and pure SF CO{sub 2} as the mobile phase. Model studies on simple N-alkylation reactions were also carried out using pur SF CO{sub 2} as the reaction medium on a modified alumina support. (L)-Deprenyl was synthesized from only 100 {mu}g of the starting labelling substrate using 500 mg of alumina impregnated with triphenylphosphine diiodide (20% by wt.) and maintained at 170{degrees}C. The methylating agent, methyl iodide, was generated in situ from methanol, but was always present in excess of the substrate. Studies are in progress to reduce methanol amounts. Pressure studies of SF CO{sub 2} ranging from 3000 to 6000 psi showed an 80% increase in the methylation reaction relative to the amount of starting substrate suggesting an effect of the fluid density. Temperature was also a critical parameter here as the reaction did not proceed at 80{degrees}C for similiar pressures.

  5. Reaction-diffusion models of decontamination

    DEFF Research Database (Denmark)

    Hjorth, Poul G.

    A contaminant, which also contains a polymer is in the form of droplets on a solid surface. It is to be removed by the action of a decontaminant, which is applied in aqueous solution. The contaminant is only sparingly soluble in water, so the reaction mechanism is that it slowly dissolves...... in the aqueous solution and then is oxidized by the decontaminant. The polymer is insoluble in water, and so builds up near the interface, where its presence can impede the transport of contaminant. In these circumstances, Dstl wish to have mathematical models that give an understanding of the process, and can...

  6. Construction, Modeling and Testing of a Low-Flow, Large-Diameter Aerosol Flow System for the Study of the Formation and Reactions of Tropospheric Aerosols

    Science.gov (United States)

    Ezell, M. J.; Johnson, S. N.; Yu, Y.; Pokkunuri, P.; Perraud, V.; Bruns, E.; Alexander, M.; Zelenyuk, A.; Dabdub, D.; Finlayson-Pitts, B. J.

    2008-12-01

    A unique, high-volume, low-flow, stainless steel aerosol flow system for the study of the formation and reactions of aerosols relevant to the troposphere has been constructed, modeled and experimentally tested. The total flow tube length is 7.3 m which includes a 1.2 m section used for mixing. The flow tube is equipped with ultraviolet lamps for photolysis. The diameter of 0.45 m results in a smaller surface to volume ratio than is found in many other flow systems and reduces the contribution of wall reactions. The latter is also reduced by frequent cleaning of the flow tube walls which is feasible due to the ease of disassembly of the flow tube. Flow systems present a major advantage over chamber studies in that continuous sampling under stable conditions over long periods of time is possible, increasing the amount of sample available for analysis and permitting a wide variety of analytical techniques to be applied simultaneously. In this system, the large volume (1000 L) and low flow speed (2 cm/minute) result in a residence time of nearly an hour; and equally spaced sampling ports allow for time-resolved measurements of aerosol and gas-phase products. The central features of this system have been modeled using computational fluid dynamics software and experimentally probed using inert gases and aerosols. Instrumentation attached directly to this flow system includes a NOx analyzer, an ozone analyzer, relative humidity and temperature probes, a scanning mobility particle sizer (SMPS) spectrometer, an aerodynamic particle sizer (APS) spectrometer, GC-MS, integrating nephelometer, and FTIR. Particles are collected using impactors and filters, and analyzed by a variety of techniques including FTIR, electrospray ionization mass spectrometry (ESI-MS), atmospheric pressure chemical ionization mass spectrometry (APCI-MS), GC-MS, HPLC-UV and HPLC-MS. In addition, for selected studies, an aerosol mass spectrometer (AMS), a single particle mass spectrometer (SPLAT II) and

  7. The study of 12C(α,γ astrophysical reaction using 12C(6Li,d and 12C(7Li,t reaction at 20 MeV and in the framework of the potential model

    Directory of Open Access Journals (Sweden)

    Adhikari S.

    2015-01-01

    Full Text Available The triton angular distribution in the 12C(7Li,t16O reaction has been measured at 20 MeV incident energy. Comparison of the data with Finite Range DWBA and CDCC-CRC calculations show that breakup coupling effects are prominent in the transfer to the ground state. This observation is similar to that in the 12C(6Li,d reaction at the same incident energy. The alpha spectroscopic factor of the 16O ground state is determined (Sα=0.25 from a comparison of the measured angular distribution with respect to the CDCC-CRC calculations. The E2 S-factor of the 12C(α,γ reaction at 300 keV in the framework of a potential model is determined to be about 118 keV-barn.

  8. Systems approach to excitation-energy and electron transfer reaction networks in photosystem II complex: model studies for chlorophyll a fluorescence induction kinetics.

    Science.gov (United States)

    Matsuoka, Takeshi; Tanaka, Shigenori; Ebina, Kuniyoshi

    2015-09-07

    Photosystem II (PS II) is a protein complex which evolves oxygen and drives charge separation for photosynthesis employing electron and excitation-energy transfer processes over a wide timescale range from picoseconds to milliseconds. While the fluorescence emitted by the antenna pigments of this complex is known as an important indicator of the activity of photosynthesis, its interpretation was difficult because of the complexity of PS II. In this study, an extensive kinetic model which describes the complex and multi-timescale characteristics of PS II is analyzed through the use of the hierarchical coarse-graining method proposed in the authors׳ earlier work. In this coarse-grained analysis, the reaction center (RC) is described by two states, open and closed RCs, both of which consist of oxidized and neutral special pairs being in quasi-equilibrium states. Besides, the PS II model at millisecond scale with three-state RC, which was studied previously, could be derived by suitably adjusting the kinetic parameters of electron transfer between tyrosine and RC. Our novel coarse-grained model of PS II can appropriately explain the light-intensity dependent change of the characteristic patterns of fluorescence induction kinetics from O-J-I-P, which shows two inflection points, J and I, between initial point O and peak point P, to O-J-D-I-P, which shows a dip D between J and I inflection points.

  9. A molecular modeling study of the changes of some steric properties of the precatalysts during the olefin metathesis reaction.

    Science.gov (United States)

    Marx, Frans T I; Jordaan, Johan H L; Lachmann, Gerhard; Vosloo, Hermanus C M

    2014-07-15

    The productive self-metathesis of 1-octene with a series of new phosphine ligated Grubbs-type precatalysts was studied. The resulting structures were used to compare some steric properties of the new precatalysts with those of well-known precatalysts. The possibility of α-CC agnostic stabilization as well as the ability of the ligands to shield the metal was studied. A comparison of the obtained data, pointed to the unlikelihood that α-CC agostic stabilization is a major contribution to the stabilization of the various metallacyclobutane rings. The similarity in the ability of the ligands to shield the metal also raised questions about the comparison of experimentally observed trends with those obtained theoretically.

  10. Quantum toy model for black-hole back-reaction

    CERN Document Server

    Maia, Clovis

    2007-01-01

    We propose a simple quantum field theoretical toy model for black hole evaporation and study the back-reaction of Hawking radiation onto the classical background. It turns out that the horizon is also ``pushed back'' in this situation (i.e., the interior region shrinks) but this back-reaction is not caused by energy conservation but by momentum balance. The effective heat capacity and the induced entropy variation can have both signs -- depending on the parameters of the model. PACS: 04.62.+v, 04.70.Dy.

  11. Modeling stochasticity in biochemical reaction networks

    Science.gov (United States)

    Constantino, P. H.; Vlysidis, M.; Smadbeck, P.; Kaznessis, Y. N.

    2016-03-01

    Small biomolecular systems are inherently stochastic. Indeed, fluctuations of molecular species are substantial in living organisms and may result in significant variation in cellular phenotypes. The chemical master equation (CME) is the most detailed mathematical model that can describe stochastic behaviors. However, because of its complexity the CME has been solved for only few, very small reaction networks. As a result, the contribution of CME-based approaches to biology has been very limited. In this review we discuss the approach of solving CME by a set of differential equations of probability moments, called moment equations. We present different approaches to produce and to solve these equations, emphasizing the use of factorial moments and the zero information entropy closure scheme. We also provide information on the stability analysis of stochastic systems. Finally, we speculate on the utility of CME-based modeling formalisms, especially in the context of synthetic biology efforts.

  12. Voter Model Perturbations and Reaction Diffusion Equations

    CERN Document Server

    Cox, J Theodore; Perkins, Edwin

    2011-01-01

    We consider particle systems that are perturbations of the voter model and show that when space and time are rescaled the system converges to a solution of a reaction diffusion equation in dimensions $d \\ge 3$. Combining this result with properties of the PDE, some methods arising from a low density super-Brownian limit theorem, and a block construction, we give general, and often asymptotically sharp, conditions for the existence of non-trivial stationary distributions, and for extinction of one type. As applications, we describe the phase diagrams of three systems when the parameters are close to the voter model: (i) a stochastic spatial Lotka-Volterra model of Neuhauser and Pacala, (ii) a model of the evolution of cooperation of Ohtsuki, Hauert, Lieberman, and Nowak, and (iii) a continuous time version of the non-linear voter model of Molofsky, Durrett, Dushoff, Griffeath, and Levin. The first application confirms a conjecture of Cox and Perkins and the second confirms a conjecture of Ohtsuki et al in the ...

  13. Alpha resonant scattering for astrophysical reaction studies

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, H.; Kahl, D.; Nakao, T. [Center for Nuclear Study (CNS), University of Tokyo, RIKEN campus, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Wakabayashi, Y.; Kubano, S. [The Institute of Physical and Chemical Research (RIKEN), 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Hashimoto, T. [Research Center for Nuclear Physics (RCNP), Osaka University, 10-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Hayakawa, S. [Istituto Nazionale Fisica Nucleare - Laboratori Nazionali del Sud (INFN-LNS), Via S. Sofia 62, 95125 Catania (Italy); Kawabata, T. [Department of Physics, Kyoto University, Kita-Shirakawa, Kyoto 606-8502 (Japan); Iwasa, N. [Department of Physics, Tohoku University, Aoba, Sendai, Miyagi 980-8578 (Japan); Teranishi, T. [Department of Physics, Kyushu University, 6-10-1 Hakozaki, Fukuoka 812-8581 (Japan); Kwon, Y. K. [Institute for Basic Science, 70, Yuseong-daero 1689-gil, Yuseong-gu, Daejeon 305-811 (Korea, Republic of); Binh, D. N. [30 MeV Cyclotron Center, Tran Hung Dao Hospital, Hoan Kiem District, Hanoi (Viet Nam); Khiem, L. H.; Duy, N. G. [Institute of Physics, Vietnam Academy of Science and Technology, 18 Hong Quoc Viet, Nghia do, Hanoi (Viet Nam)

    2014-05-02

    Several alpha-induced astrophysical reactions have been studied at CRIB (CNS Radioactive Ion Beam separator), which is a low-energy RI beam separator at Center for Nuclear Study (CNS) of the University of Tokyo. One of the methods to study them is the α resonant scattering using the thick-target method in inverse kinematics. Among the recent studies at CRIB, the measurement of {sup 7}Be+α resonant scattering is discussed. Based on the result of the experiment, we evaluated the contributions of high-lying resonances for the {sup 7}Be(α,γ) reaction, and proposed a new cluster band in {sup 11}C.

  14. The geochemical reactions resulting from CO{sub 2} injection into the Midale Formation, Weyburn oilfield : a laboratory experimental and modelling study

    Energy Technology Data Exchange (ETDEWEB)

    Azaroual, M.; Durst, P.; Czernichowski-Lauriol, I. [Bureau de Recherches Geologiques et Minieres, Orleans (France); Olsen, D.; Stentoft, N.; Springer, N. [Geological Survey of Denmark and Greenland (Denmark); Rochelle, C.A.; Pearce, J.; Bateman, K.; Birchall, D. [British Geological Survey, Nottingham (United Kingdom)

    2005-07-01

    One aspect of the International Energy Agency's (IEA) Weyburn CO2 Monitoring and Storage Project is the identification of geochemical changes that occur following the injection of carbon dioxide (CO{sub 2}) into the Midale Formation of the Weyburn Field in southern Saskatchewan. This paper summarized the fluid chemical and mineralogical changes noted during laboratory experiments on Midale core from the Weyburn Field. The reactions between injected CO{sub 2}, Midale lithologies and porewaters under temperatures and pressures representative of in-situ conditions were explored. The laboratory studies involved closed system batch experiments reacting samples of Midale reservoir rocks and cap rock with synthetic saline reservoir porewaters. Flow experiments were also performed based on both core flood approaches and column experiments. The duration of experiments ranged from 1 week to 6 months. Changes in fluid chemistry, mineralogy, porosity and permeability were measured. The results were then used to verify predictions from geochemical modelling activities. Experimental and theoretical studies of the effects of CO{sub 2} injection into the Midale lithologies showed variable amounts of carbonate mineral dissolution, some precipitation of gypsum, inhibition of anhydrite dissolution, and slow reactivity of alumino-silicate minerals. These indications helped develop an hypothesis and approaches to simulate the long term evolution of a one dimensional model representing CO{sub 2} injection into the host Midale Marly formation. . 3 refs., 4 figs.

  15. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  16. Fundamental studies of retrograde reactions in direct liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Serio, M.A.; Solomon, P.R.; Kroo, E.; Charpenay, S.; Bassilakis, R.

    1991-12-17

    The overall objective of the program was to improve the understanding of retrograde reactions and their dependencies on coal rank and structure, and/or coal modifications and reaction conditions. Because retrograde reactions are competitive with bond breaking reactions, an understanding of both is required to shift the competition in favor of the latter. Related objectives were to clarify the conflicting observations reported in literature on such major topics as the role of oxygen groups in retrograde reactions and to provide a bridge from very fundamental studies on pure compounds to phenomenological studies on actual coal. This information was integrated into the FG-DVC model, which was improved and extended to the liquefaction context.

  17. Modelling population growth with delayed nonlocal reaction in 2-dimensions.

    Science.gov (United States)

    Liang, Dong; Wu, Jianhong; Zhang, Fan

    2005-01-01

    In this paper, we consider the population growth of a single species living in a two-dimensional spatial domain. New reaction-difusion equation models with delayed nonlocal reaction are developed in two-dimensional bounded domains combining diferent boundary conditions. The important feature of the models is the reflection of the joint efect of the difusion dynamics and the nonlocal maturation delayed efect. We consider and ana- lyze numerical solutions of the mature population dynamics with some wellknown birth functions. In particular, we observe and study the occurrences of asymptotically stable steady state solutions and periodic waves for the two-dimensional problems with nonlocal delayed reaction. We also investigate numerically the efects of various parameters on the period, the peak and the shape of the periodic wave as well as the shape of the asymptotically stable steady state solution.

  18. Composition of reaction intermediates for stoichiometric and fuel-rich dimethyl ether flames: flame-sampling mass spectrometry and modeling studies.

    Science.gov (United States)

    Wang, Juan; Chaos, Marcos; Yang, Bin; Cool, Terrill A; Dryer, Fred L; Kasper, Tina; Hansen, Nils; Osswald, Patrick; Kohse-Höinghaus, Katharina; Westmoreland, Phillip R

    2009-03-07

    Molecular-beam synchrotron photoionization mass spectrometry and electron-ionization mass spectrometry are used for measurements of species mole fraction profiles for low-pressure premixed dimethyl ether (DME) flames with equivalence ratios ranging from near-stoichiometric conditions (Phi = 0.93) to fuel-rich flames near the limits of flat-flame stability (Phi = 1.86). The results are compared with predictions of a recently modified kinetic model for DME combustion [Zhao et al., Int. J. Chem. Kinet., 2008, 40, 1-18] that has been extensively tested against laminar flame speed measurements, jet-stirred reactor experiments, pyrolysis and oxidation experiments in flow reactors, species measurements for burner-stabilized flames and ignition delay measurements in shock tubes. The present comprehensive measurements of the composition of reaction intermediates over a broad range of equivalence ratios considerably extends the range of the previous experiments used for validation of this model and allows for an accurate determination of contributions of individual reactions to the formation or destruction of any given flame species. The excellent agreement between measurements and predictions found for all major and most intermediate species over the entire range of equivalence ratios provides a uniquely sensitive test of details of the kinetic model. The dependence on equivalence ratio of the characteristic reaction paths in DME flames is examined within the framework of reaction path analyses.

  19. Shell-model study of 31S at excitations relevant to the thermonuclear 30P(p,γ)31S reaction rate

    Science.gov (United States)

    Bouhelal, M.; Haas, F.

    2016-07-01

    Recent experimental data about the 30P(p, γ) reaction have been reported, where a list of confirmed 31S excited states within 500 keV of the 30P(p, γ)31S threshold at Ex = 6131 keV and their properties were studied. Definitive constraints on J^{π} are only given for two levels; the other ones are either tentative (five states) or undefined (six states). In order to confirm the proposed spin/parity assignments and to determine the unknown ones a comparison with shell-model calculations is crucial. We have performed a shell-model calculation using the (0+1)hbarω PSDPF interaction to calculate the excitation energy spectrum of mass 31 ( 31S - 31P up to 7000 keV. Between 6100 and 6700 keV, an excitation energy region of astrophysical interest, we obtain a set of negative-parity states that are good candidates for the observed ones. A complete spectrum of positive- and negative-parity states can now be proposed based also on a comparison with the 31P spectrum up to 7000 keV.

  20. Sequestration of Sr(II) by calcium oxalate—A batch uptake study and EXAFS analysis of model compounds and reaction products

    Science.gov (United States)

    Singer, David M.; Johnson, Stephen B.; Catalano, Jeffrey G.; Farges, François; Brown, Gordon E., Jr.

    2008-10-01

    Calcium oxalate monohydrate (CaC 2O 4·H 2O—abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II) aq following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4-10, with initial Sr solution concentrations, [Sr] aq, ranging from 1 × 10 -4 to 1 × 10 -3 M and ionic strengths ranging of 0.001-0.1 M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr aq for two days, the solution Ca concentration, [Ca] aq, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr aq removed from solution was nearly equal to the total [Ca] aq after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr

  1. Product PCNPsurv or the "reduced" evaporation residue cross section σER/σfusion for "hot" fusion reactions studied with the dynamical cluster-decay model

    Science.gov (United States)

    Chopra, Sahila; Kaur, Arshdeep; Hemdeep, Gupta, Raj K.

    2016-04-01

    The product PCNPsurv of compound nucleus (CN) fusion probability PCN and survival probability Psurv is calculated to determine the reduced evaporation residue cross section σER/σfusion , denoted σERreduced, with (total) fusion cross section σfusion given as a sum of CN-formation cross section σCN and non-CN cross section σnCN for each reaction, where σCN is the sum of evaporation residue cross section σER and fusion-fission cross section σff and σnCN, if not measured, is estimated empirically as the difference between measured and calculated σfusion. Our calculations of PCN and Psurv, based on the dynamical cluster-decay model, were successfully made for some 17 "hot" fusion reactions, forming different CN of mass numbers ACN˜100 -300 , with deformations of nuclei up to hexadecapole deformations and "compact" orientations for both coplanar (Φc=0∘ ) and noncoplanar (Φc≠0∘ ) configurations, using various different nuclear interaction potentials. Interesting variations of σERreduced with CN excitation energy E*, fissility parameter χ , CN mass ACN, and Coulomb parameter Z1Z2 show that, independent of entrance channel, different isotopes of CN, and nuclear interaction potentials used, the dominant quantity in the product is Psurv, which classifies all the studied CN into three groups of weakly fissioning, radioactive, and strongly fissioning superheavy nuclei, with relative magnitudes of σERreduced˜1 , ˜10-6 , and ˜10-11 , which, like for PCN, get further grouped in two dependencies of (i) weakly fissioning and strongly fissioning superheavy nuclei decreasing with increasing E* and (ii) radioactive nuclei increasing with increasing E*.

  2. Model for reaction kinetics in pyrolysis of wood

    Energy Technology Data Exchange (ETDEWEB)

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kumar, S. [Banaras Hindu Univ., Varanasi (India)

    1996-12-31

    A reaction model for the pyrolysis of small and large particles of wood Is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The of heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 7 refs., 3 figs., 2 tabs.

  3. Model for reaction kinetics in pyrolysis of wood

    Energy Technology Data Exchange (ETDEWEB)

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kuma, S. [Banaras Hindu Univ., Varanasi (India)

    1996-12-31

    A reaction model for the pyrolysis of small and large particles of wood is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 6 refs., 3 figs., 2 tabs.

  4. Modeling violent reaction following low speed impact on confined explosives

    Science.gov (United States)

    Curtis, John Philip; Jones, Andrew; Hughes, Christopher; Reaugh, John

    2012-03-01

    To ensure the safe storage and deployment of explosives it is important to understand the mechanisms that give rise to ignition and reaction growth in low speed impacts. The High Explosive Response to Mechanical Stimulus (HERMES) material model, integrated in the Lagrangian code LSDYNA, has been developed to model the progress of the reaction after such an impact. The low speed impact characteristics of an HMX based formulation have been examined using the AWE Steven Test. Axisymmetric simulations of an HMX explosive in the AWE Steven Test have been performed. A sensitivity study included the influence of friction, mesh resolution, and confinement. By comparing the experimental and calculated results, key model parameters which determine the explosive's response in this configuration have been identified. The model qualitatively predicts the point of ignition within the vehicle. Future refinements are discussed.

  5. Theoretical Study of Sodium-Water Surface Reaction Mechanism

    Science.gov (United States)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).

  6. A reaction diffusion model of pattern formation in clustering of adatoms on silicon surfaces

    Directory of Open Access Journals (Sweden)

    Trilochan Bagarti

    2012-12-01

    Full Text Available We study a reaction diffusion model which describes the formation of patterns on surfaces having defects. Through this model, the primary goal is to study the growth process of Ge on Si surface. We consider a two species reaction diffusion process where the reacting species are assumed to diffuse on the two dimensional surface with first order interconversion reaction occuring at various defect sites which we call reaction centers. Two models of defects, namely a ring defect and a point defect are considered separately. As reaction centers are assumed to be strongly localized in space, the proposed reaction-diffusion model is found to be exactly solvable. We use Green's function method to study the dynamics of reaction diffusion processes. Further we explore this model through Monte Carlo (MC simulations to study the growth processes in the presence of a large number of defects. The first passage time statistics has been studied numerically.

  7. 溜冰机器人地面反作用力的建模研究%Modeling Study of Ground Reaction Force for a Biped Skating Robot

    Institute of Scientific and Technical Information of China (English)

    李金良; 孙友霞

    2014-01-01

    The ground reaction force for a biped skating robot was calculated and analyzed,and a modeling method for the ground reaction force by using convex optimization was proposed. On the basis of reasonable assumption,the modeling of ground reaction force was transformed as a minimization problem of robot kinetic energy after collision under condition with certain constrains,and as a stand-ard convex optimization form. By using CVX software of convex optimization to calculate and simulate the ground reaction force,the re-sults prove the effectiveness of the method.%对两足溜冰机器人的地面反作用力进行了分析与计算,提出了应用凸优化方法进行地面反作用力的建模方法。在合理假设的基础上,将地面反作用力建模问题转换为在一定约束条件下使碰撞后的溜冰机器人动能达到最小的问题,并转化为凸优化的标准形式。应用凸优化程序CVX进行了地面反作用力的计算与仿真,结果证明了该方法的有效性。

  8. A Multiple Reaction Modelling Framework for Microbial Electrochemical Technologies

    Science.gov (United States)

    Oyetunde, Tolutola; Sarma, Priyangshu M.; Ahmad, Farrukh; Rodríguez, Jorge

    2017-01-01

    A mathematical model for the theoretical evaluation of microbial electrochemical technologies (METs) is presented that incorporates a detailed physico-chemical framework, includes multiple reactions (both at the electrodes and in the bulk phase) and involves a variety of microbial functional groups. The model is applied to two theoretical case studies: (i) A microbial electrolysis cell (MEC) for continuous anodic volatile fatty acids (VFA) oxidation and cathodic VFA reduction to alcohols, for which the theoretical system response to changes in applied voltage and VFA feed ratio (anode-to-cathode) as well as membrane type are investigated. This case involves multiple parallel electrode reactions in both anode and cathode compartments; (ii) A microbial fuel cell (MFC) for cathodic perchlorate reduction, in which the theoretical impact of feed flow rates and concentrations on the overall system performance are investigated. This case involves multiple electrode reactions in series in the cathode compartment. The model structure captures interactions between important system variables based on first principles and provides a platform for the dynamic description of METs involving electrode reactions both in parallel and in series and in both MFC and MEC configurations. Such a theoretical modelling approach, largely based on first principles, appears promising in the development and testing of MET control and optimization strategies. PMID:28054959

  9. Studying the triple - α reaction in hyperspherical harmonic approach

    Science.gov (United States)

    Nguyen, Ngoc; Nunes, Filomena

    2010-11-01

    The triple-α reaction is studied by using hyperspherical harmonic (HH) method [1]. Starting from three body model, we determine the 2^+ state and the 0^+ resonance as well as the quadrupole strength function B(E2). The triple-α reaction rate are calculated. We also carefully consider the contributions of the nonresonant continuum states to the reaction rate at low temperature (T Ogata, M.Kan, M.Kamimura, Prog. Theor. Phys. 122, 1055 (2009).[0pt] [3] R. de Diego, E. Garrido, D.V. Fedorov, A.S. Jensen, arXiv:1005.5647v1.

  10. Testing and validation of numerical models of groundwater flow, solute transport and chemical reactions in fractured granites: A quantitative study of the hydrogeological and hydrochemical impact produced

    Energy Technology Data Exchange (ETDEWEB)

    Molinero Huguet, J.

    2001-07-01

    This work deals with numerical modeling of groundwater flow, solute transport and chemical reactions through fractured media. These models have been developed within the framework of research activities founded by ENRESA , the Spanish Company for Nuclear Waste Management. This project is the result of a collaborative agreement between ENRESA and his equivalent Swedish Company (SKB) through the research project Task Force 5 of the Aspo Underground Laboratory. One of the objectives of this project is to assess quantitatively th hydrogeological and hydrochemical impact produced by the construction of a Deep Geological Repository in fractured granites. This is important because the new conditions altered construction impact will constitute the initial conditions for the repository closure stage. A second goo l of this work deals with testing the ability of current numerical tools to cope simultaneously with the complex hydrogeological and hydrochemical settlings, which are expected to take place in actual nuclear waste underground repositories constructed in crystalline fractured bed racks. This study has been undertaken through the performance of numerical models, which have subsequently been applied to simulate the hydrogeological and hydrochemical behavior of a granite massif, at a kilo metrical scale, during construction of the Aspo Hard Rock Underground Laboratory (Sweden). The Aspo Hard Rock Laboratory is a prototype, full-scale underground facility launched and operated by SKB. The main aim of the laboratory is to provide an opportunity for research, development and demonstration in a realistic rock environment down to the depth planned for the future deep repository. The framework of this underground facility provides a unique opportunity to attempt the objectives of the present dissertation. (Author)

  11. Elastodynamic modeling and joint reaction prediction for 3-PRS PKM

    Institute of Scientific and Technical Information of China (English)

    张俊; 赵艳芹

    2015-01-01

    To gain a thorough understanding of the load state of parallel kinematic machines (PKMs), a methodology of elastodynamic modeling and joint reaction prediction is proposed. For this purpose, a Sprint Z3 model is used as a case study to illustrate the process of joint reaction analysis. The substructure synthesis method is applied to deriving an analytical elastodynamic model for the 3-PRS PKM device, in which the compliances of limbs and joints are considered. Each limb assembly is modeled as a spatial beam with non-uniform cross-section supported by lumped virtual springs at the centers of revolute and spherical joints. By introducing the deformation compatibility conditions between the limbs and the platform, the governing equations of motion of the system are obtained. After degenerating the governing equations into quasi-static equations, the effects of the gravity on system deflections and joint reactions are investigated with the purpose of providing useful information for the kinematic calibration and component strength calculations as well as structural optimizations of the 3-PRS PKM module. The simulation results indicate that the elastic deformation of the moving platform in the direction of gravity caused by gravity is quite large and cannot be ignored. Meanwhile, the distributions of joint reactions are axisymmetric and position-dependent. It is worthy to note that the proposed elastodynamic modeling method combines the benefits of accuracy of finite element method and concision of analytical method so that it can be used to predict the stiffness characteristics and joint reactions of a PKM throughout its entire workspace in a quick and accurate manner. Moreover, the present model can also be easily applied to evaluating the overall rigidity performance as well as statics of other PKMs with high efficiency after minor modifications.

  12. Leprosy Reaction in Thai Population: A 20-Year Retrospective Study

    Directory of Open Access Journals (Sweden)

    Poonkiat Suchonwanit

    2015-01-01

    Full Text Available Background. Leprosy is a chronic infectious disease that presents with varying dermatological and neurological symptoms. The leprosy reactions occur over the chronic course of the disease and lead to extensive disability and morbidity. Objective. To analyze and identify the risk factors which contribute to leprosy reactions. Methods. In a retrospective study, we reviewed the medical records of leprosy patients registered at the leprosy clinic, Ramathibodi Hospital, Thailand, between March 1995 and April 2015. One hundred and eight patients were included; descriptive analysis was used for baseline characteristics and a binary logistic regression model was applied for identifying risk factors correlated with leprosy reactions. Results. Of the 108 cases analyzed, 51 were male and 57 were female. The mean age of presentation was 45 years. The borderline tuberculoid type was the most common clinical form. Leprosy reactions were documented in 61 cases (56.5%. The average time to reaction was 8.9 months. From multivariate analysis, risk factors for leprosy reactions were being female, positive bacillary index status, and MB treatment regimen. Conclusions. Leprosy reactions are common complications in leprosy patients. Being female, positive bacillary index status, and multibacillary treatment regimen are significantly associated with the reactions. Early detection in cases with risk factors followed by appropriate treatment could prevent the morbidity of leprosy patients.

  13. BlenX-based compositional modeling of complex reaction mechanisms

    CERN Document Server

    Zámborszky, Judit; 10.4204/EPTCS.19.6

    2010-01-01

    Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model buildin...

  14. Molecular beam studies of reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y.T. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.

  15. Forced thermal cycling of catalytic reactions: experiments and modelling

    DEFF Research Database (Denmark)

    Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune;

    2007-01-01

    Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...... by dynamic thermal limitations of the reactor. (c) 2007 Elsevier B.V. All rights reserved....

  16. Reaction Wheel Disturbance Model Extraction Software Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel mechanical noise is one of the largest sources of disturbance forcing on space-based observatories. Such noise arises from mass imbalance, bearing...

  17. Reaction Wheel Disturbance Model Extraction Software Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel disturbances are some of the largest sources of noise on sensitive telescopes. Such wheel-induced mechanical noises are not well characterized....

  18. Modelling Chemical Reasoning to Predict and Invent Reactions.

    Science.gov (United States)

    Segler, Marwin H S; Waller, Mark P

    2016-11-11

    The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery.

  19. Detailed reduction of reaction mechanisms for flame modeling

    Science.gov (United States)

    Wang, Hai; Frenklach, Michael

    1991-01-01

    A method for reduction of detailed chemical reaction mechanisms, introduced earlier for ignition system, was extended to laminar premixed flames. The reduction is based on testing the reaction and reaction-enthalpy rates of the 'full' reaction mechanism using a zero-dimensional model with the flame temperature profile as a constraint. The technique is demonstrated with numerical tests performed on the mechanism of methane combustion.

  20. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  1. Theoretical studies of the dynamics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, A.F. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Recent research effort has focussed on several reactions pertinent to combustion. The formation of the formyl radical from atomic hydrogen and carbon monoxide, recombination of alkyl radicals and halo-alkyl radicals with halogen atoms, and the thermal dissociation of hydrogen cyanide and acetylene have been studied by modeling. In addition, the inelastic collisions of NCO with helium have been investigated.

  2. Spallation reactions studied with 4-detector arrays

    Indian Academy of Sciences (India)

    J Galin

    2001-07-01

    Recently there has been a renewed interest in the study of spallation reactions in basic nuclear physics as well as in potential applications. Spallation reactions induced by light projectiles (protons, antiprotons, pions, etc.) in the GeV range allow the formation of hot nuclei which do not suffer the collective excitations (compression, rotation, deformation) unavoidable when using massive projectiles. Such nuclei provide an ideal testbench for probing their decay as a function of excitation energy. In these investigations, 4-detector arrays for charged particles and neutrons play a major role in the event-by-event sorting according to the excitation energy of the nucleus. Spallation reactions induced on heavy nuclei allow the conversion of the incident GeV proton into several tens of evaporated neutrons. The neutron production in thick targets has been investigated in great detail thanks to the use of high efficiency neutron detector arrays. When scattered on samples of inert or biological materials, these neutrons can be used to study details of the material structure. They could also be utilized for the transmutation of long-lived nuclear wastes or for the feeding of sub-critical nuclear reactors. The role of different types of multi-detector arrays is highlighted in this paper. Several references are also given for different uses of high efficiency neutron detectors in other contexts.

  3. Studying barrier-discharge-stimulated plasmachemical reactions

    Science.gov (United States)

    Malanichev, V. E.; Malashin, M. V.; Moshkunov, S. I.; Nebogatkin, S. V.; Khomich, V. Yu.; Shmelev, V. M.

    2017-05-01

    Barrier-discharge stimulation of chemical reactions has been studied in the case of methane oxidation by atmospheric oxygen with the formation of carbon monoxide and hydrogen. Experiments in a plasmachemical reactor demonstrated the possibility of increasing the yield of synthesis gas (syngas) by means of plasma pretreatment of the initial mixture of air and methane in a 7: 1 ratio at atmospheric pressure. The output-gas composition was determined by gas chromatography. It is established that the plasma-discharge treatment of the initial gas mixture leads to a 15% increase in the amount of syngas at the reactor output and increases the reaction selectivity with respect to hydrogen and carbon monoxide by 3.2 and 6.5%, respectively.

  4. Turing instability in reaction-diffusion models on complex networks

    Science.gov (United States)

    Ide, Yusuke; Izuhara, Hirofumi; Machida, Takuya

    2016-09-01

    In this paper, the Turing instability in reaction-diffusion models defined on complex networks is studied. Here, we focus on three types of models which generate complex networks, i.e. the Erdős-Rényi, the Watts-Strogatz, and the threshold network models. From analysis of the Laplacian matrices of graphs generated by these models, we numerically reveal that stable and unstable regions of a homogeneous steady state on the parameter space of two diffusion coefficients completely differ, depending on the network architecture. In addition, we theoretically discuss the stable and unstable regions in the cases of regular enhanced ring lattices which include regular circles, and networks generated by the threshold network model when the number of vertices is large enough.

  5. Molecular-dynamics study of detonation. II. The reaction mechanism

    Science.gov (United States)

    Rice, Betsy M.; Mattson, William; Grosh, John; Trevino, S. F.

    1996-01-01

    In this work, we investigate mechanisms of chemical reactions that sustain an unsupported detonation. The chemical model of an energetic crystal used in this study consists of heteronuclear diatomic molecules that, at ambient pressure, dissociate endothermically. Subsequent association of the products to form homonuclear diatomic molecules provides the energy release that sustains the detonation. A many-body interaction is used to simulate changes in the electronic bonding as a function of local atomic environment. The consequence of the many-body interaction in this model is that the intramolecular bond is weakened with increasing density. The mechanism of the reaction for this model was extracted by investigating the details of the molecular properties in the reaction zone with two-dimensional molecular dynamics. The mechanism for the initiation of the reaction in this model is pressure-induced atomization. There was no evidence of excitation of vibrational modes to dissociative states. This particular result is directly attributable to the functional form and choice of parameters for this model, but might also have more general applicability.

  6. Modeling the isotope effect in Walden inversion reactions

    Science.gov (United States)

    Schechter, Israel

    1991-05-01

    A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH 3T and CH 2TF from the reaction T + CH 3F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.

  7. Developed Hybrid Model for Propylene Polymerisation at Optimum Reaction Conditions

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-02-01

    Full Text Available A statistical model combined with CFD (computational fluid dynamic method was used to explain the detailed phenomena of the process parameters, and a series of experiments were carried out for propylene polymerisation by varying the feed gas composition, reaction initiation temperature, and system pressure, in a fluidised bed catalytic reactor. The propylene polymerisation rate per pass was considered the response to the analysis. Response surface methodology (RSM, with a full factorial central composite experimental design, was applied to develop the model. In this study, analysis of variance (ANOVA indicated an acceptable value for the coefficient of determination and a suitable estimation of a second-order regression model. For better justification, results were also described through a three-dimensional (3D response surface and a related two-dimensional (2D contour plot. These 3D and 2D response analyses provided significant and easy to understand findings on the effect of all the considered process variables on expected findings. To diagnose the model adequacy, the mathematical relationship between the process variables and the extent of polymer conversion was established through the combination of CFD with statistical tools. All the tests showed that the model is an excellent fit with the experimental validation. The maximum extent of polymer conversion per pass was 5.98% at the set time period and with consistent catalyst and co-catalyst feed rates. The optimum conditions for maximum polymerisation was found at reaction temperature (RT 75 °C, system pressure (SP 25 bar, and 75% monomer concentration (MC. The hydrogen percentage was kept fixed at all times. The coefficient of correlation for reaction temperature, system pressure, and monomer concentration ratio, was found to be 0.932. Thus, the experimental results and model predicted values were a reliable fit at optimum process conditions. Detailed and adaptable CFD results were capable

  8. Catalytic Hydrogenation Reaction of Naringin-Chalcone. Study of the Electrochemical Reaction

    Directory of Open Access Journals (Sweden)

    B. A. López de Mishima

    2000-03-01

    Full Text Available The electrocatalytic hydrogenation reaction of naringin derivated chalcone is studied. The reaction is carried out with different catalysts in order to compare with the classic catalytic hydrogenation.

  9. Modeling Study of the Impact of Heterogeneous Reactions on Dust Surfaces on Aerosol Optical Depth and Direct Radiative Forcing over East Asia in Springtime

    Institute of Scientific and Technical Information of China (English)

    LI Jia-Wei; HAN Zhi-Wei

    2011-01-01

    The spatial distributions and interannual variations of aerosol concentrations, aerosol optical depth (AOD), aerosol direct radiative forcings, and their responses to heterogeneous reactions on dust surfaces over East Asia in March 2006-10 were investigated by utilizing a regional coupled climate-chemistry/aerosol model. Anthropogenic aerosol concentrations (inorganic + carbonaceous) were higher in March 2006 and 2008, whereas soil dust reached its highest levels in March 2006 and 2010, resulting in stronger aerosol radiative forcings in these periods. The domain and five-year (2006-10) monthly mean concentrations of anthropogenic and dust aerosols, AOD, and radiative forcings at the surface (SURF) and at the top of the atmosphere (TOA) in March were 2.4 μg m 3 13.1 lag m^-3, 0.18, -19.0 W m^-2, and -7.4 W m^-2, respectively. Heterogeneous reactions led to an increase of total inorganic aerosol concentration; however, the ambient inorganic aerosol concentration decreased, resulting in a smaller AOD and weaker aerosol radiative forcings. In March 2006 and 2010, the changes in ambient inorganic aerosols, AOD, and aerosol radiative forcings were more evident. In terms of the domain and five-year averages, the total inorganic aerosol concentrations increased by 13.7% (0.17 μg m^-3) due to heterogeneous reactions, but the ambient inorganic aerosol concentrations were reduced by 10.5% (0.13 lag m-3). As a result, the changes in AOD, SURF and TOA radiative forcings were estimated to be -3.9% (-0.007), -1.7% (0.34 W m^-2), and -4.3% (0.34 W m^-2), respectively, in March over East Asia.

  10. DSMC Modeling of Flows with Recombination Reactions

    Science.gov (United States)

    2017-06-23

    rarefied gas dynamics community has seen the development of efficient algorithms for modern computer architectures16–19 which dramatically expand the area of...that participate in recombination. ACKNOWLEDGMENTS The work was supported by the Air Force Office of Sci - entific Research (Program Officer Dr. Ivett...flow,” Prog. Aerosp. Sci . 72, 66–79 (2015). 14R. D. Levine,Molecular Reaction Dynamics (Cambridge University Press, Cambridge, 2005). 15A. Alexeenko and

  11. Reaction pathways of the dissociation of methylal: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Frey, H.-M.; Beaud, P.; Gerber, T.; Mischler, B.; Radi, P.P.; Tzannis, A.-P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Schemata for modelling combustion processes do not yet include reaction rates for oxygenated fuels like methylal (DMM) which is considered as an additive or replacement for diesel due to its low sooting propensity. Density functional theory (DFT) studies of the possible reaction pathways for different dissociation steps of methylal are presented. Cleavage of a hydrogen bond to the methoxy group or the central carbon atom were simulated at the BLYP/6-311++G{sup **} level of theory. The results are compared to the experiment when dissociating and/or ionising DMM with femtosecond pulses. (author) 1 fig., 1 tab., 1 ref.

  12. Effect of reactions in small eddies on biomass gasification with eddy dissipation concept - Sub-grid scale reaction model.

    Science.gov (United States)

    Chen, Juhui; Yin, Weijie; Wang, Shuai; Meng, Cheng; Li, Jiuru; Qin, Bai; Yu, Guangbin

    2016-07-01

    Large-eddy simulation (LES) approach is used for gas turbulence, and eddy dissipation concept (EDC)-sub-grid scale (SGS) reaction model is employed for reactions in small eddies. The simulated gas molar fractions are in better agreement with experimental data with EDC-SGS reaction model. The effect of reactions in small eddies on biomass gasification is emphatically analyzed with EDC-SGS reaction model. The distributions of the SGS reaction rates which represent the reactions in small eddies with particles concentration and temperature are analyzed. The distributions of SGS reaction rates have the similar trend with those of total reactions rates and the values account for about 15% of the total reactions rates. The heterogeneous reaction rates with EDC-SGS reaction model are also improved during the biomass gasification process in bubbling fluidized bed.

  13. Reaction dynamics studies for the system 7Be+58Ni

    Science.gov (United States)

    Torresi, D.; Mazzocco, M.; Acosta, L.; Boiano, A.; Boiano, C.; Diaz-Torres, A.; Fierro, N.; Glodariu, T.; Grilj, L.; Guglielmetti, A.; Keeley, N.; La Commara, M.; Martel, I.; Mazzocchi, C.; Molini, P.; Pakou, A.; Parascandolo, C.; Parkar, V. V.; Patronis, N.; Pierroutsakou, D.; Romoli, M.; Rusek, K.; Sanchez-Benitez, A. M.; Sandoli, M.; Signorini, C.; Silvestri, R.; Soramel, F.; Stiliaris, E.; Strano, E.; Stroe, L.; Zerva, K.

    2015-04-01

    The study of reactions induced by exotic weakly bound nuclei at energies around the Coulomb barrier had attracted a large interest in the last decade, since the features of these nuclei can deeply affect the reaction dynamics. The discrimination between different reaction mechanisms is, in general, a rather difficult task. It can be achieved by using detector arrays covering high solid angle and with high granularity that allow to measure the reaction products and, possibly, coincidences between them, as, for example, recently done for stable weakly bound nuclei [1, 2]. We investigated the collision of the weakly bound nucleus 7Be on a 58Ni target at the beam energy of 1.1 times the Coulomb barrier, measuring the elastic scattering angular distribution and the energy and angular distributions of 3He and 4He. The 7Be radioactive ion beam was produced by the facility EXOTIC at INFN-LNL with an energy of 22 MeV and an intensity of ~3×105 pps. Results showed that the 4He yeld is about 4 times larger than 3He yield, suggesting that reaction mechanisms other than the break-up mostly produce the He isotopes. Theoretical calculations for transfer channels and compound nucleus reactions suggest that complete fusion accounts for (41±5%) of the total reaction cross section extracted from optical model analysis of the elastic scattering data, and that 3He and 4He stripping are the most populated reaction channels among direct processes. Eventually estimation of incomplete fusion contributions to the 3,4He production cross sections was performed through semi-classical calculations with the code PLATYPUS [3].

  14. Kinetic modelling of GlmU reactions - prioritization of reaction for therapeutic application.

    Directory of Open Access Journals (Sweden)

    Vivek K Singh

    Full Text Available Mycobacterium tuberculosis(Mtu, a successful pathogen, has developed resistance against the existing anti-tubercular drugs necessitating discovery of drugs with novel action. Enzymes involved in peptidoglycan biosynthesis are attractive targets for antibacterial drug discovery. The bifunctional enzyme mycobacterial GlmU (Glucosamine 1-phosphate N-acetyltransferase/ N-acetylglucosamine-1-phosphate uridyltransferase has been a target enzyme for drug discovery. Its C- and N- terminal domains catalyze acetyltransferase (rxn-1 and uridyltransferase (rxn-2 activities respectively and the final product is involved in peptidoglycan synthesis. However, the bifunctional nature of GlmU poses difficulty in deciding which function to be intervened for therapeutic advantage. Genetic analysis showed this as an essential gene but it is still unclear whether any one or both of the activities are critical for cell survival. Often enzymatic activity with suitable high-throughput assay is chosen for random screening, which may not be the appropriate biological function inhibited for maximal effect. Prediction of rate-limiting function by dynamic network analysis of reactions could be an option to identify the appropriate function. With a view to provide insights into biochemical assays with appropriate activity for inhibitor screening, kinetic modelling studies on GlmU were undertaken. Kinetic model of Mtu GlmU-catalyzed reactions was built based on the available kinetic data on Mtu and deduction from Escherichia coli data. Several model variants were constructed including coupled/decoupled, varying metabolite concentrations and presence/absence of product inhibitions. This study demonstrates that in coupled model at low metabolite concentrations, inhibition of either of the GlmU reactions cause significant decrement in the overall GlmU rate. However at higher metabolite concentrations, rxn-2 showed higher decrement. Moreover, with available intracellular

  15. Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions.

    Science.gov (United States)

    Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya

    2016-06-21

    Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long

  16. BlenX-based compositional modeling of complex reaction mechanisms

    Directory of Open Access Journals (Sweden)

    Judit Zámborszky

    2010-02-01

    Full Text Available Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model building in stochastic process algebras are discussed. A biological example on circadian clock is presented as a case study of BlenX compositionality.

  17. Abundances in Astrophysical Environments: Reaction Network Simulations with Reaction Rates from Many-nucleon Modeling

    Science.gov (United States)

    Amason, Charlee; Dreyfuss, Alison; Launey, Kristina; Draayer, Jerry

    2017-01-01

    We use the ab initio (first-principle) symmetry-adapted no-core shell model (SA-NCSM) to calculate reaction rates of significance to type I X-ray burst nucleosynthesis. We consider the 18O(p,γ)19F reaction, which may influence the production of fluorine, as well as the 16O(α,γ)20Ne reaction, which is key to understanding the production of heavier elements in the universe. Results are compared to those obtained in the no-core sympletic shell model (NCSpM) with a schematic interaction. We discuss how these reaction rates affect the relevant elemental abundances. We thank the NSF for supporting this work through the REU Site in Physics & Astronomy (NSF grant #1560212) at Louisiana State University. This work was also supported by the U.S. NSF (OCI-0904874, ACI -1516338) and the U.S. DOE (DE-SC0005248).

  18. Toluene pyrolysis studies and high temperature reactions of propargyl chloride

    Energy Technology Data Exchange (ETDEWEB)

    Kern, R.D.; Chen, H.; Qin, Z. [Univ. of New Orleans, LA (United States)

    1993-12-01

    The main focus of this program is to investigate the thermal decompositions of fuels that play an important role in the pre-particle soot formation process. It has been demonstrated that the condition of maximum soot yield is established when the reaction conditions of temperature and pressure are sufficient to establish a radical pool to support the production of polyaromatic hydrocarbon species and the subsequent formation of soot particles. However, elevated temperatures result in lower soot yields which are attributed to thermolyses of aromatic ring structures and result in the bell-shaped dependence of soot yield on temperature. The authors have selected several acyclic hydrocarbons to evaluate the chemical thermodynamic and kinetic effects attendant to benzene formation. To assess the thermal stability of the aromatic ring, the authors have studied the pyrolyses of benzene, toluene, ethylbenzene, chlorobenzene and pyridine. Time-of-flight mass spectrometry (TOF) is employed to analyze the reaction zone behind reflected shock waves. Reaction time histories of the reactants, products, and intermediates are constructed and mechanisms are formulated to model the experimental data. The TOF work is often performed with use of laser schlieren densitometry (LS) to measure density gradients resulting from the heats of various reactions involved in a particular pyrolytic system. The two techniques, TOF and LS, provide independent and complementary information about ring formation and ring rupture reactions.

  19. Unified studies of structure and reactions in light unstable nuclei

    Directory of Open Access Journals (Sweden)

    Ito Makoto

    2016-01-01

    Full Text Available The generalized two-center cluster model (GTCM, which can treat covalent, ionic and atomic configurations in general systems with two inert cores plus valence nucleons, is formulated in the basis of the microscopic cluster model. In this model, the covalent configurations constructed by the molecular orbital (MO method and the atomic (or ionic configuration obtained by the valence bonding (VB method can be described in a consistent manner. GTCM is applied to the light neutron-rich system, 10,12Be = α + α + XN (X = 2,4, and the unified studies of the structural changes and the reaction problem are performed. In the structure study, the calculated energy levels are characterized in terms of the chemical bonding like structures, such as the covalent MO or ionic VB structures. The chemical bonding structures changes from level to level within a small energy interval. In the unbound region, the structure problem with the total system of α + α + XN and the reaction problem, induced by the collision of an asymptotic VB state of α+6,8He, are combined by GTCM. The properties of unbound resonant states are discussed in a close connection to the reaction mechanism, and some enhancement factors originated from the properties of the intrinsic states are predicted in the reaction observables. The unified calculation of the structures and the reactions is applied to the Coulomb shift problem in the mirror system, such the 10Be and 10C nuclei. The Coulomb displacement energy of the mirror systems are discussed.

  20. Study on Disproportionation Reaction of FCC Gasoline on Acid Catalyst

    Institute of Scientific and Technical Information of China (English)

    Xu Youhao; Wang Xieqing

    2004-01-01

    Based on the experimental data relating to the reaction of FCC gasoline on acid catalyst the analysis of product distribution, and composition of gasoline and diesel fractions have been analyzed. The occurrence of disproportionation reaction of FCC gasoline on acid catalyst and the network of disproportionation reaction have been identified. Study has also shown that different reaction temperatures can result in different pathways of disproportionation reactions on acid catalyst.

  1. Reaction between Chromium(III) and EDTA Ions: an Overlooked Mechanism of Case Study Reaction of Chemical Kinetics.

    Science.gov (United States)

    Cerar, Janez

    2015-01-01

    Widely cited and accepted explanation of reaction mechanism of the case study reaction of chemical kinetics between Cr(III) ions and ethylenediaminetetraacetic acid (EDTA) contradicts modern chromium(III) coordination chemistry data. Absorption UV and visible light spectra were recorded during the reaction between aqueous solution of Cr(NO(3))(3) and EDTA in order to obtain new information about this reaction. Analysis of the spectra showed that only very small fraction of intermediates may be present in solution during the course of the reaction. The reaction scheme was established and according to it calculations based on a simplified model were carried out. Literature data for constants were used if known, otherwise, adjusted values of their sound estimates were applied. Reasonable agreement of the model calculations with the experimental data was obtained for pH values 3.8 and 4.5 but the model failed to reproduce measured rate of reaction at pH 5.5, probably due to the use of the oversimplified model.

  2. Formal modeling of a system of chemical reactions under uncertainty.

    Science.gov (United States)

    Ghosh, Krishnendu; Schlipf, John

    2014-10-01

    We describe a novel formalism representing a system of chemical reactions, with imprecise rates of reactions and concentrations of chemicals, and describe a model reduction method, pruning, based on the chemical properties. We present two algorithms, midpoint approximation and interval approximation, for construction of efficient model abstractions with uncertainty in data. We evaluate computational feasibility by posing queries in computation tree logic (CTL) on a prototype of extracellular-signal-regulated kinase (ERK) pathway.

  3. Charge-transfer reaction of 2,3-dichloro-1,4-naphthoquinone with crizotinib: Spectrophotometric study, computational molecular modeling and use in development of microwell assay for crizotinib.

    Science.gov (United States)

    Alzoman, Nourah Z; Alshehri, Jamilah M; Darwish, Ibrahim A; Khalil, Nasr Y; Abdel-Rahman, Hamdy M

    2015-01-01

    The reaction of 2,3-dichloro-1,4-naphthoquinone (DCNQ) with crizotinib (CZT; a novel drug used for treatment of non-small cell lung cancer) was investigated in different solvents of varying dielectric constants and polarity indexes. The reaction produced a red-colored product. Spectrophotometric investigations confirmed that the reaction proceeded through charge-transfer (CT) complex formation. The molar absorptivity of the complex was found to be linearly correlated with the dielectric constant and polarity index of the solvent; the correlation coefficients were 0.9567 and 0.9069, respectively. The stoichiometric ratio of DCNQ:CZT was found to be 2:1 and the association constant of the complex was found to be 1.07 × 10(2) l/mol. The kinetics of the reaction was studied; the order of the reaction, rate and rate constant were determined. Computational molecular modeling for the complex between DCNQ and CZT was conducted, the sites of interaction on CZT molecule were determined, and the mechanism of the reaction was postulated. The reaction was employed as a basis in the development of a novel 96-microwell assay for CZT in a linear range of 4-500 μg/ml. The assay limits of detection and quantitation were 2.06 and 6.23 μg/ml, respectively. The assay was validated as per the guidelines of the International Conference on Harmonization (ICH) and successfully applied to the analysis of CZT in its bulk and capsules with good accuracy and precision. The assay has high throughput and consumes a minimum volume of organic solvents thus it reduces the exposures of the analysts to the toxic effects of organic solvents, and significantly reduces the analysis cost.

  4. Modeling Electric Double-Layers Including Chemical Reaction Effects

    DEFF Research Database (Denmark)

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

    2014-01-01

    A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...

  5. Modeling reaction noise with a desired accuracy by using the X level approach reaction noise estimator (XARNES) method.

    Science.gov (United States)

    Konkoli, Zoran

    2012-07-21

    A novel computational method for modeling reaction noise characteristics has been suggested. The method can be classified as a moment closure method. The approach is based on the concept of correlation forms which are used for describing spatially extended many body problems where particle numbers change in space and time. In here, it was shown how the formalism of spatially extended correlation forms can be adapted to study well mixed reaction systems. Stochastic fluctuations in particle numbers are described by selectively capturing correlation effects up to the desired order, ξ. The method is referred to as the ξ-level Approximation Reaction Noise Estimator method (XARNES). For example, the ξ=1 description is equivalent to the mean field theory (first-order effects), the ξ=2 case corresponds to the previously developed PARNES method (pair effects), etc. The main idea is that inclusion of higher order correlation effects should lead to better (more accurate) results. Several models were used to test the method, two versions of a simple complex formation model, the Michaelis-Menten model of enzymatic kinetics, the smallest bistable reaction network, a gene expression network with negative feedback, and a random large network. It was explicitly demonstrated that increase in ξ indeed improves accuracy in all cases investigated. The approach has been implemented as automatic software using the Mathematica programming language. The user only needs to input reaction rates, stoichiometry coefficients, and the desired level of computation ξ.

  6. Biomass torrefaction: modeling of reaction thermochemistry.

    Science.gov (United States)

    Bates, Richard B; Ghoniem, Ahmed F

    2013-04-01

    Based on the evolution of volatile and solid products predicted by a previous model for willow torrefaction (Bates and Ghoniem, 2012) a thermochemical model has been developed to describe their thermal, chemical, and physical properties as well as the rates of heat release. The first stage of torrefaction, associated with hemicellulose decomposition, is exothermic releasing between 40 and 280 kJ/kginitial. The second stage is associated with the decomposition of the remaining lignocellulosic components, completes over a longer period, and is predicted to be either endothermic or exothermic depending on the temperature and assumed solid properties. Cumulative heat release increases with the degree of torrefaction quantified by the mass loss. The rate of mass loss and rate of heat release increase with higher temperatures. The higher heating value of volatiles produced during torrefaction was estimated to be between 4.4 and 16 MJ/kg increasing with the level of mass loss.

  7. Biogeochemical Transport and Reaction Model (BeTR) v1

    Energy Technology Data Exchange (ETDEWEB)

    2016-04-18

    The Biogeochemical Transport and Reaction Model (BeTR) is a F90 code that enables reactive transport modeling in land modules of earth system models (e.g. CESM, ACME). The code adopts the Objective-Oriented-Design, and allows users to plug in their own biogeochemical (BGC) formulations/codes, and compare them to other existing BGC codes in those ESMs. The code takes information of soil physics variables, such as variables, such as temperature, moisture, soil density profile; water flow, etc., from a land model to track the movement of different chemicals in presence of biogeochemical reactions.

  8. Coulomb dissociation studies for astrophysical thermonuclear reactions

    Energy Technology Data Exchange (ETDEWEB)

    Motobayashi, T. [Dept. of Physics, Rikkyo Univ., Toshima, Tokyo (Japan)

    1998-06-01

    The Coulomb dissociation method was applied to several radiative capture processes of astrophysical interest. The method has an advantage of high experimental efficiency, which allow measurements with radioactive nuclear beams. The reactions {sup 13}N(p,{gamma}){sup 14}O and {sup 7}Be(p,{gamma}){sup 8}B are mainly discussed. They are the key reaction in the hot CNO cycle in massive stars and the one closely related to the solar neutrino problem, respectively. (orig.)

  9. Geochemical controls on shale groundwaters: Results of reaction path modeling

    Energy Technology Data Exchange (ETDEWEB)

    Von Damm, K.L.; VandenBrook, A.J.

    1989-03-01

    The EQ3NR/EQ6 geochemical modeling code was used to simulate the reaction of several shale mineralogies with different groundwater compositions in order to elucidate changes that may occur in both the groundwater compositions, and rock mineralogies and compositions under conditions which may be encountered in a high-level radioactive waste repository. Shales with primarily illitic or smectitic compositions were the focus of this study. The reactions were run at the ambient temperatures of the groundwaters and to temperatures as high as 250/degree/C, the approximate temperature maximum expected in a repository. All modeling assumed that equilibrium was achieved and treated the rock and water assemblage as a closed system. Graphite was used as a proxy mineral for organic matter in the shales. The results show that the presence of even a very small amount of reducing mineral has a large influence on the redox state of the groundwaters, and that either pyrite or graphite provides essentially the same results, with slight differences in dissolved C, Fe and S concentrations. The thermodynamic data base is inadequate at the present time to fully evaluate the speciation of dissolved carbon, due to the paucity of thermodynamic data for organic compounds. In the illitic cases the groundwaters resulting from interaction at elevated temperatures are acid, while the smectitic cases remain alkaline, although the final equilibrium mineral assemblages are quite similar. 10 refs., 8 figs., 15 tabs.

  10. 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.

  11. Random incidence absorption coefficients of porous absorbers based on local and extended reaction models

    DEFF Research Database (Denmark)

    Jeong, Cheol-Ho

    2011-01-01

    Room surfaces have been extensively modeled as locally reacting in room acoustic predictions although such modeling could yield significant errors under certain conditions. Therefore, this study aims to propose a guideline for adopting the local reaction assumption by comparing predicted random...... incidence acoustical characteristics of typical building elements made of porous materials assuming extended and local reaction. For each surface reaction, five well-established wave propagation models, the Delany-Bazley, Miki, Beranek, Allard-Champoux, and Biot model, are employed. Effects of the flow...

  12. A Lattice Boltzmann Model for Oscillating Reaction-Diffusion

    Science.gov (United States)

    Rodríguez-Romo, Suemi; Ibañez-Orozco, Oscar; Sosa-Herrera, Antonio

    2016-07-01

    A computational algorithm based on the lattice Boltzmann method (LBM) is proposed to model reaction-diffusion systems. In this paper, we focus on how nonlinear chemical oscillators like Belousov-Zhabotinsky (BZ) and the chlorite-iodide-malonic acid (CIMA) reactions can be modeled by LBM and provide with new insight into the nature and applications of oscillating reactions. We use Gaussian pulse initial concentrations of sulfuric acid in different places of a bidimensional reactor and nondiffusive boundary walls. We clearly show how these systems evolve to a chaotic attractor and produce specific pattern images that are portrayed in the reactions trajectory to the corresponding chaotic attractor and can be used in robotic control.

  13. Reaction Networks For Interstellar Chemical Modelling: Improvements and Challenges

    CERN Document Server

    Wakelam, V; Herbst, E; Troe, J; Geppert, W; Linnartz, H; Oberg, K; Roueff, E; Agundez, M; Pernot, P; Cuppen, H M; Loison, J C; Talbi, D

    2010-01-01

    We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes -- ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination -- is reviewed. Emphasis is placed on those reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust p...

  14. Molecular beam chemiluminescence studies of the NO + O/sub 3/ reaction and modeling of global NO/sub 2/ distribution

    Energy Technology Data Exchange (ETDEWEB)

    Kowalczyk, M.

    1980-11-01

    The results of a crossed molecular beam study of the chemiluminescent reaction NO + 0/sub 3/ ..-->.. NO/sub 2/ + 0/sub 2/ are discussed. The chemiluminescence as a function of collision energy and an excitation function were obtained using a translationally cooled supersonic NO beam. An investigation into the role of the internal energy states using an effusive NO beam and a supersonic O/sub 3/ beam has been presented. The results show that chemiluminescence enhancement occurs when high and low temperature NO experiments are compared. The role that other energy modes may have is discussed. The observed enhancement is consistent with the concept that the chemiluminescence cross section increases with NO molecular rotation for low J states. The second part discusses the role of NO/sub 2/ in preserving a global ozone balance. NO/sub 2/ vertical profiles based on Noxon's (1979) column measurements were derived. The method of instantaneous rates was used to calculate the rate of ozone production and destruction by O/sub x/ and NO/sub x/ on a grid that covered the entire globe. The results were presented as a function of altitude and latitude in contour plots.

  15. Theoretical Model Calculation for d + 8Li Reaction

    Institute of Scientific and Technical Information of China (English)

    HAN Yin-Lu; GUO Hai-Rui; ZHANG Yue; ZHANG Jing-Shang

    2008-01-01

    Based on the theoretical models for light nuclei, the calculations of reaction cross sections and the angular distributions for d+8Li reaction are performed. Since all of the particle emissions are from the compound nucleus to the discrete levels, the angular momentum coupling effect in pre-equilibrium mechanism is taken into account. The three-body break-up process and the recoil effect are involved. The theoretical calculated results are compared to existing experimental data.

  16. An Investigation of Model Catalyzed Hydrocarbon Formation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tysoe, W. T.

    2001-05-02

    Work was focused on two areas aimed at understanding the chemistry of realistic catalytic systems: (1) The synthesis and characterization of model supported olefin metathesis catalysts. (2) Understanding the role of the carbonaceous layer present on Pd(111) single crystal model catalysts during reaction.

  17. Model-order reduction of biochemical reaction networks

    NARCIS (Netherlands)

    Rao, Shodhan; Schaft, Arjan van der; Eunen, Karen van; Bakker, Barbara M.; Jayawardhana, Bayu

    2013-01-01

    In this paper we propose a model-order reduction method for chemical reaction networks governed by general enzyme kinetics, including the mass-action and Michaelis-Menten kinetics. The model-order reduction method is based on the Kron reduction of the weighted Laplacian matrix which describes the gr

  18. Kinetic Study of the Heck Reaction: An Interdisciplinary Experiment

    Science.gov (United States)

    Gozzi, Christel; Bouzidi, Naoual

    2008-01-01

    The aim of this experiment is to study and calculate the kinetic constant of a Heck reaction: the arylation of but-3-en-2-ol by iodobenzene catalyzed by palladium acetate in presence of triethylamine in DMF. The reaction leads to a mixture of two ketones. Students use GC analysis to quantify reagents and products of reaction. They control the…

  19. The fundamental Diagram of Pedestrian Model with Slow Reaction

    CERN Document Server

    Fang, Jun; Hu, Hao; Xu, Zhaohui; Li, Huan

    2015-01-01

    The slow-to-start models are a classical cellular automata model in simulating vehicle traffic. However, to our knowledge, the slow-to-start effect has not considered in modeling pedestrian dynamic. We verify the similar behavior between pedestrian and vehicle, and propose an new lattice gas (LG) model called the slow reaction (SR) model to describe the pedestrian's delayed reaction in single-file movement. We simulate and reproduce the Seyfried's field experiments at the research centre Julich, and use its empirical data to validate our SR model. We compare the SR model with the standard LG model. We test different probability of slow reaction ps in SR model and found the simulation data of ps=0.3 fit the empirical data best. The RMS error of mean velocity of SR model is smaller than that of standard LG model. In the range of ps=0.1~0.3, our fundamental diagram between velocity and density by simulation coincides with field experiments. The distribution of individual velocity in fundamental diagram in SR mod...

  20. Study of Reaction Mechanism in Tracer Munitions

    Science.gov (United States)

    1974-12-01

    Regression Rates (Furnished by Frankford Arsenal) 35 13 Calculated Heat Fluxes and Energy Partitions 43 4 I NOMENCLATURE B = preexponential factor... anhydride disproportionates in a fast step: N2 0 3 - 2 + NO (4) so that the resulting dioxide can react with more nitrite in another fast reaction: Sr

  1. Small-scale behaviour in deterministic reaction models

    Energy Technology Data Exchange (ETDEWEB)

    Politi, Paolo [Istituto dei Sistemi Complessi, Consiglio Nazionale delle Ricerche, Via Madonna del Piano 10, 50019 Sesto Fiorentino (Italy); Ben-Avraham, Daniel, E-mail: paolo.politi@isc.cnr.i, E-mail: benavraham@clarkson.ed [Physics Department, Clarkson University, Potsdam, NY 13699-5820 (United States)

    2010-10-08

    In a recent paper published in this journal (2009 J. Phys. A: Math. Theor. 42 495004) we studied a one-dimensional particles system where nearest particles attract with a force inversely proportional to a power {alpha} of their distance and coalesce upon encounter. Numerics yielded a distribution function h(z) for the gap between neighbouring particles, with h(z) {approx} z{sup {beta}({alpha})} for small z and {beta}({alpha}) > {alpha}. We can now prove analytically that in the strict limit of z {yields} 0, {beta} = {alpha} for {alpha} > 0, corresponding to the mean-field result, and we compute the length scale where the mean field breaks down. More generally, in that same limit correlations are negligible for any similar reaction model where attractive forces diverge with vanishing distance. The actual meaning of the measured exponent {beta}({alpha}) remains an open question.

  2. Adverse reactions to intravenous iodinated contrast media: a prospective study

    Directory of Open Access Journals (Sweden)

    Dhruv J. Modi

    2012-06-01

    Full Text Available Background: Adverse reactions to intravenous iodinated contrast media may be classified as general and organ-specific, such as contrast-induced nephrotoxicity. General adverse reactions may be sub classified into acute and delayed types. Acute general adverse reactions can range from transient minor reactions to life-threatening severe reactions. This study was done to determine clinical adverse effects of the iodinated contrast media. Methods: Data of 899 consecutive patients at C.U. Shah Medical College and Hospital, Surendranagar, who received sodium meglumine diatrizoate intravenous iodinated contrast media during the period of May 2011 to April 2012, were collected for any adverse drug reactions. Results: Out of 899, 189 patients developed adverse contrast reactions. The incidences of mild, moderate and severe adverse reactions were 19.47%, 1.33% and 0.28%, respectively. There were no differences in the incidence of adverse reactions according to gender (males 21.1%; females 20.7%; p= >0.05 or age (p= >0.05. The incidence of adverse reactions was significantly higher in patients with a history of previous reactions (50% than in those with no history (21.25%; p= <0.05. Conclusions: The skin was the most commonly affected site of reactions. In reactions, mild forms were more common compared to moderate and severe. [Int J Basic Clin Pharmacol 2012; 1(3.000: 211-215

  3. Chemical reaction networks as a model to describe UVC- and radiolytically-induced reactions of simple compounds.

    Science.gov (United States)

    Dondi, Daniele; Merli, Daniele; Albini, Angelo; Zeffiro, Alberto; Serpone, Nick

    2012-05-01

    When a chemical system is submitted to high energy sources (UV, ionizing radiation, plasma sparks, etc.), as is expected to be the case of prebiotic chemistry studies, a plethora of reactive intermediates could form. If oxygen is present in excess, carbon dioxide and water are the major products. More interesting is the case of reducing conditions where synthetic pathways are also possible. This article examines the theoretical modeling of such systems with random-generated chemical networks. Four types of random-generated chemical networks were considered that originated from a combination of two connection topologies (viz., Poisson and scale-free) with reversible and irreversible chemical reactions. The results were analyzed taking into account the number of the most abundant products required for reaching 50% of the total number of moles of compounds at equilibrium, as this may be related to an actual problem of complex mixture analysis. The model accounts for multi-component reaction systems with no a priori knowledge of reacting species and the intermediates involved if system components are sufficiently interconnected. The approach taken is relevant to an earlier study on reactions that may have occurred in prebiotic systems where only a few compounds were detected. A validation of the model was attained on the basis of results of UVC and radiolytic reactions of prebiotic mixtures of low molecular weight compounds likely present on the primeval Earth.

  4. Implementation of a vibrationally linked chemical reaction model for DSMC

    Science.gov (United States)

    Carlson, A. B.; Bird, Graeme A.

    1994-01-01

    A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.

  5. Reaction mechanism study of 7Li(7Li, 6He) reaction at above Coulomb barrier energies

    Indian Academy of Sciences (India)

    V V Parkar; V Jha; S Santra; B J Roy; K Ramachandran; A Shrivastava; K Mahata; A Chatterjee; S Kailas

    2009-02-01

    The elastic scattering and the 6He angular distributions were measured in 7Li + 7Li reaction at two energies, lab = 20 and 25 MeV. FRDWBA calculations have been performed to explain the measured 6He data. The calculations were very sensitive to the choice of the optical model potentials in entrance and exit channels. The one-step proton transfer was found to be the dominant reaction mechanism in 6He production.

  6. ALTERNATING DIRECTION FINITE ELEMENT METHOD FOR SOME REACTION DIFFUSION MODELS

    Institute of Scientific and Technical Information of China (English)

    江成顺; 刘蕴贤; 沈永明

    2004-01-01

    This paper is concerned with some nonlinear reaction - diffusion models. To solve this kind of models, the modified Laplace finite element scheme and the alternating direction finite element scheme are established for the system of patrical differential equations. Besides, the finite difference method is utilized for the ordinary differential equation in the models. Moreover, by the theory and technique of prior estimates for the differential equations, the convergence analyses and the optimal L2- norm error estimates are demonstrated.

  7. Kinetic modeling for thermal dehydration of ferrous oxalate dihydrate polymorphs: a combined model for induction period-surface reaction-phase boundary reaction.

    Science.gov (United States)

    Ogasawara, Haruka; Koga, Nobuyoshi

    2014-04-03

    In this study, ferrous oxalate dihydrate polymorph particles, α- and β-phases, with square bipyramidal and quadratic prismatic shapes, respectively, were synthesized. Thermal dehydration of the samples was subjected to kinetic study as a typical reaction that indicates a significant induction period and a sigmoidal mass-loss behavior. On the basis of the formal kinetic analysis of the mass-loss traces recorded under isothermal, nonisothermal, and constant transformation rate conditions and the morphological observations of the surface textures of the partially reacted sample particles, a combined kinetic model for the induction period-surface reaction-phase boundary reaction was developed. The sigmoidal mass-loss behavior after the significant induction period under isothermal conditions was satisfactorily simulated by the combined kinetic model. The kinetic parameters for the component processes of induction period, surface reaction, and phase boundary reaction were separately determined from the kinetic simulation. The differences in the kinetic behaviors of the induction period and the phase boundary reaction between α- and β-phase samples were well described by the kinetic parameters. The applicability of the combined kinetic model to practical systems was demonstrated through characterizing the physicogeometrical kinetics of the thermal dehydration of ferrous oxalate dihydrate polymorphs.

  8. Micellar Effects on Nucleophilic Addition Reaction and Applicability of Enzyme Catalysis Model

    Directory of Open Access Journals (Sweden)

    R. K. London Singh

    2012-01-01

    Full Text Available This study describes the effect of anionic and cationic micelles on nucleophilic addition reaction of rosaniline hydrochloride (RH with hydroxide under pseudo-first order condition. Strong inhibitory effect is observed due to SDS micelle, whereas CTAB catalysed the reaction. This is explained on the basis of electrostatic and hydrophobic interactions which are simultaneously operating in the reaction system. The kinetic data obtained is quantitatively analysed by applying the positive cooperativity model of enzyme catalysis. Binding constants and influence of counterions on the reaction have also been investigated.

  9. Stability of convective patterns in reaction fronts: a comparison of three models.

    Science.gov (United States)

    Vasquez, Desiderio A; Coroian, Dan I

    2010-09-01

    Autocatalytic reaction fronts generate density gradients that may lead to convection. Fronts propagating in vertical tubes can be flat, axisymmetric, or nonaxisymmetric, depending on the diameter of the tube. In this paper, we study the transitions to convection as well as the stability of different types of fronts. We analyze the stability of the convective reaction fronts using three different models for front propagation. We use a model based on a reaction-diffusion-advection equation coupled to the Navier-Stokes equations to account for fluid flow. A second model replaces the reaction-diffusion equation with a thin front approximation where the front speed depends on the front curvature. We also introduce a new low-dimensional model based on a finite mode truncation. This model allows a complete analysis of all stable and unstable fronts.

  10. A study on the ester interchange reaction of dimethyl naphthalate with ethylene glycol

    Energy Technology Data Exchange (ETDEWEB)

    Sho, S.Y.; Cheong, S.I [Hannam University, Taejeon (Korea)

    2001-01-01

    The kinetics of ester interchange reaction of dimethyl naphthalate (DMN) with ethylene glycol (EG) has been studied in the range of 180-200 deg. C using zinc and manganese catalysts. The reaction was performed in a semibatch reactor under nonisothermal condition and the degree of reaction was calculated from experimental data of methanol removal rate and reaction temperature. As a reaction model, both the functional group model and the molecular species model were applied and analysed. In case of zinc catalysts, the ratio of reaction rate of methyl hydroxyethyl naphthalate (MHEN) with EG on that of DMN with EG is about 1.4, whereas in case of manganese catalyst the ration is about 4.3, which implies that the reaction rate is quite dependent on the type of catalyst. In case of zinc catalyst, the reaction order of catalyst concentration on either DMN or MHEN and EG is less than 1, whereas in case of manganese catalyst, the reaction order is larger than 1. The activation energy for zinc and manganese catalyst, irrespective of the type of molecular species, e. g., DMN and MHEN, were found to be 25000 and 28750 cal/mol, respectively. As a result of comparing two reaction model, the molecular species model fits well for the experimental dat. (author). 12 refs., 1 tab., 8 figs.

  11. Neutrino nucleus reactions within the GiBUU model

    CERN Document Server

    Lalakulich, O; Mosel, U

    2011-01-01

    The GiBUU model, which implements all reaction channels relevant at medium neutrino energy, is used to investigate the neutrino and antineutrino scattering on iron. Results for integrated cross sections are compared with NOMAD and MINOS data. It is shown, that final state interaction can noticeably change the spectra of the outgoing hadrons. Predictions for the Miner$\

  12. Modeling of calcium-based sorbent reactions with sulfur dioxide

    Directory of Open Access Journals (Sweden)

    Tomanović Ivan

    2015-01-01

    Full Text Available A mathematical model of calcium sorbent reactions for simulation of sulfur dioxide reduction from pulverized coal combustion fl e gasses is developed, implemented within numerical code and validated against available measurements under controlled conditions. The model attempts to closely resemble reactions of calcination, sintering and sulfation, occurring during the sorbent particles motion in the furnace. The sulfation is based on PSSM (Partially Sintered Spheres Model, coupled with simulated particle calcination and sintering. Complex geometry of the particle is taken into account, with the assumption that it consists of spherical grains in contact with each other. Numerical simulations of drop down tube reactors were performed for both CaCO3 and Ca(OH2 sorbent particles and results were compared with available experimental data from literature. The sorbent reactions model will be further used for simulations of desulfurization reactions in turbulent gas-particle flow under coalcombustion conditions. [Projekat Ministarstva nauke Republike Srbije, br. TR-33018: Increase in energy and ecology efficiency of processes in pulverized coal-fired furnace and optimization of utility steam boiler air preheater by using in-house developed software tools

  13. Evidence for a transition state model compound of in-plane vinylic SN2 reaction.

    Science.gov (United States)

    Yamaguchi, Torahiko; Yamamoto, Yohsuke; Fujiwara, Yoshihisa; Tanimoto, Yoshifumi

    2005-06-23

    [reaction: see text] To isolate a transition state model compound of an in-plane vinylic S(N)2 reaction, vinyl bromide 6 bearing a newly synthesized tridentate ligand derived from 1,8-dimethoxythioxanthen-9-one (5) was prepared as a precursor. Although irradiation of 6 gave demethylated benzofuran 12, a transient broad peak which indicates formation of the desired transition state model compound was observed in the laser flash photolytic study.

  14. Python framework for kinetic modeling of electronically excited reaction pathways

    Science.gov (United States)

    Verboncoeur, John; Parsey, Guy; Guclu, Yaman; Christlieb, Andrew

    2012-10-01

    The use of plasma energy to enhance and control the chemical reactions during combustion, a technology referred to as ``plasma assisted combustion'' (PAC), can result in a variety of beneficial effects: e.g. stable lean operation, pollution reduction, and wider range of p-T operating conditions. While experimental evidence abounds, theoretical understanding of PAC is at best incomplete, and numerical tools still lack in reliable predictive capabilities. In the context of a joint experimental-numerical effort at Michigan State University, we present here an open-source modular Python framework dedicated to the dynamic optimization of non-equilibrium PAC systems. Multiple sources of experimental reaction data, e.g. reaction rates, cross-sections and oscillator strengths, are used in order to quantify the effect of data uncertainty and limiting assumptions. A collisional-radiative model (CRM) is implemented to organize reactions by importance and as a potential means of measuring a non-Maxwellian electron energy distribution function (EEDF), when coupled to optical emission spectroscopy data. Finally, we explore scaling laws in PAC parameter space using a kinetic global model (KGM) accelerated with CRM optimized reaction sequences and sparse stiff integrators.

  15. Cohabitation reaction-diffusion model for virus focal infections

    Science.gov (United States)

    Amor, Daniel R.; Fort, Joaquim

    2014-12-01

    The propagation of virus infection fronts has been typically modeled using a set of classical (noncohabitation) reaction-diffusion equations for interacting species. However, for some single-species systems it has been recently shown that noncohabitation reaction-diffusion equations may lead to unrealistic descriptions. We argue that previous virus infection models also have this limitation, because they assume that a virion can simultaneously reproduce inside a cell and diffuse away from it. For this reason, we build a several-species cohabitation model that does not have this limitation. Furthermore, we perform a sensitivity analysis for the most relevant parameters of the model, and we compare the predicted infection speed with observed data for two different strains of the T7 virus.

  16. Study of the Kinetics of an S[subscript N]1 Reaction by Conductivity Measurement

    Science.gov (United States)

    Marzluff, Elaine M.; Crawford, Mary A.; Reynolds, Helen

    2011-01-01

    Substitution reactions, a central part of organic chemistry, provide a model system in physical chemistry to study reaction rates and mechanisms. Here, the use of inexpensive and readily available commercial conductivity probes coupled with computer data acquisition for the study of the temperature and solvent dependence of the solvolysis of…

  17. Reactions of lactose during heat treatment of milk: a quantitative study.

    NARCIS (Netherlands)

    Berg, H.E.

    1993-01-01

    The kinetics of the chemical reactions of lactose during heat treatment of milk were studied. Skim milk and model solutions resembling milk were heated. Reaction products were determined and the influence of varying lactose, casein and fat concentration on the formation of these products was studied

  18. Neutron-induced reaction studies using stored ions

    Science.gov (United States)

    Glorius, Jan; Litvinov, Yuri A.; Reifarth, René

    2015-11-01

    Storage rings provide unique possibilities for investigations of nuclear reactions. Radioactive ions can be stored if the ring is connected to an appropriate facility and reaction studies are feasible at low beam intensities because of the recycling of beam particles. Using gas jet or droplet targets, charged particle-induced reactions on short-lived isotopes can be studied in inverse kinematics. In such a system a high-flux reactor could serve as a neutron target extending the experimental spectrum to neutron-induced reactions. Those could be studied over a wide energy range covering the research fields of nuclear astrophysics and reactor safety, transmutation of nuclear waste and fusion.

  19. Consistent post-reaction vibrational energy redistribution in DSMC simulations using TCE model

    Science.gov (United States)

    Borges Sebastião, Israel; Alexeenko, Alina

    2016-10-01

    The direct simulation Monte Carlo (DSMC) method has been widely applied to study shockwaves, hypersonic reentry flows, and other nonequilibrium flow phenomena. Although there is currently active research on high-fidelity models based on ab initio data, the total collision energy (TCE) and Larsen-Borgnakke (LB) models remain the most often used chemistry and relaxation models in DSMC simulations, respectively. The conventional implementation of the discrete LB model, however, may not satisfy detailed balance when recombination and exchange reactions play an important role in the flow energy balance. This issue can become even more critical in reacting mixtures involving polyatomic molecules, such as in combustion. In this work, this important shortcoming is addressed and an empirical approach to consistently specify the post-reaction vibrational states close to thermochemical equilibrium conditions is proposed within the TCE framework. Following Bird's quantum-kinetic (QK) methodology for populating post-reaction states, the new TCE-based approach involves two main steps. The state-specific TCE reaction probabilities for a forward reaction are first pre-computed from equilibrium 0-D simulations. These probabilities are then employed to populate the post-reaction vibrational states of the corresponding reverse reaction. The new approach is illustrated by application to exchange and recombination reactions relevant to H2-O2 combustion processes.

  20. Neutrino-nucleus reactions based on recent structure studies

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Toshio [Department of Physics and Graduate School of Integrated Basic Sciences, College of Humanities and Sciences, Nihon University, Sakurajosui 3-25-40, Setagaya-ku, Tokyo 156-8550 (Japan); National Astronomical Observatory of Japan, Mitaka, Tokyo 181-8588 (Japan)

    2015-05-15

    Neutrino-nucleus reactions are studied with the use of new shell model Hamiltonians, which have proper tensor components in the interactions and prove to be successful in the description of Gamow-Teller (GT) strengths in nuclei. The new Hamiltonians are applied to obtain new neutrino-nucleus reaction cross sections in {sup 12}C, {sup 13}C, {sup 56}Fe and {sup 56}Ni induced by solar and supernova neutrinos. The element synthesis by neutrino processes in supernova explosions is discussed with the new cross sections. The enhancement of the production yields of {sup 7}Li, {sup 11}B and {sup 55}Mn is obtained while fragmented GT strength in {sup 56}Ni with two-peak structure is found to result in smaller e-capture rates at stellar environments. The monopole-based universal interaction with tensor force of π+ρ meson exchanges is used to evaluate GT strength in {sup 40}Ar and ν-induced reactions on {sup 40}Ar. It is found to reproduce well the experimental GT strength in {sup 40}Ar.

  1. Comparative Study Between Ethylbenzene Disproportionation Reaction and its Ethylation Reaction with Ethanol over ZSM-5

    KAUST Repository

    Tukur, N. M.

    2009-06-23

    Ethylation of ethylbenzene with ethanol has been studied over ZSM-5 catalyst in a riser simulator that mimics the operation of a fluidized-bed reactor. The feed molar ratio of ethylbenzene:ethanol is 1:1. The study was carried out at 350, 400, 450, and 500°C for reaction times of 3, 5, 7, 10, 13, and 15 s. Comparisons are made between the results of the ethylbenzene ethylation reaction with that of ethylbenzene disproportionation reaction earlier reported. The effect of reaction conditions on ethylbenzene reactivity, p-diethylbenzene selectivity, total diethylbenzene (DEB) isomers selectivity, p-DEB-to-m-DEB ratio, benzene-to-DEB molar ratio, and benzene selectivity, are reported. Benzene selectivity is about 10 times more in the EB disproportion reaction as compared to its ethylation reaction with ethanol at 350°C. In addition, the results showed a p-DEB/m-DEB ratio for the EB ethylation reaction varying between 1.2-1.7, which is greater than the equilibrium values. Increase in temperature shifts the alkylation/dealkylation equilibrium towards dealkylation, thereby decreasing conversion and selectivity to DEB. © Springer Science+Business Media, LLC 2009.

  2. Complex reaction noise in a molecular quasispecies model

    Science.gov (United States)

    Hochberg, David; Zorzano, María-Paz; Morán, Federico

    2006-05-01

    We have derived exact Langevin equations for a model of quasispecies dynamics. The inherent multiplicative reaction noise is complex and its statistical properties are specified completely. The numerical simulation of the complex Langevin equations is carried out using the Cholesky decomposition for the noise covariance matrix. This internal noise, which is due to diffusion-limited reactions, produces unavoidable spatio-temporal density fluctuations about the mean field value. In two dimensions, this noise strictly vanishes only in the perfectly mixed limit, a situation difficult to attain in practice.

  3. On the relevance of the H2 + O reaction pathway for the surface formation of interstellar water - A combined experimental and modeling study

    CERN Document Server

    Lamberts, Thanja; Fedoseev, Gleb; Ioppolo, Sergio; Chuang, Ko-Ju; Linnartz, Harold

    2014-01-01

    The formation of interstellar water has been commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10-20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H2 + O has been proposed to contribute significantly to the formation of water as well. However, gas phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H2 and O. These reactants are brought together in a matrix of CO2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The amount of water detected with the quadrupole mass spectrometer upon TPD is found to o...

  4. Dynamic order reduction of thin-film deposition kinetics models: A reaction factorization approach

    Energy Technology Data Exchange (ETDEWEB)

    Adomaitis, Raymond A., E-mail: adomaiti@umd.edu [Department of Chemical and Biomolecular Engineering, Institute for Systems Research, University of Maryland, College Park, Maryland 20742 (United States)

    2016-01-15

    A set of numerical tools for the analysis and dynamic dimension reduction of chemical vapor and atomic layer deposition (ALD) surface reaction models is developed in this work. The approach is based on a two-step process where in the first, the chemical species surface balance dynamic equations are factored to effectively decouple the (nonlinear) reaction rates, a process that eliminates redundant dynamic modes and that identifies conserved quantities. If successful, the second phase is implemented to factor out redundant dynamic modes when species relatively minor in concentration are omitted; if unsuccessful, the technique points to potential model structural problems. An alumina ALD process is used for an example consisting of 19 reactions and 23 surface and gas-phase species. Using the approach developed, the model is reduced by nineteen modes to a four-dimensional dynamic system without any knowledge of the reaction rate values. Results are interpreted in the context of potential model validation studies.

  5. NASTRAN buckling study of a linear induction motor reaction rail

    Science.gov (United States)

    Williams, J. G.

    1973-01-01

    NASTRAN was used to study problems associated with the installation of a linear induction motor reaction rail test track. Specific problems studied include determination of the critical axial compressive buckling stress and establishment of the lateral stiffness of the reaction rail under combined loads. NASTRAN results were compared with experimentally obtained values and satisfactory agreement was obtained. The reaction rail was found to buckle at an axial compressive stress of 11,400 pounds per square inch. The results of this investigation were used to select procedures for installation of the reaction rail.

  6. Modelling biochemical reaction systems by stochastic differential equations with reflection.

    Science.gov (United States)

    Niu, Yuanling; Burrage, Kevin; Chen, Luonan

    2016-05-07

    In this paper, we gave a new framework for modelling and simulating biochemical reaction systems by stochastic differential equations with reflection not in a heuristic way but in a mathematical way. The model is computationally efficient compared with the discrete-state Markov chain approach, and it ensures that both analytic and numerical solutions remain in a biologically plausible region. Specifically, our model mathematically ensures that species numbers lie in the domain D, which is a physical constraint for biochemical reactions, in contrast to the previous models. The domain D is actually obtained according to the structure of the corresponding chemical Langevin equations, i.e., the boundary is inherent in the biochemical reaction system. A variant of projection method was employed to solve the reflected stochastic differential equation model, and it includes three simple steps, i.e., Euler-Maruyama method was applied to the equations first, and then check whether or not the point lies within the domain D, and if not perform an orthogonal projection. It is found that the projection onto the closure D¯ is the solution to a convex quadratic programming problem. Thus, existing methods for the convex quadratic programming problem can be employed for the orthogonal projection map. Numerical tests on several important problems in biological systems confirmed the efficiency and accuracy of this approach.

  7. EMPIRE: Nuclear Reaction Model Code System for Data Evaluation

    Science.gov (United States)

    Herman, M.; Capote, R.; Carlson, B. V.; Obložinský, P.; Sin, M.; Trkov, A.; Wienke, H.; Zerkin, V.

    2007-12-01

    EMPIRE is a modular system of nuclear reaction codes, comprising various nuclear models, and designed for calculations over a broad range of energies and incident particles. A projectile can be a neutron, proton, any ion (including heavy-ions) or a photon. The energy range extends from the beginning of the unresolved resonance region for neutron-induced reactions (∽ keV) and goes up to several hundred MeV for heavy-ion induced reactions. The code accounts for the major nuclear reaction mechanisms, including direct, pre-equilibrium and compound nucleus ones. Direct reactions are described by a generalized optical model (ECIS03) or by the simplified coupled-channels approach (CCFUS). The pre-equilibrium mechanism can be treated by a deformation dependent multi-step direct (ORION + TRISTAN) model, by a NVWY multi-step compound one or by either a pre-equilibrium exciton model with cluster emission (PCROSS) or by another with full angular momentum coupling (DEGAS). Finally, the compound nucleus decay is described by the full featured Hauser-Feshbach model with γ-cascade and width-fluctuations. Advanced treatment of the fission channel takes into account transmission through a multiple-humped fission barrier with absorption in the wells. The fission probability is derived in the WKB approximation within the optical model of fission. Several options for nuclear level densities include the EMPIRE-specific approach, which accounts for the effects of the dynamic deformation of a fast rotating nucleus, the classical Gilbert-Cameron approach and pre-calculated tables obtained with a microscopic model based on HFB single-particle level schemes with collective enhancement. A comprehensive library of input parameters covers nuclear masses, optical model parameters, ground state deformations, discrete levels and decay schemes, level densities, fission barriers, moments of inertia and γ-ray strength functions. The results can be converted into ENDF-6 formatted files using the

  8. Model studies on the release of aroma compounds from structured and nonstructured oil systems using proton-transfer reaction mass spectrometry.

    Science.gov (United States)

    Landy, Pascale; Pollien, Philippe; Rytz, Andreas; Leser, Martin E; Sagalowicz, Laurent; Blank, Imre; Spadone, Jean-Claude

    2007-03-07

    Relative retention, volatility, and temporal release of volatile compounds taken from aldehyde, ester, and alcohol chemical classes were studied at 70 degrees C in model systems using equilibrium static headspace analysis and real time dynamic headspace analysis. These systems were medium-chain triglycerides (MCT), sunflower oil, and two structured systems, i.e., water-in-oil emulsion and L2 phase (water-in-oil microemulsion). Hydrophilic domains of the emulsion type media retained specifically the hydrophilic compounds and alcohols. Four kinetic parameters characterizing the concentration- and time-dependent releases were extracted from the aroma release curves. Most of the kinetic parameter values were higher in structured systems than in oils particularly when using MCT. The oil nature was found to better control the dynamic release profiles than the system structures. The release parameters were well-related (i) to the volatile hydrophobicity as a function of the oil used and (ii) to the retention data in the specific case of the L2 phase due to a specific release behavior of alcohols.

  9. A model for reaction-assisted polymer dissolution in LIGA.

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Richard S.

    2004-05-01

    A new chemically-oriented mathematical model for the development step of the LIGA process is presented. The key assumption is that the developer can react with the polymeric resist material in order to increase the solubility of the latter, thereby partially overcoming the need to reduce the polymer size. The ease with which this reaction takes place is assumed to be determined by the number of side chain scissions that occur during the x-ray exposure phase of the process. The dynamics of the dissolution process are simulated by solving the reaction-diffusion equations for this three-component, two-phase system, the three species being the unreacted and reacted polymers and the solvent. The mass fluxes are described by the multicomponent diffusion (Stefan-Maxwell) equations, and the chemical potentials are assumed to be given by the Flory-Huggins theory. Sample calculations are used to determine the dependence of the dissolution rate on key system parameters such as the reaction rate constant, polymer size, solid-phase diffusivity, and Flory-Huggins interaction parameters. A simple photochemistry model is used to relate the reaction rate constant and the polymer size to the absorbed x-ray dose. The resulting formula for the dissolution rate as a function of dose and temperature is ?t to an extensive experimental data base in order to evaluate a set of unknown global parameters. The results suggest that reaction-assisted dissolution is very important at low doses and low temperatures, the solubility of the unreacted polymer being too small for it to be dissolved at an appreciable rate. However, at high doses or at higher temperatures, the solubility is such that the reaction is no longer needed, and dissolution can take place via the conventional route. These results provide an explanation for the observed dependences of both the dissolution rate and its activation energy on the absorbed dose.

  10. Force-Depending Radiation Reaction study in an undulator devise

    CERN Document Server

    López, Gustavo V

    2016-01-01

    The effect of force-depending radiation reaction on charge motion traveling inside an undulator is studied using the new force approach for radiation reaction. The effect on the dynamics of a charged particle is determined with the hope that this one can be measured experimentally and can be determined whether or not this approach points on the right direction to understand the nature of radiation reaction.

  11. Modelling of structural effects on chemical reactions in turbulent flows

    Energy Technology Data Exchange (ETDEWEB)

    Gammelsaeter, H.R.

    1997-12-31

    Turbulence-chemistry interactions are analysed using algebraic moment closure for the chemical reaction term. The coupling between turbulence and chemical length and time scales generate a complex interaction process. This interaction process is called structural effects in this work. The structural effects are shown to take place on all scales between the largest scale of turbulence and the scales of the molecular motions. The set of equations describing turbulent correlations involved in turbulent reacting flows are derived. Interactions are shown schematically using interaction charts. Algebraic equations for the turbulent correlations in the reaction rate are given using the interaction charts to include the most significant couplings. In the frame of fundamental combustion physics, the structural effects appearing on the small scales of turbulence are proposed modelled using a discrete spectrum of turbulent scales. The well-known problem of averaging the Arrhenius law, the specific reaction rate, is proposed solved using a presumed single variable probability density function and a sub scale model for the reaction volume. Although some uncertainties are expected, the principles are addressed. Fast chemistry modelling is shown to be consistent in the frame of algebraic moment closure when the turbulence-chemistry interaction is accounted for in the turbulent diffusion. The modelling proposed in this thesis is compared with experimental data for an laboratory methane flame and advanced probability density function modelling. The results show promising features. Finally it is shown a comparison with full scale measurements for an industrial burner. All features of the burner are captured with the model. 41 refs., 33 figs.

  12. Matrix isolation as a tool for studying interstellar chemical reactions

    Science.gov (United States)

    Ball, David W.; Ortman, Bryan J.; Hauge, Robert H.; Margrave, John L.

    1989-01-01

    Since the identification of the OH radical as an interstellar species, over 50 molecular species were identified as interstellar denizens. While identification of new species appears straightforward, an explanation for their mechanisms of formation is not. Most astronomers concede that large bodies like interstellar dust grains are necessary for adsorption of molecules and their energies of reactions, but many of the mechanistic steps are unknown and speculative. It is proposed that data from matrix isolation experiments involving the reactions of refractory materials (especially C, Si, and Fe atoms and clusters) with small molecules (mainly H2, H2O, CO, CO2) are particularly applicable to explaining mechanistic details of likely interstellar chemical reactions. In many cases, matrix isolation techniques are the sole method of studying such reactions; also in many cases, complexations and bond rearrangements yield molecules never before observed. The study of these reactions thus provides a logical basis for the mechanisms of interstellar reactions. A list of reactions is presented that would simulate interstellar chemical reactions. These reactions were studied using FTIR-matrix isolation techniques.

  13. Spallation reactions. A successful interplay between modeling and applications

    CERN Document Server

    David, J -C

    2015-01-01

    The spallation reactions are a type of nuclear reaction which occur in space by interaction of the cosmic rays with interstellar bodies. The first spallation reactions induced with an accelerator took place in 1947 at the Berkeley cyclotron (University of California) with 200 MeV deuterons and 400 MeV alpha beams. They highlighted the multiple emission of neutrons and charged particles and the production of a large number of residual nuclei far different from the target nuclei. The same year R. Serber describes the reaction in two steps: a first and fast one with high-energy particle emission leading to an excited remnant nucleus, and a second one, much slower, the de-excitation of the remnant. In 2010 IAEA organized a worskhop to present the results of the most widely used spallation codes within a benchmark of spallation models. If one of the goals was to understand the deficiencies, if any, in each code, one remarkable outcome points out the overall high-quality level of some models and so the great improv...

  14. Transverse flow reactor studies of the dynamics of radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Macdonald, R.G. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Radical reactions are in important in combustion chemistry; however, little state-specific information is available for these reactions. A new apparatus has been constructed to measure the dynamics of radical reactions. The unique feature of this apparatus is a transverse flow reactor in which an atom or radical of known concentration will be produced by pulsed laser photolysis of an appropriate precursor molecule. The time dependence of individual quantum states or products and/or reactants will be followed by rapid infrared laser absorption spectroscopy. The reaction H + O{sub 2} {yields} OH + O will be studied.

  15. STUDY ON SIDE REACTION IN THE SYNTHESIS OF HYPERCROSSLINKED POLYMERS

    Institute of Scientific and Technical Information of China (English)

    ZHANG Bo; LI Aimin; TAO Weihua; YANG Weiben

    2008-01-01

    The systematical study about side reactions have revealed the formation mechanism of oxygen-containing groups of hypercrosslinked polymers.Surface chemistry and functionality of the polymers are characterized by Fourier-transform infrared spectroscopy (FT-IR), solid state nuclear magnetic resonance (NMR) and contact angle.The results showed that the ether groups were from chioromethylated reaction, and the alcohol groups arose from partial hydrolysis of chloromethyl groups during the post-crosslinking reaction, and the carbonyl functionality was formed by further oxidation of the alcohol groups.Catalyst and solvent used in the postcrosslinking reaction would greatly influence the surface chemistry of the polymer.

  16. Variational Flooding Study of a SN2 Reaction.

    Science.gov (United States)

    Piccini, GiovanniMaria; McCarty, James J; Valsson, Omar; Parrinello, Michele

    2017-02-02

    We have studied the reaction dynamics of a prototypical organic reaction using a variationally optimized truncated bias to accelerate transitions between educt and product reactant states. The asymmetric SN2 nucleophilic substitution reaction of fluoromethane and chloromethane CH3F + Cl(-) ⇌ CH3Cl + F(-) is considered, and many independent biased molecular dynamics simulations have been performed at 600, 900, and 1200 K, collecting several hundred transitions at each temperature. The transition times and relative rate constants have been obtained for both reaction directions. The activation energies extracted from an Arrhenius plot compare well with standard static calculations.

  17. Towards many-body based nuclear reaction modelling

    Science.gov (United States)

    Hilaire, Stéphane; Goriely, Stéphane

    2016-06-01

    The increasing need for cross sections far from the valley of stability poses a challenge for nuclear reaction models. So far, predictions of cross sections have relied on more or less phenomenological approaches, depending on parameters adjusted to available experimental data or deduced from systematic expressions. While such predictions are expected to be reliable for nuclei not too far from the experimentally known regions, it is clearly preferable to use more fundamental approaches, based on sound physical principles, when dealing with very exotic nuclei. Thanks to the high computer power available today, all the ingredients required to model a nuclear reaction can now be (and have been) microscopically (or semi-microscopically) determined starting from the information provided by a nucleon-nucleon effective interaction. This concerns nuclear masses, optical model potential, nuclear level densities, photon strength functions, as well as fission barriers. All these nuclear model ingredients, traditionally given by phenomenological expressions, now have a microscopic counterpart implemented in the TALYS nuclear reaction code. We are thus now able to perform fully microscopic cross section calculations. The quality of these ingredients and the impact of using them instead of the usually adopted phenomenological parameters will be discussed. Perspectives for the coming years will be drawn on the improvements one can expect.

  18. Thermodynamic Study of Hydrolysis Reactions in Aqueous Solution from Ab Initio Potential and Molecular Dynamics Simulations

    Directory of Open Access Journals (Sweden)

    S. Tolosa

    2013-01-01

    Full Text Available A procedure for the theoretical study of chemical reactions in solution by means of molecular dynamics simulations of aqueous solution at infinite dilution is described using ab initio solute-solvent potentials and TIP3P water model to describe the interactions. The procedure is applied to the study of neutral hydrolysis of various molecules (HCONH2, HNCO, HCNHNH2, and HCOOCH3 via concerted and water-assisted mechanisms. We used the solvent as a reaction coordinate and the free energy curves for the calculation of the properties related with the reaction mechanism, namely, reaction and activation energies.

  19. Shock Tube and Modeling Study of the H + O2 = OH + O Reaction over a Wide Range of Composition, Pressure, and Temperature

    Science.gov (United States)

    Ryu, Si-Ok; Hwang, Soon Muk; Rabinowitz, Martin Jay

    1995-01-01

    The rate coefficient of the reaction H + 02 = OH + 0 was determined using OH laser absorption spectroscopy behind reflected shock waves over the temperature range 1050-2500 K and the pressure range 0.7-4.0 atm. Eight mixtures and three stoichiometries were used. Two distinct and independent criteria were employed in the evaluation of k(sub 1). Our recommended expression for k(sub 1) is k(sub 1) = 7.13 x 10(exp 13)exp(-6957 K/T) cm(exp 3)mol(exp -1)s(exp -1) with a statistical uncertainty of 6%. A critical review of recent evaluations of k(sub 1) yields a consensus expression given by k(sub 1) = 7.82 x 10(exp 13)exp(-7105 K/7) cm(exp 3)mol(exp -1)s(exp -1) over the temperature range 960-5300 K. We do not support a non-Arrhenius rate coefficient expression, nor do we find evidence of composition dependence upon the determination of k(sub 1).

  20. Theoretical Studies on N2H+O Reaction

    Institute of Scientific and Technical Information of China (English)

    L(U) Ying-wen; L(U) Wen-cai; SU Zhong-min

    2008-01-01

    The N2H+O potential energy profile was studied at the CCSD(T)/6-311G++(dfp)//MP2/6-311G(d,p) level.Reactions associated with four intermediates(cis-HNNO, trans-HNNO, NNHO, and NNOH) were investigated. The results indicate that N2H+O reaction toward H+N2O is more favored than that toward N2+OH, consistent with previous experimental studies. The pathways for the two reactions are found to go through cis-HNNO, transition state, and finally to the products. The N2H+O→NH+NO reaction was studied in detail. Product NO in such a reaction is likely to occur via cis-HNNO, followed by trans-HNNO, and finally dissociates into NH+NO. These results suggest that N2H+O→NH+NO is an important channel in NO production.

  1. Study of the reaction gamma p -> p pi(0)eta

    NARCIS (Netherlands)

    Horn, I.; Anisovich, A. V.; Anton, G.; Bantes, R.; Bartholomy, O.; Beck, R.; Beloglazov, Y.; Bogendoerfer, R.; Castelijns, R.; Crede, V.; Ehmanns, A.; Ernst, J.; Fabry, I.; Flemming, H.; Foesel, A.; Fuchs, M.; Funke, Ch.; Gothe, R.; Gridnev, A.; Gutz, E.; Hoeffgen, S.; Hoessi, J.; Junkersfeld, J.; Kalinowsky, H.; Klein, F.; Klempt, E.; Koch, H.; Konrad, M.; Kopf, B.; Krusche, B.; Langheinrich, J.; Loehner, H.; Lopatin, I.; Lotz, J.; Matthaey, H.; Menze, D.; Messchendorp, J.; Metag, V.; Nikonov, V. A.; Novinski, D.; Ostrick, M.; van Pee, H.; Sarantsev, A. V.; Schmidt, C.; Schmieden, H.; Schoch, B.; Suft, G.; Sumachev, V.; Szczepanek, T.; Thoma, U.; Walther, D.; Weinheimer, Ch.

    2008-01-01

    The reaction gamma p -> p pi(0)eta has been studied with the CBELSA detector at the tagged photon beam of the Bonn electron stretcher facility. The reaction shows contributions from Delta(+)(1232)eta, N(1535)(+) pi(0) and pa(0)(980) as intermediate states. A partial-wave analysis suggests that the r

  2. Mathematical modeling of precipitation and dissolution reactions in microbiological systems.

    Science.gov (United States)

    Rittmann, Bruce E; Banaszak, James E; VanBriesen, Jeanne M; Reed, Donald T

    2002-01-01

    We expand the biogeochemical model CCBATCH to include a precipitation/dissolution sub-model that contains kinetic and equilibrium options. This advancement extends CCBATCH's usefulness to situations in which microbial reactions cause or are affected by formation or dissolution of a solid phase. The kinetic option employs a rate expression that explicitly includes the intrinsic kinetics for reaction or mass-transport control, the difference from thermodynamic equilibrium, and the aqueous concentration of the rate-limiting metal or ligand. The equilibrium feature can be used alone, and it also serves as check that the kinetic rate never is too fast and "overshoots" equilibrium. The features of the expanded CCBATCH are illustrated by an example in which the precipitation of Fe(OH)3(s) allows the biodegradation of citric acid, even though complexes are strong and not bioavailable. Precipitation releases citrate ligand, and biodegradation of the citrate increases the pH.

  3. Electromagnetic studies of nuclear structure and reactions

    Science.gov (United States)

    Hersman, F. W.; Dawson, J. F.; Heisenberg, J. H.; Calarco, J. R.

    1990-06-01

    This report contains papers on the following topics: giant resonance studies; deep inelastic scattering studies; high resolution nuclear structure work; and relativistic RPA; and field theory in the Schroedinger Representation.

  4. Thermal degradation reaction mechanism of xylose: A DFT study

    Science.gov (United States)

    Huang, Jinbao; He, Chao; Wu, Longqin; Tong, Hong

    2016-08-01

    The thermal degradation reaction mechanism of xylose as hemicellulose model compound was investigated by using density functional theory methods M062X with the 6-31++G(d,p) basis set. Eight possible pyrolytic reaction pathways were proposed and the standard kinetic and thermodynamic parameters in all reaction pathways were calculated at different temperatures. In reaction pathway (1), xylose is first transformed into acyclic containing-carbonyl isomer, and then the isomer further decomposes through four possible pyrolysis pathways (1-1)-(1-4). Pathways (2) and (3) depict an immediate ring-opening process through the simultaneous breaking of C-O and C-C bonds. Pathways (4)-(7) describe the pyrolysis processes of various anhydro-xyloses through a direct ring-opening process. Pathway (8) gives the evolutionary process of pyranones. The calculation results show that reaction pathways (1), (2) and (5) are the major reaction channels and reaction pathways (3), (4), and (6)-(8) are the competitive reaction channels in pyrolysis of xylose. The major products of xylose pyrolysis are low molecular products such as 2-furaldehyde, glycolaldehyde, acetaldehyde, methylglyoxal and acetone, and the main competitive products are formaldehyde, formic acid, acetic acid, CO2, CH4, acetol, pyranone, and so on.

  5. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  6. A unifying kinetic framework for modeling oxidoreductase-catalyzed reactions

    OpenAIRE

    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...

  7. Heck-type reactions of imine derivatives: a DFT study.

    Science.gov (United States)

    Li, Zhe; Fu, Yao; Zhang, Song-Lin; Guo, Qing-Xiang; Liu, Lei

    2010-06-01

    The mechanism of a recently discovered intramolecular Heck-type coupling of oximes with aryl halides (Angew. Chem. Int. Ed. 2007, 46, 6325) was systematically studied by using density functional methods enhanced with a polarized continuum solvation model. The overall catalytic cycle of the reaction was found to consist of four steps: oxidative addition, migratory insertion, beta-H elimination, and catalyst regeneration, whereas an alternative base-promoted C-H activation pathway was determined to be less favorable. Migratory insertion was found to be the rate determining step in the catalytic cycle. The apparent activation barrier of migratory insertion of the (E)-oxime was +20.5 kcal mol(-1), whereas the barrier of (Z)-oxime was as high as +32.7 kcal mol(-1). However, (Z)-oxime could isomerize to form the more active (E)-oxime with the assistance of K(2)CO(3), so that both the (E)- and (Z)-oxime substrates could be transformed to the desired product. Our calculations also indicated that the Z product was predominant in the equilibrium of the isomerization of the imine double bond, which constituted the reason for the good Z-selectivity observed for the reaction. Furthermore, we examined the difference between the intermolecular Heck-type reactions of imines and of olefins. It was found that in the intermolecular Heck-type coupling of imines, the apparent activation barrier of migratory insertion was as high as +35 kcal mol(-1), which should be the main obstacle of the reaction. The analysis also revealed the main problem for the intermolecular Heck-type reactions of imines, which was that the breaking of a C=N pi bond was much more difficult than the breaking of a C=C pi bond. After systematic examination of a series of substituted imines, (Z)-N-amino imine and N-acetyl imine were found to have relatively low barriers of migratory insertion, so that they might be possible substrates for intermolecular Heck-type coupling.

  8. Progress in Nanoscale Studies of Hydrogen Reactions in Construction Materials

    Science.gov (United States)

    Schweitzer, J. S.; Livingston, R. A.; Cheung, J.; Rolfs, C.; Becker, H.-W.; Kubsky, S.; Spillane, T.; Zickefoose, J.; Castellote, M.; Bengtsson, N.; Galan, I.; de Viedma, P. G.; Brendle, S.; Bumrongjaroen, W.; Muller, I.

    Nuclear resonance reaction analysis (NRRA) has been applied to measure the nanoscale distribution of hydrogen with depth in the hydration of cementitious phases. This has provided a better understanding of the mechanisms and kinetics of cement hydration during the induction period that is critical to improved concrete technology. NRRA was also applied to measure the hydrogen depth profiles in other materials used in concrete construction such as fly ash and steel. By varying the incident beam energy one measures a profile with a depth resolution of a few nanometers. Time-resolved measurements are achieved by stopping the chemical reactions at specific times. Effects of temperature, sulfate concentration, accelerators and retarders, and superplasticizers have been investigated. Hydration of fly ashes has been studied with synthetic glass specimens whose chemical compositions are modeled on those of actual fly ashes. A combinatorial chemistry approach was used where glasses of different compositions are hydrated in various solutions for a fixed time. The resulting hydrogen depth profiles show significant differences in hydrated phases, rates of depth penetration and amount of surface etching. Hydrogen embrittlement of steel was studied on slow strain rate specimens under different corrosion potentials.

  9. Recent studies in heavy ion induced fission reactions

    Science.gov (United States)

    Choudhury, R. K.

    2001-08-01

    Nuclear fission process involves large scale shape changes of the nucleus, while it evolves from a nearly spherical configuration to two separated fission fragments. The dynamics of these shape changes in the nuclear many body system is governed by a strong interplay of the collective and single particle degrees of freedom. With the availability of heavy ion accelerators, there has been an impetus to study the nuclear dynamics through the investigations of nucleus--nucleus collisions involving fusion and fission process. From the various investigations carried out in the past years, it is now well recognized that there is large scale damping of collective modes in heavy ion induced fission reactions, which in other words implies that nuclear motion is highly viscous. In recent years, there have been many experimental observations in heavy ion induced fission reactions at medium bombarding energies, which suggest possible occurrence of various non-equilibrium modes of fission such as quasi-fission, fast fission and pre-equilibrium fission, where some of the internal degrees of freedom of the nucleus is not fully equilibrated. We have carried out extensive investigations on the fission fragment angular distributions at near barrier bombarding energies using heavy fissile targets. The measured fragment anisotropies when compared with the standard saddle point model (SSPM) calculations show that for projectile-target systems having zero or low ground state spins, the angular anisotropy exhibits a peak-like behaviour at the sub barrier energies, which cannot be explained by the SSPM calculations. For projectiles or targets with large ground state spins, the anomalous peaking gets washed out due to smearing of the K-distribution by the intrinsic entrance channel spins. Recently studies have been carried out on the spin distributions of fission fragments through the gamma ray multiplicity measurements. The fission fragments acquire spin mainly from two sources: (i) due to

  10. Stability Analysis of a Reaction-Diffusion System Modeling Atherogenesis

    KAUST Repository

    Ibragimov, Akif

    2010-01-01

    This paper presents a linear, asymptotic stability analysis for a reaction-diffusionconvection system modeling atherogenesis, the initiation of atherosclerosis, as an inflammatory instability. Motivated by the disease paradigm articulated by Ross, atherogenesis is viewed as an inflammatory spiral with a positive feedback loop involving key cellular and chemical species interacting and reacting within the intimal layer of muscular arteries. The inflammatory spiral is initiated as an instability from a healthy state which is defined to be an equilibrium state devoid of certain key inflammatory markers. Disease initiation is studied through a linear, asymptotic stability analysis of a healthy equilibrium state. Various theorems are proved, giving conditions on system parameters guaranteeing stability of the health state, and a general framework is developed for constructing perturbations from a healthy state that exhibit blow-up, which are interpreted as corresponding to disease initiation. The analysis reveals key features that arterial geometry, antioxidant levels, and the source of inflammatory components (through coupled third-kind boundary conditions or through body sources) play in disease initiation. © 2010 Society for Industrial and Applied Mathematics.

  11. THE ASYMPTOTIC LIMIT FOR A COMBUSTION MODEL IN REGARD TO INFINITE REACTION RATE

    Institute of Scientific and Technical Information of China (English)

    Ying Longan

    2008-01-01

    The Zeldovich-von Neumann-Doring model and the Chapman-Jouguet model for a simplified combustion model-Majda's model is studied. The author proves a uniform maximum norm estimate, then proves that as the rate of chemical reaction tends to infinity the solutions to the Zeldovich-von Neumann-Doring model tend to that of the Chapman-Jouguet model. The type of combustion waves is studied. This result is compared with the result of the projection and finite difference method for the same model.

  12. The use of the dusty-gas model for the description of mass transport with chemical reaction in porous media

    NARCIS (Netherlands)

    Veldsink, J.W.; Damme, R.M.J. van; Versteeg, G.F.; Swaaij, W.P.M. van

    1995-01-01

    In the present study, mass transport accompanied by chemical reactions in porous media is studied according to the Fick model and the dusty-gas model. For mass transport accompanied by a chemical reaction in catalyst structures showing a plane, line, or point of symmetry, the approximate analytical

  13. Mathematical Model of Synthesis Catalyst with Local Reaction Centers

    Directory of Open Access Journals (Sweden)

    I. V. Derevich

    2017-01-01

    Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

  14. The modelling of counter-rotating twin screw extruders as reactors for single-component reactions

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Capel, J.E.; Wal, D.J. van der; Janssen, L.P.B.M.

    1994-01-01

    Numerical models are useful to study the behaviour of the extruder as a polymerization reactor. With a correct numerical model a theoretical analysis of the influence of several reaction and extruder parameters can be made, the limitations of the use of the extruder reactor can be determined and the

  15. A model for the [gamma]p[yields][pi][sup +][pi][sup -]p reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gomez Tejedor, J.A. (Dept. de Fisica Teorica, Centro Mixto Universidad de Valencia-CSIC, Burjassot (Spain) IFIC, Centro Mixto Universidad de Valencia-CSIC, Burjassot (Spain)); Oset, E. (Dept. de Fisica Teorica, Centro Mixto Universidad de Valencia-CSIC, Burjassot (Spain) IFIC, Centro Mixto Universidad de Valencia-CSIC, Burjassot (Spain))

    1994-05-09

    We have studied the [gamma]p[yields][pi][sup +][pi][sup -]p reaction using a model which includes N, [Delta](1232), N[sup *](1440) and N[sup *](1520) intermediate baryonic states and the [rho]-meson as intermediate 2[pi]-resonance. The model reproduces fairly well experimental cross sections below E[sub [gamma

  16. The modelling of counter-rotating twin screw extruders as reactors for single-component reactions

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Capel, J.E.; Wal, D.J. van der; Janssen, L.P.B.M.

    1994-01-01

    Numerical models are useful to study the behaviour of the extruder as a polymerization reactor. With a correct numerical model a theoretical analysis of the influence of several reaction and extruder parameters can be made, the limitations of the use of the extruder reactor can be determined and the

  17. Study of alpha one antitrypsin activity in lepra reaction.

    Science.gov (United States)

    Sengupta, S R; Dhole, T N; Jahagirdar, V L; Yemul, V L; Chawhan, R N

    1983-04-01

    In our earlier study (Yemul et, al, 1983) we have reported elevation of serum alpha one antitrypsin levels in patients of lepromatous leprosy and lepra reaction. In this study estimation of serum alpha one antitrypsin levels in fifty lepra reaction patients (8 of type 1 and 42 of type II) and fifty age and sex matched healthy controls is described. Alpha one antitrypsin levels were elevated in lepra reaction patients (type I--mean value of 332 mg% and S.D. +/- 118.8 and type II--mean value of 450 mg% and S.D. +/- 73.7) when compared with the healthy controls (mean value of 285 mg% and S.D. +/- 66.05). The increase in levels in type II lepra reaction patients was statistically significant. The results are discussed to correlate the increased levels of alpha one antitrypsin and the high bacterial load leading to the release of various proteases in type II lepra reaction.

  18. A complex reaction time study (Sternberg) in space flight

    Science.gov (United States)

    Thornton, W.; Uri, John; Moore, Tom

    1993-01-01

    Simple and complex (Sternberg) reaction time studies were flown on three and seven day Shuttle flights in 1985. Three subjects did selftesting with an onboard handheld calculator without difficulty. There was little change in simple reaction time. One subject demonstrated a decrease in the processing rate during space motion sickness while a second exhibited an increase in complex reaction time without a change in processing rate during a period of high work load. The population was too small to demonstrate significant changes. This study demonstrates the ease and practicality of such measurements and indicates the potential value of such studies in space.

  19. A complex reaction time study (Sternberg) in space flight

    Science.gov (United States)

    Thornton, W.; Uri, John; Moore, Tom

    1993-01-01

    Simple and complex (Sternberg) reaction time studies were flown on three and seven day Shuttle flights in 1985. Three subjects did selftesting with an onboard handheld calculator without difficulty. There was little change in simple reaction time. One subject demonstrated a decrease in the processing rate during space motion sickness while a second exhibited an increase in complex reaction time without a change in processing rate during a period of high work load. The population was too small to demonstrate significant changes. This study demonstrates the ease and practicality of such measurements and indicates the potential value of such studies in space.

  20. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    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.

  1. Genome-scale Metabolic Reaction Modeling: a New Approach to Geomicrobial Kinetics

    Science.gov (United States)

    McKernan, S. E.; Shapiro, B.; Jin, Q.

    2014-12-01

    Geomicrobial rates, rates of microbial metabolism in natural environments, are a key parameter of theoretical and practical problems in geobiology and biogeochemistry. Both laboratory- and field-based approaches have been applied to study rates of geomicrobial processes. Laboratory-based approaches analyze geomicrobial kinetics by incubating environmental samples under controlled laboratory conditions. Field methods quantify geomicrobial rates by observing the progress of geomicrobial processes. To take advantage of recent development in biogeochemical modeling and genome-scale metabolic modeling, we suggest that geomicrobial rates can also be predicted by simulating metabolic reaction networks of microbes. To predict geomicrobial rates, we developed a genome-scale metabolic model that describes enzyme reaction networks of microbial metabolism, and simulated the network model by accounting for the kinetics and thermodynamics of enzyme reactions. The model is simulated numerically to solve cellular enzyme abundance and hence metabolic rates under the constraints of cellular physiology. The new modeling approach differs from flux balance analysis of system biology in that it accounts for the thermodynamics and kinetics of enzymatic reactions. It builds on subcellular metabolic reaction networks, and hence also differs from classical biogeochemical reaction modeling. We applied the new approach to Methanosarcina acetivorans, an anaerobic, marine methanogen capable of disproportionating acetate to carbon dioxide and methane. The input of the new model includes (1) enzyme reaction network of acetoclastic methanogenesis, and (2) representative geochemical conditions of freshwater sedimentary environments. The output of the simulation includes the proteomics, metabolomics, and energy and matter fluxes of M. acetivorans. Our simulation results demonstrate the predictive power of the new modeling approach. Specifically, the results illustrate how methanogenesis rates vary

  2. A New Geochemical Reaction Model for Groundwater Systems

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Through a survey of the literature on geology, hydrogeology and hydrogeochemistry, this paper presents a hydrogeochemical model for the groundwater system in a dross-dumping area of the Shandong Aluminium Plant. It is considered that the groundwater-bearing medium is a mineral aggregate and that the interactions between groundwater and the groundwater-bearing medium can be described as a series of geochemical reactions. On that basis, the principle of minimum energy and the equations of mass balance, electron balance and electric neutrality are applied to construct a linear programming mathematical model for the calculation of mass transfer between water and rock with the simplex method.

  3. Universal model for exoergic bimolecular reactions and inelastic processes

    CERN Document Server

    Gao, Bo

    2010-01-01

    From a rigorous multichannel quantum-defect formulation of bimolecular processes, we derive a fully quantal and analytic model for the total rate of exoergic bimolecular reactions and/or inelastic processes that is applicable over a wide range of temperatures including the ultracold regime. The theory establishes a connection between the ultracold chemistry and the regular chemistry by showing that the same theory that gives the quantum threshold behavior agrees with the classical Gorin model at higher temperatures. In between, it predicts that the rates for identical bosonic molecules and distinguishable molecules would first decrease with temperature outside of the Wigner threshold region, before rising after a minimum is reached.

  4. Reply to the comment of S. Rayne on "QSAR model reproducibility and applicability: A case study of rate constants of hydroxyl radical reaction models applied to polybrominated diphenyl ethers and (benzo-)triazoles".

    Science.gov (United States)

    Gramatica, Paola; Kovarich, Simona; Roy, Partha Pratim

    2013-07-30

    We appreciate the interest of Dr. Rayne on our article and we completely agree that the dataset of (benzo-)triazoles, which were screened by the hydroxyl radical reaction quantitative structure-activity relationship (QSAR) model, was not only composed of benzo-triazoles but also included some simpler triazoles (without the condensed benzene ring), such as the chemicals listed by Dr. Rayne, as well as some related heterocycles (also few not aromatic). We want to clarify that in this article (as well as in other articles in which the same dataset was screened), for conciseness, the abbreviations (B)TAZs and BTAZs were used as general (and certainly too simplified) notations meaning an extended dataset of benzo-triazoles, triazoles, and related compounds. Copyright © 2013 Wiley Periodicals, Inc.

  5. Synthesis of 3-tetrazolylmethyl-azepino[4,5-b]indol-4-ones in two reaction steps: (Ugi-azide/N-acylation/SN2)/free radical cyclization and docking studies to a 5-Ht(6) model.

    Science.gov (United States)

    Gordillo-Cruz, Raul E; Rentería-Gómez, Angel; Islas-Jácome, Alejandro; Cortes-García, Carlos J; Díaz-Cervantes, Erik; Robles, Juvencio; Gámez-Montaño, Rocío

    2013-10-14

    A series of nine novel 3-tetrazolylmethyl-azepino[4,5-b]indol-4-ones were prepared in moderate to good overall yields in only two reaction steps. The first step consisted of a one-pot sequential process of an Ugi-azide multicomponent reaction, N-acylation and SN2 to give the xanthates. The second step was an intramolecular cyclization under free radical conditions. Also, their binding modes have been modelled using docking techniques.

  6. Combustion of Bimodal Nano/Micro Aluminum Suspension with New Reaction Rate Model

    Directory of Open Access Journals (Sweden)

    M. Bidabadi

    2008-01-01

    Full Text Available In this study a mathematical model for combustion of bimodal particle in lean flow was developed. The difference between structure of flame in this work and previous ones was that, in those flame was divided by five zones and reaction rate was considered to be constant in reaction zones and also zero in post flame zone. In reality it was obvious with respect to shape and size of different particles in dust, reaction didn't end suddenly. In the present research the heat loss term, which was assumed to be linearly proportional to temperature difference, was added to the energy conservation equation and reaction rate was considered proportional to available amount of fuel, leading to exponentially decreasing of reaction rate. The flame speed and temperature distribution were obtained by solving the energy equation in each zone and matching the temperature and heat flux at the interfacial boundaries. Calculated values of flame speed were in good agreement with experimental data.

  7. Thermochemical model for shock-induced chemical reactions in porous thermite: The heat detonation model

    Energy Technology Data Exchange (ETDEWEB)

    Boslough, M.B.

    1989-01-01

    A thermochemical model has been developed that treats a shock-induced solid state chemical reaction as a special type of detonation, called a ''heat detonation'' to distinguish it from an ordinary explosive detonation and describe the final form that the chemical energy takes. According to shock temperature measurements, chemical energy can be released from porous reactive solids on a time scale shorter than shock-transit times in laboratory samples. By comparing the experimental shock temperature for porous thermite to that calculated by the model, the amount of thermite reacted when shocked to about 4 GPa was estimated to be between 60 and 70%. Calculated shock temperatures are extremely strong functions of the extent of reaction, but are relatively insensitive to the initial porosity and amount of volatile impurities. Thus, shock temperature measurements are the most useful for real-time studies of shock-induced exothermic chemical reactions in solids. 11 refs., 5 figs., 1 tab.

  8. Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2014-01-01

    Full Text Available Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p SCRF=(PCM, solvent = 1,2-ethanediol optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H2N–NH2 and (H2O8. A ready reaction channel of acetone → acetone hydrazine (Me2C=N–NH2 was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N2 extrusion step from the isopropyl diimine intermediate (Me2C(H–N=N–H. Two base-catalyzed reactions were investigated by models of the ketone, H2N–NH2 and OH−(H2O7. Here, ketones are acetone and acetophenone. While routes of the ketone → hydrazone → diimine are similar, those from the diimines are different. From the isopropyl diimine, the N2 extrusion and the C–H bond formation takes place concomitantly. The concomitance leads to the propane product concertedly. From the (1-phenylethyl substituted diimine, a carbanion intermediate is formed. The para carbon of the phenyl ring of the anion is subject to the protonation, which leads to a 3-ethylidene-1,4-cyclohexadiene intermediate. Its [1,5]-hydrogen migration gives the ethylbenzene product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates.

  9. Crossed molecular beam studies of unimolecular reaction dynamics. [Angular and velocity distributions

    Energy Technology Data Exchange (ETDEWEB)

    Buss, R.J.

    1979-04-01

    The study of seven radical-molecule reactions using the crossed molecular beam technique with supersonic nozzle beams is reported. Product angular and velocity distributions were obtained and compared with statistical calculations in order to identify dynamical features of the reactions. In the reaction of chlorine and fluorine atoms with vinyl bromide, the product energy distributions are found to deviate from predictions of the statistical model. A similar effect is observed in the reaction of chlorine atoms with 1, 2 and 3-bromopropene. The reaction of oxygen atoms with ICl and CF/sub 3/I has been used to obtain an improved value of the IO bond energy, 55.0 +- 2.0 kcal mol/sup -1/. In all reactions studied, the product energy and angular distributions are found to be coupled, and this is attributed to a kinematic effect of the conservation of angular momentum.

  10. Combustion of Bimodal Nano/Micro Aluminum Suspension with New Reaction Rate Model

    OpenAIRE

    M. Bidabadi; N. Moallemi; I. Shafieenejad; M. Jadidi

    2008-01-01

    In this study a mathematical model for combustion of bimodal particle in lean flow was developed. The difference between structure of flame in this work and previous ones was that, in those flame was divided by five zones and reaction rate was considered to be constant in reaction zones and also zero in post flame zone. In reality it was obvious with respect to shape and size of different particles in dust, reaction didn't end suddenly. In the present research the heat loss term, which was as...

  11. Theoretical Study on Reaction Mechanism of Aluminum-Water System

    Institute of Scientific and Technical Information of China (English)

    Yun-lan Sun; Yan Tian; Shu-fen Li

    2008-01-01

    A theoretical study on the reaction of aluminum with water in the gas phase was performed using the hybrid density functional B3LYP and QCISD(T) methods with the 6-311+G(d,p) and the 6-311++G(d,p) basis sets. The results show that there are three possible reaction pathways that involve four isomers, seven transition structures, and two possible products for the reaction of aluminum with water. The two most favorable reaction pathways were found, whose intermediates and products agreed quite well with experimental results. The enthalpy and Gibbs free energy change of the reaction between AI and H2O at 298 and 2000 K were calculated. Some results are also in good agreement with the previous calculations or experimental results.

  12. Reactions of Lignin Model Compounds in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Holladay, John E.; Binder, Joseph B.; Gray, Michel J.; White, James F.; Zhang, Z. Conrad

    2009-09-15

    Lignin, a readily available form of biomass, awaits novel chemistry for converting it to valuable aromatic chemicals. Recent work has demonstrated that ionic liquids are excellent solvents for processing woody biomass and lignin. Seeking to exploit ionic liquids as media for depolymerization of lignin, we investigated reactions of lignin model compounds in these solvents. Using Brønsted acid catalysts in 1-ethyl-3-methylimidazolium triflate at moderate temperatures, we obtained up to 11.6% yield of the dealkylation product guaiacol from the model compound eugenol and cleaved phenethyl phenyl ether, a model for lignin ethers. Despite these successes, acid catalysis failed in dealkylation of the unsaturated model compound 4-ethylguaiacol and did not produce monomeric products from organosolv lignin, demonstrating that further work is required to understand the complex chemistry of lignin depolymerization.

  13. Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Allen, Wesley D. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry; Schaefer, III, Henry F. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry

    2015-11-14

    This is the final report of the theoretical studies of elementary hydrocarbon species and their reactions. Part A has a bibliography of publications supported by DOE from 2010 to 2016 and Part B goes into recent research highlights.

  14. Studies on Absorption and Elimination of Dietary Maillard Reaction Products

    National Research Council Canada - National Science Library

    FÖRSTER, ANKE; KÜHNE, YVONNE; HENLE, T.OMAS

    2005-01-01

    A bstract : A nine‐day dietary study involving 18 healthy volunteers was performed in order to investigate the influence of nutrition on the urinary excretion of the Maillard reaction products (MRPs...

  15. Density Functional Study on the Reaction Mechanism for the Reaction of Ni+ with Ethane

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Dong-Ju(张冬菊); LIU,Cheng-Bu(刘成卜); LIU,Yong-Jun(刘永军); HU,Hai-Quan(胡海泉)

    2002-01-01

    The mechanism of the reaction of Ni+ (2D) with ethane in the gas-phase was studied by using density functional theory. Both the B3LYP and BLYP functionals with standard all-electron basis sets are used to give the detailed information of the potential energy surface (PES) of [Ni, C2, H6 ] +. Tne mechanisms forming the products CH4 and H2 in the reaction of Ni+with ethane are proposed. The reductive eliminations of CH4and H2 are typical addition-elimination reactions. Each of the two reactions consists of two elementary steps: C-C or CH bond activations to form inserted species followed by isomerizations to form product-like intermediate. The rate determining steps for the elimination reatcions of forming CH4 and H2 are the isomerizations of the inserted species rather than C-C or C-H bond activations. The elimination reaction of forming H2 was found to be thermodynamically favored compared to that of CH4.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fan [ORNL; Yeh, Gour-Tsyh [University of Central Florida, Orlando; Parker, Jack C [ORNL; Brooks, Scott C [ORNL; Pace, Molly [ORNL; Kim, Young Jin [ORNL; Jardine, Philip M [ORNL; Watson, David B [ORNL

    2007-01-01

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

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

    Science.gov (United States)

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

    2007-06-01

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

  18. Kinetic and mechanistic studies of free-radical reactions in combustion

    Energy Technology Data Exchange (ETDEWEB)

    Tully, F.P. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    Combustion is driven by energy-releasing chemical reactions. Free radicals that participate in chain reactions carry the combustion process from reactants to products. Research in chemical kinetics enables us to understand the microscopic mechanisms involved in individual chemical reactions as well as to determine the rates at which they proceed. Both types of information are required for an understanding of how flames burn, why engines knock, how to minimize the production of pollutants, and many other important questions in combustion. In this program the authors emphasize accurate measurements over wide temperature ranges of the rates at which ubiquitous free radicals react with stable molecules. The authors investigate a variety of OH, CN, and CH + stable molecule reactions important to fuel conversion, emphasizing application of the extraordinarily precise technique of laser photolysis/continuous-wave laser-induced fluorescence (LP/cwLIF). This precision enables kinetic measurements to serve as mechanistic probes. Since considerable effort is required to study each individual reaction, prudent selection is critical. Two factors encourage selection of a specific reaction: (1) the rates and mechanisms of the subject reaction are required input to a combustion model; and (2) the reaction is a chemical prototype which, upon characterization, will provide fundamental insight into chemical reactivity, facilitate estimation of kinetic parameters for similar reactions, and constrain and test the computational limits of reaction-rate theory. Most studies performed in this project satisfy both conditions.

  19. Study on Mathematical Models of the Reaction of In - situ Combustion%火烧油层燃烧反应数学模型研究

    Institute of Scientific and Technical Information of China (English)

    张方礼; 刘其成; 赵庆辉; 张勇; 程海清

    2012-01-01

    Mathematical models of combustion kinetics of three - dimensional four phases and seven components are established and the formulae of pyrolyzation and oxidization of all conponents of crude oil are derived under conditions of porous media in view of the properties of reservoir in - situ combustion,using Arrhenius formula and adopting fuel conversion percentage. The relationships between mass transfer and phase equilibrium among all components are established by means of double - film theory and both mass conservation equation and energy conservation equation for the combustion process of in - situ combustion are also established based on the relationship of molecular diffusion and convective - dispersive of all components in porous medium,thus providing reliable bases for the physical simulation of in - situ combustion and field test design.%针对稠油油藏火烧油层特点,利用Arrhenius公式,采用燃料转化率方法,建立了火烧油层三维四相七组分燃烧动力学模型,推导出多孔介质条件下原油各组分热解与氧化反应速率表达式.通过双膜理论解决了各组分在相间的质量传递及相平衡关系,并根据各组分在多孔介质中分子扩散与对流弥散关系,建立了火烧油层燃烧过程中各组分的质量、能量守恒方程,为火烧油层物理模拟、数值模拟及现场试验方案设计提供了可靠的依据.

  20. Modeling adsorption and reactions of organic molecules at metal surfaces.

    Science.gov (United States)

    Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias

    2014-11-18

    CONSPECTUS: The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdW(surf) method that accurately accounts for the collective electronic

  1. Trojan Horse Method for neutrons-induced reaction studies

    Science.gov (United States)

    Gulino, M.; Asfin Collaboration

    2017-09-01

    Neutron-induced reactions play an important role in nuclear astrophysics in several scenario, such as primordial Big Bang Nucleosynthesis, Inhomogeneous Big Bang Nucleosynthesis, heavy-element production during the weak component of the s-process, explosive stellar nucleosynthesis. To overcome the experimental problems arising from the production of a neutron beam, the possibility to use the Trojan Horse Method to study neutron-induced reactions has been investigated. The application is of particular interest for reactions involving radioactive nuclei having short lifetime.

  2. Mechanical reaction-diffusion model for bacterial population dynamics

    CERN Document Server

    Ngamsaad, Waipot

    2015-01-01

    The effect of mechanical interaction between cells on the spreading of bacterial population was investigated in one-dimensional space. A nonlinear reaction-diffusion equation has been formulated as a model for this dynamics. In this model, the bacterial cells are treated as the rod-like particles that interact, when contacting each other, through the hard-core repulsion. The repulsion introduces the exclusion process that causes the fast diffusion in bacterial population at high density. The propagation of the bacterial density as the traveling wave front in long time behavior has been analyzed. The analytical result reveals that the front speed is enhanced by the exclusion process---and its value depends on the packing fraction of cell. The numerical solutions of the model have been solved to confirm this prediction.

  3. A time-delayed model for radiation reaction in electrodynamics

    CERN Document Server

    Faci, Sofiane; Satheeshkumar, V H

    2016-01-01

    The dynamics of a radiating charge is one of the oldest unsettled problems in classical physics. The standard Lorentz-Abraham-Dirac (LAD) equation of motion is known to suffer from several pathologies and ambiguities. This paper briefly reviews these issues, and reports on a new model that fixes these difficulties in a natural way. This model is based on a hypothesis that there is an infinitesimal time delay between action and reaction. This can be related to Feynman's regularization scheme, leading to a quasi-local QED with a natural UV cutoff, hence without the need for renormalization as the divergences are absent. Besides leading to a pathology-free equation of motion, the new model predicts a modification of the Larmor formula that is testable with current and near future ultra-intense lasers.

  4. Reaction times to weak test lights. [psychophysics biological model

    Science.gov (United States)

    Wandell, B. A.; Ahumada, P.; Welsh, D.

    1984-01-01

    Maloney and Wandell (1984) describe a model of the response of a single visual channel to weak test lights. The initial channel response is a linearly filtered version of the stimulus. The filter output is randomly sampled over time. Each time a sample occurs there is some probability increasing with the magnitude of the sampled response - that a discrete detection event is generated. Maloney and Wandell derive the statistics of the detection events. In this paper a test is conducted of the hypothesis that the reaction time responses to the presence of a weak test light are initiated at the first detection event. This makes it possible to extend the application of the model to lights that are slightly above threshold, but still within the linear operating range of the visual system. A parameter-free prediction of the model proposed by Maloney and Wandell for lights detected by this statistic is tested. The data are in agreement with the prediction.

  5. Modeling the Reactions of Energetic Materials in the Condensed Phase

    Energy Technology Data Exchange (ETDEWEB)

    Fried, L E; Manaa, M R; Lewis, J P

    2003-12-03

    High explosive (HE) materials are unique for having a strong exothermic reactivity, which has made them desirable for both military and commercial applications. Although the history of HE materials is long, condensed-phase properties are poorly understood. Understanding the condensed-phase properties of HE materials is important for determining stability and performance. Information regarding HE material properties (for example, the physical, chemical, and mechanical behaviors of the constituents in plastic-bonded explosive, or PBX, formulations) is necessary in efficiently building the next generation of explosives as the quest for more powerful energetic materials (in terms of energy per volume) moves forward. In addition, understanding the reaction mechanisms has important ramifications in disposing of such materials safely and cheaply, as there exist vast stockpiles of HE materials with corresponding contamination of earth and groundwater at these sites, as well as a military testing sites The ability to model chemical reaction processes in condensed phase energetic materials is rapidly progressing. Chemical equilibrium modeling is a mature technique with some limitations. Progress in this area continues, but is hampered by a lack of knowledge of condensed phase reaction mechanisms and rates. Atomistic modeling is much more computationally intensive, and is currently limited to very short time scales. Nonetheless, this methodology promises to yield the first reliable insights into the condensed phase processes responsible for high explosive detonation. Further work is necessary to extend the timescales involved in atomistic simulations. Recent work in implementing thermostat methods appropriate to shocks may promise to overcome some of these difficulties. Most current work on energetic material reactivity assumes that electronically adiabatic processes dominate. The role of excited states is becoming clearer, however. These states are not accessible in perfect

  6. Systematic development of reduced reaction mechanisms for dynamic modeling

    Science.gov (United States)

    Frenklach, M.; Kailasanath, K.; Oran, E. S.

    1986-01-01

    A method for systematically developing a reduced chemical reaction mechanism for dynamic modeling of chemically reactive flows is presented. The method is based on the postulate that if a reduced reaction mechanism faithfully describes the time evolution of both thermal and chain reaction processes characteristic of a more complete mechanism, then the reduced mechanism will describe the chemical processes in a chemically reacting flow with approximately the same degree of accuracy. Here this postulate is tested by producing a series of mechanisms of reduced accuracy, which are derived from a full detailed mechanism for methane-oxygen combustion. These mechanisms were then tested in a series of reactive flow calculations in which a large-amplitude sinusoidal perturbation is applied to a system that is initially quiescent and whose temperature is high enough to start ignition processes. Comparison of the results for systems with and without convective flow show that this approach produces reduced mechanisms that are useful for calculations of explosions and detonations. Extensions and applicability to flames are discussed.

  7. Opportunities for nuclear reaction studies at future facilities

    CERN Document Server

    Veselsky, Martin; Vujisicova, Nikoleta; Souliotis, Georgios A

    2016-01-01

    Opportunities for investigations of nuclear reactions at the future nuclear physics facilities such as radioactive ion beam facilities and high-power laser facilities are considered. Post-accelerated radioactive ion beams offer possibilities for study of the role of isospin asymmetry in the reaction mechanisms at various beam energies. Fission barrier heights of neutron-deficient nuclei can be directly determined at low energies. Post-accelerated radioactive ion beams, specifically at the future facilities such as HIE-ISOLDE, SPIRAL-2 or RAON-RISP can be also considered as a candidate for production of very neutron-rich nuclei via mechanism of multi-nucleon transfer. High-power laser facilities such as ELI-NP offer possibilities for nuclear reaction studies with beams of unprecedented properties. Specific cases such as ternary reactions or even production of super-heavy elements are considered.

  8. Reaction-diffusion-branching models of stock price fluctuations

    Science.gov (United States)

    Tang, Lei-Han; Tian, Guang-Shan

    Several models of stock trading (Bak et al., Physica A 246 (1997) 430.) are analyzed in analogy with one-dimensional, two-species reaction-diffusion-branching processes. Using heuristic and scaling arguments, we show that the short-time market price variation is subdiffusive with a Hurst exponent H=1/4. Biased diffusion towards the market price and blind-eyed copying lead to crossovers to the empirically observed random-walk behavior ( H=1/2) at long times. The calculated crossover forms and diffusion constants are shown to agree well with simulation data.

  9. Parametric pattern selection in a reaction-diffusion model.

    Directory of Open Access Journals (Sweden)

    Michael Stich

    Full Text Available We compare spot patterns generated by Turing mechanisms with those generated by replication cascades, in a model one-dimensional reaction-diffusion system. We determine the stability region of spot solutions in parameter space as a function of a natural control parameter (feed-rate where degenerate patterns with different numbers of spots coexist for a fixed feed-rate. While it is possible to generate identical patterns via both mechanisms, we show that replication cascades lead to a wider choice of pattern profiles that can be selected through a tuning of the feed-rate, exploiting hysteresis and directionality effects of the different pattern pathways.

  10. Study on Immobilized Lipase Catalyzed Transesterification Reaction of Tung Oil

    Institute of Scientific and Technical Information of China (English)

    XU Gui-zhuan; ZHANG Bai-liang; LIU Sheng-yong; YUE Jian-zhi

    2006-01-01

    The transesterification reaction conditions of tung oil with methanol have been studied in this article, with immobilized lipase NOVO435 as catalyst. The response surface methodology was used to optimize the transesterification reaction of tung oil in a nonsolvent system. The optimal conditions were rotation rate 200 r/min, molar ratio of methanol to oil 2.2:1,reaction temperature 43℃, and the catalyst amount 14% (based on the weight of oil). After reacting for 18 h, 67.5% of the oil was converted to its corresponding methyl esters (the theoretical ester conversion was 73.3%). The lipase was washed by organic solvents after each reaction and was reused again. The esters conversion of tung oil was decreased by 6% after the lipase was reused for 120 h. The theoretical amount of methanol was added in two steps, 85% ester conversion was obtained after 36 h of reaction (theoretical ester conversion was 100%). The molar ratio of methanol to oil, the catalyst amount, the reaction temperature, and reaction time were all highly significant factors, and there was a relative significant interaction between every two factors.

  11. NMR spectroscopic study on methanolysis reaction of vegetable oil

    Energy Technology Data Exchange (ETDEWEB)

    Fangming Jin; Kohei Kawasaki; Hisanori Kishida; Kazuyuki Tohji; Takehoko Moriya; Heiji Enomoto [Tohoku University, Sendai (Japan). Graduate School of Environmental Studies

    2007-05-15

    This study is to clarify the pathways of the transesterification of vegetable oil by applying NMR to the identification of intermediates in the transesterification reaction. Results showed that the significant methanolysis product was sn-1,3-diglycerides in diglycerides, and sn-2-monoglycerides was not found. These analytical results suggest that the methanolysis reaction may occur easily at the sn-2-position for both sn-tri- and sn-1,2-diglycerides. Short communication. 16 refs., 6 figs., 2 tabs.

  12. Catalytic Studies of Sodium Hydroxide and Carbon Monoxide Reaction

    Directory of Open Access Journals (Sweden)

    Surendra K. Saxena

    2012-11-01

    Full Text Available We have studied the effect of ball milling on alumina mixed nickel, magnetite and Raney nickel on the reaction: 2NaOH(s + CO (g = Na2CO3 (s + H2 (g and determined the optimum particle size for the catalysts. The best performance was shown by a 2 h ball milled Raney nickel with average crystallite size of 209 Å. This reaction serves the dual purpose of carbon sequestration and yielding hydrogen gas.

  13. Modified landfill gas generation rate model of first-order kinetics and two-stage reaction

    Institute of Scientific and Technical Information of China (English)

    Jiajun CHEN; Hao WANG; Na ZHANG

    2009-01-01

    This investigation was carried out to establish a new domestic landfill gas (LFG) generation rate model that takes into account the impact ofleachate recirculation. The first-order kinetics and two-stage reaction (FKTSR) model of the LFG generation rate includes mechanisms of the nutrient balance for biochemical reaction in two main stages. In this study, the FKTSR model was modified by the introduction of the outflow function and the organic acid conversion coefficient in order to represent the in-situ condition of nutrient loss through leachate. Laboratory experiments were carried out to simulate the impact of leachate recirculation and verify the modified FKTSR model. The model calibration was then calculated by using the experimental data. The results suggested that the new model was in line with the experimental data. The main parameters of the modified FKTSR model, including the LFG production potential (L0), the reaction rate constant in the first stage (K1), and the reaction rate constant in the second stage (K2) of 64.746 L, 0.202 d-1, and 0.338 d-1,respectively, were comparable to the old ones of 42.069 L,0.231 d-1, and 0.231 d-1. The new model is better able to explain the mechanisms involved in LFG generation.

  14. Recent direct reaction experimental studies with radioactive tin beams

    CERN Document Server

    Jones, K L; Allmond, J M; Ayres, A; Bardayan, D W; Baugher, T; Bazin, D; Berryman, J S; Bey, A; Bingham, C; Cartegni, L; Cerizza, G; Chae, K Y; Cizewski, J A; Gade, A; Galindo-Uribarri, A; Garcia-Ruiz, R F; Grzywacz, R; Howard, M E; Kozub, R L; Liang, J F; Manning, B; Matos, M; McDaniel, S; Miller, D; Nesaraja, C D; O'Malley, P D; Padgett, S; Padilla-Rodal, E; Pain, S D; Pittman, S T; Radford, D C; Ratkiewicz, A; Schmitt, K T; Shore, A; Smith, M S; Stracener, D W; Stroberg, S R; Tostevin, J; Varner, R L; Weisshaar, D; Wimmer, K; Winkler, R

    2015-01-01

    Direct reaction techniques are powerful tools to study the single-particle nature of nuclei. Performing direct reactions on short-lived nuclei requires radioactive ion beams produced either via fragmentation or the Isotope Separation OnLine (ISOL) method. Some of the most interesting regions to study with direct reactions are close to the magic numbers where changes in shell structure can be tracked. These changes can impact the final abundances of explosive nucleosynthesis. The structure of the chain of tin isotopes is strongly influenced by the Z=50 proton shell closure, as well as the neutron shell closures lying in the neutron-rich, N=82, and neutron-deficient, N=50, regions. Here we present two examples of direct reactions on exotic tin isotopes. The first uses a one-neutron transfer reaction and a low-energy reaccelerated ISOL beam to study states in 131Sn from across the N=82 shell closure. The second example utilizes a one-neutron knockout reaction on fragmentation beams of neutron-deficient 106,108Sn...

  15. Phase transitions in a holographic s + p model with back-reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Zhang-Yu [Kunming University of Science and Technology, Kunming (China); Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China); Shanghai Jiao Tong University, INPAC, Department of Physics, and Shanghai Key Laboratory of Particle Physics and Cosmology, Shanghai (China); Cai, Rong-Gen [Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China); Gao, Xin [Virginia Tech, Department of Physics, Blacksburg, VA (United States); Li, Li [University of Crete, Department of Physics, Crete Center for Theoretical Physics, Heraklion (Greece); Zeng, Hui [Kunming University of Science and Technology, Kunming (China); Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China)

    2015-11-15

    In a previous paper (Nie et al. in JHEP 1311:087, arXiv:1309.2204 [hep-th], 2013), we presented a holographic s + p superconductor model with a scalar triplet charged under an SU(2) gauge field in the bulk. We also study the competition and coexistence of the s-wave and p-wave orders in the probe limit. In this work we continue to study the model by considering the full back-reaction. The model shows a rich phase structure and various condensate behaviors such as the ''n-type'' and ''u-type'' ones, which are also known as reentrant phase transitions in condensed matter physics. The phase transitions to the p-wave phase or s + p coexisting phase become first order in strong back-reaction cases. In these first order phase transitions, the free energy curve always forms a swallow tail shape, in which the unstable s + p solution can also play an important role. The phase diagrams of this model are given in terms of the dimension of the scalar order and the temperature in the cases of eight different values of the back-reaction parameter, which show that the region for the s + p coexisting phase is enlarged with a small or medium back-reaction parameter but is reduced in the strong back-reaction cases. (orig.)

  16. 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

  17. Effects of midazolam and phenobarbital on brain oxidative reactions induced by pentylenetetrazole in a convulsion model.

    Science.gov (United States)

    Arai, Yukiko; Maeda, Shigeru; Higuchi, Hitoshi; Tomoyasu, Yumiko; Shimada, Masahiko; Miyawaki, Takuya

    2012-04-01

    Brain oxidative reactions are involved in epilepsy as well as neurodegenerative diseases. In animal convulsion models, some anticonvulsants have been found to suppress oxidative reactions associated with convulsions. However, the effect of anticonvulsants on brain oxidative reactions has not fully been clarified. Midazolam and phenobarbital are often used as an intravenous anesthetic, and are known to have anticonvulsive effect, but antioxidative effect of these drugs has rarely been studied. Thus, the purpose of this study was to evaluate the effects of these drugs on the degree of convulsions and brain oxidative reactions in an animal convulsion model. In order to evaluate brain oxidative reactions, we measured malondialdehyde (MDA) level and heme oxygenase (HO)-1 mRNA expression level in the brain of mice in a convulsion model generated by a single injection of pentylenetetrazole (PTZ). We evaluated the effects of midazolam and phenobarbital on the degree of PTZ-induced convulsions and on the changes in brain MDA level and HO-1 mRNA expression level. After PTZ injection, severe convulsions were observed in all mice. MDA level was increased in the whole brain, while HO-1 mRNA expression level was increased only in the hippocampus. Both midazolam and phenobarbital prevented the convulsions and suppressed the increase in both MDA level and HO-1 mRNA expression level in the brain. In this study, both midazolam and phenobarbital suppressed PTZ-induced MDA and HO-1 reactions in the brain, suggesting that these drugs inhibit brain oxidative reactions in a convulsion model.

  18. Reaction-Multi Diffusion Model for Nutrient Release and Autocatalytic Degradation of PLA-Coated Controlled-Release Fertilizer

    Directory of Open Access Journals (Sweden)

    Sayed Ameenuddin Irfan

    2017-03-01

    Full Text Available A mathematical model for the reaction-diffusion equation is developed to describe the nutrient release profiles and degradation of poly(lactic acid (PLA-coated controlled-release fertilizer. A multi-diffusion model that consists of coupled partial differential equations is used to study the diffusion and chemical reaction (autocatalytic degradation simultaneously. The model is solved using an analytical-numerical method. Firstly, the model equation is transformed using the Laplace transformation as the Laplace transform cannot be inverted analytically. Numerical inversion of the Laplace transform is used by employing the Zakian method. The solution is useful in predicting the nutrient release profiles at various diffusivity, concentration of extraction medium, and reaction rates. It also helps in explaining the transformation of autocatalytic concentration in the coating material for various reaction rates, times of reaction, and reaction-multi diffusion. The solution is also applicable to the other biodegradable polymer-coated controlled-release fertilizers.

  19. The $^{136}$Xe + $^{208}$Pb reaction: A test of models of multi-nucleon transfer reactions

    CERN Document Server

    Barrett, J S; Loveland, W; Zhu, S; Ayangeakaa, A D; Carpenter, M P; Greene, J P; Janssens, R V F; Lauritsen, T; McCutchan, E A; Sonzogni, A A; Chiara, C J; Harker, J L; Walters, W B

    2015-01-01

    The yields of over 200 projectile-like fragments (PLFs) and target-like fragments (TLFs) from the interaction of (E$_{c.m.}$=450 MeV) $^{136}$Xe with a thick target of $^{208}$Pb were measured using Gammasphere and off-line $\\gamma$-ray spectroscopy, giving a comprehensive picture of the production cross sections in this reaction.The measured yields were compared to predictions of the GRAZING model and the predictions of Zagrebaev and Greiner using a quantitative metric, the theory evaluation factor, {\\bf tef}. The GRAZING model predictions are adequate for describing the yields of nuclei near the target or projectile but grossly underestimate the yields of all other products. The predictions of Zagrebaev and Greiner correctly describe the magnitude and maxima of the observed TLF transfer cross sections for a wide range of transfers ($\\Delta$Z = -8 to $\\Delta$Z = +2). However for $\\Delta$Z =+4, the observed position of the maximum in the distribution is four neutrons richer than the predicted maximum. The pre...

  20. Extended kinetic model of real-time polymerase chain reaction process

    Science.gov (United States)

    Fedorov, A. A.; Sochivko, D. G.; Varlamov, D. A.; Kurochkin, V. E.

    2016-11-01

    Real-time polymerase chain reaction (real-time PCR) is the main molecular genetic method used for qualitative and quantitative analysis of specific nucleic acid sequences in many areas of biomedical research. Theoretical study of pCr models allows to estimate the influence of various reaction components and parameters, and to determine the unknown parameter values by approximating the experimental real-time PCR curves. An extended kinetic model of real-time PCR is presented. The model takes into account the enzyme activity based on Michaelis-Menten kinetics, the hybridization of complementary DNA fragments, the presence of a fluorescent probe used for detection of the reaction products, and the temperature dependence of primers and probe hybridization.

  1. 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...

  2. Modelling of Serpentine Continuous Flow Polymerase Chain Reaction Microfluidics

    Directory of Open Access Journals (Sweden)

    Abubakar Mohammed

    2012-03-01

    Full Text Available The continuous flow Polymerase Chain Reaction (PCR microfluidics DNA amplification device is a recent discovery aimed at eliminating the cyclic hold experienced while using the alternative stationary device.The Application of Computational Fluid Dynamics is increasingly growing and can help achieve optimal designs before actual fabrication. This paper presents a CFD modelling of a continuous flow serpentine PCR device with narrow and wider channels. There are two temperature regions at 950C and 600C for denaturation and annealing respectively. Extension is achieved along the middle of the channel at 720C owing to temperature gradient. The model require a pressure of 42.6KPa for a 30 cycle amplification.

  3. A reaction-diffusion model of human brain development.

    Directory of Open Access Journals (Sweden)

    Julien Lefèvre

    2010-04-01

    Full Text Available Cortical folding exhibits both reproducibility and variability in the geometry and topology of its patterns. These two properties are obviously the result of the brain development that goes through local cellular and molecular interactions which have important consequences on the global shape of the cortex. Hypotheses to explain the convoluted aspect of the brain are still intensively debated and do not focus necessarily on the variability of folds. Here we propose a phenomenological model based on reaction-diffusion mechanisms involving Turing morphogens that are responsible for the differential growth of two types of areas, sulci (bottom of folds and gyri (top of folds. We use a finite element approach of our model that is able to compute the evolution of morphogens on any kind of surface and to deform it through an iterative process. Our model mimics the progressive folding of the cortical surface along foetal development. Moreover it reveals patterns of reproducibility when we look at several realizations of the model from a noisy initial condition. However this reproducibility must be tempered by the fact that a same fold engendered by the model can have different topological properties, in one or several parts. These two results on the reproducibility and variability of the model echo the sulcal roots theory that postulates the existence of anatomical entities around which the folding organizes itself. These sulcal roots would correspond to initial conditions in our model. Last but not least, the parameters of our model are able to produce different kinds of patterns that can be linked to developmental pathologies such as polymicrogyria and lissencephaly. The main significance of our model is that it proposes a first approach to the issue of reproducibility and variability of the cortical folding.

  4. Image guided personalization of reaction-diffusion type tumor growth models using modified anisotropic eikonal equations.

    Science.gov (United States)

    Konukoglu, Ender; Clatz, Olivier; Menze, Bjoern H; Stieltjes, Bram; Weber, Marc-André; Mandonnet, Emmanuel; Delingette, Hervé; Ayache, Nicholas

    2010-01-01

    Reaction-diffusion based tumor growth models have been widely used in the literature for modeling the growth of brain gliomas. Lately, recent models have started integrating medical images in their formulation. Including different tissue types, geometry of the brain and the directions of white matter fiber tracts improved the spatial accuracy of reaction-diffusion models. The adaptation of the general model to the specific patient cases on the other hand has not been studied thoroughly yet. In this paper, we address this adaptation. We propose a parameter estimation method for reaction-diffusion tumor growth models using time series of medical images. This method estimates the patient specific parameters of the model using the images of the patient taken at successive time instances. The proposed method formulates the evolution of the tumor delineation visible in the images based on the reaction-diffusion dynamics; therefore, it remains consistent with the information available. We perform thorough analysis of the method using synthetic tumors and show important couplings between parameters of the reaction-diffusion model. We show that several parameters can be uniquely identified in the case of fixing one parameter, namely the proliferation rate of tumor cells. Moreover, regardless of the value the proliferation rate is fixed to, the speed of growth of the tumor can be estimated in terms of the model parameters with accuracy. We also show that using the model-based speed, we can simulate the evolution of the tumor for the specific patient case. Finally, we apply our method to two real cases and show promising preliminary results.

  5. Catalytic hydrotreatment studies with model compounds. Quarterly report, April 1-June 30, 1986. [Hydrodeoxygenation of reaction intermediates of dibenzofuran - 2 phenylphenol, 2-cyclohexylphenol, trans-2-phenylhexanol, and 2-cyclohexylcyclohexanol

    Energy Technology Data Exchange (ETDEWEB)

    Satterfield, C.N.; LaVopa, V.

    1986-01-01

    Studies of the hydrodeoxygenation (HDO) of dibenzofuran continued. To help clarify the reaction network four possible reaction intermediates were studied in detail: 2 phenyl phenol, 2-cyclohexylphenol, trans-2-phenyl-cyclohexanol, and 2-cyclohexylcyclohexanol. All four intermediates are more reactive than dibenzofuran itself. The most detailed study previously reported on the HDO of dibenzofuran is that of Krishnamurthy and Shah (1979). However, our product distributions differ from theirs in several significant ways and we note that in some cases they did not recover a major portion of their products. We are presently attempting to see if their study and ours can be reconciled. 6 figs., 2 tabs.

  6. Fundamental studies of retrograde reactions in direct liquefaction. Final report, September 20, 1988--November 20, 1990

    Energy Technology Data Exchange (ETDEWEB)

    Serio, M.A.; Solomon, P.R.; Kroo, E.; Charpenay, S.; Bassilakis, R.

    1991-12-17

    The overall objective of the program was to improve the understanding of retrograde reactions and their dependencies on coal rank and structure, and/or coal modifications and reaction conditions. Because retrograde reactions are competitive with bond breaking reactions, an understanding of both is required to shift the competition in favor of the latter. Related objectives were to clarify the conflicting observations reported in literature on such major topics as the role of oxygen groups in retrograde reactions and to provide a bridge from very fundamental studies on pure compounds to phenomenological studies on actual coal. This information was integrated into the FG-DVC model, which was improved and extended to the liquefaction context.

  7. Recent studies in heavy ion induced fission reactions

    Indian Academy of Sciences (India)

    R K Choudhury

    2001-08-01

    Nuclear fission process involves large scale shape changes of the nucleus, while it evolves from a nearly spherical configuration to two separated fission fragments. The dynamics of these shape changes in the nuclear many body system is governed by a strong interplay of the collective and single particle degrees of freedom. With the availability of heavy ion accelerators, there has been an impetus to study the nuclear dynamics through the investigations of nucleus–nucleus collisions involving fusion and fission process. From the various investigations carried out in the past years, it is now well recognized that there is large scale damping of collective modes in heavy ion induced fission reactions, which in other words implies that nuclear motion is highly viscous. In recent years, there have been many experimental observations in heavy ion induced fission reactions at medium bombarding energies, which suggest possible occurrence of various non-equilibrium modes of fission such as quasi-fission, fast fission and pre-equilibrium fission, where some of the internal degrees of freedom of the nucleus is not fully equilibrated. We have carried out extensive investigations on the fission fragment angular distributions at near barrier bombarding energies using heavy fissile targets. The measured fragment anisotropies when compared with the standard saddle point model (SSPM) calculations show that for projectile-target systems having zero or low ground state spins, the angular anisotropy exhibits a peak-like behaviour at the sub barrier energies, which cannot be explained by the SSPM calculations. For projectiles or targets with large ground state spins, the anomalous peaking gets washed out due to smearing of the -distribution by the intrinsic entrance channel spins. Recently studies have been carried out on the spin distributions of fission fragments through the gamma ray multiplicity measurements. The fission fragments acquire spin mainly from two

  8. $K^{+}$ momentum spectrum from $(K^{-},K^{+})$ reactions in intranuclear cascade model

    CERN Document Server

    Nara, Y; Harada, T; Engel, A

    1996-01-01

    In a framework of intranuclear cascade (INC) type calculation, we study a momentum spectrum in reactions \\KK at a beam momentum of 1.65 GeV/c. INC model calculations are compared with the relativistic impulse approximation (RIA) calculations to perform the detailed study of the reaction mechanism. We find that the INC model can reproduce the experimental data on various targets. Especially, in the low-momentum region, the forward-angle cross sections of the $(K^-,K^+)$ reaction on from light to heavy targets are consistently explained with the two-step strangeness exchange and production processes with various intermediate mesons, and $\\phi$, $a_0$ and $f_0$ productions and their decay into $K^+K^-$. In the two-step processes, inclusion of meson and hyperon resonances is found to be essential.

  9. Reaction studies of hot silicon, germanium and carbon atoms

    Energy Technology Data Exchange (ETDEWEB)

    Gaspar, P.P.

    1990-11-01

    The goal of this project was to increase the authors understanding of the interplay between the kinetic and electronic energy of free atoms and their chemical reactivity by answering the following questions: (1) what is the chemistry of high-energy carbon silicon and germanium atoms recoiling from nuclear transformations; (2) how do the reactions of recoiling carbon, silicon and germanium atoms take place - what are the operative reaction mechanisms; (3) how does the reactivity of free carbon, silicon and germanium atoms vary with energy and electronic state, and what are the differences in the chemistry of these three isoelectronic atoms This research program consisted of a coordinated set of experiments capable of achieving these goals by defining the structures, the kinetic and internal energy, and the charge states of the intermediates formed in the gas-phase reactions of recoiling silicon and germanium atoms with silane, germane, and unsaturated organic molecules, and of recoiling carbon atoms with aromatic molecules. The reactions of high energy silicon, germanium, and carbon atoms created by nuclear recoil were studied with substrates chosen so that their products illuminated the mechanism of the recoil reactions. Information about the energy and electronic state of the recoiling atoms at reaction was obtained from the variation in end product yields and the extent of decomposition and rearrangement of primary products (usually reactive intermediates) as a function of total pressure and the concentration of inert moderator molecules that remove kinetic energy from the recoiling atoms and can induce transitions between electronic spin states. 29 refs.

  10. Reaction dynamics of {sup 34-38}Mg projectile with carbon target using Glauber model

    Energy Technology Data Exchange (ETDEWEB)

    Shama, Mahesh K., E-mail: maheshphy82@gmail.com [School of Physics and Material Sciences, Thapar University Patiala-147004 (India); Department of Applied Sciences, Chandigarh Engineering College, Landran Mohali-140307 (India); Panda, R. N. [Department of Physics, ITER, Shiksha O Anusandhan University, Bhubaneswar-751030 (India); Sharma, Manoj K. [School of Physics and Material Sciences, Thapar University Patiala-147004 (India); Patra, S. K. [Institute of Physics, Sachivalaya marg Bhubneswar-751005 (India)

    2015-08-28

    We have studied nuclear reaction cross-sections for {sup 34-38}Mg isotopes as projectile with {sup 12}C target at projectile energy 240AMeV using Glauber model with the conjunction of densities from relativistic mean filed formalism. We found good agreement with the available experimental data. The halo status of {sup 37}Mg is also investigated.

  11. Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition.

    Science.gov (United States)

    Elliott, Simon D; Dey, Gangotri; Maimaiti, Yasheng; Ablat, Hayrensa; Filatova, Ekaterina A; Fomengia, Glen N

    2016-07-01

    Recent progress in the simulation of the chemistry of atomic layer deposition (ALD) is presented for technologically important materials such as alumina, silica, and copper metal. Self-limiting chemisorption of precursors onto substrates is studied using density functional theory so as to determine reaction pathways and aid process development. The main challenges for the future of ALD modeling are outlined.

  12. Quantitative models of hydrothermal fluid-mineral reaction: The Ischia case

    Science.gov (United States)

    Di Napoli, Rossella; Federico, Cinzia; Aiuppa, Alessandro; D'Antonio, Massimo; Valenza, Mariano

    2013-03-01

    The intricate pathways of fluid-mineral reactions occurring underneath active hydrothermal systems are explored in this study by applying reaction path modelling to the Ischia case study. Ischia Island, in Southern Italy, hosts a well-developed and structurally complex hydrothermal system which, because of its heterogeneity in chemical and physical properties, is an ideal test sites for evaluating potentialities/limitations of quantitative geochemical models of hydrothermal reactions. We used the EQ3/6 software package, version 7.2b, to model reaction of infiltrating waters (mixtures of meteoric water and seawater in variable proportions) with Ischia's reservoir rocks (the Mount Epomeo Green Tuff units; MEGT). The mineral assemblage and composition of such MEGT units were initially characterised by ad hoc designed optical microscopy and electron microprobe analysis, showing that phenocrysts (dominantly alkali-feldspars and plagioclase) are set in a pervasively altered (with abundant clay minerals and zeolites) groundmass. Reaction of infiltrating waters with MEGT minerals was simulated over a range of realistic (for Ischia) temperatures (95-260 °C) and CO2 fugacities (10-0.2 to 100.5) bar. During the model runs, a set of secondary minerals (selected based on independent information from alteration minerals' studies) was allowed to precipitate from model solutions, when saturation was achieved. The compositional evolution of model solutions obtained in the 95-260 °C runs were finally compared with compositions of Ischia's thermal groundwaters, demonstrating an overall agreement. Our simulations, in particular, well reproduce the Mg-depleting maturation path of hydrothermal solutions, and have end-of-run model solutions whose Na-K-Mg compositions well reflect attainment of full-equilibrium conditions at run temperature. High-temperature (180-260 °C) model runs are those best matching the Na-K-Mg compositions of Ischia's most chemically mature water samples

  13. Application of a non-equilibrium reaction model for describing horizontal well performance in foamy oil

    Energy Technology Data Exchange (ETDEWEB)

    Luigi, A.; Saputelli, B.; Carlas, M.; Canache, P.; Lopez, E. [DPVS Exploracion y Produccion (Venezuela)

    1998-12-31

    This study was designed to determine the activation energy ranges and frequency factor ranges in chemical reactions in heavy oils of the Orinoco Belt in Venezuela, in order to account for the kinetics of physical changes that occur in the morphology of gas-oil dispersion. A non-equilibrium reaction model was used to model foamy oil behaviour observed at SDZ-182 horizontal well in the Zuata field. Results showed that activation energy for the first reaction ranged from 0 to 0.01 BTU/lb-mol and frequency factor from 0.001 to 1000 l/day. For the second reaction the activation energy was 50x10{sub 3} BTU/lb-mol and the frequency factor 2.75x10{sub 1}2 l/day. The second reaction was highly sensitive to the modifications in activation energy and frequency factor. However, both the activation energy and frequency factor were independent of variations for the first reaction. In the case of the activation energy, the results showed that the high sensitivity of this parameter reflected the impact that temperature has on the representation of foamy oil behaviour. 8 refs., 2 tabs., 6 figs.

  14. Bayesian analysis of the linear reaction norm model with unknown covariates.

    Science.gov (United States)

    Su, G; Madsen, P; Lund, M S; Sorensen, D; Korsgaard, I R; Jensen, J

    2006-07-01

    The reaction norm model is becoming a popular approach for the analysis of genotype x environment interactions. In a classical reaction norm model, the expression of a genotype in different environments is described as a linear function (a reaction norm) of an environmental gradient or value. An environmental value is typically defined as the mean performance of all genotypes in the environment, which is usually unknown. One approximation is to estimate the mean phenotypic performance in each environment and then treat these estimates as known covariates in the model. However, a more satisfactory alternative is to infer environmental values simultaneously with the other parameters of the model. This study describes a method and its Bayesian Markov Chain Monte Carlo implementation that makes this possible. Frequentist properties of the proposed method are tested in a simulation study. Estimates of parameters of interest agree well with the true values. Further, inferences about genetic parameters from the proposed method are similar to those derived from a reaction norm model using true environmental values. On the other hand, using phenotypic means as proxies for environmental values results in poor inferences.

  15. Theoretical Study on the Mechanism of Sonogashira Coupling Reaction

    Institute of Scientific and Technical Information of China (English)

    CHEN Li-Ping; HONG San-Guo; HOU Hao-Qing

    2008-01-01

    The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT (density functional theory) calculations. The model system studied consists of Pd(PH3)2 as the starting catalyst complex, phenyl bromide as the substrate and acetylene as the terminal alkyne, without regarding to the co-catalyst and base. Mechanistically and energetically plausible catalytic cycles for the cross-coupling have been identified. The DFT analysis shows that the catalytic cycle occurs in three stages: oxidative addition of phenyl bromide to the palladium center, alkynylation of palladium(II) intermediate, and reductive elimination to phenylacetylene. In the oxidative addition, the neutral and anionic pathways have been investigated, which could both give rise to cis-configured palladium(II) diphosphine intermediate. Starting from the palladium(II) diphosphine intermediate, the only identifiable pathway in alkynylation involves the dissociation of Br group and the formation of square-planar palladium(II) intermediate, in which the phenyl and alkynyl groups are oriented cis to each other. Due to the close proximity of phenyl and alkynyl groups, the reductive elimination of phenylacetylene proceeds smoothly.

  16. A Reaction-Diffusion Model of Cholinergic Retinal Waves

    Science.gov (United States)

    Lansdell, Benjamin; Ford, Kevin; Kutz, J. Nathan

    2014-01-01

    Prior to receiving visual stimuli, spontaneous, correlated activity in the retina, called retinal waves, drives activity-dependent developmental programs. Early-stage waves mediated by acetylcholine (ACh) manifest as slow, spreading bursts of action potentials. They are believed to be initiated by the spontaneous firing of Starburst Amacrine Cells (SACs), whose dense, recurrent connectivity then propagates this activity laterally. Their inter-wave interval and shifting wave boundaries are the result of the slow after-hyperpolarization of the SACs creating an evolving mosaic of recruitable and refractory cells, which can and cannot participate in waves, respectively. Recent evidence suggests that cholinergic waves may be modulated by the extracellular concentration of ACh. Here, we construct a simplified, biophysically consistent, reaction-diffusion model of cholinergic retinal waves capable of recapitulating wave dynamics observed in mice retina recordings. The dense, recurrent connectivity of SACs is modeled through local, excitatory coupling occurring via the volume release and diffusion of ACh. In addition to simulation, we are thus able to use non-linear wave theory to connect wave features to underlying physiological parameters, making the model useful in determining appropriate pharmacological manipulations to experimentally produce waves of a prescribed spatiotemporal character. The model is used to determine how ACh mediated connectivity may modulate wave activity, and how parameters such as the spontaneous activation rate and sAHP refractory period contribute to critical wave size variability. PMID:25474327

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

    Energy Technology Data Exchange (ETDEWEB)

    Trowbridge, L.D.

    2000-04-01

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

  18. A numerical evaluation of prediction accuracy of CO2 absorber model for various reaction rate coefficients

    Directory of Open Access Journals (Sweden)

    Shim S.M.

    2012-01-01

    Full Text Available The performance of the CO2 absorber column using mono-ethanolamine (MEA solution as chemical solvent are predicted by a One-Dimensional (1-D rate based model in the present study. 1-D Mass and heat balance equations of vapor and liquid phase are coupled with interfacial mass transfer model and vapor-liquid equilibrium model. The two-film theory is used to estimate the mass transfer between the vapor and liquid film. Chemical reactions in MEA-CO2-H2O system are considered to predict the equilibrium pressure of CO2 in the MEA solution. The mathematical and reaction kinetics models used in this work are calculated by using in-house code. The numerical results are validated in the comparison of simulation results with experimental and simulation data given in the literature. The performance of CO2 absorber column is evaluated by the 1-D rate based model using various reaction rate coefficients suggested by various researchers. When the rate of liquid to gas mass flow rate is about 8.3, 6.6, 4.5 and 3.1, the error of CO2 loading and the CO2 removal efficiency using the reaction rate coefficients of Aboudheir et al. is within about 4.9 % and 5.2 %, respectively. Therefore, the reaction rate coefficient suggested by Aboudheir et al. among the various reaction rate coefficients used in this study is appropriate to predict the performance of CO2 absorber column using MEA solution. [Acknowledgement. This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF, funded by the Ministry of Education, Science and Technology (2011-0017220].

  19. Theoretical study of reaction mechanism for NCO + HCNO

    Science.gov (United States)

    Zhang, Weichao; Du, Benni; Feng, Changjun

    2007-07-01

    A detailed quantum chemical study is performed on the mechanism of the NCO + HCNO reaction, which has never been studied by theory. The potential energy surface for this reaction is characterized at the B3LYP/6-311++G(d,p) level of theory, combined with high-level CBS-QB3 single point energy calculation. Four possible product channels have been investigated. From the calculations it can be seen that the formation of HCN + NO + CO is the dominant product channel, while the pathway to products of HCNN + CO 2 is expected to be minor one, and these conclusions are in good agreement with the experimental results.

  20. Quantum Chemical Study on Reaction of Acetaldehyde with Hydroxyl Radical

    Institute of Scientific and Technical Information of China (English)

    LI,Ming(李明); ZHANG,Jin-Sheng(张金生); SHEN,Wei(申伟); MENG,Qing-Xi(孟庆喜)

    2004-01-01

    The reaction of acetaldehyde with hydroxyl radical was studied by means of quantum chemical methods. The geometries for all the stationary points on the potential energy surfaces were optimized fully, respectively, at the G3MP2, G3, and MP2/6-311++G(d,p) levels. Single-point energies of all the species were calculated at the QCISD/6-311 + +G(d,p) level. The mechanism of the reaction studied was confirmed. The predicted product is acetyl radical that is in agreement with the experiment.

  1. Three-Body Model Analysis of Subbarrier alpha Transfer Reaction

    CERN Document Server

    Fukui, Tokuro; Yahiro, Masanobu

    2011-01-01

    Subbarrier alpha transfer reaction 13C(6Li,d)17O(6.356 MeV, 1/2+) at 3.6 MeV is analyzed with a alpha + d + 13C three-body model, and the asymptotic normalization coefficient (ANC) for alpha + 13C --> 17O(6.356 MeV, 1/2+), which essentially determines the reaction rate of 13C(alpha,n)16O, is extracted. Breakup effects of 6Li in the initial channel and those of 17O in the final channel are investigated with the continuum-discretized coupled-channels method (CDCC). The former is found to have a large back-coupling to the elastic channel, while the latter turns out significantly small. The transfer cross section calculated with Born approximation to the transition operator, including breakup states of 6Li, gives (C_{alpha 13C}{17O*})^2 =1.03 \\pm 0.29 fm^{-1}. This result is consistent with the value obtained by the previous DWBA calculation.

  2. A multi-pathway model for Photosynthetic reaction center

    CERN Document Server

    Qin, M; Yi, X X

    2015-01-01

    Charge separation in light-harvesting complexes occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine (QHE). Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem {\\rm II} reaction center (PS{\\rm II} RC) to describe the charge separation. Our model mainly considers two charge-separation pathways more than that in the published literature. The two pathways can interfere via cross-couplings and work together to enhance the charge-separation yields. We explore how these cross-couplings increase the current and voltage of the charge separation and discuss the advantages of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PS{\\rm II} RC and dephasing induced by environments is also explored, and extension ...

  3. Reactions of aqueous chlorine and chlorine dioxide with model food compounds.

    Science.gov (United States)

    Fukayama, M Y; Tan, H; Wheeler, W B; Wei, C I

    1986-01-01

    Chlorine and chlorine dioxide (ClO2), common disinfecting and bleaching chemicals used in the food industry, are potent oxidizing and chlorinating agents. Unfortunately, little is known about the nature of the reactions of chlorine with organic food constituents. This presentation reviews published information concerning the reactions of chlorine gas (Cl2[g]), aqueous chlorine, and ClO2 with model food compounds, the fate of chlorine during the chlorination of specific food products, and the potential toxicity of the reaction products. Fatty acids and their methyl esters react with chlorine with the degree of incorporation corresponding to their degree of unsaturation. Aqueous chlorine oxidizes and chlorinates lipids and amino acids much more readily than ClO2. Several amino acids are highly susceptible to oxidation and chlorination by chlorine compounds. Reactions of chlorine and ClO2 with several food products, including flour and shrimp, have also been characterized. In one model system, 99% of Cl2(g) either reacted with components of flour or was consumed by oxidation/chlorination reactions. The lipids extracted from the chlorinated flour contained significant amounts of chlorine. Exposure of shrimp to hypochlorous acid (HOCl) solution resulted in significant incorporation of chlorine into the edible portion. Although significant quantities of chlorine can be incorporated into specific model compounds and food products, the health risks associated with exposure to chlorinated organic products are unknown. Preliminary studies using the Ames Salmonella/microsome mutagenicity assay indicate that the reaction products from mixtures of aqueous chlorine and various lipids or tryptophan are nonmutagenic. Nevertheless, additional studies are warranted, so that the toxicological significance of these reaction products can be understood more fully. PMID:3545804

  4. Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

    Directory of Open Access Journals (Sweden)

    Javier Morales

    Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

  5. Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study

    Science.gov (United States)

    Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else

    2012-01-01

    Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966

  6. Study of the Reaction $np \\rightarrow np \\pi^+ \\pi^-$ at Intermediate Energies

    OpenAIRE

    Jerusalimov, A. P.; Troyan, Yu. A.; Troyan, A. Yu.; Belyaev, A. V.; Plekhanov, E. B.

    2011-01-01

    The reaction $np \\rightarrow np \\pi^+ \\pi^-$ was studied at the various momenta of incident neutrons. It was shown that the characteristics of the reaction at the momenta above 3 GeV/c could be described by the model of reggeized $\\pi$ exchange (OPER). At the momenta below 3 GeV/c, it was necessary to use additionally the mechanism of one baryon exchange (OBE).

  7. Study of quinones reactions with wine nucleophiles by cyclic voltammetry.

    Science.gov (United States)

    Oliveira, Carla M; Barros, António S; Ferreira, António C S; Silva, Artur M S

    2016-11-15

    Quinones are electrophilic species which can react with various nucleophiles, like wine antioxidants, such as sulfur dioxide or ascorbic acid, thiols, amino acids, and numerous polyphenols. These reactions are very important in wine aging because they mediate oxygen reactions during both production and bottle aging phases. In this work, the major challenge was to determine the interaction between ortho-quinones and wine nucleophiles (amino acids, thiols, and the antioxidants SO2 and ascorbic acid), by cyclic voltammetry. Wine-model solutions with gallic acid, caffeic acid, or (+)-catechin and nucleophilic compounds were used. To understand the effect of nucleophilic addition in wine, a white wine with the same added nucleophiles was also analysed. Cyclic voltammograms were taken with glassy carbon electrode or screen-printed carbon electrodes, respectively, for wine-model and white wines solutions, in the absence and in the presence of nucleophiles. A nucleophilic order profile related to the cathodic current intensity decrease was observed.

  8. Traveling Wave Solutions of Reaction-Diffusion Equations Arising in Atherosclerosis Models

    Directory of Open Access Journals (Sweden)

    Narcisa Apreutesei

    2014-05-01

    Full Text Available In this short review article, two atherosclerosis models are presented, one as a scalar equation and the other one as a system of two equations. They are given in terms of reaction-diffusion equations in an infinite strip with nonlinear boundary conditions. The existence of traveling wave solutions is studied for these models. The monostable and bistable cases are introduced and analyzed.

  9. Modelling combustion reactions for gas flaring and its resulting emissions

    Directory of Open Access Journals (Sweden)

    O. Saheed Ismail

    2016-07-01

    Full Text Available Flaring of associated petroleum gas is an age long environmental concern which remains unabated. Flaring of gas maybe a very efficient combustion process especially steam/air assisted flare and more economical than utilization in some oil fields. However, it has serious implications for the environment. This study considered different reaction types and operating conditions for gas flaring. Six combustion equations were generated using the mass balance concept with varying air and combustion efficiency. These equations were coded with a computer program using 12 natural gas samples of different chemical composition and origin to predict the pattern of emission species from gas flaring. The effect of key parameters on the emission output is also shown. CO2, CO, NO, NO2 and SO2 are the anticipated non-hydrocarbon emissions of environmental concern. Results show that the quantity and pattern of these chemical species depended on percentage excess/deficiency of stoichiometric air, natural gas type, reaction type, carbon mass content, impurities, combustion efficiency of the flare system etc. These emissions degrade the environment and human life, so knowing the emission types, pattern and flaring conditions that this study predicts is of paramount importance to governments, environmental agencies and the oil and gas industry.

  10. Theoretical Study on Catalyst Activation of Palladacycles in Heck Reaction

    Institute of Scientific and Technical Information of China (English)

    WANG Chen; FU Yao; LI Zhe; GUO Qing-Xiang

    2008-01-01

    A computational study with the B3PW91 density functional theory was carried out on the activation process of palladacycles as catalysts in the Heck reaction.Two possible pathways (i.e.anion reductive cleavage of the Pd-C bond,and olefin insertion into the Pd-C bond followed by β-H elimination)were taken into consideration.Computational results indicate that the palladacycles are activated via olefin insertion into the Pd-C bond followed by β-H elimination in the reaction conditions.

  11. Studies on the cyclization reaction of D-aspartic acid

    Institute of Scientific and Technical Information of China (English)

    Yu Chuan Li; Si Ping Pang; Yong Zhong Yu

    2007-01-01

    The cyclization reaction of D-aspartic acid was studied, the carboxyl groups of D-aspartic acid were protected by benzyl alcohol to give compound D-dibenzyl aspartate. Then (4R)-benzyl azetidine-2-one-4-carboxylate and meso-3,6-disubstituted piperazine2,5-diones were synthesized via intramolecular cyclization and intermolecular cyclization of D-dibenzyl aspartate, respectively, and their structures were confirmed by 1H NMR and MS. Both cyclization reaction conditions were also investigated in detail.

  12. Theoretical studies of the reaction e+ e- --> K+ K- gamma

    CERN Document Server

    Lesniak, Leonard

    2016-01-01

    We present studies of the e+ e- --> K+ K- gamma reaction for the e+e- center-of-mass energies close to the phi(1020) meson mass. Different mechanisms leading to the final state are considered. The strong interaction amplitudes of the K+K- pairs in the S-wave are taken into account. In addition, the photon emission in the initial state, the final state radiation effects and all the possible interference terms are included in the transition matrix elements. The K+K- effective mass distributions and the angular dependence of the reaction cross-section are calculated.

  13. Reactions of aqueous chlorine and chlorine dioxide with model food compounds

    Energy Technology Data Exchange (ETDEWEB)

    Fukayama, M.Y.; Tan, H.; Wheeler, W.B.; Wei, C.

    1986-11-01

    This presentation reviews published information concerning the reactions of chlorine gas (CL/sub 2/(g)), aqueous chlorine, and ClO/sub 2/ with model food compounds, the fate of chlorine during the chlorination of specific food products, and the potential toxicity of the reaction products. Fatty acids and their methyl esters react with chlorine with the degree of incorporation corresponding to their degree of unsaturation. Aqueous chlorine oxidizes and chlorinates lipids and amino acids much more readily than ClO/sub 2/. Several amino acids are highly susceptible to oxidation and chlorination by chlorine compounds. Reactions of chlorine and ClO/sub 2/ with several food products, including flour and shrimp, have also been characterized. Although significant quantities of chlorine can be incorporated into specific model compounds and food products, the health risks associated with exposure to chlorinated organic products are unknown. Preliminary studies using the Ames Salmonella/microsome mutagenicity assay indicate that the reaction products from mixtures of aqueous chlorine and various lipids or tryptophan are nonmutagenic. Nevertheless, additional studies are warranted, so that the toxicological significance of these reaction products can be understood more fully.

  14. Study of Daedalus Interstellar Spacecraft Reaction Chamber and Thrust Structure

    Science.gov (United States)

    Reddy, S. K.; Benaroya, H.

    Project Daedalus was the 1978 trade study that proved the feasibility of space travel utilizing fusion-based propulsion (Inertial Confinement Fusion). This paper analyzes some of the key structural aspects of the Daedalus spacecraft, in particular, the reaction chamber and thrust structure that is integral to the Daedalus spacecraft, which supports the loads resulting from the fusion reactions. First, the reaction chamber is studied computationally in terms of static loading and vibrational characteristics utilizing the finite element method. Next, a proposed bracing system is integrated into the reaction chamber and the effects are studied. Lastly, the field coils with their supporting truss structure are added to the assembly. Concepts are introduced for actuators and course-correction mechanisms that ensure the spacecraft maintains the required trajectory to rendezvous with the target system. Present-day materials and manufacturing considerations are explored based on the assumptions made in the Daedalus study. Testing, qualification, and assembly of the spacecraft are also discussed. This paper is a summary of the first author's Master's Thesis at Rutgers University.

  15. [The contamination under polymerase chain reaction studies: problems and solutions].

    Science.gov (United States)

    Titov, V N; Ameliushkina, V A; Rozhkova, T A

    2015-01-01

    The study was carried out to determine risk factors of false positive and false negative results under polymerase chain reaction-analysis of clinical material. The samples with high viral load can be the source of false positive results. The contamination with nucleic acids can occur at any section of polymerase chain reaction analysis. The study data permitted to establish that the most sensitive stage is isolation and purification of nucleic acids especially under manual mode of operation. The detection of positive signal in most samples of one setting indicates total contamination. The cases when only several samples are polluted are special challenge. The presence of sample with high concentration of viral nucleic acid and several samples with low concentration in one setting means necessity of repeated analysis beginning with stage of isolation of nucleic acid. The analysis of curves of accumulation of products of amplification, their forms and positioning on chart is the obligatory stage of polymerase chain reaction study in real time regimen. These actions permit to exclude the readouts of false negative testing results to departments. The study conclusions are equipotent for polymerase chain reaction testing of any nucleic acid targets.

  16. Sum Frequency Generation Studies of Hydrogenation Reactions on Platinum Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Krier, James M. [Univ. of California, Berkeley, CA (United States)

    2013-08-31

    Sum Frequency Generation (SFG) vibrational spectroscopy is used to characterize intermediate species of hydrogenation reactions on the surface of platinum nanoparticle catalysts. In contrast to other spectroscopy techniques which operate in ultra-high vacuum or probe surface species after reaction, SFG collects information under normal conditions as the reaction is taking place. Several systems have been studied previously using SFG on single crystals, notably alkene hydrogenation on Pt(111). In this thesis, many aspects of SFG experiments on colloidal nanoparticles are explored for the first time. To address spectral interference by the capping agent (PVP), three procedures are proposed: UV cleaning, H2 induced disordering and calcination (core-shell nanoparticles). UV cleaning and calcination physically destroy organic capping while disordering reduces SFG signal through a reversible structural change by PVP.

  17. NATO Advanced Study Institute on Advances in Chemical Reaction Dynamics

    CERN Document Server

    Capellos, Christos

    1986-01-01

    This book contains the formal lectures and contributed papers presented at the NATO Advanced Study Institute on. the Advances in Chemical Reaction Dynamics. The meeting convened at the city of Iraklion, Crete, Greece on 25 August 1985 and continued to 7 September 1985. The material presented describes the fundamental and recent advances in experimental and theoretical aspects of, reaction dynamics. A large section is devoted to electronically excited states, ionic species, and free radicals, relevant to chemical sys­ tems. In addition recent advances in gas phase polymerization, formation of clusters, and energy release processes in energetic materials were presented. Selected papers deal with topics such as the dynamics of electric field effects in low polar solutions, high electric field perturbations and relaxation of dipole equilibria, correlation in picosecond/laser pulse scattering, and applications to fast reaction dynamics. Picosecond transient Raman spectroscopy which has been used for the elucidati...

  18. (n,xn γ reaction cross section measurements for (n,xn reaction studies

    Directory of Open Access Journals (Sweden)

    Rouki Chariklia

    2013-03-01

    Full Text Available In the context of improvement of nuclear data bases for future nuclear reactor researches, we study (n,xn reactions experimentally with the help of the (n,xn γ technique. The experiments are performed at the GELINA facility which delivers a pulsed, white neutron beam. Several measurement campaigns have been performed on 235U, 232Th, 182,183,184,186W and 238U isotopes. A compilation of all these experimental cross sections (mostly still preliminary compared to theoretical predictions will be discussed.

  19. Piecewise linear and Boolean models of chemical reaction networks

    Science.gov (United States)

    Veliz-Cuba, Alan; Kumar, Ajit; Josić, Krešimir

    2014-01-01

    Models of biochemical networks are frequently complex and high-dimensional. Reduction methods that preserve important dynamical properties are therefore essential for their study. Interactions in biochemical networks are frequently modeled using Hill functions (xn/(Jn + xn)). Reduced ODEs and Boolean approximations of such model networks have been studied extensively when the exponent n is large. However, while the case of small constant J appears in practice, it is not well understood. We provide a mathematical analysis of this limit, and show that a reduction to a set of piecewise linear ODEs and Boolean networks can be mathematically justified. The piecewise linear systems have closed form solutions that closely track those of the fully nonlinear model. The simpler, Boolean network can be used to study the qualitative behavior of the original system. We justify the reduction using geometric singular perturbation theory and compact convergence, and illustrate the results in network models of a toggle switch and an oscillator. PMID:25412739

  20. Piecewise linear and Boolean models of chemical reaction networks.

    Science.gov (United States)

    Veliz-Cuba, Alan; Kumar, Ajit; Josić, Krešimir

    2014-12-01

    Models of biochemical networks are frequently complex and high-dimensional. Reduction methods that preserve important dynamical properties are therefore essential for their study. Interactions in biochemical networks are frequently modeled using Hill functions ([Formula: see text]). Reduced ODEs and Boolean approximations of such model networks have been studied extensively when the exponent [Formula: see text] is large. However, while the case of small constant [Formula: see text] appears in practice, it is not well understood. We provide a mathematical analysis of this limit and show that a reduction to a set of piecewise linear ODEs and Boolean networks can be mathematically justified. The piecewise linear systems have closed-form solutions that closely track those of the fully nonlinear model. The simpler, Boolean network can be used to study the qualitative behavior of the original system. We justify the reduction using geometric singular perturbation theory and compact convergence, and illustrate the results in network models of a toggle switch and an oscillator.

  1. Neutron Scattering in Hydrogenous Moderators, Studied by Time Dependent Reaction Rate Method

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, L.G.; Moeller, E.; Purohit, S.N.

    1966-03-15

    The moderation and absorption of a neutron burst in water, poisoned with the non-1/v absorbers cadmium and gadolinium, has been followed on the time scale by multigroup calculations, using scattering kernels for the proton gas and the Nelkin model. The time dependent reaction rate curves for each absorber display clear differences for the two models, and the separation between the curves does not depend much on the absorber concentration. An experimental method for the measurement of infinite medium reaction rate curves in a limited geometry has been investigated. This method makes the measurement of the time dependent reaction rate generally useful for thermalization studies in a small geometry of a liquid hydrogenous moderator, provided that the experiment is coupled to programs for the calculation of scattering kernels and time dependent neutron spectra. Good agreement has been found between the reaction rate curve, measured with cadmium in water, and a calculated curve, where the Haywood kernel has been used.

  2. Study of the {sup 7}Be(p,{gamma}){sup 8}B and {sup 7}Li(n,{gamma}){sup 8}Li capture reactions using the shell model embedded in the continuum

    Energy Technology Data Exchange (ETDEWEB)

    Bennaceur, K.; Ploszajczak, M. [Grand Accelerateur National d`Ions Lourds (GANIL), 14 - Caen (France); Nowacki, F. [Grand Accelerateur National d`Ions Lourds (GANIL), 14 - Caen (France)]|[Strasbourg-1 Univ., 67 (France). Lab. de Physique Theorique; Okolowicz, J. [Grand Accelerateur National d`Ions Lourds (GANIL), 14 - Caen (France)]|[Institute of Nuclear Physics, Krakow (Poland)

    1999-02-01

    The realistic shell model which includes the coupling between many-particle (quasi-)bound states and the continuum of one-particle scattering states is applied to the spectroscopy of mirror nuclei: {sup 8}B and {sup 8}Li, as well as to the description of low energy cross sections (the astrophysical S factors) in the capture reactions: {sup 7}Be(p,{gamma}){sup 8}B and {sup 7}Li(n,{gamma}){sup 8}Li. (author) 49 refs.

  3. (Process Models of Counselor Judgment: Proposal and Reactions.)

    Science.gov (United States)

    Strohmer, Douglas C.; And Others

    1982-01-01

    Studied competing process models of counselors' clinical judgment for their capacity to account for variance in prognostic judgments and further tested for parsimony. Patton discusses problems of logic and data analysis in the model's formulation. Provides Stromer's response to the critique. (RC)

  4. (Process Models of Counselor Judgment: Proposal and Reactions.)

    Science.gov (United States)

    Strohmer, Douglas C.; And Others

    1982-01-01

    Studied competing process models of counselors' clinical judgment for their capacity to account for variance in prognostic judgments and further tested for parsimony. Patton discusses problems of logic and data analysis in the model's formulation. Provides Stromer's response to the critique. (RC)

  5. CLINICOPATHOLOGICAL STUDY OF LICHENOID REACTIONS: A RETROSPECTIVE ANALYSIS

    Directory of Open Access Journals (Sweden)

    Ravikant

    2015-04-01

    Full Text Available BACKGROUND: Lichenoid dermatose s refer to various, clinically different inflammatory dermatoses which share in common, various essential lichenoid histologic features. AIMS AND OBJECTIVE: In this study we have analysed the different clinicopathological aspects in lichenoid reactions, as prompt diagnosis of these lesions can greatly influence the morbidity associated with the disease. STUDY DESIGN: This was a 14 month retrospective analysis of cases presenting to the department of dermatology from June 2013 till July 2014. MATERIALS AND METHODS: All new patients diagnosed with lichenoid reaction clinically and histopathologically were included in the study. INCLUSION CRITERIA: All newly diagnosed cases of Lichenoid tissue reactions within the time period mentioned above . EXCLUSION CRITERI A: Patients whose adequate records were unavailable Statistical Analysis: The SPSS, version 13 software was used to statistically analyse the data. RESULTS: A total of 66 cases were diagnosed as lichenoid reactions, 51 were lichen planus and 15 had licheno id eruptions. Males (53% were more commonly affected than female s (47%, with lower limbs (69. 69% being the most common site of predilection. Oral lesions were seen among eleven patients. Histopathologically, the most consistent findings with lichenoid r eaction was the presence of a lymphocytic infiltrate followed by vacuolar degeneration of basal cell layer, hyperkeratosis, hypergranulosis, acanthosis, pigment incontinence and a band like infiltrate over the basal layer. CONCLUSION: In our study, Licheno id reactions were more common among adults from the 2 nd to 4 th decade and can show ed a male preponderance, with the most frequent archetype being lichen planus. Thus this study emphasises on the need of histological analysis in various clinically similar c ases of lichenoid dermatoses in order to arrive at a definitive diagnosis.

  6. Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

    Science.gov (United States)

    Scott, Carl D.; Farhat, Samir; Greendyke, Robert B.

    2004-01-01

    The development of processes to produce fullerenes and carbon nanotubes has largely been empirical. Fullerenes were first discovered in the soot produced by laser ablation of graphite [1]and then in the soot of electric arc evaporated carbon. Techniques and conditions for producing larger and larger quantities of fullerenes depended mainly on trial and error empirical variations of these processes, with attempts to scale them up by using larger electrodes and targets and higher power. Various concepts of how fullerenes and carbon nanotubes were formed were put forth, but very little was done based on chemical kinetics of the reactions. This was mainly due to the complex mixture of species and complex nature of conditions in the reactors. Temperatures in the reactors varied from several thousand degrees Kelvin down to near room temperature. There are hundreds of species possible, ranging from atomic carbon to large clusters of carbonaceous soot, and metallic catalyst atoms to metal clusters, to complexes of metals and carbon. Most of the chemical kinetics of the reactions and the thermodynamic properties of clusters and complexes have only been approximated. In addition, flow conditions in the reactors are transient or unsteady, and three dimensional, with steep spatial gradients of temperature and species concentrations. All these factors make computational simulations of reactors very complex and challenging. This article addresses the development of the chemical reaction involved in fullerene production and extends this to production of carbon nanotubes by the laser ablation/oven process and by the electric arc evaporation process. In addition, the high-pressure carbon monoxide (HiPco) process is discussed. The article is in several parts. The first one addresses the thermochemical aspects of modeling; and considers the development of chemical rate equations, estimates of reaction rates, and thermodynamic properties where they are available. The second part

  7. The reaction between iodine and organic coatings under severe PWR accident conditions. An experimental parameter study

    Energy Technology Data Exchange (ETDEWEB)

    Hellmann, S.; Funke, F.; Greger, G.U.; Bleier, A.; Morell, W. [Siemens AG, Power Generation Group, Erlangen (Germany)

    1996-12-01

    An extensive experimental parameter study was performed on the deposition and on the resuspension kinetics in the reaction system iodine/organically coated surfaces. Both reactions in the gas phase and in the liquid phase were investigated and kinetic rate constants suitable for modelling were derived. Previous experimental studies on the reaction of iodine with organic coated surfaces were mostly limited to temperatures below 100{sup o}C. Thus, this parameter study aims at filling a gap and providing kinetic data on heterogeneous reactions with organic surfaces in the accident-relevant temperature range of 100-160{sup o}C. Two types of laboratory experiments carried out at Siemens/KWU using coatings representative for German power plants (epoxy-tape paint), namely gas phase tests and liquid phase tests. (author) 6 figs., 6 tabs., 5 refs.

  8. Multiphasic Reaction Modeling for Polypropylene Production in a Pilot-Scale Catalytic Reactor

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-06-01

    Full Text Available In this study, a novel multiphasic model for the calculation of the polypropylene production in a complicated hydrodynamic and the physiochemical environments has been formulated, confirmed and validated. This is a first research attempt that describes the development of the dual-phasic phenomena, the impact of the optimal process conditions on the production rate of polypropylene and the fluidized bed dynamic details which could be concurrently obtained after solving the model coupled with the CFD (computational fluid dynamics model, the basic mathematical model and the moment equations. Furthermore, we have established the quantitative relationship between the operational condition and the dynamic gas–solid behavior in actual reaction environments. Our results state that the proposed model could be applied for generalizing the production rate of the polymer from a chemical procedure to pilot-scale chemical reaction engineering. However, it was assumed that the solids present in the bubble phase and the reactant gas present in the emulsion phase improved the multiphasic model, thus taking into account that the polymerization took place mutually in the emulsion besides the bubble phase. It was observed that with respect to the experimental extent of the superficial gas velocity and the Ziegler-Natta feed rate, the ratio of the polymer produced as compared to the overall rate of production was approximately in the range of 9%–11%. This is a significant amount and it should not be ignored. We also carried out the simulation studies for comparing the data of the CFD-dependent dual-phasic model, the emulsion phase model, the dynamic bubble model and the experimental results. It was noted that the improved dual-phasic model and the CFD model were able to predict more constricted and safer windows at similar conditions as compared to the experimental results. Our work is unique, as the integrated developed model is able to offer clearer ideas

  9. Mathematical modelling of light-induced electric reaction of Cucurbita pepo L. leaves

    Directory of Open Access Journals (Sweden)

    Jan Stolarek

    2014-01-01

    Full Text Available The bioelectRIc reactions of 14-16 day old plants of pumpkin (Cucurbita pepo L. and internodal cells of Nitellopsis obtusa to the action of visible and ultraviolet light (UV-C were studied. The possibility of analyzing the bioelectric reaction of pumpkin plants induced by visible light by means of mathematical modelling using a linear differential equation of the second order was considered. The solution of this equation (positive and negative functions can, in a sufficient way, reflect the participation of H+ and CI- ions in the generation of the photoelectric response in green plant cells.

  10. Instability Criterion of One-Dimensional Detonation Wave with Three-Step Chain Branching Reaction Model

    Institute of Scientific and Technical Information of China (English)

    TENG Hong-Hui; JIANG Zong-Lin

    2011-01-01

    @@ One-dimensional detonation waves are simulated with the three-step chain branching reaction model, and the instability criterion is studied.The ratio of the induction zone length and the reaction zone length may be used to decide the instability, and the detonation becomes unstable with the high ratio.However, the ratio is not invariable with different heat release values.The critical ratio, corresponding to the transition from the stable detonation to the unstable detonation, has a negative correlation with the heat release.An empirical relation of the Chapman-Jouguet Mach number and the length ratio is proposed as the instability criterion.

  11. A combined experimental, theoretical, and Van't Hoff model study for identity methyl, proton, hydrogen atom, and hydride exchange reactions. Correlation with three-center four-, three-, and two-electron systems

    Science.gov (United States)

    Buck, Henk M.

    We have studied carbon transfer reactions following an SN2 reaction profile. With ab initio calculations and experimental geometries concerning the nature of the various complexes indicated as stable, intermediate, and transition state we were able to show the additional value of van't Hoff's tetrahedral configuration by changing its geometry via a trigonal pyramid into a trigonal bipyramid. The ratio of the apical bond and corresponding tetrahedral bond distances is then nearly 1.333. The relevance of this approach has also been shown for identity proton-(hydrogen atom-, and hydride-) in-line reactions. The use of this geometrical transmission will be demonstrated for the hydrogen bonding distances in e.g., DNA duplexes and other biological (supra) molecular systems.

  12. Synthesis of superheavy elements: Uncertainty analysis to improve the predictive power of reaction models

    Science.gov (United States)

    Lü, Hongliang; Boilley, David; Abe, Yasuhisa; Shen, Caiwan

    2016-09-01

    Background: Synthesis of superheavy elements is performed by heavy-ion fusion-evaporation reactions. However, fusion is known to be hindered with respect to what can be observed with lighter ions. Thus some delicate ambiguities remain on the fusion mechanism that eventually lead to severe discrepancies in the calculated formation probabilities coming from different fusion models. Purpose: In the present work, we propose a general framework based upon uncertainty analysis in the hope of constraining fusion models. Method: To quantify uncertainty associated with the formation probability, we propose to propagate uncertainties in data and parameters using the Monte Carlo method in combination with a cascade code called kewpie2, with the aim of determining the associated uncertainty, namely the 95 % confidence interval. We also investigate the impact of different models or options, which cannot be modeled by continuous probability distributions, on the final results. An illustrative example is presented in detail and then a systematic study is carried out for a selected set of cold-fusion reactions. Results: It is rigorously shown that, at the 95 % confidence level, the total uncertainty of the empirical formation probability appears comparable to the discrepancy between calculated values. Conclusions: The results obtained from the present study provide direct evidence for predictive limitations of the existing fusion-evaporation models. It is thus necessary to find other ways to assess such models for the purpose of establishing a more reliable reaction theory, which is expected to guide future experiments on the production of superheavy elements.

  13. Scaffolding Students' Online Critiquing of Expert- and Peer-generated Molecular Models of Chemical Reactions

    Science.gov (United States)

    Chang, Hsin-Yi; Chang, Hsiang-Chi

    2013-08-01

    In this study, we developed online critiquing activities using an open-source computer learning environment. We investigated how well the activities scaffolded students to critique molecular models of chemical reactions made by scientists, peers, and a fictitious peer, and whether the activities enhanced the students' understanding of science models and chemical reactions. The activities were implemented in an eighth-grade class with 28 students in a public junior high school in southern Taiwan. The study employed mixed research methods. Data collected included pre- and post-instructional assessments, post-instructional interviews, and students' electronic written responses and oral discussions during the critiquing activities. The results indicated that these activities guided the students to produce overall quality critiques. Also, the students developed a more sophisticated understanding of chemical reactions and scientific models as a result of the intervention. Design considerations for effective model critiquing activities are discussed based on observational results, including the use of peer-generated artefacts for critiquing to promote motivation and collaboration, coupled with critiques of scientific models to enhance students' epistemological understanding of model purpose and communication.

  14. Test of statistical model cross section calculations for $\\alpha$-induced reactions on $^{107}$Ag at energies of astrophysical interest

    CERN Document Server

    Yalcin, C; Rauscher, T; Kiss, G G; Özkan, N; Güray, R T; Halász, Z; Szücs, T; Fülöp, Zs; Korkulu, Z; Somorjai, E

    2015-01-01

    Astrophysical reaction rates, which are mostly derived from theoretical cross sections, are necessary input to nuclear reaction network simulations for studying the origin of $p$ nuclei. Past experiments have found a considerable difference between theoretical and experimental cross sections in some cases, especially for ($\\alpha$,$\\gamma$) reactions at low energy. Therefore, it is important to experimentally test theoretical cross section predictions at low, astrophysically relevant energies. The aim is to measure reaction cross sections of $^{107}$Ag($\\alpha$,$\\gamma$)$^{111}$In and $^{107}$Ag($\\alpha$,n)$^{110}$In at low energies in order to extend the experimental database for astrophysical reactions involving $\\alpha$ particles towards lower mass numbers. Reaction rate predictions are very sensitive to the optical model parameters and this introduces a large uncertainty into theoretical rates involving $\\alpha$ particles at low energy. We have also used Hauser-Feshbach statistical model calculations to s...

  15. Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

    Science.gov (United States)

    Ding, Liangbing; Xiong, Feng; Jin, Yuekang; Wang, Zhengming; Sun, Guanghui; Huang, Weixin

    2016-11-30

    CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

  16. An automatic modeling system of the reaction mechanisms for chemical vapor deposition processes using real-coded genetic algorithms.

    Science.gov (United States)

    Takahashi, Takahiro; Nakai, Hiroyuki; Kinpara, Hiroki; Ema, Yoshinori

    2011-09-01

    The identification of appropriate reaction models is very helpful for developing chemical vapor deposition (CVD) processes. In this study, we have developed an automatic system to model reaction mechanisms in the CVD processes by analyzing the experimental results, which are cross-sectional shapes of the deposited films on substrates with micrometer- or nanometer-sized trenches. We designed the inference engine to model the reaction mechanism in the system by the use of real-coded genetic algorithms (RCGAs). We studied the dependence of the system performance on two methods using simple genetic algorithms (SGAs) and the RCGAs; the one involves the conventional GA operators and the other involves the blend crossover operator (BLX-alpha). Although we demonstrated that the systems using both the methods could successfully model the reaction mechanisms, the RCGAs showed the better performance with respect to the accuracy and the calculation cost for identifying the models.

  17. Spontaneous monitoring of adverse reactions to drugs by Italian dermatologists: a pilot study. Gruppo Italiano Studi Epidemiologici in Dermatologia.

    Science.gov (United States)

    1991-01-01

    During 1988, the Gruppo Italiano Studi Epidemiologici in Dermatologia (GISED) coordinated a pilot study aimed at evaluating the feasibility of a system for spontaneous monitoring of adverse drug reactions in dermatological practice in Italy. Approximately 400 dermatologists were asked to collaborate, and 141 agreed to the study. Procedures similar to those well established in other surveillance programs (including the use of standard forms and standardized assessment procedure) were adopted. In a 2-month period 775 reports were collected, of which 711 were maintained after careful evaluation. The general profile of the adverse reactions reported was in accordance with the experience derived by other spontaneous surveillance programs. The main purpose of spontaneous reporting systems is the identification of new reactions, and a model analysis was proposed, in our study, with reference to skin reactions to bamifylline. The demonstration of the feasibility of a drug-monitoring program in Italy, where little tradition exists in the area, is the most important result of our study.

  18. Generic Model-Based Tailor-Made Design and Analysis of Biphasic Reaction Systems

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata

    contribution of this thesis is the development of a systematic modelling framework for the biphasic reaction system. The developed framework consists of three modules describing phase equilibria, reactions and mass transfer, and material balances of such processes. Correlative and predictive thermodynamic......-elementary reaction rate laws. Extents of reaction are used to calculate the species material balances. The resulting mathematical model contains temperature dependent reaction rate parameters,equilibrium constants, and partition coefficients; where only the reaction rates are to be regressed to a minimum of time...

  19. Modeling and Fuzzy Logic Control of an Active Reaction Compensating Platform System

    Directory of Open Access Journals (Sweden)

    Y.J. Lin

    1995-01-01

    Full Text Available This article presents the application of the fuzzy logic (FL concept to the active control of a multiple degree of freedom reaction compensating platform system that is designed and used for isolating vibratory disturbances of space-based devices. The physical model used is a scaled down two-plate platform system. In this work, simulation is performed and presented. According to the desired performance specifications, a full range of investigation regarding the development of an FL stabilization controller for the system is conducted. Specifically, the study includes four stages: comprehensive dynamic modeling of the reaction compensating system; analysis of the dynamic responses of the platform system when it is subjected to various disturbances; design of an FL controller capable of filtering the vibratory disturbances transmitted to the bottom plate of the platform system; performance evaluation of the developed FL controller through computer simulations. To simplify the simulation work, the system model is linearized and the system component parameter variations are not considered. The performance of the FL controller is tested by exciting the system with an impulsive force applied at an arbitrarily chosen point on the top plate. It is shown that the proposed FL controller is robust in that the resultant active system is well stabilized when subjected to a random external disturbance. The comparative study of the performances of the FL controlled active reaction and passive reaction compensating systems also reveals that the FL controlled system achieves significant improvements in reducing vibratory accelerations over passive systems.

  20. Refractory-Slag-Metal-Inclusion Multiphase Reactions Modeling Using Computational Thermodynamics: Kinetic Model for Prediction of Inclusion Evolution in Molten Steel

    Science.gov (United States)

    Shin, Jae Hong; Chung, Yongsug; Park, Joo Hyun

    2017-02-01

    The refractory-slag-metal-inclusion multiphase reaction model was developed by integrating the refractory-slag, slag-metal, and metal-inclusion elementary reactions in order to predict the evolution of inclusions during the secondary refining processes. The mass transfer coefficient in the metal and slag phase, and the mass transfer coefficient of MgO in the slag were employed in the present multiphase reactions modeling. The "Effective Equilibrium Reaction Zone (EERZ) Model" was basically employed. In this model, the reaction zone volume per unit step for metal and slag phase, which is dependent on the `effective reaction zone depth' in each phase, should be defined. Thus, we evaluated the effective reaction zone depth from the mass transfer coefficient in metal and slag phase at 1873 K (1600 °C) for the desulfurization reaction which was measured in the present study. Because the dissolution rate of MgO from the refractory to slag phase is one of the key factors affecting the slag composition, the mass transfer coefficient of MgO in the ladle slag was also experimentally determined. The calculated results for the variation of the composition of slag and molten steel as a function of reaction time were in good agreement with the experimental results. The MgAl2O4 spinel inclusion was observed at the early to middle stage of the reaction, whereas the liquid oxide inclusion was mainly observed at the final stage of the refining reaction. The content of CaO sharply increased, and the SiO2 content increased mildly with the increasing reaction time, while the content of Al2O3 in the inclusion drastically decreased. Even though there is slight difference between the calculated and measured results, the refractory-slag-metal multiphase reaction model constructed in the present study exhibited a good predictability of the inclusion evolution during ladle refining process.

  1. Study on the Reaction Mechanism of Naphthalene with Oxalyl Chloride

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The reaction of naphthalene with oxalyl chloride in the presence of anhydrous AlCl3 was investigated. The homolog of dinaphthyl methanone can be obtained mainly from this reaction. Naphthalene conversion does not have evident correlation with the amount of AlCl3. The results show that the reaction proceeds via carbon cation electrophilic substitution reaction-free radical substitution reaction pathway.

  2. A thermochemical model for shock-induced reactions (heat detonations) in solids

    Energy Technology Data Exchange (ETDEWEB)

    Boslough, M.B. (Sandia National Laboratories, Albuquerque, New Mexico 87185 (US))

    1990-02-01

    Recent advances in studies of shock-induced chemistry in reactive solids have led to the recognition of a new class of energetic materials which are unique in their response to shock waves. Experimental work has shown that chemical energy can be released on a time scale shorter than shock-transit times in laboratory samples. However, for many compositions, the reaction products remain in the condensed state upon release from high pressure, and no sudden expansion takes place. Nevertheless, if such a reaction is sufficiently rapid, it can be modeled as a type of detonation, termed heat detonation'' in the present paper. It is shown that unlike an explosive detonation, an unsupported heat detonation will decay to zero unless certain conditions are met. An example of such a reaction is Fe{sub 2}O{sub 3} +2Al+shock{r arrow}Al{sub 2} O{sub 3} +2Fe (the standard thermite reaction). A shock-wave equation of state is determined from a mixture theory for reacted and unreacted porous thermite. The calculated shock temperatures are compared to experimentally measured shock temperatures, demonstrating that a shock-induced reaction takes place. Interpretation of the measured temperature history in the context of the thermochemical model implies that the principal rate-controlling kinetic mechanism is dynamic mixing at the shock front. Despite the similarity in thermochemical modeling of heat detonations to explosive detonations, the two processes are qualitatively very different in reaction mechanism as well as in the form the energy takes upon release, with explosives producing mostly work and heat detonations producing mostly heat.

  3. Kinetic study of free fatty acid esterification reaction catalyzed by recoverable and reusable hydrochloric acid.

    Science.gov (United States)

    Su, Chia-Hung

    2013-02-01

    The catalytic performance and recoverability of several homogeneous acid catalysts (hydrochloric, sulfuric, and nitric acids) for the esterification of enzyme-hydrolyzed free fatty acid (FFA) and methanol were studied. Although all tested catalysts drove the reaction to a high yield, hydrochloric acid was the only catalyst that could be considerably recovered and reused. The kinetics of the esterification reaction catalyzed by hydrochloric acid was investigated under varying catalyst loading (0.1-1M), reaction temperature (303-343K), and methanol/FFA molar ratio (1:1-20:1). In addition, a pseudo-homogeneous kinetic model incorporating the above factors was developed. A good agreement (r(2)=0.98) between the experimental and calculated data was obtained, thus proving the reliability of the model. Furthermore, the reusability of hydrochloric acid in FFA esterification can be predicted by the developed model. The recoverable hydrochloric acid achieved high yields of FFA esterification within five times of reuse.

  4. Crossed-beam studies of the dynamics of radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Liu, K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    The objective of this program is to characterize the detailed dynamics of elementary radical reactions and to provide a better understanding of radical reactivity in general. The radical beam is typically generated by a laser photolysis method. After colliding with the reacting molecule in a crossed-beam apparatus, the reaction product state distribution is interrogated by laser spectroscopic techniques. Several radicals of combustion significance, such as O, CH, OH, CN and NCO have been successfully generated and their collisional behavior at the state-to-state integral cross section level of detail has been studied in this manner. During the past year, the detection system has been converted from LIF to REMPI schemes, and the emphasis of this program shifted to investigate the product angular distributions. Both inelastic and reactive processes have been studied.

  5. Contribution to the modelling of gas-solid reactions and reactors; Contribution a la modelisation des reactions et des reacteurs gaz-solide

    Energy Technology Data Exchange (ETDEWEB)

    Patisson, F

    2005-09-15

    Gas-solid reactions control a great number of major industrial processes involving matter transformation. This dissertation aims at showing that mathematical modelling is a useful tool for both understanding phenomena and optimising processes. First, the physical processes associated with a gas-solid reaction are presented in detail for a single particle, together with the corresponding available kinetic grain models. A second part is devoted to the modelling of multiparticle reactors. Different approaches, notably for coupling grain models and reactor models, are illustrated through various case studies: coal pyrolysis in a rotary kiln, production of uranium tetrafluoride in a moving bed furnace, on-grate incineration of municipal solid wastes, thermogravimetric apparatus, nuclear fuel making, steel-making electric arc furnace. (author)

  6. Improved Quantum Molecular Dynamics Model and its Application to Fusion Reaction Near Barrier

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    An improved quantum molecular dynamics model is proposed. By using this model, the properties of ground state of nuclei from 6Li to 208Pb can be described very well with one set of parameters. The fusion reactions for 40Ca+90Zr, 40Ca+96Zr and 48Ca+90Zr at the energy near the barrier are studied by this model. The experimental data of the fusion cross sections for 40Ca+90,96Zr at the energy near the barrier can be reproduced remarkably well without introducing any new parameters. The mechanism

  7. First-principles modeling of catalysts: novel algorithms and reaction mechanisms

    Science.gov (United States)

    Richard, Bryan Goldsmith

    A molecular level understanding of a reaction mechanism and the computation of rates requires knowledge of the stable structures and the corresponding transition states that connect them. Temperature, pressure, and environment effects must be included to bridge the 'materials gap' so one can reasonably compare ab initio (first-principles, i.e., having no empirical parameters) predictions with experimental measurements. In this thesis, a few critical problems pertaining to ab initio modeling of catalytic systems are addressed; namely, 1) the issue of building representative models of isolated metal atoms grafted on amorphous supports, 2) modeling inorganic catalytic reactions in non-ideal solutions where the solvent participates in the reaction mechanism, and 3) bridging the materials gap using ab initio thermodynamics to predict the stability of supported nanoparticles under experimental reaction conditions. In Chapter I, a background on first-principles modeling of heterogeneous and homogenous catalysts is provided. Subsequently, to address the problem of modeling catalysis by isolated metal atoms on amorphous supports, we present in Chapter II a sequential-quadratic programming algorithm that systematically predicts the structure and reactivity of isolated active sites on insulating amorphous supports. Modeling solution phase reactions is also a considerable challenge for first-principles modeling, yet when done correctly it can yield critical kinetic and mechanistic insight that can guide experimental investigations. In Chapter III, we examine the formation of peroxorhenium complexes by activation of H2O2, which is key in selective oxidation reactions catalyzed by CH3ReO3 (methyltrioxorhenium, MTO). New experiments and density functional theory (DFT) calculations were conducted to better understand the activation of H2O2 by MTO and to provide a strong experimental foundation for benchmarking computational studies involving MTO and its derivatives. It was found

  8. Theoretical Study of Reaction Mechanism of 1-Propenyl Radical with NO

    Institute of Scientific and Technical Information of China (English)

    Xue-li Cheng; Yan-yun Zhao; Feng Li; Ren-tao Wu

    2008-01-01

    The reaction system of 1-propenyl radical with NO is an ideal model for studying the intermolecu- lax and intramolecular reactions of complex organic free radicals containing C=C double bonds. On the basis of the full optimization of all species with the Gaussian 98 package at the B3LYP/6- 311++G** level, the reaction mechanism was elucidated extensively using the vibrational mode analy- sis. There are seven reaction pathways and five sets of small molecule end products: CH2O+CH3CN, CH2CHCN+H2O, CH3CHO+HCN, CH3CHO+HNC, and CH3CCH+HNO. The channel of C3H5·+NO→IM1→TS1→IM2→TS2→IM3→TS3→CH3CHO+HCN is thermodynamically most favorable.

  9. An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

    Science.gov (United States)

    Kemppainen, Erno; Halme, Janne; Lund, Peter D

    2016-05-11

    Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells.

  10. Reaction Between Thin Gold Wires and Pb-Sn-In Solder (37.5%, 37.5%, 25%), Part A: The Radial Reaction Inside The Solder Mounds, Its Linear Reaction Model, Statistical Variation of Reaction Rate, and Induced Structural Changes In The Solder Mounds.

    Energy Technology Data Exchange (ETDEWEB)

    Siekhaus, W J

    2011-01-19

    Thermodynamics favors the reaction between indium and gold, since the heat of formation of AuIn{sub 2} is 6 kcal/mole, substantially larger than the heat of formation of any other possible reaction product. Thermodynamic equilibrium between gold and the elements in the solder mound is reached only when ALL gold is converted to AuIn{sub 2}. There are two aspects to this conversion: (A) the reaction WITHIN the solder mound (called here 'radial reaction') and (B) the reaction OUTSIDE the solder mound (called here 'axial reaction') and the transition from (A) to (B). The reaction between thin gold detonator wires and the In/Pb/Sn solder mound in older detonators has been looked at repeatedly. There are, in addition, two studies which look at the reaction between indium and gold in planar geometry. All data are shown in tables I to V. It is the objective of this section dealing with aspect (A), to combine all of these results into a reaction model and to use this reaction model to reliably and conservatively predict the gold-solder reaction rate of soldered gold bridge-wires as a function of storage temperature and time.

  11. Qualitative Analysis on a Reaction-Diffusion Prey Predator Model and the Corresponding Steady-States

    Institute of Scientific and Technical Information of China (English)

    Qunyi BIE; Rui PENG

    2009-01-01

    The authors study a diffusive prey-predator model subject to the homogeneous Neumann boundary condition and give some qualitative descriptions of solutions to this reaction-diffusion system and its corresponding steady-state problem.The local and global stability of the positive constant steady-state are discussed,and then some results for nonexistence of positive non-constant steady-states are derived.

  12. KINETIC MODEL FOR DIFFUSION-CONTROLLED INTERMOLECULAR REACTION OF HOMOGENOUS POLYMER UNDER STEADY SHEAR

    Institute of Scientific and Technical Information of China (English)

    Meng-ge Liu; Wei Yu; Chi-xing Zhou

    2006-01-01

    The kinetic model for diffusion-controlled intermolecular reaction of homogenous polymer under steady shear was theoretically studied. The classic formalism and the concept of conformation ellipsoids were integrated to get a new equation, which directly correlates the rate constant with shear rate. It was found that the rate constant is not monotonic with shear rate. The scale of rate constant is N-1.5 (N is the length of chains), which is in consistent with de Gennes's result.

  13. Chemical reaction model of cathode failure in large prebaked anode aluminum reduction cells

    Institute of Scientific and Technical Information of China (English)

    赵群; 谢雁丽; 高炳亮; 邱竹贤; 赵无畏

    2002-01-01

    By partial and general dissection of large prebaked alumina electrolysis cells, the macro appearance, chemical composition and phase variations were studied employing actual observations and measurements on the cells together with X-ray diffraction phase analysis and scanning electron microscopy of samples from different locations. According to the practical production, a chemical reaction model of aluminum reduction cell failure was set up in order to reduce the incidence of cell failure and extend pot service life.

  14. Some studies on the reaction between fly ash and lime

    Indian Academy of Sciences (India)

    A Basumajumdar; A K Das; N Bandyopadhyay; S Maitra

    2005-04-01

    The reaction between fly ash (FA) and lime is extensively exploited for the manufacture of building bricks, blocks and aggregates. To get a better idea of this reaction, FA from different sources were mixed in different ratios with lime and compacted. The compacts were treated both by ordinary water and hydrothermal curing to promote lime bearing hydrate bond formation e.g. CaO–SiO2–H2O (C–S–H), CaO–Al2O3–H2O (C–A–H) etc. The decrease in free lime content in these compacts was measured as a function of curing time and curing process. This drop in this content was correlated to the chemical composition of the fly ashes. The mathematical relationships between free lime remaining in the compacts after its maximum decrease in concentration and lime binding modulus (a ratio between the amount of added lime and the total amount of lime binding constituents present in FA) for both types of curing were developed. Further, the rate of decrease in free CaO content under both types of curing conditions was compared from kinetic study. From this study the orders of the reactions and rate constants were found out.

  15. Chemical reaction and dust formation studies in laboratory hydrocarbon plasmas.

    Science.gov (United States)

    Hippler, Rainer; Majumdar, Abhijit; Thejaswini, H. C.

    Plasma chemical reaction studies with relevance to, e.g., Titan's atmosphere have been per-formed in various laboratory plasmas [1,2]. Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH4 /N2 and CH4 /Ar gas mixtures by means of mass spectrometry. The main reaction scheme is production of H2 by fragmenta-tion of CH4 , but also production of larger hydrocarbons like Cn Hm with n up to 10 including formation of different functional CN groups is observed. [1] A. Majumdar and R. Hippler, Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition, Rev. Sci. Instrum. 78, 075103 (2007) [2] H.T. Do, G. Thieme, M. Frühlich, H. Kersten, and R. Hippler, Ion Molecule and Dust Particle Formation in Ar/CH4 , Ar/C2 H2 and Ar/C3 H6 Radio-frequency Plasmas, Contrib. Plasma Phys. 45, No. 5-6, 378-384 (2005)

  16. Direct reaction experimental studies with beams of radioactive tin ions

    Energy Technology Data Exchange (ETDEWEB)

    Jones, K. L., E-mail: kgrzywac@utk.edu; Ayres, A.; Bey, A.; Burcher, S.; Cartegni, L.; Cerizza, G. [Department of Physics and Astronomy, University of Tennessee, Knoxville, TN 37996 (United States); Ahn, S. [Department of Physics and Astronomy, University of Tennessee, Knoxville, TN 37996 (United States); National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Allmond, J. M.; Beene, J. R.; Galindo-Uribarri, A.; Liang, J. F.; Nesaraja, C. D.; Pain, S. D.; Radford, D. C.; Schmitt, K. T.; Smith, M. S.; Stracener, D. W.; Varner, R. L. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Bardayan, D. W. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Baugher, T. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 (United States); and others

    2015-10-15

    The tin chain of isotopes provides a unique region in which to investigate the evolution of single-particle structure, spreading from N = 50 at {sup 100}Sn, through 10 stable isotopes and the N = 82 shell closure at {sup 132}Sn out into the r-process path. Direct reactions performed on radioactive ion beams are sensitive spectroscopic tools for studying exotic nuclei. Here we present one experiment knocking out neutrons from tin isotopes that are already neutron deficient and two reactions that add a neutron to neutron-rich {sup 130}Sn. Both techniques rely on selective particle identification and the measurement of γ rays in coincidence with charged ions. We present the goals of the two experiments and the particle identification for the channels of interest. The final results will be presented in future publications.

  17. Direct Reaction Experimental Studies with Beams of Radioactive Tin Ions

    Energy Technology Data Exchange (ETDEWEB)

    Jones, K. L. [University of Tennessee, Knoxville (UTK); Ahn, S.H. [University of Tennessee, Knoxville (UTK); Allmond, James M [ORNL; Ayres, A. [University of Tennessee, Knoxville (UTK); Bardayan, Daniel W [ORNL; Baugher, T. [Michigan State University, East Lansing; Bazin, D. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Beene, James R [ORNL; Berryman, J. S. [Michigan State University, East Lansing; Bey, A. [University of Tennessee, Knoxville (UTK); Bingham, C. R. [University of Tennessee, Knoxville (UTK); Cartegni, L. [University of Tennessee, Knoxville (UTK); Chae, K. Y. [University of Tennessee, Knoxville (UTK)/Sungkyunkwan University, Korea; Cizewski, J. A. [Rutgers University; Gade, A. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Galindo-Uribarri, Alfredo {nmn} [ORNL; Garcia-Ruiz, R.F. [Instituut voor Kernen Stralingsfysica, KU Leuven, B-3001, Leuven, Belgium; Grzywacz, Robert Kazimierz [ORNL; Howard, Meredith E [ORNL; Kozub, R. L. [Tennessee Technological University (TTU); Liang, J Felix [ORNL; Manning, Brett M [ORNL; Matos, M. [Louisiana State University; McDaniel, S. [Michigan State University, East Lansing; Miller, D. [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Padgett, S [University of Tennessee, Knoxville (UTK); Padilla-Rodal, Elizabeth [Universidad Nacional Autonoma de Mexico (UNAM); Pain, Steven D [ORNL; Pittman, S. T. [University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL); Radford, David C [ORNL; Ratkiewicz, Andrew J [ORNL; Schmitt, Kyle [ORNL; Smith, Michael Scott [ORNL; Stracener, Daniel W [ORNL; Stroberg, S. [Michigan State University, East Lansing; Tostevin, Jeffrey A [ORNL; Varner Jr, Robert L [ORNL; Weisshaar, D. [Michigan State University, East Lansing; Wimmer, K. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL)/Central Michigan University; Winkler, R. [Michigan State University, East Lansing

    2015-01-01

    The tin chain of isotopes provides a unique region in which to investigate the evolution of single-particle structure, spreading from N = 50 at Sn-100, through 10 stable isotopes and the N = 82 shell closure at Sn-132 out into the r-process path. Direct reactions performed on radioactive ion beams are sensitive spectroscopic tools for studying exotic nuclei. Here we present one experiment knocking out neutrons from tin isotopes that are already neutron deficient and two reactions that add a neutron to neutron-rich Sn-130. Both techniques rely on selective particle identification and the measurement of gamma rays in coincidence with charged ions. We present the goals of the two experiments and the particle identification for the channels of interest. The final results will be presented in future publications.

  18. Constructing and visualizing chemical reaction networks from pi-calculus models

    OpenAIRE

    M. John; H.-J. Schulz; H. Schumann; A. M. Uhrmacher; Andrea Unger

    2013-01-01

    International audience; The pi-calculus, in particular its stochastic version the stochastic pi-calculus, is a common modeling formalism to concisely describe the chemical reactions occurring in biochemical systems. However, it remains largely unexplored how to transform a biochemical model expressed in the stochastic pi-calculus back into a set of meaningful reactions. To this end, we present a two step approach of first translating model states to reaction sets and then visualizing sequence...

  19. Reaction norm model with unknown environmental covariate to analyze heterosis by environment interaction.

    Science.gov (United States)

    Su, G; Madsen, P; Lund, M S

    2009-05-01

    Crossbreeding is currently increasing in dairy cattle production. Several studies have shown an environment-dependent heterosis [i.e., an interaction between heterosis and environment (H x E)]. An H x E interaction is usually estimated from a few discrete environment levels. The present study proposes a reaction norm model to describe H x E interaction, which can deal with a large number of environment levels using few parameters. In the proposed model, total heterosis consists of an environment-independent part, which is described as a function of heterozygosity, and an environment-dependent part, which is described as a function of heterozygosity and environmental value (e.g., herd-year effect). A Bayesian approach is developed to estimate the environmental covariates, the regression coefficients of the reaction norm, and other parameters of the model simultaneously in both linear and nonlinear reaction norms. In the nonlinear reaction norm model, the H x E is approximated using linear splines. The approach was tested using simulated data, which were generated using an animal model with a reaction norm for heterosis. The simulation study includes 4 scenarios (the combinations of moderate vs. low heritability and moderate vs. low herd-year variation) of H x E interaction in a nonlinear form. In all scenarios, the proposed model predicted total heterosis very well. The correlation between true heterosis and predicted heterosis was 0.98 in the scenarios with low herd-year variation and 0.99 in the scenarios with moderate herd-year variation. This suggests that the proposed model and method could be a good approach to analyze H x E interactions and predict breeding values in situations in which heterosis changes gradually and continuously over an environmental gradient. On the other hand, it was found that a model ignoring H x E interaction did not significantly harm the prediction of breeding value under the simulated scenarios in which the variance for environment

  20. A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan

    Science.gov (United States)

    Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, David

    2016-11-01

    Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed. Preliminary studies of two reactions have been carried out to check the reliability and efficacy of kinetics measurements: (i) Rate constants of the reaction of CH3 + ions with molecular oxygen were measured at different temperatures, which indicate values in agreement with previous ion cyclotron resonance measurements ostensibly made at 300 K. (ii) Formation of CH3 + ions in the reaction of N2 + ions with CH4 molecules were studied at temperatures within the range 240-310 K which showed a small but statistically significant decrease of the ratio of product CH3 + ions to reactant N2 + ions with reaction temperature.

  1. Static and dynamical critical behavior of the monomer-monomer reaction model with desorption

    Science.gov (United States)

    da Costa, E. C.; Rusch, Flávio Roberto

    2016-06-01

    We studied in this work the monomer-monomer reaction model on a linear chain. The model is described by the following reaction: A + B → AB, where A and B are two monomers that arrive at the surface with probabilities yA and yB, respectively, and we have considered desorption of the monomer B with probability α. The model is studied in the adsorption controlled limit where the reaction rate is infinitely larger than the adsorption rate. We employ site and pair mean-field approximations as well as static and dynamical Monte Carlo simulations. We show that the model exhibits a continuous phase transition between an active steady state and an A-absorbing state, when the parameter yA is varied through a critical value, which depends on the value of α. Monte Carlo simulations and finite-size scaling analysis near the critical point are used to determine the static critical exponents β and ν⊥ and the dynamical critical exponents ν∥ and z. The results found for the monomer-monomer reaction model with B desorption, in the linear chain, are different from those found by E. V. Albano (Albano, 1992) and are in accordance with the values obtained by Jun Zhuo and Sidney Redner (Zhuo and Redner, 1993), and endorse the conjecture of Grassberger, which states that any system undergoing a continuous phase transition from an active steady state to a single absorbing state, exhibits the same critical behavior of the directed percolation universality class.

  2. Statistical model analysis of α -induced reaction cross sections of 64Zn at low energies

    Science.gov (United States)

    Mohr, P.; Gyürky, Gy.; Fülöp, Zs.

    2017-01-01

    Background: α -nucleus potentials play an essential role in the calculation of α -induced reaction cross sections at low energies in the statistical model. Uncertainties of these calculations are related to ambiguities in the adjustment of the potential parameters to experimental elastic scattering angular distributions (typically at higher energies) and to the energy dependence of the effective α -nucleus potentials. Purpose: The present work studies cross sections of α -induced reactions for 64Zn at low energies and their dependence on the chosen input parameters of the statistical model calculations. The new experimental data from the recent Atomki experiments allow for a χ2-based estimate of the uncertainties of calculated cross sections at very low energies. Method: Recently measured data for the (α ,γ ), (α ,n ), and (α ,p ) reactions on 64Zn are compared to calculations in the statistical model. A survey of the parameter space of the widely used computer code talys is given, and the properties of the obtained χ2 landscape are discussed. Results: The best fit to the experimental data at low energies shows χ2/F ≈7.7 per data point, which corresponds to an average deviation of about 30% between the best fit and the experimental data. Several combinations of the various ingredients of the statistical model are able to reach a reasonably small χ2/F , not exceeding the best-fit result by more than a factor of 2. Conclusions: The present experimental data for 64Zn in combination with the statistical model calculations allow us to constrain the astrophysical reaction rate within about a factor of 2. However, the significant excess of χ2/F of the best fit from unity demands further improvement of the statistical model calculations and, in particular, the α -nucleus potential.

  3. Reaction norm model to describe environmental sensitivity across first lactation in dairy cattle under tropical conditions.

    Science.gov (United States)

    Bignardi, Annaiza Braga; El Faro, Lenira; Pereira, Rodrigo Junqueira; Ayres, Denise Rocha; Machado, Paulo Fernando; de Albuquerque, Lucia Galvão; Santana, Mário Luiz

    2015-10-01

    Reaction norm models have been widely used to study genotype by environment interaction (G × E) in animal breeding. The objective of this study was to describe environmental sensitivity across first lactation in Brazilian Holstein cows using a reaction norm approach. A total of 50,168 individual monthly test day (TD) milk yields (10 test days) from 7476 complete first lactations of Holstein cattle were analyzed. The statistical models for all traits (10 TDs and for 305-day milk yield) included the fixed effects of contemporary group, age of cow (linear and quadratic effects), and days in milk (linear effect), except for 305-day milk yield. A hierarchical reaction norm model (HRNM) based on the unknown covariate was used. The present study showed the presence of G × E in milk yield across first lactation of Holstein cows. The variation in the heritability estimates implies differences in the response to selection depending on the environment where the animals of this population are evaluated. In the average environment, the heritabilities for all traits were rather similar, in range from 0.02 to 0.63. The scaling effect of G × E predominated throughout most of lactation. Particularly during the first 2 months of lactation, G × E caused reranking of breeding values. It is therefore important to include the environmental sensitivity of animals according to the phase of lactation in the genetic evaluations of Holstein cattle in tropical environments.

  4. Empirical valence bond model of an SN2 reaction in polar and nonpolar solvents

    Science.gov (United States)

    Benjamin, Ilan

    2008-08-01

    A new model for the substitution nucleophilic reaction (SN2) in solution is described using the empirical valence bond (EVB) method. The model includes a generalization to three dimensions of a collinear gas phase EVB model developed by Mathis et al. [J. Mol. Liq. 61, 81 (1994)] and a parametrization of solute-solvent interactions of four different solvents (water, ethanol, chloroform, and carbon tetrachloride). The model is used to compute (in these four solvents) reaction free energy profiles, reaction and solvent dynamics, a two-dimensional reaction/solvent free energy map, as well as a number of other properties that in the past have mostly been estimated.

  5. Modelling of reaction cross sections and prompt neutron emission

    Science.gov (United States)

    Hambsch, F.-J.; Tudora, A.; Oberstedt, S.

    2010-10-01

    Accurate nuclear data concerning reaction cross sections and the emission of prompt fission neutrons (i.e. multiplicity and spectra) as well as other fission fragment data are of great importance for reactor physics design, especially for the new Generation IV nuclear energy systems. During the past years for several actinides (238U(n, f) and 237Np(n, f)) both the reaction cross sections and prompt neutron multiplicities and spectra have been calculated within the frame of the EFNUDAT project.

  6. Comparison of a Reaction Front Model and a Finite Difference Model for the Simulation of Solid Absorption Process

    Institute of Scientific and Technical Information of China (English)

    ZikangWu; ArneJakobsen; 等

    1994-01-01

    The pupose of this paper is to investigate the validity of a lumped model,i.e.a reaction front model,for the simulation of solid absorption process.A distributed model is developed for solid absorption process,and a dimensionless RF number is suggested to predict the qualitative shape of reaction degree profile.The simulation results from the reaction front model are compared with those from the distributed model solved by a finite difference scheme,and it is shown that they are in good agreement in almost all cased.no matter whether there is reaction front or not.

  7. A general paradigm to model reaction-based biogeochemical processes in batch systems

    Science.gov (United States)

    Fang, Yilin; Yeh, Gour-Tsyh; Burgos, William D.

    2003-04-01

    This paper presents the development and illustration of a numerical model of reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions. The objective is to provide a general paradigm for modeling reactive chemicals in batch systems, with expectations that it is applicable to reactive chemical transport problems. The unique aspects of the paradigm are to simultaneously (1) facilitate the segregation (isolation) of linearly independent kinetic reactions and thus enable the formulation and parameterization of individual rates one reaction by one reaction when linearly dependent kinetic reactions are absent, (2) enable the inclusion of virtually any type of equilibrium expressions and kinetic rates users want to specify, (3) reduce problem stiffness by eliminating all fast reactions from the set of ordinary differential equations governing the evolution of kinetic variables, (4) perform systematic operations to remove redundant fast reactions and irrelevant kinetic reactions, (5) systematically define chemical components and explicitly enforce mass conservation, (6) accomplish automation in decoupling fast reactions from slow reactions, and (7) increase the robustness of numerical integration of the governing equations with species switching schemes. None of the existing models to our knowledge has included these scopes simultaneously. This model (BIOGEOCHEM) is a general computer code to simulate biogeochemical processes in batch systems from a reaction-based mechanistic standpoint, and is designed to be easily coupled with transport models. To make the model applicable to a wide range of problems, programmed reaction types include aqueous complexation, adsorption-desorption, ion-exchange, oxidation-reduction, precipitation-dissolution, acid-base reactions, and microbial mediated reactions. In addition, user-specified reaction types can be programmed into the model. Any reaction can be treated as fast/equilibrium or slow

  8. An Interface Stretching-Diffusion Model for Mixing-Limited Reactions During Convective Mixing

    Science.gov (United States)

    Hidalgo, J. J.; Dentz, M.; Cabeza, Y.; Carrera, J.

    2014-12-01

    We study the behavior of mixing-limited dissolution reactions under the unstable flow conditions caused by a Rayleigh-Bénard convective instability in a two fluids system. The reactions produce a dissolution pattern that follows the ascending fluids's interface where the largest concentration gradients and maximum mixing are found. Contrary to other chemical systems, the mixing history engraved by the dissolution does not map out the fingering geometry of the unstable flow. The temporal scaling of the mixing Χ and the reaction rate r are explained by a stretching-diffusion model of the interface between the fluids. The model accurately reproduces the three observed regimes: a diffusive regime at which Χ, r ~ t-1/2; a convective regime of at which the interface contracts to the Batchelor scale resulting in a constant Χf and r independent of the Rayleigh number; and an attenuated convection regime in which Χ and r decay faster than diffusion as t-3/2 and t-1, respectevely, because of the decompression of the interface and weakened reactions caused by the accumulation of dissolved fluid below the interface.

  9. In situ infrared (FTIR) study of the borohydride oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Concha, B. Molina; Chatenet, M. [Laboratoire d' Electrochimie et de Physico-chimie, des Materiaux et des Interfaces (LEPMI), UMR 5631 CNRS/Grenoble-INP/UJF, 1130 Rue de la Piscine, BP75, 38402 Saint Martin d' Heres Cedex (France); Coutanceau, C.; Hahn, F. [Laboratoire de Catalyse en Chimie Organique (LACCO), UMR 6503 CNRS, Universite de Poitiers, 40 Av. du, Recteur Pineau, 86000 Poitiers (France)

    2009-01-15

    The direct borohydride fuel cell (DBFC) is an interesting alternative for the electrochemical power generation at lower temperatures due to its high anode theoretical specific capacity (5 A h g{sup -1}). However, the borohydride oxidation reaction (BOR) is a very complex eight-electron reaction, influenced by the nature of the electrode material (catalytic or not with respect to BH{sub 4}{sup -} hydrolysis), the [BH{sub 4}{sup -}][OH{sup -}] ratio and the temperature. In order to understand the BOR mechanism, we performed in situ infrared reflectance spectroscopy measurements (SPAIRS technique) in 1 M NaOH/1 M NaBH{sub 4} with the aim to study intermediate reactions occurring on a gold electrode (a poor BH{sub 4}{sup -} hydrolysis catalyst). We monitored several bands in B-H (1184 cm{sup -1}) and B-O bond regions (1326 and 1415 cm{sup -1}), appearing sequentially with increasing electrode polarisation. Thanks to these experimental findings, we propose possible initial elementary steps for the BOR. (author)

  10. A reaction-based river/stream water quality model: Model development and numerical schemes

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Jardine, Philip M.

    2008-01-01

    SummaryThis paper presents the conceptual and mathematical development of a numerical model of sediment and reactive chemical transport in rivers and streams. The distribution of mobile suspended sediments and immobile bed sediments is controlled by hydrologic transport as well as erosion and deposition processes. The fate and transport of water quality constituents involving a variety of chemical and physical processes is mathematically described by a system of reaction equations for immobile constituents and advective-dispersive-reactive transport equations for mobile constituents. To circumvent stiffness associated with equilibrium reactions, matrix decomposition is performed via Gauss-Jordan column reduction. After matrix decomposition, the system of water quality constituent reactive transport equations is transformed into a set of thermodynamic equations representing equilibrium reactions and a set of transport equations involving no equilibrium reactions. The decoupling of equilibrium and kinetic reactions enables robust numerical integration of the partial differential equations (PDEs) for non-equilibrium-variables. Solving non-equilibrium-variable transport equations instead of individual water quality constituent transport equations also reduces the number of PDEs. A variety of numerical methods are investigated for solving the mixed differential and algebraic equations. Two verification examples are compared with analytical solutions to demonstrate the correctness of the code and to illustrate the importance of employing application-dependent numerical methods to solve specific problems.

  11. Theoretical reaction rates of the $^{12}$C($\\alpha$,$\\gamma$)$^{16}$O reaction from the potential model

    CERN Document Server

    Katsuma, M

    2015-01-01

    The radiative capture cross sections of $^{12}$C($\\alpha$,$\\gamma$)$^{16}$O and derived reaction rates are calculated from the direct capture potential model. The resulting $S$-factor at low energies is found to be dominated by $E$2 transition to the $^{16}$O ground state. The $E$1 and $E$2 $S$-factors at $E_{c.m.}=0.3$ MeV are $S_{E1}\\approx3$ keV~b and $S_{E2}=150^{+41}_{-17}$ keV~b, respectively. The sum of the cascade transition through the excited state of $^{16}$O is $S_{\\rm casc}= 18\\pm4.5$ keV~b. The derived reaction rates at low temperatures seem to be concordant with those from the previous evaluation. For astrophysical applications, our reaction rates below $T_9=3$ are provided in an analytic expression.

  12. Required levels of catalysis for emergence of autocatalytic sets in models of chemical reaction systems.

    Science.gov (United States)

    Hordijk, Wim; Kauffman, Stuart A; Steel, Mike

    2011-01-01

    The formation of a self-sustaining autocatalytic chemical network is a necessary but not sufficient condition for the origin of life. The question of whether such a network could form "by chance" within a sufficiently complex suite of molecules and reactions is one that we have investigated for a simple chemical reaction model based on polymer ligation and cleavage. In this paper, we extend this work in several further directions. In particular, we investigate in more detail the levels of catalysis required for a self-sustaining autocatalytic network to form. We study the size of chemical networks within which we might expect to find such an autocatalytic subset, and we extend the theoretical and computational analyses to models in which catalysis requires template matching.

  13. Required Levels of Catalysis for Emergence of Autocatalytic Sets in Models of Chemical Reaction Systems

    Directory of Open Access Journals (Sweden)

    Wim Hordijk

    2011-05-01

    Full Text Available The formation of a self-sustaining autocatalytic chemical network is a necessary but not sufficient condition for the origin of life. The question of whether such a network could form “by chance” within a sufficiently complex suite of molecules and reactions is one that we have investigated for a simple chemical reaction model based on polymer ligation and cleavage. In this paper, we extend this work in several further directions. In particular, we investigate in more detail the levels of catalysis required for a self-sustaining autocatalytic network to form. We study the size of chemical networks within which we might expect to find such an autocatalytic subset, and we extend the theoretical and computational analyses to models in which catalysis requires template matching.

  14. Experimental study of the astrophysical gamma-process reaction 124Xe(alpha,gamma)128Ba

    CERN Document Server

    Halász, Z; Gyürky, Gy; Elekes, Z; Fülöp, Zs; Szücs, T; Kiss, G G; Szegedi, N; Rauscher, T; Görres, J; Wiescher, M

    2016-01-01

    The synthesis of heavy, proton rich isotopes in the astrophysical gamma-process proceeds through photodisintegration reactions. For the improved understanding of the process, the rates of the involved nuclear reactions must be known. The reaction 128Ba(g,a)124Xe was found to affect the abundance of the p nucleus 124Xe. Since the stellar rate for this reaction cannot be determined by a measurement directly, the aim of the present work was to measure the cross section of the inverse 124Xe(a,g)128Ba reaction and to compare the results with statistical model predictions. Of great importance is the fact that data below the (a,n) threshold was obtained. Studying simultaneously the 124Xe(a,n)127Ba reaction channel at higher energy allowed to further identify the source of a discrepancy between data and prediction. The 124Xe + alpha cross sections were measured with the activation method using a thin window 124Xe gas cell. The studied energy range was between E = 11 and 15 MeV close above the astrophysically relevant...

  15. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    Energy Technology Data Exchange (ETDEWEB)

    Basilevsky, M. V.; Mitina, E. A. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); Odinokov, A. V. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow (Russian Federation); Titov, S. V. [Karpov Institute of Physical Chemistry, 3-1/12, Building 6, Obuha pereulok, Moscow (Russian Federation)

    2013-12-21

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ{sub 0}=ℏω{sub 0}/k{sub B}T where ω{sub 0} is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ{sub 0} < 1 − 3) and for low (ξ{sub 0}≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the

  16. A Model to Predict Shopper Reaction to Commissary Stockouts

    Science.gov (United States)

    1989-12-01

    38). For these reasons, many firms such as British Airways, Coca - Cola , Domino’s Pizza, Four Seasons Hotels, General Electric (GE), and General Motors...causes consumers to switch brands . Researchers have analyzed response time, inflation, sales promotions, and brand loyalty in hopes of determining...review is Wernerfelt’s study on brand loyalty . The author attempted to develop a model which illustrates why a consumer remains loyal to a brand although

  17. DL-ADR: a novel deep learning model for classifying genomic variants into adverse drug reactions.

    Science.gov (United States)

    Liang, Zhaohui; Huang, Jimmy Xiangji; Zeng, Xing; Zhang, Gang

    2016-08-10

    Genomic variations are associated with the metabolism and the occurrence of adverse reactions of many therapeutic agents. The polymorphisms on over 2000 locations of cytochrome P450 enzymes (CYP) due to many factors such as ethnicity, mutations, and inheritance attribute to the diversity of response and side effects of various drugs. The associations of the single nucleotide polymorphisms (SNPs), the internal pharmacokinetic patterns and the vulnerability of specific adverse reactions become one of the research interests of pharmacogenomics. The conventional genomewide association studies (GWAS) mainly focuses on the relation of single or multiple SNPs to a specific risk factors which are a one-to-many relation. However, there are no robust methods to establish a many-to-many network which can combine the direct and indirect associations between multiple SNPs and a serial of events (e.g. adverse reactions, metabolic patterns, prognostic factors etc.). In this paper, we present a novel deep learning model based on generative stochastic networks and hidden Markov chain to classify the observed samples with SNPs on five loci of two genes (CYP2D6 and CYP1A2) respectively to the vulnerable population of 14 types of adverse reactions. A supervised deep learning model is proposed in this study. The revised generative stochastic networks (GSN) model with transited by the hidden Markov chain is used. The data of the training set are collected from clinical observation. The training set is composed of 83 observations of blood samples with the genotypes respectively on CYP2D6*2, *10, *14 and CYP1A2*1C, *1 F. The samples are genotyped by the polymerase chain reaction (PCR) method. A hidden Markov chain is used as the transition operator to simulate the probabilistic distribution. The model can perform learning at lower cost compared to the conventional maximal likelihood method because the transition distribution is conditional on the previous state of the hidden Markov

  18. Esterification with ethanol to produce biodiesel from high acidity raw materials. Kinetic studies and analysis of secondary reactions

    Energy Technology Data Exchange (ETDEWEB)

    Pisarello, M.L.; Dalla Costa, B.; Mendow, G.; Querini, C.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE)-(FIQ-UNL, CONICET), Santiago del Estero 2654-Santa Fe, S3000AOJ (Argentina)

    2010-09-15

    In this work, the esterification reaction of free fatty acids (FFA) in sunflower oil, coconut oil and concentrated FFA, with ethanol, methanol and ethanol 96%, using homogeneous acid catalysts to produce biodiesel is studied. Kinetic parameters are estimated with a simplified model, and then used to predict the reaction behavior. Reactions other than the reversible esterification are considered to explain the behavior that this system displays. Such reactions are the triglycerides conversion by acid catalyzed transesterification and hydrolysis. In addition, we include kinetic studies of the reaction that occur between the sulphuric acid and methanol (or ethanol), forming mono and dialkylsulphates. This reaction produces water and consumes methanol (or ethanol), and consequently has a direct impact in the esterification reaction rate and equilibrium conversion. The concentration of sulphuric acid decreases to less than 50% of the initial value due to the reaction with the alcohol. A minimum in the acidity due to the free fatty acids as a function of time was clearly observed during the reaction, which has not been reported earlier. This behavior is related to the consecutive reactions that take place during the esterification of FFA in the presence of triglycerides. The phase separation due to the presence of water, which is generated during the reaction, is also studied. (author)

  19. C-13 isotopic studies of the surface catalysed reactions of methane

    Energy Technology Data Exchange (ETDEWEB)

    Long, M.A.; He, S.J.X.; Adebajo, M. [University of New South Wales, Sydney, NSW (Australia). School of Chemistry

    1997-10-01

    The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and {sup 13}C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane{sup 13}C, which show that methylation of aromatics such as naphthalene by the methane{sup 13}C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

  20. A fractional model of a dynamical Brusselator reaction-diffusion system arising in triple collision and enzymatic reactions

    Science.gov (United States)

    Singh, Jagdev; Rashidi, M. M.; Kumar, Devendra; Swroop, Ram

    2016-12-01

    In this paper, we study a dynamical Brusselator reaction-diffusion system arising in triple collision and enzymatic reactions with time fractional Caputo derivative. The present article involves a more generalized effective approach, proposed for the Brusselator system say q-homotopy analysis transform method (q-HATM), providing the family of series solutions with nonlocal generalized effects. The convergence of the q-HATM series solution is adjusted and controlled by auxiliary parameter ℏ and asymptotic parameter n. The numerical results are demonstrated graphically. The outcomes of the study show that the q-HATM is computationally very effective and accurate to analyze nonlinear fractional differential equations.

  1. Physicochemical studies on the reaction between formaldehyde and DNA.

    Science.gov (United States)

    FREIFELDER, D; DAVISON, P F

    1963-01-01

    The reaction between formaldehyde and phage T7 DNA has been studied by optical absorbance and sedimentation measurements. Through the course of denaturation, OD(200) and s(20, w) rise; after the attainment of full hyperchromicity the s(20, w) falls sharply, suggesting a decrease in molecular weight. Conditions in which formaldehyde causes cross-linking are defined. Some experimental applications of the denaturation technique are given. Evidence which suggests that preformed single-strand interruptions may exist in phage DNA is briefly discussed.

  2. Physicochemical Studies on the Reaction between Formaldehyde and DNA

    Science.gov (United States)

    Freifelder, David; Davison, Peter F.

    1963-01-01

    The reaction between formaldehyde and phage T7 DNA has been studied by optical absorbance and sedimentation measurements. Through the course of denaturation, OD200 and s20, w rise; after the attainment of full hyperchromicity the s20, w falls sharply, suggesting a decrease in molecular weight. Conditions in which formaldehyde causes cross-linking are defined. Some experimental applications of the denaturation technique are given. Evidence which suggests that preformed single-strand interruptions may exist in phage DNA is briefly discussed. PMID:13959526

  3. A new setup for the underground study of capture reactions

    CERN Document Server

    Casella, C; Lemut, A; Limata, B; Bemmerer, D; Bonetti, R; Broggini, C; Campajola, L; Cocconi, P; Corvisiero, P; Cruz, J; D'Onofrio, A; Formicola, A; Fülöp, Z; Gervino, G; Gialanella, L; Guglielmetti, A; Gustavino, C; Gyürky, G; Loiano, A; Imbriani, G; Jesus, A P; Junker, M; Musico, P; Ordine, A; Parodi, F; Parolin, M; Pinto, J V; Prati, P; Ribeiro, J P; Roca, V; Rogalla, D; Rolfs, C; Romano, M; Rossi-Alvarez, C; Rottura, A; Schuemann, F; Somorjai, E; Strieder, F; Terrasi, F; Trautvetter, H P; Vomiero, A; Zavatarelli, S

    2002-01-01

    For the study of astrophysically relevant capture reactions in the underground laboratory LUNA a new setup of high sensitivity has been implemented. The setup includes a windowless gas target, a 4 pi BGO summing crystal, and beam calorimeters. The setup has been recently used to measure the d(p,gamma) sup 3 He cross-section for the first time within its solar Gamow peak, i.e. down to 2.5 keV c.m. energy. The features of the optimized setup are described.

  4. Study of all Reaction Channels in Deuteron-Deuteron Scattering

    Science.gov (United States)

    Ramazani-Moghaddam-Arani, A.; Amir-Ahmadi, H. R.; Bacher, A. D.; Bailey, C. D.; Biegun, A.; Eslami-Kalantari, M.; Gašparić, I.; Joulaeizadeh, L.; Kalantar-Nayestanaki, N.; Kistryn, St.; Kozela, A.; Mardanpour, H.; Messchendorp, J. G.; Micherdzinska, A. M.; Moeini, H.; Shende, S. V.; Stephan, E.; Stephenson, E. J.; Sworst, R.

    Few-nucleon systems can be used as fundamental laboratories for studying details of the nuclear force effects. We performed a series of deuteron-deuteron scattering experiments at intermediate energies. The experiments exploited BINA and BBS experimental setups and polarized deuteron beams with kinetic energies of 65 and 90 MeV/nucleon. These experiments aim to measure differential cross sections, vector and tensor analyzing powers of all available reaction channels in deuteron-deuteron scattering. With these data we will provide a systematic database, which will be used to test present theoretical approximations and upcoming ab-initio calculations in four-nucleon system.

  5. Electrochemical studies of reaction of ciprofloxcin and DNA

    Institute of Scientific and Technical Information of China (English)

    Qiaocui SHI; Sufen WANG; Bin ZHU; Min JI

    2008-01-01

    The electrochemical behavior of ciprofloxacin (CFX) and its interaction with the natural calf thymus DNA (ctDNA) is studied by using pulse difference voltammetry on a carbon electrode. CFX shows a well-defined oxidative peak at+0.88 V. As a result of reaction with ctDNA,the oxidative peak of CFX decreased markedly. According to the electrochemical equation deduced in this paper, the binding constant of 1.36 × 105 (mol/L)-1 and the binding size of 1.94 (base pairs) of CFX with ctDNA were obtained by nonlinear fit analysis of the electrochemical data. The mechanism of the interaction was explored.

  6. Modelling of reaction cross sections and prompt neutron emission

    Directory of Open Access Journals (Sweden)

    Oberstedt S.

    2010-10-01

    Full Text Available Accurate nuclear data concerning reaction cross sections and the emission of prompt fission neutrons (i.e. multiplicity and spectra as well as other fission fragment data are of great importance for reactor physics design, especially for the new Generation IV nuclear energy systems. During the past years for several actinides (238U(n, f and 237Np(n, f both the reaction cross sections and prompt neutron multiplicities and spectra have been calculated within the frame of the EFNUDAT project.

  7. Fusion and quasifission studies in reactions forming Rn via evaporation residue measurements

    Science.gov (United States)

    Shamlath, A.; Prasad, E.; Madhavan, N.; Laveen, P. V.; Gehlot, J.; Nasirov, A. K.; Giardina, G.; Mandaglio, G.; Nath, S.; Banerjee, Tathagata; Vinodkumar, A. M.; Shareef, M.; Jhingan, A.; Varughese, T.; Kumar, Dvgrks; Devi, P. Sandya; Khushboo, Jisha, P.; Kumar, Neeraj; Hosamani, M. M.; Kailas, S.

    2017-03-01

    Background: Formation of the compound nucleus (CN) is highly suppressed by quasifission in heavy-ion collisions involving massive nuclei. Though considerable progress has been made in the understanding of fusion-fission and quasifission, the exact dependence of fusion probability on various entrance channel variables is not completely clear, which is very important for the synthesis of new heavy and superheavy elements. Purpose: To study the interplay between fusion and quasifission in reactions forming CN in the boundary region where the fusion probability starts to deviate from unity. Methods: Fusion evaporation residue cross sections were measured for the Si,3028+180Hf reactions using the Hybrid Recoil Mass Analyser at IUAC, New Delhi. Experimental data were compared with data from other reactions forming the same CN or isotopes of the CN. Theoretical calculations were performed using the dinuclear system and statistical models. Results: Reduced evaporation residue cross sections were observed for the reactions studied compared with the asymmetric reaction forming the same CN, indicating fusion suppression in more symmetric systems. The observations are consistent with fission fragment measurements performed in the same or similar systems. Larger ER cross sections are observed with increase in mass in the isotopic chain of the CN. Conclusions: Fusion probability varies significantly with the entrance channels in reactions forming the same CN. While complete fusion occurs for the 16O+194Pt reaction, the fusion probability drops to approximately 60 -70 % for the 30Si+180Hf and less than 20 % for the 50Ti+160Gd reactions, respectively, forming the same CN at similar excitation energies.

  8. Evolution of Autocatalytic Sets in Computational Models of Chemical Reaction Networks

    Science.gov (United States)

    Hordijk, Wim

    2016-06-01

    Several computational models of chemical reaction networks have been presented in the literature in the past, showing the appearance and (potential) evolution of autocatalytic sets. However, the notion of autocatalytic sets has been defined differently in different modeling contexts, each one having some shortcoming or limitation. Here, we review four such models and definitions, and then formally describe and analyze them in the context of a mathematical framework for studying autocatalytic sets known as RAF theory. The main results are that: (1) RAF theory can capture the various previous definitions of autocatalytic sets and is therefore more complete and general, (2) the formal framework can be used to efficiently detect and analyze autocatalytic sets in all of these different computational models, (3) autocatalytic (RAF) sets are indeed likely to appear and evolve in such models, and (4) this could have important implications for a possible metabolism-first scenario for the origin of life.

  9. Evolution of Autocatalytic Sets in Computational Models of Chemical Reaction Networks.

    Science.gov (United States)

    Hordijk, Wim

    2016-06-01

    Several computational models of chemical reaction networks have been presented in the literature in the past, showing the appearance and (potential) evolution of autocatalytic sets. However, the notion of autocatalytic sets has been defined differently in different modeling contexts, each one having some shortcoming or limitation. Here, we review four such models and definitions, and then formally describe and analyze them in the context of a mathematical framework for studying autocatalytic sets known as RAF theory. The main results are that: (1) RAF theory can capture the various previous definitions of autocatalytic sets and is therefore more complete and general, (2) the formal framework can be used to efficiently detect and analyze autocatalytic sets in all of these different computational models, (3) autocatalytic (RAF) sets are indeed likely to appear and evolve in such models, and (4) this could have important implications for a possible metabolism-first scenario for the origin of life.

  10. Reaction-subdiffusion front propagation in a comblike model of spiny dendrites

    Science.gov (United States)

    Iomin, A.; Méndez, V.

    2013-07-01

    Fractional reaction-diffusion equations are derived by exploiting the geometrical similarities between a comb structure and a spiny dendrite. In the framework of the obtained equations, two scenarios of reaction transport in spiny dendrites are explored, where both a linear reaction in spines and nonlinear Fisher-Kolmogorov-Petrovskii-Piskunov reactions along dendrites are considered. In the framework of fractional subdiffusive comb model, we develop a Hamilton-Jacobi approach to estimate the overall velocity of the reaction front propagation. One of the main effects observed is the failure of the front propagation for both scenarios due to either the reaction inside the spines or the interaction of the reaction with the spines. In the first case the spines are the source of reactions, while in the latter case, the spines are a source of a damping mechanism.

  11. Study of the (p,d/sup 3/He) reaction as a quasi-free reaction process

    Energy Technology Data Exchange (ETDEWEB)

    Cowley, A. A.; Roos, P. G.; Chant, N. S.; Woody, R. III; Holmgren, H. D.; Goldberg, D. A.

    1976-11-01

    The (p,d/sup 3/He) reaction on /sup 6/Li, /sup 7/Li, /sup 9/Be, and /sup 12/C has been investigated in conjunction with studies of the (p,p..cap alpha..) reaction on the same targets. Coincident data for all four targets were obtained at a bombarding energy of 100 MeV for numerous angle pairs in order to test the reaction mechanism. Comparisons of the (p,d/sup 3/He) data to both (p,p..cap alpha..) data and distorted wave impulse approximation calculations (DWIA) indicate a dominance of the direct quasi-free reaction process (p + alpha yields d + /sup 3/He). The absolute alpha-particle spectroscopic factors extracted using DWIA analysis are in agreement with the values obtained in the (p,p..cap alpha..) reaction.

  12. Reaction of Np atom with H₂O in the gas phase: reaction mechanisms and ab initio molecular dynamics study.

    Science.gov (United States)

    Li, Peng; Niu, Wenxia; Gao, Tao; Wang, Hongyan

    2014-10-01

    The gas-phase reaction of an Np atom with H2O was investigated using density functional theory and ab initio molecular dynamics. The reaction mechanisms and the corresponding potential energy profiles for different possible spin states were analyzed. Three reaction channels were found in the mechanism study: the isomerization channel, the H2 elimination channel, and the H atom elimination channel. The latter two were observed in the dynamics simulation. It was found that the branching ratio of the title reaction depends on the initial kinetic energy along the transition vector. Product energy distributions for the reaction were evaluated by performing direct classical trajectory calculations on the lowest sextet potential energy surface. The results indicate that most of the available energy appears as the translational energy of the products. The overall results indicate that the H2 elimination channel with low kinetic energy is thermodynamically favored but competes with the H atom elimination channel with higher kinetic energy.

  13. Mass action realizations of reaction kinetic system models on various time scales

    Energy Technology Data Exchange (ETDEWEB)

    Hangos, K M; Szederkenyi, G, E-mail: hangos@scl.sztaki.hu, E-mail: szeder@scl.sztaki.hu [Process Control Research Group, Computer and Automation Reseach Institute, Kende u. 13-17, H-1111 Budapest (Hungary)

    2011-01-01

    Complex chemical reaction networks often exhibit different dynamic behaviour on different time scales. A combined approach is proposed in this work for determining physically meaningful mass action realizations of complex chemical reaction networks that describe its dynamic behaviour on different time scales. This is achieved by appropriately reducing the detailed overall mass action kinetic scheme using quasi steady state assumptions fit to the particular time scale, and then searching for an optimal realization using mixed integer linear programing. Furthermore, the relationship between the properties (reversibility, deficiency, stability) of the obtained realizations of the same system on different time scales are also investigated and related to the same properties of the detailed overall model. It is shown that the reduced models obtained by quasi steady state assumptions may show exotic nonlinear behaviour, such as oscillations, when the original detailed is globally asymptotically stable. The proposed methods are illustrated by using a simple Michaelis-Menten type reaction kinetic example. The simplified versions of the well known Brusselator model have also been investigated and presented as a case study.

  14. DFT Study on the (S)-Proline-catalyzed Direct Aldol Reaction between Acetone and 4-Nitrobenzaldehyde

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    DFT/6-31G* calculations were applied to study the direct aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by (S)-proline. Four transition states associated with the stereo-controlling step, corresponding to syn and anti arrangements of methylene moiety related to the carboxylic acid group in enamine intermediate and re and si attacks to the aldehyde carbonyl carbon have been obtained. The solvent effect of DMSO was investigated with polarized continuum model. The computed energies of transition states reveal the stereo-selectivity of the reaction.

  15. A Note on a Nonlocal Nonlinear Reaction-Diffusion Model

    OpenAIRE

    Walker, Christoph

    2011-01-01

    We give an application of the Crandall-Rabinowitz theorem on local bifurcation to a system of nonlinear parabolic equations with nonlocal reaction and cross-diffusion terms as well as nonlocal initial conditions. The system arises as steady-state equations of two interacting age-structured populations.

  16. Parallel iterative reaction path optimization in ab initio quantum mechanical/molecular mechanical modeling of enzyme reactions.

    Science.gov (United States)

    Liu, Haiyan; Lu, Zhenyu; Cisneros, G Andres; Yang, Weitao

    2004-07-08

    The determination of reaction paths for enzyme systems remains a great challenge for current computational methods. In this paper we present an efficient method for the determination of minimum energy reaction paths with the ab initio quantum mechanical/molecular mechanical approach. Our method is based on an adaptation of the path optimization procedure by Ayala and Schlegel for small molecules in gas phase, the iterative quantum mechanical/molecular mechanical (QM/MM) optimization method developed earlier in our laboratory and the introduction of a new metric defining the distance between different structures in the configuration space. In this method we represent the reaction path by a discrete set of structures. For each structure we partition the atoms into a core set that usually includes the QM subsystem and an environment set that usually includes the MM subsystem. These two sets are optimized iteratively: the core set is optimized to approximate the reaction path while the environment set is optimized to the corresponding energy minimum. In the optimization of the core set of atoms for the reaction path, we introduce a new metric to define the distances between the points on the reaction path, which excludes the soft degrees of freedom from the environment set and includes extra weights on coordinates describing chemical changes. Because the reaction path is represented by discrete structures and the optimization for each can be performed individually with very limited coupling, our method can be executed in a natural and efficient parallelization, with each processor handling one of the structures. We demonstrate the applicability and efficiency of our method by testing it on two systems previously studied by our group, triosephosphate isomerase and 4-oxalocrotonate tautomerase. In both cases the minimum energy paths for both enzymes agree with the previously reported paths.

  17. Competitive reaction- and feedback effects based on VARX models of pooled store data

    NARCIS (Netherlands)

    Horvath, C; Leeflang, PSH; Wieringa, JE; Wittink, DR

    2005-01-01

    We apply a model that accommodates dynamic phenomena in demand- and reaction functions. The latter functions capture reactions to actions as well as to consequences of actions. We estimate a fixed effects VARX model with dynamic and interactive effects for multiple brands based on pooled time series

  18. Spreading Speed for a Periodic Reaction-diffusion Model with Nonmonotone Birth Function

    Institute of Scientific and Technical Information of China (English)

    HUANG Ye-hui; WENG Pei-xuan

    2012-01-01

    A reaction-diffusion model for a single spccies with age structure and nonlocal reaction for periodic time t is derived.Some results about the model with monotone birth function are firstly introduced,and then by constructing two auxiliary equations and squeezing method,the spreading speed for the system with nonmonotone birth function is obtained.

  19. A study of systolic time intervals in lepra reaction.

    Science.gov (United States)

    Zawar, P B; Chawhan, R N; Mahajani, V V

    1983-10-01

    Systolic time intervals (STI) were measured in 20 control subjects and 20 cases of lepromatous leprosy in lepra reaction. Significant differences in the pre-ejection period (PEP), PEP/LVET and isovolumic contraction (IVCT) were observed between the groups. The abnormalities of STI observed in patients of lepra reaction are characteristic of left ventricular dysfunction in patients of lepra reaction.

  20. Kinetic Study of the Austempering Reactions in Ductile Irons

    Science.gov (United States)

    Pérez, M. J.; Cisneros, M. M.; Almanza, E.; Haro, S.

    2012-11-01

    Kinetics of the reaction that occur during the austempering heat treatment in unalloyed and alloyed ductile irons with 1Cu-0.25Mo, 1Ni-0.25Mo, and 0.7Cu-1Ni-0.25Mo, was studied. The austenitization and austempering cycles were achieved by isothermal dilatometry in cylindrical samples of 2 mm in diameter and 12 mm in length. The specimens were austenitized at 870 °C for 120 min, followed by isothermal holding for 300 min at temperatures between 270 and 420 °C. Kinetic parameters such as the order of reaction " n" and the rate of reaction " k" were calculated using the Johnson-Mehl equation while the empirical activation energy was calculated by means of the Arrhenius equation. It was found that the values of " k" decreased with the addition of Cu, Ni, and Mo as well as with the reduction of the isothermal temperature. The activation energy changes with the austempering temperature, in the range 30,348-58,250 J/mol when the heat treatment was carried out between 370 and 420 °C and 10,336-26,683 J/mol when the temperature varied from 270 to 350 °C. The microstructures in samples austempered at 370 and 315 °C were observed by transmission electron microscopy. No carbides precipitation was observed on samples heat treated at 370 °C for less than 120 min, while at 315 °C carbides of hexagonal structure ɛ(Fe2.4C) were found from the beginning of the transformation. The smallest value of activation energy and a slower kinetic transformation seem to be related with the presence of a carbide phase. Additionally, the time results obtained for transformation fractions of 0.05 and 0.95 by the dilatometry analysis were used to build the temperature-time-transformation diagrams for the irons.

  1. THE MODELING OF COUNTER-ROTATING TWIN-SCREW EXTRUDERS AS REACTORS FOR SINGLE-COMPONENT REACTIONS

    NARCIS (Netherlands)

    GANZEVELD, KJ; CAPEL, JE; VANDERWAL, DJ; JANSSEN, LPBM

    1994-01-01

    Numerical models are useful to study the behaviour of the extruder as a polymerization reactor. With a correct numerical model a theoretical analysis of the influence of several reaction and extruder parameters can be made, the limitations of the use of the extruder reactor can be determined and the

  2. THE MODELING OF COUNTER-ROTATING TWIN-SCREW EXTRUDERS AS REACTORS FOR SINGLE-COMPONENT REACTIONS

    NARCIS (Netherlands)

    GANZEVELD, KJ; CAPEL, JE; VANDERWAL, DJ; JANSSEN, LPBM

    Numerical models are useful to study the behaviour of the extruder as a polymerization reactor. With a correct numerical model a theoretical analysis of the influence of several reaction and extruder parameters can be made, the limitations of the use of the extruder reactor can be determined and the

  3. Theoretical Studies on F(-) + NH2Cl Reaction: Nucleophilic Substitution at Neutral Nitrogen.

    Science.gov (United States)

    Liu, Xu; Zhang, Jiaxu; Yang, Li; Sun, Rui

    2016-05-26

    The SN2 reactions at N center, denoted as SN2@N, has been recognized to play a significant role in carcinogenesis, although they are less studied and less understood. The potential energy profile for the model reaction of SN2@N, chloramine (NH2Cl) with fluorine anion (F(-)), has been characterized by extensive electronic structure calculations. The back-side SN2 channel dominates the reaction with the front-side SN2 channel becoming feasible at higher energies. The minimum energy pathway shows a resemblance to the well-known double-well potential model for SN2 reactions at carbon. However, the complexes involving nitrogen on both sides of the reaction barrier are characterized by NH---X (X = F or Cl) hydrogen bond and possess C1 symmetry, in contrast to the more symmetric ion-dipole carbon analogues. In the F(-) + NH2Cl system, the proton transfer pathway is found to become more competitive with the SN2 pathway than in the F(-) + CH3Cl system. The calculations reported here indicate that stationary point properties on the F(-) + NH2Cl potential energy surface are slightly perturbed by the theories employed. The MP2 and CAM-B3LYP, as well as M06-2X and MPW1K functionals give overall best agreement with the benchmark CCSD(T)/CBS energies for the major SN2 reaction channel, and are recommended as the preferred methods for the direct dynamics simulations to uncover the dynamic behaviors of the title reaction.

  4. Modeling subsurface contaminant reactions and transport at the watershed scale

    Energy Technology Data Exchange (ETDEWEB)

    Gwo, J.P.; Jardine, P.M.; D`Azevedo, E.F. [Oak Ridge National Lab., TN (United States); Wilson, G.V. [Desert Research Inst., Las Vegas, NV (United States). Water Resources Center

    1997-12-01

    The objectives of this research are: (1) to numerically examine the multiscale effects of physical and chemical mass transfer processes on watershed scale, variably saturated subsurface contaminant transport, and (2) to conduct numerical simulations on watershed scale reactive solute transport and evaluate their implications to uncertainty characterization and cost benefit analysis. Concurrent physical and chemical nonequilibrium caused by inter aggregate gradients of pressure head and solute concentration and intra-aggregate geochemical and microbiological processes, respectively, may arise at various scales and flowpaths. To this date, experimental investigations of these complex processes at watershed scale remain a challenge and numerical studies are often needed for guidance of water resources management and decision making. This research integrates the knowledge bases developed during previous experimental and numerical investigations at a proposed waste disposal site at the Oak Ridge National Laboratory to study the concurrent effects of physical and chemical nonequilibrium. Comparison of numerical results with field data indicates that: (1) multiregion, preferential flow and solute transport exist under partially saturated condition and can be confirmed theoretically, and that (2) mass transfer between pore regions is an important process influencing contaminant movement in the subsurface. Simulations of watershed scale, multi species reactive solute transport suggest that dominance of geochemistry and hydrodynamics may occur simultaneously at different locales and influence the movement of one species relative to another. Execution times on the simulations of the reactive solute transport model also indicate that the model is ready to assist the selection of important parameters for site characterization.

  5. Modeling subsurface contaminant reactions and transport at the watershed scale

    Energy Technology Data Exchange (ETDEWEB)

    Gwo, J.P.; Jardine, P.M.; D`Azevedo, E.F. [Oak Ridge National Lab., TN (United States); Wilson, G.V. [Desert Research Inst., Las Vegas, NV (United States). Water Resources Center

    1997-12-01

    The objectives of this research are: (1) to numerically examine the multiscale effects of physical and chemical mass transfer processes on watershed scale, variably saturated subsurface contaminant transport, and (2) to conduct numerical simulations on watershed scale reactive solute transport and evaluate their implications to uncertainty characterization and cost benefit analysis. Concurrent physical and chemical nonequilibrium caused by inter aggregate gradients of pressure head and solute concentration and intra-aggregate geochemical and microbiological processes, respectively, may arise at various scales and flowpaths. To this date, experimental investigations of these complex processes at watershed scale remain a challenge and numerical studies are often needed for guidance of water resources management and decision making. This research integrates the knowledge bases developed during previous experimental and numerical investigations at a proposed waste disposal site at the Oak Ridge National Laboratory to study the concurrent effects of physical and chemical nonequilibrium. Comparison of numerical results with field data indicates that: (1) multiregion, preferential flow and solute transport exist under partially saturated condition and can be confirmed theoretically, and that (2) mass transfer between pore regions is an important process influencing contaminant movement in the subsurface. Simulations of watershed scale, multi species reactive solute transport suggest that dominance of geochemistry and hydrodynamics may occur simultaneously at different locales and influence the movement of one species relative to another. Execution times on the simulations of the reactive solute transport model also indicate that the model is ready to assist the selection of important parameters for site characterization.

  6. Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 1, Catalyzed reactions with wood models and wood polymers

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2011-01-01

    To better understand adhesive interactions with wood, reactions between model compounds of wood and a model compound of polymeric methylene diphenyl diisocyanate (pMDI) were characterized by solution-state NMR spectroscopy. For comparison, finely ground loblolly pine sapwood, milled-wood lignin and holocellulose from the same wood were isolated and derivatized with...

  7. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Krupka, Kenneth M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cantrell, Kirk J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2010-09-01

    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  8. Study of Reaction Between Slag and Carbonaceous Materials

    Science.gov (United States)

    Maroufi, Samane; Mayyas, Mohannad; Mansuri, Irshad; O'Kane, Paul; Skidmore, Catherine; Jin, Zheshi; Fontana, Andrea; Sahajwalla, Veena

    2017-10-01

    The chemical interaction of a typical slag of EAF with three different carbon sources, coke, rubber-derived carbon (RDC), coke-RDC blend, was studied in atmospheric pressure at 1823 K (1550 °C). Using an IR-gas analyzer, off-gases evolved from the sample were monitored. While the coke-RDC blend exhibited the best reducing performance in reaction with molten slag, the RDC sample showed poor interaction with the molten slag. The gasification of the coke, RDC, and coke-RDC blend was also carried out under oxidizing conditions using a gas mixture of CO2 (4 wt pct) and Ar (96 wt pct) and it was shown that the RDC sample had the highest rate of gasification step C0 \\mathop{\\longrightarrow}\\limits{{k3 }}{CO} + nCf (11.6 site/g s (×6.023 × 1023/2.24 × 104)). This may be attributed to its disordered structure confirmed by Raman spectra and its nano-particle morphology observed by FE-SEM. The high reactivity of RDC with CO2 provided evidence that the Boudouard reaction was fast during the interaction with molten slag. However, low reduction rate of iron oxide from slag with RDC can be attributed to the initial weak contact between RDC and molten slag implying that the contact between carbonaceous matter and slag plays significant roles in the reduction of iron oxide from slag.

  9. Modeling of Chemical Reactions in Afterburning for the Reduction of N2O

    DEFF Research Database (Denmark)

    Gustavsson, Lennart; Glarborg, Peter; Leckner, Bo

    1996-01-01

    Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions.......Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions....

  10. Theoretical modeling of the kinetics of barrierless reactions. Final report: DE-FG02-98ER14902

    Energy Technology Data Exchange (ETDEWEB)

    Klippenstein, Stephen J.

    2003-01-03

    Recent progress is reported on a research program aimed at developing and applying sophisticated transition state theory-based models for the kinetics of barrierless reactions of importance in combustion. Various applications involving the coupling of the variable reaction coordinate (VRC) transition state theory (TST) methodology with ab initio quantum chemical evaluations and/or master equation simulations were provided. Reactions studied included the C{sub 3}H{sub 3} + H and C{sub 3}H{sub 5} + H addition reactions, C{sub 2}H{sub 3} + C{sub 2}H{sub 2} and C{sub 2}H{sub 5} + O{sub 2} reactions, and the unimolecular dissociation of ketene.

  11. Travelling wave and convergence in stage-structured reaction-diffusion competitive models with nonlocal delays

    Energy Technology Data Exchange (ETDEWEB)

    Xu Rui [Department of Applied Mathematics, Xi' an Jiaotong University, Xi' an 710049 (China)]. E-mail: rxu88@yahoo.com.cn; Chaplain, M.A.J. [Department of Mathematics, University of Dundee, Dundee DD1 4HN (United Kingdom); Davidson, F.A. [Department of Mathematics, University of Dundee, Dundee DD1 4HN (United Kingdom)

    2006-11-15

    In this paper, we first investigate a stage-structured competitive model with time delays, harvesting, and nonlocal spatial effect. By using an iterative technique recently developed by Wu and Zou (Wu J, Zou X. Travelling wave fronts of reaction-diffusion systems with delay. J Dynam Differen Equat 2001;13:651-87), sufficient conditions are established for the existence of travelling front solution connecting the two boundary equilibria in the case when there is no positive equilibrium. The travelling wave front corresponds to an invasion by a stronger species which drives the weaker species to extinction. Secondly, we consider a stage-structured competitive model with time delays and nonlocal spatial effect when the domain is finite. We prove the global stability of each of the nonnegative equilibria and demonstrate that the more complex model studied here admits three possible long term behaviors: coexistence, bistability and dominance as is the case for the standard Lotka-Voltera competitive model.

  12. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways.

    Science.gov (United States)

    Jin, Biao; Rolle, Massimo

    2016-03-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available.

  13. Experimental study of η meson photoproduction reaction at MAMI

    Directory of Open Access Journals (Sweden)

    Kashevarov V. L.

    2015-01-01

    Full Text Available New data for the differential cross sections, polarization observables T, F, and E in the reaction of η photoproduction on proton from the threshold up to a center-of-mass energy of W=1.9 GeV are presented. The data were obtained with the Crystal-Ball/TAPS detector setup at the Glasgow tagged photon facility of the Mainz Microtron MAMI. The polarization measurements were made using a frozen-spin butanol target and circularly polarized photon beam. The results are compared to existing experimental data and different PWA predictions. The data solve a long-standing problem related the angular dependence of older T data close to threshold. The unexpected relative phase motion between s- and d-wave amplitudes required by the old data is not confirmed. At higher energies, all model predictions fail to reproduce the new polarization data indicating a significant impact on our understanding of the underlying dynamics of η meson photoproduction. Furthermore, we present a fit of the new data and existing data from GRAAL for ∑ asymmetry based on an expansion in terms of associated Legendre polynomials. A Legendre decomposition shows the sensitivity to small partialwave contributions. The sensitivity of the Legendre coefficients to the nucleon resonance parameters is shown using the ηMAID isobar model.

  14. CFD modeling of reaction and mass transfer through a single pellet:Catalytic oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    Siavash Seyednej adian; Nakisa Yaghobi; Ramin Maghrebi; Leila Vafajoo

    2011-01-01

    In this study a mathematical model of a small scale single pellet for the oxidative coupling of methane (OCM) over titanite pervoskité isdeveloped.The method is based on a computational fluid dynamics (CFD) code which known as Fluent may be adopted to model the reactions that take place inside the porous catalyst pellet.The steady state single pellet model is coupled with a kinetic model and the intra-pellet concentration profiles of species are provided.Subsequent to achieving this goal,a nonlinear reaction network consisting of nine catalytic reactions and one gas phase reaction as an external program is successfully implemented to CFD-code as a reaction term in solving the equations.This study is based on the experimental design which is conducted in a differential reactor with a Sn/BaTiO3 catalyst (7-8 mesh) at atmospheric pressure,GHSV of 12000 h-1,ratio of methane to oxygen of 2,and three different temperatures of 1023,1048 and 1073 K.The modeling results such as selectivity and conversion at the pellet exit are in good agreement with the experimental data.Therefore,it is suggested that to achieve high yield in OCM process the modeling of the single pellet should be considered as the heart of catalytic fixed bed reactor.

  15. Total Reaction Cross Section in an Isospin-Dependent Quantum Molecular Dynamics Model

    Institute of Scientific and Technical Information of China (English)

    魏义彬; 蔡翔舟; 沈文庆; 马余刚; 张虎勇; 钟晨; 郭威; 陈金根; 马国亮; 王鲲

    2003-01-01

    The isospin-dependent quantum molecular dynamics (IDQMD) model is used to study the total reaction cross section σR. The energy-dependent Pauli volumes of neutrons and protons have been discussed and introduced into the IDQMD calculation to replace the widely used energy-independent Pauli volumes. The modified IDQMD calculation can reproduce the experimental cr R well for both stable and exotic nuclei induced reactions. Comparisons of the calculated σn induced by 11Li with different initial density distributions have been performed. It is shown that the calculation by using the experimentally deduced density distribution with a long tail can fit the experimental excitation function better than that by using the Skyrme-Hartree-Fock calculated density without long tails. It is also found that σR at high energy is sensitive to the long tail of density distribution.

  16. Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

    Science.gov (United States)

    Poux, T; Bonnefont, A; Ryabova, A; Kéranguéven, G; Tsirlina, G A; Savinova, E R

    2014-07-21

    Hydrogen peroxide has been identified as a stable intermediate of the electrochemical oxygen reduction reaction on various electrodes including metal, metal oxide and carbon materials. In this article we study the hydrogen peroxide oxidation and reduction reactions in alkaline medium using a rotating disc electrode (RDE) method on oxides of the perovskite family (LaCoO3, LaMnO3 and La0.8Sr0.2MnO3) which are considered as promising electrocatalytic materials for the cathode of liquid and solid alkaline fuel cells. The experimental findings, such as the higher activity of Mn-compared to that of Co-perovskites, the shape of RDE curves, and the influence of the H2O2 concentration, are rationalized with the help of a microkinetic model.

  17. Electron capture rates in stars studied with heavy ion charge exchange reactions

    CERN Document Server

    Bertulani, C A

    2015-01-01

    Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean $\\sim$ 50 MeV/nucleon and higher) are now routinely used to extract information of interest for nuclear astrophysics. This is of extreme relevance as many of the nuclei involved in stellar evolution are short-lived. Therefore, indirect methods became the focus of recent studies carried out in major nuclear physics facilities. Among such methods, heavy ion charge exchange is thought to be a useful tool to infer Gamow-Teller matrix elements needed to describe electron capture rates in stars and also double beta-decay experiments. In this short review, I provide a theoretical guidance based on a simple reaction model for charge exchange reactions.

  18. Study of neutron-rich nuclei using deep-inelastic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, I.Y.; Asztalos, S.; Deleplanque, M.; Cederwall, B.; Diamond, R.M.; Fallon, P.; Macchiavelli, A.O.; Phair, L.; Stephens, F.S.; Wozniak, G.J. [Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Frauendorf, S.G. [Research Center Rossendorf, Dresden (Germany); Becker, J.A.; Henry, E.A. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Hua, P.F.; Sarantites, D.G. [Washington University, St. Louis, Missouri 63130 (United States); Saladin, J.X. [University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States); Yu, C.H. [University of Rochester, Rochester, New York 14627 (United States)

    1997-08-01

    We have used the {sup 48}Ca+{sup 176}Yb reaction to study the population of high-spin states in neutron-rich nuclei by deep-inelastic reactions. Using Gammasphere, we observed gamma transitions from nuclei several neutrons richer than the target. Yrast states with spin up to 20 were populated in this reaction. High-spin states in {sup 175,177,178}Yb were observed. In this region of reduced pairing, a reference based on experimental data was used to derive experimental Routhians. Systematics of experimental Routhians in neutron-rich Yb nuclei compare well with cranked shell-model calculations. {copyright} {ital 1997} {ital The American Physical Society}

  19. A GPU Reaction Diffusion Soil-Microbial Model

    Science.gov (United States)

    Falconer, Ruth; Houston, Alasdair; Schmidt, Sonja; Otten, Wilfred

    2014-05-01

    Parallelised algorithms are frequent in bioinformatics as a consequence of the close link to informatics - however in the field of soil science and ecology they are less prevalent. A current challenge in soil ecology is to link habitat structure to microbial dynamics. Soil science is therefore entering the 'big data' paradigm as a consequence of integrating data pertinent to the physical soil environment obtained via imaging and theoretical models describing growth and development of microbial dynamics permitting accurate analyses of spatio-temporal properties of different soil microenvironments. The microenvironment is often captured by 3D imaging (CT tomography) which yields large datasets and when used in computational studies the physical sizes of the samples that are amenable to computation are less than 1 cm3. Today's commodity graphics cards are programmable and possess a data parallel architecture that in many cases is capable of out-performing the CPU in terms of computational rates. The programmable aspect is achieved via a low-level parallel programming language (CUDA, OpenCL and DirectX). We ported a Soil-Microbial Model onto the GPU using the DirectX Compute API. We noted a significant computational speed up as well as an increase in the physical size that can be simulated. Some of the drawbacks of such an approach were concerned with numerical precision and the steep learning curve associated with GPGPU technologies.

  20. Constitutive Relations for Reactive Transport Modeling: Effects of Chemical Reactions on Multi-Phase Flow Properties

    Science.gov (United States)

    Zhang, S.; Liu, H. H.; van Dijke, M. I.; Geiger, S.; Agar, S. M.

    2016-12-01

    The relationship between flow properties and chemical reactions is key to modeling subsurface reactive transport. This study develops closed-form equations to describe the effects of mineral precipitation and dissolution on multiphase flow properties (capillary pressure and relative permeabilities) of porous media. The model accounts for the fact that precipitation/dissolution only takes place in the water-filled part of pore space. The capillary tube concept was used to connect pore-scale changes to macroscopic hydraulic properties. Precipitation/dissolution induces changes in the pore radii of water-filled pores and consequently in the pore-size distribution. The updated pore-size distribution is converted back to a new capillary pressure-water saturation relation from which the new relative permeabilities are calculated. Pore network modeling is conducted on a Berea sandstone to validate the new continuum-scale relations. The pore network modeling results are satisfactorily predicted by the new closed-form equations. Currently the effects of chemical reactions on flow properties are represented as a relation between permeability and porosity in reactive transport modeling. Porosity is updated after chemical calculations from the change of mineral volumes, then permeability change is calculated from the porosity change using an empirical permeability-porosity relation, most commonly the Carman-Kozeny relation, or the Verma-Pruess relation. To the best of our knowledge, there are no closed-form relations available yet for the effects of chemical reactions on multi-phase flow properties, and thus currently these effects cannot be accounted for in reactive transport modeling. This work presents new constitutive relations to represent how chemical reactions affect multi-phase flow properties on the continuum scale based on the conceptual model of parallel capillary tubes. The parameters in our new relations are either pre-existing input in a multi-phase flow

  1. Computational Chemistry in the Undergraduate Laboratory: A Mechanistic Study of the Wittig Reaction

    Science.gov (United States)

    Albrecht, Birgit

    2014-01-01

    The Wittig reaction is one of the most useful reactions in organic chemistry. Despite its prominence early in the organic chemistry curriculum, the exact mechanism of this reaction is still under debate, and this controversy is often neglected in the classroom. Introducing a simple computational study of the Wittig reaction illustrates the…

  2. Theoretical study of the dark-oxidation reaction mechanisms for organic polymers

    Science.gov (United States)

    Wang, Guixiu; Zhu, Rongxiu; Zhang, Dongju; Liu, Chengbu

    2006-08-01

    To model the dark-oxidation mechanism of organic polymers, the reactions of the corresponding model compounds, including cumene, methyl 2-methylbutyrate, methyl methacrylate and methylacrylic acid, with triplet O 2 molecule, have been studied by performing density functional theory calculations at the UB3LYP/6-31G(d) level. The calculated results show that these model compounds can be oxygenated by O 2 via an H-abstract mechanism. The structures of initial contact charge transfer complexes, transition states, intermediates of cage-like pairs of radicals, and final hydro-peroxides involved in the reactions have been shown in details. The present results are expected to provide a general guidance for understanding the dark-oxidation mechanism of organic polymers.

  3. A three-variable model of deterministic chaos in the Belousov-Zhabotinsky reaction

    Science.gov (United States)

    Györgyi, László; Field, Richard J.

    1992-02-01

    CHAOS is exhibited by a wide variety of systems governed by nonlinear dynamic laws1-3. Its most striking feature is an apparent randomness which seems to contradict its deterministic origin. The best-studied chaotic chemical system is the Belousov-Zhabotinsky (BZ) reaction4-6 in a continuous-flow stirred-tank reactor (CSTR). Here we present a simple mechanism for the BZ reaction which allows us to develop a description in terms of a set of differential equations containing only three variables, the minimum number required to generate chaos in a continuous (non-iterative) dynamical system2. In common with experiments, our model shows aperiodicity and transitions between periodicity and chaos near bifurcations between oscillatory and steady-state behaviour, which occur at both low and high CSTR flow rates. While remaining closely related to a real chaotic chemical system, our model is sufficiently simple to allow detailed mathematical analysis. It also reproduces many other features of the BZ reaction better than does the simple Oregonator7 (which cannot produce chaos).

  4. Local administration of growth hormone enhances periimplant bone reaction in an osteoporotic rabbit model.

    Science.gov (United States)

    Tresguerres, Isabel F; Clemente, Celia; Donado, Manuel; Gómez-Pellico, Luis; Blanco, Luis; Alobera, Miguel Angel; Tresguerres, Jesús A F

    2002-12-01

    The purpose of this study was to determine whether rhGH administered locally during the surgical placement of an implant, in the tibia of an osteoporotic rabbit model, would induce qualitative and quantitative differences in peri-implant bone reaction. Eight New Zealand rabbits were ovariectomized and fed with a low-calcium diet (with 0.07% of calcium) to induce osteoporosis. After 6 weeks, an experimental titanium sheet was inserted into the rabbit tibiae. The rabbits were randomly divided into two groups. The experimental group was treated with 4 IU of rhGH added locally into the ostectomy as a lyophilized powder and the control group was left without any treatment. After 2 weeks, animals were sacrificed, tibial sections were prepared and bone-titanium interface was examined at light microscopy, using Masson, hematoxylin-eosin and Pichrosirius stains. Light microscopic morphometry and densitometry were used to comparatively quantitate bone reaction. Local administration of rhGH during the surgical placement of titanium sheets on the tibiae of an osteoporotic rabbit model enhances periosteal and transcortical reaction and mineralization of osteoid 14 days later around titanium sheets, without increasing bone resorption.

  5. Study of {sup 19}C by breakup reactions; Etude du {sup 19}C par reactions de cassure

    Energy Technology Data Exchange (ETDEWEB)

    Liegard, Emmanuel [Lab. de Physique Corpusculaire, Caen Univ., 14 Caen (France)

    1998-01-07

    To date studies of halo nuclei have been principally focussed on the A 11 systems {sup 11}Li and {sup 11}Be. The evolution of the properties of the halo with the mass of the system and the binding energy and angular momentum of the halo nucleons is a question of fundamental importance. It was in this spirit that the present study of {sup 19}C (S{sub n} = 240 {+-} 100 keV) was undertaken. The experiment was performed at GANIL using a secondary {sup 19}C beam ({approx_equal} 15 pps at 36 MeV/nucleon) produced via fragmentation. The experimental setup which included the neutron array DEMON, provided for identification of the core-breakup and dissociation reaction channels. In the first case, a very narrow single neutron angular distribution (FWHM = 64 {+-} 17 MeV/c) was observed for {sup 19}C, in contrast to that found for three `reference` nuclei {sup 21}N, {sup 22}O and {sup 24}F (FWHM {approx_equal} 165 MeV/c). This result could be interpreted within the framework of the core-breakup reaction model of a one-neutron halo nucleus. The results obtained for dissociation, while supporting the existence of the halo, indicated that it is not well developed. In addition, a comparison between the present results, the parallel momentum distributions for the core ({sup 18}C) and theoretical predictions have allowed conclusions to be drawn regarding the configuration of the valence neutron. In particular, a purely 2s{sub 1/2} of 1d{sub 5/2} configuration is excluded and mixing, possible with core excited states, must be considered. A probable ground state spin-parity assignment of 3{sup +}/2 or 5{sup +}/2 is suggested. (author) 150 refs., 278 figs., 28 tabs.

  6. SurfKin: an ab initio kinetic code for modeling surface reactions.

    Science.gov (United States)

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-05

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts.

  7. Modeling of the Reaction Mechanism of Enzymatic Radical C–C Coupling by Benzylsuccinate Synthase

    Directory of Open Access Journals (Sweden)

    Maciej Szaleniec

    2016-04-01

    Full Text Available Molecular modeling techniques and density functional theory calculations were performed to study the mechanism of enzymatic radical C–C coupling catalyzed by benzylsuccinate synthase (BSS. BSS has been identified as a glycyl radical enzyme that catalyzes the enantiospecific fumarate addition to toluene initiating its anaerobic metabolism in the denitrifying bacterium Thauera aromatica, and this reaction represents the general mechanism of toluene degradation in all known anaerobic degraders. In this work docking calculations, classical molecular dynamics (MD simulations, and DFT+D2 cluster modeling was employed to address the following questions: (i What mechanistic details of the BSS reaction yield the most probable molecular model? (ii What is the molecular basis of enantiospecificity of BSS? (iii Is the proposed mechanism consistent with experimental observations, such as an inversion of the stereochemistry of the benzylic protons, syn addition of toluene to fumarate, exclusive production of (R-benzylsuccinate as a product and a kinetic isotope effect (KIE ranging between 2 and 4? The quantum mechanics (QM modeling confirms that the previously proposed hypothetical mechanism is the most probable among several variants considered, although C–H activation and not C–C coupling turns out to be the rate limiting step. The enantiospecificity of the enzyme seems to be enforced by a thermodynamic preference for binding of fumarate in the pro(R orientation and reverse preference of benzyl radical attack on fumarate in pro(S pathway which results with prohibitively high energy barrier of the radical quenching. Finally, the proposed mechanism agrees with most of the experimental observations, although the calculated intrinsic KIE from the model (6.5 is still higher than the experimentally observed values (4.0 which suggests that both C–H activation and radical quenching may jointly be involved in the kinetic control of the reaction.

  8. Reaction kinetics and modeling of photoinitiated cationic polymerization of an alicyclic based diglycidyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Harikrishna, R., E-mail: r.harikrishna@ncl.res.in [Polymer Science and Engineering Division, National Chemical Laboratory, Pune 411008 (India); Ponrathnam, S. [Polymer Science and Engineering Division, National Chemical Laboratory, Pune 411008 (India); Tambe, S.S. [Chemical Engineering and Process Development Division, National Chemical Laboratory, Pune 411008 (India)

    2014-01-01

    Highlights: • Photocationic polymerization of alicyclic based diglycidyl ether was carried out. • Kinetic parameters were influenced by gelation and diffusional restrictions. • Applicability of autocatalytic model was established by nonlinear regression. • System showed higher activation energy than cycloaliphatic and aromatic diepoxides. -- Abstract: Photoinitiated cationic polymerization of cycloaliphatic diepoxides had received tremendous attention, while studies with lesser polymerizable diglycidyl ethers are comparatively less reported. The present work deals with the photoinitiated cationic polymerization of cyclohexane dimethanol diglycidyl ether followed by estimation of kinetic parameters. The effects of concentration of photoinitiator and temperature on curing performance were studied using photo differential scanning calorimeter or photo DSC with polychromatic radiation. It was observed that the rate of polymerization as well as ultimate conversion increased with increasing concentration of photoinitiator and temperature. The influences of gelation as well as diffusional restrictions have remarkable effect on cure performance. The kinetic parameters as per autocatalytic kinetic model were studied by Levenberg–Marquardt nonlinear regression method instead of conventional linear method for obtaining more accurate values of apparent rate constant. It was observed that the model fits with data from initial stages to almost towards the end of the reaction. The activation energy was found to be higher than the values reported for more reactive cycloaliphatic diepoxides. The value of pre-exponential factor increased with increase in activation energy showing influence of gelation at early stages of reaction.

  9. A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace

    Science.gov (United States)

    Kruskopf, Ari; Visuri, Ville-Valtteri

    2017-08-01

    In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.

  10. Reactions of Trimethylaluminium: Modelling the Chemical Degradation of Synthetic Lubricants.

    Science.gov (United States)

    Slaughter, Jonathan; Peel, Andrew J; Wheatley, Andrew E H

    2017-01-01

    In investigating and seeking to mimic the reactivity of trimethylaluminium (TMA) with synthetic, ester-based lubricating oils, the reaction of methyl propionate 1 was explored with 1, 2 and 3 equivalents of the organoaluminium reagent. Spectroscopic analysis points to the formation of the adduct 1(TMA) accompanied only by the low level 1:1 production of Me2 AlOCEtMe2 2 and Me2 AlOMe 3 when an equimolar amount of TMA is applied. The deployment of excess TMA favours reaction to give 2 and 3 over 1(TMA) adduct formation and spectroscopy reveals that in hydrocarbon solution substitution product 2 traps unreacted TMA to yield 2(TMA). The (1) H NMR spectroscopic observation of two Al-Me signals not attributable to free TMA and in the ratio 1:4 suggests the formation of a previously only postulated, symmetrical metallacycle in Me4 Al2 (μ(2) -Me)(μ(2) -OCEtMe2 ). In the presence of 3, 2(TMA) undergoes thermally induced exchange to yield Me4 Al2 (μ(2) -OMe)(μ(2) -OCEtMe2 ) 4 and TMA. The reaction of methyl phenylacetate 5 with TMA allows isolation of the crystalline product Me2 AlOCBnMe2 (TMA) 6(TMA), which allows the first observation of the Me4 Al2 (μ(2) -Me)(μ(2) -OR) motif in the solid state. Distances of 2.133(3) Å (Al-Mebridging ) and 1.951 Å (mean Al-Meterminal ) are recorded. The abstraction of TMA from 6(TMA) by the introduction of Et2 O has yielded 6, which exists as a dimer.

  11. Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions

    CERN Document Server

    Ramos, Pablo; Pavanello, Michele

    2015-01-01

    We have carried out a thorough benchmark of the FDE-ET method for calculating hole transfer couplings. We have considered 10 exchange-correlation functionals, 3 non-additive kinetic energy functionals and 3 basis sets. Overall, we conclude that with a 7% mean relative unsigned error, the PBE functional coupled with the PW91k non-additive Kinetic energy functional and a TZP basis set constitutes the most stable, and accurate level of theory for hole-transfer coupling calculations. The FDE-ET method is found to be an excellent tool for computing diabatic couplings for hole transfer reactions.

  12. Reactions to Discrimination, Stigmatization, Ostracism, and Other Forms of Interpersonal Rejection: A Multimotive Model

    OpenAIRE

    Richman, Laura Smart; Leary, Mark R.

    2009-01-01

    This article describes a new model that provides a framework for understanding people’s reactions to threats to social acceptance and belonging as they occur in the context of diverse phenomena such as rejection, discrimination, ostracism, betrayal, and stigmatization. People’s immediate reactions are quite similar across different forms of rejection in terms of negative affect and lowered self-esteem. However, following these immediate responses, people’s reactions are influenced by construa...

  13. Mantra, music and reaction times: a study of its applied aspects

    OpenAIRE

    Varun Malhotra, Rinku Garg, Usha Dhar, Neera Goel, Yogesh Tripathy, Iram Jaan, Sachit Goyal, Sumit Arora

    2014-01-01

    Aims &Objectives: The mechanism of the effects of music is still under scientific study and needs to be understood in a better way. We designed this study to see how music affects reaction time and concentration. The aim of our study was to study the effect of Gayatri mantra on reaction time. Material and Methods: 30 healthy subjects were selected for the study. Baseline record of Visual online Reaction time test was taken. Online visual reaction time was measured during listening to Gayatri...

  14. Molecular Simulations of RNA 2’-O-Transesterification Reaction Models in Solution

    OpenAIRE

    Radak, Brian K.; Harris, Michael E.; York, Darrin M.

    2012-01-01

    We employ quantum mechanical/molecular mechanical umbrella sampling simulations to probe the free energy surfaces of a series of increasingly complex reaction models of RNA 2’-O-transesterification in aqueous solution under alkaline conditions. Such models are valuable for understanding the uncatalyzed processes underlying catalytic cleavage of the phosphodiester backbone of RNA, a reaction of fundamental importance in biology. The chemically reactive atoms are modeled by the AM1/d-PhoT quant...

  15. A Reaction-based Diagonalization Approach to Modeling Surface Water Quality

    Science.gov (United States)

    Yu, J.; Yeh, G.; Zhang, F.; Wu, T.; Hu, G.

    2005-12-01

    There are many water quality models (e.g., WASP, QAUL2E/QUAL2K, CE-QUAL-ICM, RCA, RMA11, etc.) that have been employed by practitioners in surface water quality modeling. All of these models are similar to each others. The major differences among them are the number of water quality parameters included and the number of biogeochemical processes considered. Because of the limitation on the number of biogeochemical processes considered and, in a lesser extent, on the number of water quality parameters included, these models often perform only fairly in validation and their predictions may be unreliable, even though they can be adequately calibrated in most occasions and excellently in some occasions. Obviously, there is a need to develop a model that would allow the inclusion of any number of water quality parameters and enable the hypothesis of any number of biogeochemical processes. This paper presents the development of a numerical water quality model using a general paradigm of reaction-based approaches. In a reaction-based approach, all conceptualized biogoechemical processes are transformed into a reaction network. Through the decomposition of species governing equations via Gauss-Jordan column reduction of the reaction network, (1) redundant fast reactions and irrelevant kinetic reactions are removed from the system, which alleviates the problem of unnecessary and erroneous formulation and parameterization of these reactions, and (2) fast reactions and slow reactions are decoupled, which enables robust numerical integrations. The system of species governing equations is transformed into two sets: algebraic equations (either mass action equations or users' specified) of equilibrium variables and differential equations of kinetic variables. As a result, the model alleviates the needs of using simple partitions for fast reactions and uses kinetic-variables instead of biogeochemical species as primary dependent variables. With the diagonalization strategy, it

  16. A relativistic toy model for back-reaction

    CERN Document Server

    Plunien, G; Schützhold, R; Ruser, Marcus; Sch\\"utzhold, Ralf

    2004-01-01

    We consider a quantized massless and minimally coupled scalar field on a circular closed string with a time-dependent radius $R(t)$, whose undisturbed dynamics is governed by the Nambu-Goto action. Within the semi-classical treatment, the back-reaction of the quantum field onto the string dynamics is taken into account in terms of the renormalized expectation value of the energy-momentum tensor including the trace anomaly. The results indicate that the back-reaction could prevent the collapse of the circle $R\\downarrow0$ -- however, the semi-classical picture fails to describe the string dynamics at the turning point (i.e., possible bounce) at finite values of $R$ and $\\dot R$. The fate of the closed string after that point (e.g., oscillation or eternal acceleration) cannot be determined within the semi-classical picture and thus probably requires the full quantum treatment. PACS: 04.62.+v, 03.70.+k, 11.15.Kc, 04.60.-m.

  17. Exploratory study of nuclear reaction data utility framework of Japan charged particle reaction data group (JCPRG)

    Energy Technology Data Exchange (ETDEWEB)

    Masui, Hiroshi; Ohnishi, Akira; Kato, Kiyoshi [Hokkaido Univ., Graduate School of Science, Sapporo, Hokkaido (Japan); Ohbayasi, Yosihide [Hokkaido Univ., Meme Media Lab., Sapporo, Hokkaido (Japan); Aoyama, Shigeyoshi [Kitami Institute of Technology, Information Processing Center, Kitami, Hokkaido (Japan); Chiba, Masaki [Sapporo Gakuin Univ., Faculty of Social Information, Ebetsu, Hokkaido (Japan)

    2002-08-01

    Compilation, evaluation and dissemination are essential pieces of work for the nuclear data activities. We, Japan charged particle data group, have researched the utility framework for the nuclear reaction data on the basis of recent progress of computer and network technologies. These technologies will be not only for the data dissemination but for the compilation and evaluation assistance among the many corresponding researchers of all over the world. In this paper, current progress of our research and development is shown. (author)

  18. Structure-reactivity modeling using mixture-based representation of chemical reactions

    Science.gov (United States)

    Polishchuk, Pavel; Madzhidov, Timur; Gimadiev, Timur; Bodrov, Andrey; Nugmanov, Ramil; Varnek, Alexandre

    2017-07-01

    We describe a novel approach of reaction representation as a combination of two mixtures: a mixture of reactants and a mixture of products. In turn, each mixture can be encoded using an earlier reported approach involving simplex descriptors (SiRMS). The feature vector representing these two mixtures results from either concatenated product and reactant descriptors or the difference between descriptors of products and reactants. This reaction representation doesn't need an explicit labeling of a reaction center. The rigorous "product-out" cross-validation (CV) strategy has been suggested. Unlike the naïve "reaction-out" CV approach based on a random selection of items, the proposed one provides with more realistic estimation of prediction accuracy for reactions resulting in novel products. The new methodology has been applied to model rate constants of E2 reactions. It has been demonstrated that the use of the fragment control domain applicability approach significantly increases prediction accuracy of the models. The models obtained with new "mixture" approach performed better than those required either explicit (Condensed Graph of Reaction) or implicit (reaction fingerprints) reaction center labeling.

  19. PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC

    Science.gov (United States)

    Parkhurst, David L.; Wissmeier, Laurin

    2015-09-01

    PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst-Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants. PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.

  20. Modelling the effect of temperature on the range expansion of species by reaction-diffusion equations.

    Science.gov (United States)

    Richter, Otto; Moenickes, Sylvia; Suhling, Frank

    2012-02-01

    The spatial dynamics of range expansion is studied in dependence of temperature. The main elements population dynamics, competition and dispersal are combined in a coherent approach based on a system of coupled partial differential equations of the reaction-diffusion type. The nonlinear reaction terms comprise population dynamic models with temperature dependent reproduction rates subject to an Allee effect and mutual competition. The effect of temperature on travelling wave solutions is investigated for a one dimensional model version. One main result is the importance of the Allee effect for the crossing of regions with unsuitable habitats. The nonlinearities of the interaction terms give rise to a richness of spatio-temporal dynamic patterns. In two dimensions, the resulting non-linear initial boundary value problems are solved over geometries of heterogeneous landscapes. Geo referenced model parameters such as mean temperature and elevation are imported into the finite element tool COMSOL Multiphysics from a geographical information system. The model is applied to the range expansion of species at the scale of middle Europe.

  1. Chemistry in Disks. IV. Benchmarking gas-grain chemical models with surface reactions

    CERN Document Server

    Semenov, D; Wakelam, V; Dutrey, A; Chapillon, E; Guilloteau, St; Henning, Th; Launhardt, R; Pietu, V; Schreyer, K

    2010-01-01

    Abridged: We detail and benchmark two sophisticated chemical models developed by the Heidelberg and Bordeaux astrochemistry groups. The main goal of this study is to elaborate on a few well-described tests for state-of-the-art astrochemical codes covering a range of physical conditions and chemical processes, in particular those aimed at constraining current and future interferometric observations of protoplanetary disks. We consider three physical models: a cold molecular cloud core, a hot core, and an outer region of a T Tauri disk. Our chemical network (for both models) is based on the original gas-phase osu_03_2008 ratefile and includes gas-grain interactions and a set of surface reactions for the H-, O-, C-, S-, and N-bearing molecules. The benchmarking is performed with the increasing complexity of the considered processes: (1) the pure gas-phase chemistry, (2) the gas-phase chemistry with accretion and desorption, and (3) the full gas-grain model with surface reactions. Using atomic initial abundances ...

  2. Dynamics of Pickering Emulsions in the Presence of an Interfacial Reaction: A Simulation Study.

    Science.gov (United States)

    Zhao, Shuangliang; Zhan, Bicai; Hu, Yaofeng; Fan, Zhaoyu; Pera-Titus, Marc; Liu, Honglai

    2016-12-13

    Pickering emulsions combining surface-active and catalytic properties offer a promising platform for conducting interfacial reactions between immiscible reagents. Despite the significant progress in the design of Pickering interfacial catalysts for a broad panel of reactions, the dynamics of Pickering emulsions under reaction conditions is still poorly understood. Herein, using benzene hydroxylation with aqueous H2O2 as a model system, we explored the dynamics of benzene/water Pickering emulsions during reaction by dissipative particle dynamics. Our study points out that the surface wettability of the silica nanoparticles is affected to a higher extent by the degree of polymer grafting rather than an increase of the chain length of hydrophobic polymer moieties. A remarkable decline of the oil-in-water (O/W) interfacial tension was observed when increasing the yield of the reaction product (phenol), affecting the emulsion stability. However, phenol did not alter to an important extent the distribution of immiscible reagents around the nanoparticles sitting at the benzene/water interface. A synergistic effect between phenol and silica nanoparticles on the O/W interfacial tension of the biphasic system could be ascertained.

  3. A reaction-diffusion SIS epidemic model in an almost periodic environment

    Science.gov (United States)

    Wang, Bin-Guo; Li, Wan-Tong; Wang, Zhi-Cheng

    2015-12-01

    A susceptible-infected-susceptible almost periodic reaction-diffusion epidemic model is studied by means of establishing the theories and properties of the basic reproduction ratio {R0}. Particularly, the asymptotic behaviors of {R0} with respect to the diffusion rate {DI} of the infected individuals are obtained. Furthermore, the uniform persistence, extinction and global attractivity are presented in terms of {R0}. Our results indicate that the interaction of spatial heterogeneity and temporal almost periodicity tends to enhance the persistence of the disease.

  4. Efficiency of alternative McMC strategies illustrated using the reaction norm model

    DEFF Research Database (Denmark)

    Shariati, M; Sorensen, D

    2008-01-01

    The Markov chain Monte Carlo (MCMC) strategy provides remarkable flexibility for fitting complex hierarchical models. However, when parameters are highly correlated in their posterior distributions and their number is large, a particular MCMC algorithm may perform poorly and the resulting...... inferences may be affected. The objective of this study was to compare the efficiency (in terms of the asymptotic variance of features of posterior distributions of chosen parameters, and in terms of computing cost) of six MCMC strategies to sample parameters using simulated data generated with a reaction...

  5. Continuous Dependence in Front Propagation for Convective Reaction-Diffusion Models with Aggregative Movements

    Directory of Open Access Journals (Sweden)

    Luisa Malaguti

    2011-01-01

    Full Text Available The paper deals with a degenerate reaction-diffusion equation, including aggregative movements and convective terms. The model also incorporates a real parameter causing the change from a purely diffusive to a diffusive-aggregative and to a purely aggregative regime. Existence and qualitative properties of traveling wave solutions are investigated, and estimates of their threshold speeds are furnished. Further, the continuous dependence of the threshold wave speed and of the wave profiles on a real parameter is studied, both when the process maintains its diffusion-aggregation nature and when it switches from it to another regime.

  6. Development and validation of a risk model for predicting adverse drug reactions in older people during hospital stay: Brighton Adverse Drug Reactions Risk (BADRI model.

    Directory of Open Access Journals (Sweden)

    Balamurugan Tangiisuran

    Full Text Available Older patients are at an increased risk of developing adverse drug reactions (ADR. Of particular concern are the oldest old, which constitute an increasingly growing population. Having a validated clinical tool to identify those older patients at risk of developing an ADR during hospital stay would enable healthcare staff to put measures in place to reduce the risk of such an event developing. The current study aimed to (1 develop and (2 validate an ADR risk prediction model.We used a combination of univariate analysis and multivariate binary logistic regression to identify clinical risk factors for developing an ADR in a population of older people from a UK teaching hospital. The final ADR risk model was then validated in a European population (European dataset.Six-hundred-ninety patients (median age 85 years were enrolled in the development stage of the study. Ninety-five reports of ADR were confirmed by independent review in these patients. Five clinical variables were identified through multivariate analysis and included in our final model; each variable was attributed a score of 1. Internal validation produced an AUROC of 0.74, a sensitivity of 80%, and specificity of 55%. During the external validation stage the AUROC was 0.73, with sensitivity and specificity values of 84% and 43% respectively.We have developed and successfully validated a simple model to use ADR risk score in a population of patients with a median age of 85, i.e. the oldest old. The model is based on 5 clinical variables (≥8 drugs, hyperlipidaemia, raised white cell count, use of anti-diabetic agents, length of stay ≥12 days, some of which have not been previously reported.

  7. Development and Validation of a Risk Model for Predicting Adverse Drug Reactions in Older People during Hospital Stay: Brighton Adverse Drug Reactions Risk (BADRI) Model

    Science.gov (United States)

    Tangiisuran, Balamurugan; Scutt, Greg; Stevenson, Jennifer; Wright, Juliet; Onder, G.; Petrovic, M.; van der Cammen, T. J.; Rajkumar, Chakravarthi; Davies, Graham

    2014-01-01

    Background Older patients are at an increased risk of developing adverse drug reactions (ADR). Of particular concern are the oldest old, which constitute an increasingly growing population. Having a validated clinical tool to identify those older patients at risk of developing an ADR during hospital stay would enable healthcare staff to put measures in place to reduce the risk of such an event developing. The current study aimed to (1) develop and (2) validate an ADR risk prediction model. Methods We used a combination of univariate analysis and multivariate binary logistic regression to identify clinical risk factors for developing an ADR in a population of older people from a UK teaching hospital. The final ADR risk model was then validated in a European population (European dataset). Results Six-hundred-ninety patients (median age 85 years) were enrolled in the development stage of the study. Ninety-five reports of ADR were confirmed by independent review in these patients. Five clinical variables were identified through multivariate analysis and included in our final model; each variable was attributed a score of 1. Internal validation produced an AUROC of 0.74, a sensitivity of 80%, and specificity of 55%. During the external validation stage the AUROC was 0.73, with sensitivity and specificity values of 84% and 43% respectively. Conclusions We have developed and successfully validated a simple model to use ADR risk score in a population of patients with a median age of 85, i.e. the oldest old. The model is based on 5 clinical variables (≥8 drugs, hyperlipidaemia, raised white cell count, use of anti-diabetic agents, length of stay ≥12 days), some of which have not been previously reported. PMID:25356898

  8. Experimental study of $\\eta$ meson photoproduction reaction at MAMI

    CERN Document Server

    Kashevarov, V L

    2015-01-01

    New data for the differential cross sections, polarization observables $T$, $F$, and $E$ in the reaction of $\\eta$ photoproduction on proton from the threshold up to a center-of-mass energy of W=1.9 GeV are presented. The data were obtained with the Crystal-Ball/TAPS detector setup at the Glasgow tagged photon facility of the Mainz Microtron MAMI. The polarization measurements were made using a frozen-spin butanol target and circularly polarized photon beam. The results are compared to existing experimental data and different PWA predictions. The data solve a long-standing problem related the angular dependence of older $T$ data close to threshold. The unexpected relative phase motion between $s$- and $d$-wave amplitudes required by the old data is not confirmed. At higher energies, all model predictions fail to reproduce the new polarization data indicating a significant impact on our understanding of the underlying dynamics of $\\eta$ meson photoproduction. Furthermore, we present a fit of the new data and e...

  9. The reaction between iodine and silver under severe PWR accident conditions. An experimental parameter study

    Energy Technology Data Exchange (ETDEWEB)

    Funke, F.; Greger, G.U.; Bleier, A.; Hellmann, S.; Morell, W. [Siemens AG, Power Generation Group, Erlangen (Germany)

    1996-12-01

    An extensive experimental parameter study was performed on the kinetics in the reaction system I{sub 2}/Ag and I{sup -}/Ag in a laboratory-scale apparatus.Starting with I{sub 2} or I{sup -} solutions and silver powder suspensions, the decrease of soluted I{sub 2} or I{sup -}, respectively, due to fixation on the silver particles, was monitored as function of time using the radioactive tracer I-131. The measured data were analyzed using a model of first order kinetics with respect to the iodine concentration. However, the analysis using first order kinetics had to be performed separately in an early, fast reaction phase and in a late, slow reaction phase. The reason for this unexpected behaviour was not identified. Thus, rate constant, two for each test, were deduced from 14 I{sub 2}/Ag main tests and from 36 I{sup -}/Ag tests. No dependencies of the rate constants were found on the parameters temperature, initial iodine concentration, presence of boric acid, type of silver educt, and pretreatment of the silver educt prior to the tests. However, the stirring of the reaction solution generally enhanced the kinetics highlighting the importance of mass transfer. The I{sup -}/Ag reaction proceeded only if there was no inertization of the reaction solution by sparging with nitrogen. The temperature-independent rate constant for the early, fast I{sub 2}/Ag reaction phase is 2E-5 m/s. However, a smaller rate constant of 6E-6 m/s is recommended for use in source term calculations with IMPAIR, which already contains a first order model. Analogously, the temperature-independent I{sup -}/Ag reaction rate constant is 8E-6 m/s in an early, fast reaction phase. For use in source term calculations, a smaller rate constant of 2E-6 m/s is recommended. The lower bound of the I{sup -}/Ag rate constant was 3E-8 m/s which could be used in very conservative source term calculations. (author) 20 figs., 6 tabs., 15 refs.

  10. Monitoring, Modeling, and Diagnosis of Alkali-Silica Reaction in Small Concrete Samples

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Vivek [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cai, Guowei [Idaho National Lab. (INL), Idaho Falls, ID (United States); Gribok, Andrei V. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mahadevan, Sankaran [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-01

    Assessment and management of aging concrete structures in nuclear power plants require a more systematic approach than simple reliance on existing code margins of safety. Structural health monitoring of concrete structures aims to understand the current health condition of a structure based on heterogeneous measurements to produce high-confidence actionable information regarding structural integrity that supports operational and maintenance decisions. This report describes alkali-silica reaction (ASR) degradation mechanisms and factors influencing the ASR. A fully coupled thermo-hydro-mechanical-chemical model developed by Saouma and Perotti by taking into consideration the effects of stress on the reaction kinetics and anisotropic volumetric expansion is presented in this report. This model is implemented in the GRIZZLY code based on the Multiphysics Object Oriented Simulation Environment. The implemented model in the GRIZZLY code is randomly used to initiate ASR in a 2D and 3D lattice to study the percolation aspects of concrete. The percolation aspects help determine the transport properties of the material and therefore the durability and service life of concrete. This report summarizes the effort to develop small-size concrete samples with embedded glass to mimic ASR. The concrete samples were treated in water and sodium hydroxide solution at elevated temperature to study how ingress of sodium ions and hydroxide ions at elevated temperature impacts concrete samples embedded with glass. Thermal camera was used to monitor the changes in the concrete sample and results are summarized.

  11. Modeling light-driven proton pumps in artificial photosynthetic reaction centers.

    Science.gov (United States)

    Ghosh, Pulak Kumar; Smirnov, Anatoly Yu; Nori, Franco

    2009-07-21

    We study a model of a light-induced proton pump in artificial reaction centers. The model contains a molecular triad with four electron states (i.e., one donor state, two photosensitive group states, and one acceptor state) as well as a molecular shuttle having one electron and one proton-binding sites. The shuttle diffuses between the sides of the membrane and translocates protons energetically uphill: from the negative side to the positive side of the membrane, harnessing for this purpose the energy of the electron-charge separation produced by light. Using the methods of quantum transport theory we calculate the range of light intensity and transmembrane potentials that maximize both the light-induced proton current and the energy transduction efficiency. We also study the effect of temperature on proton pumping. The light-induced proton pump in our model gives a quantum yield of proton translocation of about 55%. Thus, our results explain previous experiments on these artificial photosynthetic reaction centers.

  12. Modeling of the symmetry factor of electrochemical proton discharge via the Volmer reaction

    DEFF Research Database (Denmark)

    Björketun, Mårten E.; Tripkovic, Vladimir; Skúlason, Egill

    2013-01-01

    A scheme for evaluating symmetry factors of elementary electrode reactions using a density functional theory (DFT) based model of the electrochemical double layer is presented. As an illustration, the symmetry factor is determined for hydrogen adsorption via the electrochemical Volmer reaction. T...

  13. Reactions to Discrimination, Stigmatization, Ostracism, and Other Forms of Interpersonal Rejection: A Multimotive Model

    Science.gov (United States)

    Richman, Laura Smart; Leary, Mark R.

    2009-01-01

    This article describes a new model that provides a framework for understanding people's reactions to threats to social acceptance and belonging as they occur in the context of diverse phenomena such as rejection, discrimination, ostracism, betrayal, and stigmatization. People's immediate reactions are quite similar across different forms of…

  14. New tools in modulating Maillard reaction from model systems to food

    NARCIS (Netherlands)

    Troise, A.D.

    2015-01-01

    New tools in modulating Maillard reaction from model systems to food
    The Maillard reaction (MR) supervises the final quality of foods and occupies a prominent place in food science. The first stable compounds, the Amadori rearrangement products (

  15. Modeling Proton- and Light Ion-Induced Reactions at Low Energies in the MARS15 Code

    Energy Technology Data Exchange (ETDEWEB)

    Rakhno, I. L. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); Mokhov, N. V. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); Gudima, K. K. [National Academy of Sciences, Cisineu (Moldova)

    2015-04-25

    An implementation of both ALICE code and TENDL evaluated nuclear data library in order to describe nuclear reactions induced by low-energy projectiles in the Monte Carlo code MARS15 is presented. Comparisons between results of modeling and experimental data on reaction cross sections and secondary particle distributions are shown.

  16. Stochastic modeling of biochemical systems with multistep reactions using state-dependent time delay.

    Science.gov (United States)

    Wu, Qianqian; Tian, Tianhai

    2016-08-24

    To deal with the growing scale of molecular systems, sophisticated modelling techniques have been designed in recent years to reduce the complexity of mathematical models. Among them, a widely used approach is delayed reaction for simplifying multistep reactions. However, recent research results suggest that a delayed reaction with constant time delay is unable to describe multistep reactions accurately. To address this issue, we propose a novel approach using state-dependent time delay to approximate multistep reactions. We first use stochastic simulations to calculate time delay arising from multistep reactions exactly. Then we design algorithms to calculate time delay based on system dynamics precisely. To demonstrate the power of proposed method, two processes of mRNA degradation are used to investigate the function of time delay in determining system dynamics. In addition, a multistep pathway of metabolic synthesis is used to explore the potential of the proposed method to simplify multistep reactions with nonlinear reaction rates. Simulation results suggest that the state-dependent time delay is a promising and accurate approach to reduce model complexity and decrease the number of unknown parameters in the models.

  17. A model for void-induced back reaction between radiolytic products in NaCl

    NARCIS (Netherlands)

    Turkin, A.A.; Dubinko, V.I.; Vainshtein, D.I.; Hartog, H.W. den

    2002-01-01

    A kinetic model is formulated for the chemical reaction between radiolytic sodium colloids and gas bubbles, which are brought into contact with each other during the exposure to ionising radiation by the growing voids. The reaction starts with the evaporation of Na atoms into the void due to the loc

  18. New tools in modulating Maillard reaction from model systems to food

    NARCIS (Netherlands)

    Troise, A.D.

    2015-01-01

    New tools in modulating Maillard reaction from model systems to food
    The Maillard reaction (MR) supervises the final quality of foods and occupies a prominent place in food science. The first stable compounds, the Amadori rearrangement products (

  19. A measurement model for general noise reaction in response to aircraft noise

    NARCIS (Netherlands)

    Kroesen, M.; Schreckenberg, D.

    2011-01-01

    In this paper a measurement model for general noise reaction (GNR) in response to aircraft noise is developed to assess the performance of aircraft noise annoyance and a direct measure of general reaction as indicators of this concept. For this purpose GNR is conceptualized as a superordinate latent

  20. Bench-scale Kinetics Study of Mercury Reactions in FGD Liquors

    Energy Technology Data Exchange (ETDEWEB)

    Gary Blythe; John Currie; David DeBerry

    2008-03-31

    This document is the final report for Cooperative Agreement DE-FC26-04NT42314, 'Kinetics Study of Mercury Reactions in FGD Liquors'. The project was co-funded by the U.S. DOE National Energy Technology Laboratory and EPRI. The objective of the project has been to determine the mechanisms and kinetics of the aqueous reactions of mercury absorbed by wet flue gas desulfurization (FGD) systems, and develop a kinetics model to predict mercury reactions in wet FGD systems. The model may be used to determine optimum wet FGD design and operating conditions to maximize mercury capture in wet FGD systems. Initially, a series of bench-top, liquid-phase reactor tests were conducted and mercury species concentrations were measured by UV/visible light spectroscopy to determine reactant and byproduct concentrations over time. Other measurement methods, such as atomic absorption, were used to measure concentrations of vapor-phase elemental mercury, that cannot be measured by UV/visible light spectroscopy. Next, a series of bench-scale wet FGD simulation tests were conducted. Because of the significant effects of sulfite concentration on mercury re-emission rates, new methods were developed for operating and controlling the bench-scale FGD experiments. Approximately 140 bench-scale wet FGD tests were conducted and several unusual and pertinent effects of process chemistry on mercury re-emissions were identified and characterized. These data have been used to develop an empirically adjusted, theoretically based kinetics model to predict mercury species reactions in wet FGD systems. The model has been verified in tests conducted with the bench-scale wet FGD system, where both gas-phase and liquid-phase mercury concentrations were measured to determine if the model accurately predicts the tendency for mercury re-emissions. This report presents and discusses results from the initial laboratory kinetics measurements, the bench-scale wet FGD tests, and the kinetics modeling

  1. Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

    Science.gov (United States)

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

    Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

  2. Geometrical Models of the Phase Space Structures Governing Reaction Dynamics

    CERN Document Server

    Waalkens, Holger

    2009-01-01

    Hamiltonian dynamical systems possessing equilibria of ${saddle} \\times {centre} \\times...\\times {centre}$ stability type display \\emph{reaction-type dynamics} for energies close to the energy of such equilibria; entrance and exit from certain regions of the phase space is only possible via narrow \\emph{bottlenecks} created by the influence of the equilibrium points. In this paper we provide a thorough pedagogical description of the phase space structures that are responsible for controlling transport in these problems. Of central importance is the existence of a \\emph{Normally Hyperbolic Invariant Manifold (NHIM)}, whose \\emph{stable and unstable manifolds} have sufficient dimensionality to act as separatrices, partitioning energy surfaces into regions of qualitatively distinct behavior. This NHIM forms the natural (dynamical) equator of a (spherical) \\emph{dividing surface} which locally divides an energy surface into two components (`reactants' and `products'), one on either side of the bottleneck. This di...

  3. Titration Calorimetry Applied to the Thermokinetics Study of Consecutive First-order Reactions

    Institute of Scientific and Technical Information of China (English)

    SHI Jing-Yan; LI Jie; WANG Zhi-Yong; LIU Yu-Wen; WANG Cun-Xin

    2008-01-01

    The thermokinetic mathematical models for consecutive first-order reactions in titration period and the stopped-titration reaction period were proposed for titration calorimetry, based on which, thermodynamic parameters (reaction enthalpies, △rHm1 and △rHm2) and kinetic parameters (rate constants, k1 and k2) of the consecutive first-order reactions could be obtained by directly simulating the calorimetric curve from a single experiment with the method of nonlinear least squares regression (NLLS).The reliability of the model has been verified by investigating the reaction of the saponification of diethyl succinate in an aqueous ethanol solvent.

  4. Model Calculation of n + 6Li Reactions Below 20 MeV

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jing-Shang; HAN Yin-Lu

    2001-01-01

    Based on the unified Hauser-Feshbach and exciton model for light nuclei, the calculations of reaction cross sections and the double-differential cross sections for n + 6Li are performed. Since all of the first-particle emissions are from the compound nucleus to the discrete levels, the angular momentum coupling effect in pre-equilibrium mechanism must be taken into account. The fitting of the measured data indicates that the three-body break-up process needs to be involved, and the pre-equilibrium reaction mechanism dominates the reaction processes. In light nucleus reactions the recoil effect must be taken into account.``

  5. Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

    DEFF Research Database (Denmark)

    Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten

    2010-01-01

    Density functional theory calculations have been performed for the three elementary steps―Tafel, Heyrovsky, and Volmer―involved in the hydrogen oxidation reaction (HOR) and its reverse, the hydrogen evolution reaction (HER). For the Pt(111) surface a detailed model consisting of a negatively...... charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting...

  6. Reaction mechanisms of aqueous monoethanolamine with carbon dioxide: a combined quantum chemical and molecular dynamics study.

    Science.gov (United States)

    Hwang, Gyeong S; Stowe, Haley M; Paek, Eunsu; Manogaran, Dhivya

    2015-01-14

    Aqueous monoethanolamine (MEA) has been extensively studied as a solvent for CO2 capture, yet the underlying reaction mechanisms are still not fully understood. Combined ab initio and classical molecular dynamics simulations were performed to revisit and identify key elementary reactions and intermediates in 25-30 wt% aqueous MEA with CO2, by explicitly taking into account the structural and dynamic effects. Using static quantum chemical calculations, we also analyzed in more detail the fundamental interactions involved in the MEA-CO2 reaction. We find that both the CO2 capture by MEA and solvent regeneration follow a zwitterion-mediated two-step mechanism; from the zwitterionic intermediate, the relative probability between deprotonation (carbamate formation) and CO2 removal (MEA regeneration) tends to be determined largely by the interaction between the zwitterion and neighboring H2O molecules. In addition, our calculations clearly demonstrate that proton transfer in the MEA-CO2-H2O solution primarily occurs through H-bonded water bridges, and thus the availability and arrangement of H2O molecules also directly impacts the protonation and/or deprotonation of MEA and its derivatives. This improved understanding should contribute to developing more comprehensive kinetic models for use in modeling and optimizing the CO2 capture process. Moreover, this work highlights the importance of a detailed atomic-level description of the solution structure and dynamics in order to better understand molecular mechanisms underlying the reaction of CO2 with aqueous amines.

  7. Quantitative global studies of reactomes and metabolomes using a vectorial representation of reactions and chemical compounds

    Directory of Open Access Journals (Sweden)

    Triviño Juan C

    2010-04-01

    Full Text Available Abstract Background Global studies of the protein repertories of organisms are providing important information on the characteristics of the protein space. Many of these studies entail classification of the protein repertory on the basis of structure and/or sequence similarities. The situation is different for metabolism. Because there is no good way of measuring similarities between chemical reactions, there is a barrier to the development of global classifications of "metabolic space" and subsequent studies comparable to those done for protein sequences and structures. Results In this work, we propose a vectorial representation of chemical reactions, which allows them to be compared and classified. In this representation, chemical compounds, reactions and pathways may be represented in the same vectorial space. We show that the representation of chemical compounds reflects their physicochemical properties and can be used for predictive purposes. We use the vectorial representations of reactions to perform a global classification of the reactome of the model organism E. coli. Conclusions We show that this unsupervised clustering results in groups of enzymes more coherent in biological terms than equivalent groupings obtained from the EC hierarchy. This hierarchical clustering produces an optimal set of 21 groups which we analyzed for their biological meaning.

  8. Dynamical Cluster-decay Model (DCM) applied to 9Li+208Pb reaction

    Science.gov (United States)

    Kaur, Arshdeep; Hemdeep; Kaushal, Pooja; Behera, Bivash R.; Gupta, Raj K.

    2017-10-01

    The decay mechanism of 217At* formed in 9Li+208Pb reaction is studied within the dynamical cluster-decay model (DCM) at various center-of-mass energies. The aim is to see the behavior of a light neutron-rich radioactive beam on a doubly-magic target nucleus for the (total) fusion cross section σfus and the individual decay channel cross sections. Experimentally, only the isotopic yield of heavy mass residues 211-214At * [equivalently, the light-particles (LPs) evaporation residue cross sections σxn for x = 3- 6 neutrons emission] are measured, with the fusion-fission (ff) component σff taken zero. For a fixed neck-length parameter ΔR, the only parameter in the DCM, we are able to fit σfus =∑x=16σxn almost exactly for 9Li on 208Pb at all E c . m .'s. However, the observed individual decay channels (3n-6n) are very poorly fitted, with unobserved channels (1n, 2n) and σff strongly over-estimated. Different ΔR values, meaning thereby different reaction time scales, are required to fit individually both the observed and unobserved evaporation residue channels (1n-6n) and σff, but then the compound nucleus (CN) contribution σCN is very small (< 1%), and the non-compound nucleus (nCN) decay cross section σnCN contributes the most towards total σfus (=σCN +σnCN). Thus, the 9Li induced reaction on doubly-magic 208Pb is more of a quasi-fission-like nCN decay, which is further analyzed in terms of the statistical CN formation probability PCN and CN survival probability Psurv. For the reaction under study, PCN < < 1 and Psurv → 1, in particular at above barrier energies.

  9. Studies on the runaway reaction of ABS polymerization process.

    Science.gov (United States)

    Hu, Kwan-Hua; Kao, Chen-Shan; Duh, Yih-Shing

    2008-11-15

    Taiwan has the largest acrylonitrile-butadiene-styrene (ABS) copolymer production in the world. Preventing on unexpected exothermic reactions and related emergency relief hazard is essential in the safety control of ABS emulsion polymerization. A VSP2 (Vent Sizing Package 2) apparatus is capable of studying both normal and abnormal conditions (e.g., cooling failure, mischarge, etc.) of industrial process. In this study, the scenarios were verified from the following abnormal conditions: loss of cooling, double charge of initiator, overcharge of monomer, without charge of solvent, and external fire. An external fire with constant heating will promote higher self-heat rate and this is recommended as the worst case scenario of emulsion polymerization on butadiene. Cooling failure coupled with bulk system of reactant was determined to be the credible worst case in ABS emulsion polymerization. Finally, the emergency vent sizing based on thermokinetics from VSP associated with DIERS methodology were used for evaluating the vent sizing and compared to that of the industrial plants.

  10. Nuclear structure and reaction studies at medium energies

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, G.W.; Ray, R.L.

    1990-10-01

    This document constitutes the (1988--1991) technical progress report for the ongoing medium energy physics research program supported by the US Department of Energy through special Research Grant FG05-88ER40444. The experiments discussed are conducted at the Los Alamos National Laboratory's (LANL) Clinton P. Anderson Meson Physics Facility (LAMPF), the Alternating Gradient Synchrotron (AGS) facility of the Brookhaven National Laboratory (BNL), and at the Fermi National Accelerator Laboratory (FNAL). The overall motivation for the work discussed in this document is driven by three main objectives: (1) provide hadron-nucleon and hadron-nucleus scattering data which serve to facilitate the study of effective two-body interactions, test (and possibly determine) nuclear structure, and help study reaction mechanisms and dynamics;(2) provide unique, first-of-a-kind exploratory'' hadron-nucleus scattering data in the hope that such data will lead to discovery of new phenomena and new physics; and (3) perform precision tests of fundamental interactions, such as rare decay searches, whose observation would imply fundamental new physics.

  11. A model for the {gamma}N{yields}{pi}{pi}N reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gomez Tejedor, J.A.; Oset, E. [Departamento de Fisica Teorica Centro Mixto Universidad de Valencia-CSIC, Burjassot, Valencia (Spain)]|[IFIC Centro Mixto Universidad de Valencia-CSIC, Burjassot, Valencia (Spain)

    1996-11-01

    We have studied the {gamma}N {yields} {pi}{pi}N reaction using a model which includes N, {Delta}(1232), N{sup *}(1440) and N{sup *}(1520) intermediate baryonic states and the {rho}-meson as intermediate {pi}{pi} resonance. The model reproduces fairly well experimental cross sections below E{sub {gamma}} = 800 MeV and invariant-mass distributions even at higher energies. One of the interesting findings of the study is that the {gamma}N{yields}N{sup *}(1520) {yields} {Delta}{pi} process is very important and interferes strongly with the dominant {Delta}-Kroll-Ruderman term to produce the experimental peak of the cross section. (author) 10 refs, 1 fig

  12. Study of $^{26}$Mg through 1p pick up reaction $^{27}$Al(d,$^{3}$He)

    CERN Document Server

    Srivastava, Vishal; Rana, T K; Manna, S; Kundu, S; Bhattacharya, S; Banerjee, K; Roy, P; Pandey, R; Mukherjee, G; Ghosh, T K; Meena, J K; Roy, T; Chaudhuri, A; Sinha, M; Saha, A K; Asgar, Md A; Dey, A; Roy, Subinit; Shaikh, Md M

    2015-01-01

    The even-even nucleus $^{26}$Mg has been studied through the reaction $^{27}$Al(d,$^{3}$He) at 25 MeV beam energy. The spectroscopic factors have been extracted upto 7.50 MeV excitation energy using local, zero range distorted wave Born approximation. The comparison of the spectroscopic factors have been done with previously reported values using the same reaction probe. The extracted spectroscopic factors for different excited states were found to be in good agreement with the previously reported values for the same. The present results were also compared with the predictions from shell model as well as rotational model. The analog states of $^{26}$Al and $^{26}$Mg were found to be in good agreement.

  13. Modeling the reaction kinetics of a hydrogen generator onboard a fuel cell -- Electric hybrid motorcycle

    Science.gov (United States)

    Ganesh, Karthik

    Owing to the perceived decline of the fossil fuel reserves in the world and environmental issues like pollution, conventional fuels may be replaced by cleaner alternative fuels. The potential of hydrogen as a fuel in vehicular applications is being explored. Hydrogen as an energy carrier potentially finds applications in internal combustion engines and fuel cells because it is considered a clean fuel and has high specific energy. However, at 6 to 8 per kilogram, not only is hydrogen produced from conventional methods like steam reforming expensive, but also there are storage and handling issues, safety concerns and lack of hydrogen refilling stations across the country. The purpose of this research is to suggest a cheap and viable system that generates hydrogen on demand through a chemical reaction between an aluminum-water slurry and an aqueous sodium hydroxide solution to power a 2 kW fuel cell on a fuel cell hybrid motorcycle. This reaction is essentially an aluminum-water reaction where sodium hydroxide acts as a reaction promoter or catalyst. The Horizon 2000 fuel cell used for this purpose has a maximum hydrogen intake rate of 28 lpm. The study focuses on studying the exothermic reaction between the reactants and proposes a rate law that best describes the rate of generation of hydrogen in connection to the surface area of aluminum available for the certain reaction and the concentration of the sodium hydroxide solution. Further, the proposed rate law is used in the simulation model of the chemical reactor onboard the hybrid motorcycle to determine the hydrogen flow rate to the fuel cell with time. Based on the simulated rate of production of hydrogen from the chemical system, its feasibility of use on different drive cycles is analyzed. The rate of production of hydrogen with a higher concentration of sodium hydroxide and smaller aluminum powder size was found to enable the installation of the chemical reactor on urban cycles with frequent stops and starts

  14. Investigation of heat induced reactions between lipid oxidation products and amino acids in lipid rich model systems and hazelnuts.

    Science.gov (United States)

    Karademir, Yeşim; Göncüoğlu, Neslihan; Gökmen, Vural

    2013-07-01

    This study aimed to investigate the contribution of lipid oxidation to non-enzymatic browning reactions in lipid rich model and actual food systems. Hazelnut oil and model reaction mixtures consisting of different amino acids were heated under certain conditions to determine possible lipid oxidation and non-enzymatic browning reaction products. In model systems, the Schiff base of 2,4-decadienal, its decarboxylated form, and reaction products formed after hydrolytic cleavage of the Schiff base or decarboxylated form were identified by high resolution mass spectrometry. No furosine was detected in hazelnuts after roasting at 160 °C while the concentration of free amino acids significantly decreased. 2,4-Decadienal reacted effectively with all amino acids studied through a Maillard type carbonyl-amine condensation pathway. (2E,4E)-Deca-2,4-dien-1-amine was identified as a typical reaction product in model systems and roasted hazelnuts. In lipid-rich foods like hazelnuts, lipid-derived carbonyls might be responsible for potential modifications of free and protein bound amino acids during heating.

  15. Improvement and extension of the generalized hard-sphere reaction probability model.

    Science.gov (United States)

    Schübler, M A; Petkow, D; Herdrich, G

    2012-04-01

    The GHS (Generalized Hard Sphere)-based standard reaction probability model commonly used in probabilistic particle methods is evaluated. We show that the original model has no general validity with respect to the molecular reaction. Mathematical consistency exists only for reactions with vanishing activation energy. For small energies close to the activation threshold the individual reaction probability for the special case of associative ionization of atomic nitrogen diverges. This makes the model extremely expensive, and nonphysical. An improved model is derived, and its implementation is verified on basis of the aforementioned reaction. Both models converge to the same value at large energies. The relative error of the original model with respect to the new model is independent of the particle pairing and, hence, of the reaction type. The error is smaller than 1% for collision energies in excess of 200 times the activation energy. For typical simulation problems like atmospheric high-enthalpy entry flows (assuming heavy-particle temperatures on the order of 10000 K) the relative error is in the order of 10(5)%.

  16. Evolution of the Maillard Reaction in Glutamine or Arginine-Dextrinomaltose Model Systems

    Directory of Open Access Journals (Sweden)

    Silvia Pastoriza

    2016-12-01

    Full Text Available Enteral formulas are foods designed for medical uses to feed patients who are unable to eat normally. They are prepared by mixing proteins, amino acids, carbohydrates and fats and submitted to sterilization. During thermal treatment, the Maillard reaction takes place through the reaction of animo acids with reducing sugars. Thus, although glutamine and arginine are usually added to improve the nutritional value of enteral formulas, their final concentration may vary. Thus, in the present paper the early, intermediate, and advanced states of the Maillard reaction were studied in model systems by measuring loss of free amino acids through the decrease of fluorescence intensity with o-phtaldialdehyde (OPA, 5-Hydroximethylfurfural (HMF, furfural, glucosylisomaltol, fluorescence, and absorbance at 420 nm. The systems were prepared by mixing glutamine or arginine with dextrinomaltose (similar ingredients to those used in special enteral formula, and heated at 100 °C, 120 °C and 140 °C for 0 to 30 min. The recorded changes in the concentration of furanic compounds was only useful for longer heating times of high temperatures, while absorbance and fluorescence measurements were useful in all the assayed conditions. In addition, easiness and sensitivity of absorbance and fluorescence make them useful techniques that could be implemented as indicators for monitoring the manufacture of special enteral formulas. Glucosylisomaltol is a useful indicator to monitor the manufacture of glutamine-enriched enteral formulas.

  17. Evolution of the Maillard Reaction in Glutamine or Arginine-Dextrinomaltose Model Systems

    Science.gov (United States)

    Pastoriza, Silvia; Rufián-Henares, José Ángel; García-Villanova, Belén; Guerra-Hernández, Eduardo

    2016-01-01

    Enteral formulas are foods designed for medical uses to feed patients who are unable to eat normally. They are prepared by mixing proteins, amino acids, carbohydrates and fats and submitted to sterilization. During thermal treatment, the Maillard reaction takes place through the reaction of animo acids with reducing sugars. Thus, although glutamine and arginine are usually added to improve the nutritional value of enteral formulas, their final concentration may vary. Thus, in the present paper the early, intermediate, and advanced states of the Maillard reaction were studied in model systems by measuring loss of free amino acids through the decrease of fluorescence intensity with o-phtaldialdehyde (OPA), 5-Hydroximethylfurfural (HMF), furfural, glucosylisomaltol, fluorescence, and absorbance at 420 nm. The systems were prepared by mixing glutamine or arginine with dextrinomaltose (similar ingredients to those used in special enteral formula), and heated at 100 °C, 120 °C and 140 °C for 0 to 30 min. The recorded changes in the concentration of furanic compounds was only useful for longer heating times of high temperatures, while absorbance and fluorescence measurements were useful in all the assayed conditions. In addition, easiness and sensitivity of absorbance and fluorescence make them useful techniques that could be implemented as indicators for monitoring the manufacture of special enteral formulas. Glucosylisomaltol is a useful indicator to monitor the manufacture of glutamine-enriched enteral formulas.

  18. A hydrodynamics-reaction kinetics coupled model for evaluating bioreactors derived from CFD simulation.

    Science.gov (United States)

    Wang, Xu; Ding, Jie; Guo, Wan-Qian; Ren, Nan-Qi

    2010-12-01

    Investigating how a bioreactor functions is a necessary precursor for successful reactor design and operation. Traditional methods used to investigate flow-field cannot meet this challenge accurately and economically. Hydrodynamics model can solve this problem, but to understand a bioreactor in sufficient depth, it is often insufficient. In this paper, a coupled hydrodynamics-reaction kinetics model was formulated from computational fluid dynamics (CFD) code to simulate a gas-liquid-solid three-phase biotreatment system for the first time. The hydrodynamics model is used to formulate prediction of the flow field and the reaction kinetics model then portrays the reaction conversion process. The coupled model is verified and used to simulate the behavior of an expanded granular sludge bed (EGSB) reactor for biohydrogen production. The flow patterns were visualized and analyzed. The coupled model also demonstrates a qualitative relationship between hydrodynamics and biohydrogen production. The advantages and limitations of applying this coupled model are discussed.

  19. Chaos in the Showalter-Noyes-Bar-Eli model of the Belousov-Zhabotinskii reaction

    Science.gov (United States)

    Lindberg, David; Turner, Jack S.; Barkley, Dwight

    1990-03-01

    The observation of robust, large-scale chaos in the Showalter-Noyes-Bar-Eli model of the Belousov-Zhabotinskii reaction is reported. The chaos observed is comparable to that found in CSTR experiments at low flow rates.

  20. Porphyrin-quinone compounds as synthetic models of the reaction centre in photosynthesis

    Science.gov (United States)

    Borovkov, V. V.; Evstigneeva, Rima P.; Strekova, L. N.; Filippovich, E. I.

    1989-06-01

    Data on the synthesis, steric structure, and photochemical properties of porphyrin-quinone compounds as synthetic models of the reaction centre in photosynthesis are examined and described systematically. The bibliography includes 113 references.

  1. Statistical Model Calculations for (n,γ Reactions

    Directory of Open Access Journals (Sweden)

    Beard Mary

    2015-01-01

    Full Text Available Hauser-Feshbach (HF cross sections are of enormous importance for a wide range of applications, from waste transmutation and nuclear technologies, to medical applications, and nuclear astrophysics. It is a well-observed result that different nuclear input models sensitively affect HF cross section calculations. Less well known however are the effects on calculations originating from model-specific implementation details (such as level density parameter, matching energy, back-shift and giant dipole parameters, as well as effects from non-model aspects, such as experimental data truncation and transmission function energy binning. To investigate the effects or these various aspects, Maxwellian-averaged neutron capture cross sections have been calculated for approximately 340 nuclei. The relative effects of these model details will be discussed.

  2. A novel approach to modeling the reaction kinetics of tetracycline antibiotics with aqueous ozone.

    Science.gov (United States)

    Hopkins, Zachary R; Blaney, Lee

    2014-01-15

    Tetracycline antibiotics represent one of the most successful classes of pharmaceuticals and are extensively used around the world for human and veterinary health. Ozone-based processes have emerged as a selective water treatment process for many pharmaceuticals. The primary objective of this study was to determine the reaction kinetics for transformation of five tetracycline antibiotics (i.e., chlortetracycline, doxycycline, oxytetracycline, rolitetracycline, and tetracycline) by ozone across the pH2 to 9 range. The apparent second-order rate constant for tetracycline was on the order of 1-6 × 10(4) M(-1) s(-1) at low pH, and 0.6-2.0 × 10(6) M(-1) s(-1) at near neutral pH. The apparent second-order rate constants did not fit a conventional pKa-based model, presumably due to the complex acid/base speciation of tetracycline antibiotics. A model that considers the net charge on tetracycline molecules in solution provided a nice fit to experimental data for all five tetracyclines. The five tetracycline antibiotics demonstrated similar reaction kinetics with ozone, and a cumulative analysis of all kinetics data provides a baseline model for other tetracycline compounds. The ozone exposure required for complete transformation of tetracycline antibiotics (10(-5) M-s) is well below that achieved during ozone disinfection processes (10(-3) M-s), indicating that ozone is an effective treatment for tetracycline antibiotics.

  3. Mangiferin antagonizes TNF-α-mediated inflammatory reaction and protects against dermatitis in a mice model.

    Science.gov (United States)

    Zhao, Yunpeng; Wang, Wenhan; Wu, Xihai; Ma, Xiaoqian; Qu, Ruize; Chen, Xiaomin; Liu, Chenghao; Liu, Yaoge; Wang, Xiaokai; Yan, Pengcheng; Zhang, Hao; Pan, Jingrui; Li, Weiwei

    2017-04-01

    This study aimed to investigate whether mangiferin played a protective role in a well-established dermatitis mouse model and tumor necrosis factor alpha (TNF-α)-induced RAW264.7 macrophages. Contact dermatitis is an inflammatory skin disease in the clinic, while its underlying mechanism still remains to be elucidated. Mangiferin, 1,3,6,7-tetrahydroxyxanthone-C2-β-d-glucoside (C-glucosyl xanthone), a natural antioxidant that was reported to inhibit inflammatory reactions, has been recently proved to be a potential therapy for inflammation. As a result, the oxazolone-induced dermatitis mice models were established to explore whether mangiferin has an anti-inflammatory role in vivo. The phosphate-buffered saline treatment groups showed emblematic skin inflammation, whereas the administration of mangiferin obviously inhibited dermatitis in the mice models. Furthermore, exogenous mangiferin alleviated the inflammatory reaction in TNF-α-induced macrophages by suppressing the production of inflammation- and oxidative stress-associated molecules. Also, mangiferin treatment repressed the activation of nuclear factor-kappaB signaling pathway. To sum up, mangiferin could provide a new target for the therapy and prevention of skin inflammation.

  4. Use of chemistry software to teach and assess model-based reaction and equation knowledge

    Directory of Open Access Journals (Sweden)

    Kevin Pyatt

    2014-12-01

    Full Text Available This study investigated the challenges students face when learning chemical reactions in a first-year chemistry course and the effectiveness of a curriculum and software implementation that was used to teach and assess student understanding of chemical reactions and equations. This study took place over a two year period in a public suburban high-school, in southwestern USA. Two advanced placement (AP chemistry classes participated, referred to here as study group A (year 1, N = 14; and study group B (year 2, N = 21. The curriculum for a first-year chemistry course (group A was revised to include instruction on reaction-types. The second year of the study involved the creation and implementation of a software solution which promoted mastery learning of reaction-types. Students in both groups benefited from the reaction-type curriculum and achieved proficiency in chemical reactions and equations.  The findings suggest there was an added learning benefit to using the reaction-type software solution. This study also found that reaction knowledge was a moderate to strong predictor of chemistry achievement. Based on regression analysis, reaction knowledge significantly predicted chemistry achievement for both groups.

  5. Transition state models for probing stereoinduction in Evans chiral auxiliary-based asymmetric aldol reactions.

    Science.gov (United States)

    Shinisha, C B; Sunoj, Raghavan B

    2010-09-08

    The use of chiral auxiliaries is one of the most fundamental protocols employed in asymmetric synthesis. In the present study, stereoselectivity-determining factors in a chiral auxiliary-based asymmetric aldol reaction promoted by TiCl(4) are investigated by using density functional theory methods. The aldol reaction between chiral titanium enolate [derived from Evans propionyl oxazolidinone (1a) and its variants oxazolidinethione (1b) and thiazolidinethione (1c)] and benzaldehyde is examined by using transition-state modeling. Different stereochemical possibilities for the addition of titanium enolates to aldehyde are compared. On the basis of the coordination of the carbonyl/thiocarbonyl group of the chiral auxiliary with titanium, both pathways involving nonchelated and chelated transition states (TSs) are considered. The computed relative energies of the stereoselectivity-determining C-C bond formation TSs in the nonchelated pathway, for both 1a and 1c, indicate a preference toward Evans syn aldol product. The presence of a ring carbonyl or thiocarbonyl group in the chiral auxiliary renders the formation of neutral TiCl(3)-enolate, which otherwise is energetically less favored as compared to the anionic TiCl(4)-enolate. Hence, under suitable conditions, the reaction between titanium enolate and aldehyde is expected to be viable through chelated TSs leading to the selective formation of non-Evans syn aldol product. Experimentally known high stereoselectivity toward Evans syn aldol product is effectively rationalized by using the larger energy differences between the corresponding diastereomeric TSs. In both chelated and nonchelated pathways, the attack by the less hindered face of the enolate on aldehyde through a chair-like TS with an equatorial disposition of the aldehydic substituent is identified as the preferred mode. The steric hindrance offered by the isopropyl group and the possible chelation are identified as the key reasons behind the interesting

  6. Time-dependent quantum dynamics study for reaction of D+CH4→CH3+HD

    Institute of Scientific and Technical Information of China (English)

    Liu Xin-Guo; Zhang Qing-Gang; Zhang Yi-Ci; Wang Ming-Liang; John Zhang Zeng-Hui

    2004-01-01

    The semirigid vibrating rotor target (SVRT) model has been applied to the study of the reaction of D+CH4 →CH3+HD using a time-dependent wave packet method. The energy dependence of the calculated reaction probability shows oscillatory structures similar to those observed in the abstraction reaction of H+H2, H+CH4 etc. We have also studied the influence of rotational and vibrational excitation of the reacting molecule (CH4) on reaction probability.The excitation of the H-CH3 stretching vibration gives significant enhancement of reaction probability, which rises significantly with the enhancement of rotational quantum number j. Finally, we have compared the cross section and the rate constant of the D+CH4 system with that of the H+CH4 system.

  7. Impact of Nuclear Reaction Uncertainties on AGB Nucleosynthesis Models

    CERN Document Server

    Bisterzo, S; Kaeppeler, F; Wiescher, M; Travaglio, C

    2012-01-01

    Asymptotic giant branch (AGB) stars with low initial mass (1 - 3 Msun) are responsible for the production of neutron-capture elements through the main s-process (main slow neutron capture process). The major neutron source is 13C(alpha, n)16O, which burns radiatively during the interpulse periods at about 8 keV and produces a rather low neutron density (10^7 n/cm^3). The second neutron source 22Ne(alpha, n)25Mg, partially activated during the convective thermal pulses when the energy reaches about 23 keV, gives rise to a small neutron exposure but a peaked neutron density (Nn(peak) > 10^11 n/cm^3). At metallicities close to solar, it does not substantially change the final s-process abundances, but mainly affects the isotopic ratios near s-path branchings sensitive to the neutron density. We examine the effect of the present uncertainties of the two neutron sources operating in AGB stars, as well as the competition with the 22Ne(alpha, gamma)26Mg reaction. The analysis is carried out on AGB the main-s process...

  8. Study on the Reaction of Benzimidazolium Salt with Amine Compounds

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The addition-hydrolysis reaction of benzimidazolium salt with some mono- andbifunctional amine nucleophiles is reported, and a novel method of biomimetic synthesis forformamides and heterocycle compounds is provided.

  9. Dynamical Coupled-Channel Model of Meson Production Reactions in the Nucleon Resonance Region

    Energy Technology Data Exchange (ETDEWEB)

    T.-S. H. Lee; A. Matsuyama; T. Sato

    2006-11-15

    A dynamical coupled-channel model is presented for investigating the nucleon resonances (N*) in the meson production reactions induced by pions and photons. Our objective is to extract the N* parameters and to investigate the meson production reaction mechanisms for mapping out the quark-gluon substructure of N* from the data. The model is based on an energy-independent Hamiltonian which is derived from a set of Lagrangians by using a unitary transformation method.

  10. AUTO-DARBOUX TRANSFORMATION AND EXACT SOLUTIONS OF THE BRUSSELATOR REACTION DIFFUSION MODEL

    Institute of Scientific and Technical Information of China (English)

    闫振亚; 张鸿庆

    2001-01-01

    Firstly, using the improved homogeneous balance method, an auto-Darboux transformation (ADT) for the Brusselator reaction diffusion model is found. Based on the ADT, several exact solutions are obtained which contain some authors' results known.Secondly, by using a series of transformations, the model is reduced into a nonlinear reaction diffusion equation and then through using sine- cosine method, more exact solutions are found which contain soliton solutions.

  11. Implicit coupling of turbulent diffusion with chemical reaction mechanisms for prognostic atmospheric dispersion models

    Energy Technology Data Exchange (ETDEWEB)

    Berlowitz, D.R.

    1996-11-01

    In the last few decades the negative impact by humans on the thin atmospheric layer enveloping the earth, the basis for life on this planet, has increased steadily. In order to halt, or at least slow down this development, the knowledge and study of these anthropogenic influence has to be increased and possible remedies have to be suggested. An important tool for these studies are computer models. With their help the atmospheric system can be approximated and the various processes, which have led to the current situation can be quantified. They also serve as an instrument to assess short or medium term strategies to reduce this human impact. However, to assure efficiency as well as accuracy, a careful analysis of the numerous processes involved in the dispersion of pollutants in the atmosphere is called for. This should help to concentrate on the essentials and also prevent excessive usage of sometimes scarce computing resources. The basis of the presented work is the EUMAC Zooming Model (ETM), and particularly the component calculating the dispersion of pollutants in the atmosphere, the model MARS. The model has two main parts: an explicit solver, where the advection and the horizontal diffusion of pollutants are calculated, and an implicit solution mechanism, allowing the joint computation of the change of concentration due to chemical reactions, coupled with the respective influence of the vertical diffusion of the species. The aim of this thesis is to determine particularly the influence of the horizontal components of the turbulent diffusion on the existing implicit solver of the model. Suggestions for a more comprehensive inclusion of the full three dimensional diffusion operator in the implicit solver are made. This is achieved by an appropriate operator splitting. A selection of numerical approaches to tighten the coupling of the diffusion processes with the calculation of the applied chemical reaction mechanisms are examined. (author) figs., tabs., refs.

  12. Study on Unexpected Cycloaddition Reactions of Imines with THF

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    An unexpected tricyclic compound 2,3,3a,4,5,9b-hexahydrophenylfuro[3,2-c] quinoline 4 and its aromatized product 6 were obtained when the cycloaddtion of imine 1 and substituted norbornene 2 was carried out in THF with a catalytic amount of boron trifluoride. The structures of the products were determined by spectral data, and the mechanism of reaction was substantiated by the imitation reaction.

  13. New Reaction Timer for Physiological and Psychological Studies

    Directory of Open Access Journals (Sweden)

    A. K. Gupta

    1983-07-01

    Full Text Available In physiological and psychological measurements, the response to some form of external stimulus is required. The instrumentation used for the measurement of Reaction Time is vital part of the main instrument system. Instrument design reported here is suitable for the measurement of Reaction. Time under environmental stress. The stimulus are visual (flash of light andauditory tone. This instrument is solidstate, portable and can be used with any electronic timer.

  14. Kinetic Studies of Reactions in Solution Using Fast Mass Spectrometry

    Science.gov (United States)

    2013-08-13

    REPORT Directorate of Chemistry and Materials Research NUMBER(S) AFOSR/RSA, 875 Randolph St., Suite 325, Rm 3112, Arlington, VA 222C 3 12...Mass Spectrometry to detect transient intermediates and decomposition products of catalyzed organometallic reactions Identifying intermediates is...in organometallic catalysis. HV N2 45o 5 mm 2 mm Reagent A Reagent B MS Secondary microdroplets Surface ~2-5 ms reaction time

  15. KINETIC MODELING OF TRANSESTERFICATION REACTION FOR BIODIESEL PRODUCTION USING HETEROGENEOUS CATALYST

    Directory of Open Access Journals (Sweden)

    N. JAYA,

    2011-04-01

    Full Text Available Biodiesel derived from renewable plant sources is monoalkyl esters of long chain fatty acids which fall in the carbon range of C12-C22. It has similar properties as mineral diesel. Various processes exist to convert vegetable oils into biodiesel. Transesterification of such vegetable oils using alcohol in the catalytic environment is most commonly used method for producing biodiesel. The equilibrium conversion of triglycerides is affected by various factors namely feed Quality (like free fatty acid content, water content etc.,type of alcohol used, molar ratio of alcohol to triglycerides, type of catalyst, amount of catalyst, reaction temperature, reaction time and stirring rates. The present work reports on the characterization of cotton seed oil and production of biodiesel. This study also reports on the optimal operating parameter for cotton seed oil inbatch reactor. The main thrust of present work was to study the kinetics, modeling and simulation of anionic ion exchange resin catalyzed transesterification of cotton seed oil. Experiments were carried out in batch reactor to generate kinetic data and a kinetic model was developed. The effect of temperature, catalyst concentration and molar ratio of methanol to triglycerides and stirring rates were investigated. A few fuel properties were alsomeasured for biodiesel to observe its competitiveness with onventional diesel fuel. The equilibrium conversions of triglycerides were observed to be in the range of 85%. It was also observed that higher conversion was achieved at 6:1 molar ratio of ethanol to oil, 2 wt.% of anionic resin catalyst ,temperature at 338 K, reaction time of 180 minutes with stirring speed 10 Hz. Model parameters such as order, activation energy and rate constants were calculated, the overall activation energy was also estimated. The rate constants werefound to increase with an increase in temperature and catalyst concentration. Various simulations were also carried out at

  16. Detailed Molecular Dynamics of the Photochromic Reaction of Spiropyran: A Semiclassical Dynamics Study

    Directory of Open Access Journals (Sweden)

    Gaohong Zhai

    2014-01-01

    Full Text Available A realistic semiclassical dynamics simulation study is reported for the photoinduced ring-opening reaction of spiropyran. The main simulation results show that one pathway involves hydrogen out-of-plane (HOOP torsion of phenyl ring nearby N atom in 254 fs on the excited state and the isomerization from cis- to trans-SP that is complete in about 10 ps on the ground state after the electron transition πσ*; the other dominate pathway corresponds to the ring-opening reaction of trans-SP to form the most stable merocyanine (MC product. Unlike the previous theoretical finding, one C−C bond cleavage on the real molecule rather than the C−N dissociation of the model one is more probable than the ring-opening reaction after the photoexcitation of SP. The simulation findings provide more important complementarity for interpreting experimental observations, confirming the previously theoretical studies of photochromic ring-opening process and even supplying other possible reaction mechanisms.

  17. Study of liquid-solid catalytic reaction of epichlorohydrin with sodium butyrate in the presence of tetrabutylammonium bromide

    Science.gov (United States)

    Huang, Qiang; Meng, Qingyi; Ban, Chunlan; Zhang, Rui; Gao, Yingyu

    2016-08-01

    The liquid-solid catalytic reaction of epichlorohydrin and sodium butyrate with tetrabutylammonium bromide as a phase transfer catalyst was studied in this paper. The shrinking core model was applied. The analysis of the reaction based on the kinetic model showed a reaction-controlled regime at temperatures varying from 90 to 100°C. The exterior diffusivity was removed between 300 and 400 rpm. The internal diffusivity was removed when the particle size was 2 × 10-4 m. Reaction rate constants were calculated at different temperatures. The correlation was obtained when the proposed kinetic model was applied to all the experimental data for predictive evaluations and the activation energy was 37.01 kJ mol-1.

  18. Systematic study of complete fusion suppression in reactions involving weakly bound nuclei at energies above the Coulomb barrier

    CERN Document Server

    Wang, Bing; Diaz-Torres, Alexis; Zhao, En-Guang; Zhou, Shan-Gui

    2016-01-01

    Complete fusion excitation functions of reactions involving breakup are studied by using the empirical coupled-channel (ECC) model with breakup effects considered. An exponential function with two parameters is adopted to describe the prompt-breakup probability in the ECC model. These two parameters are fixed by fitting the measured prompt-breakup probability or the complete fusion cross sections. The suppression of complete fusion at energies above the Coulomb barrier is studied by comparing the data with the predictions from the ECC model without the breakup channel considered. The results show that the suppression of complete fusion are roughly independent of the target for the reactions involving the same projectile.

  19. CH 1 Introduction to Chemistry. Study Guide to Minicourse I - 13 Chemical Reaction Principles.

    Science.gov (United States)

    Schlenker, Richard

    Provided is a study guide for an introductory minicourse to the principles of chemical reactions. This written text is designed to accompany a series of audio tapes and 35mm slides which the student studies at his own pace. The course presents chemical kinetics, reaction mechanisms, reaction rates, and equilibrium. (SL)

  20. Turing pattern formation on the sphere for a morphochemical reaction-diffusion model for electrodeposition

    Science.gov (United States)

    Lacitignola, Deborah; Bozzini, Benedetto; Frittelli, Massimo; Sgura, Ivonne

    2017-07-01

    The present paper deals with the pattern formation properties of a specific morpho-electrochemical reaction-diffusion model on a sphere. The physico-chemical background to this study is the morphological control of material electrodeposited onto spherical particles. The particular experimental case of interest refers to the optimization of novel metal-air flow batteries and addresses the electrodeposition of zinc onto inert spherical supports. Morphological control in this step of the high-energy battery operation is crucial to the energetic efficiency of the recharge process and to the durability of the whole energy-storage device. To rationalise this technological challenge within a mathematical modeling perspective, we consider the reaction-diffusion system for metal electrodeposition introduced in [Bozzini et al., J. Solid State Electr.17, 467-479 (2013)] and extend its study to spherical domains. Conditions are derived for the occurrence of the Turing instability phenomenon and the steady patterns emerging at the onset of Turing instability are investigated. The reaction-diffusion system on spherical domains is solved numerically by means of the Lumped Surface Finite Element Method (LSFEM) in space combined with the IMEX Euler method in time. The effect on pattern formation of variations in the domain size is investigated both qualitatively, by means of systematic numerical simulations, and quantitatively by introducing suitable indicators that allow to assign each pattern to a given morphological class. An experimental validation of the obtained results is finally presented for the case of zinc electrodeposition from alkaline zincate solutions onto copper spheres.