van Leeuwen, Theo; Djonov, Emilia
2014-01-01
After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....
Lifschitz, E.M.; Pitajewski, L.P.
1983-01-01
The textbook covers the subject under the following headings: kinetic gas theory, diffusion approximation, collisionless plasma, collisions within the plasma, plasma in the magnetic field, theory of instabilities, dielectrics, quantum fluids, metals, diagram technique for nonequilibrium systems, superconductors, and kinetics of phase transformations
Swart, C.A.M. de.
1983-01-01
The author has studied the kinetics of heparin and heparin fractions after intravenous administration in humans and in this thesis the results of this study are reported. Basic knowledge about the physico-chemical properties of heparin and its interactions with proteins resulting in anticoagulant and lipolytic effects are discussed in a review (chapter II), which also comprises some clinical aspects of heparin therapy. In chapter III the kinetics of the anticoagulant effect are described after intravenous administration of five commercial heparin preparations. A mathematical model is presented that fits best to these kinetics. The kinetics of the anticoagulant and lipolytic effects after intravenous injection of various 35 S-radiolabelled heparin fractions and their relationship with the disappearance of the radiolabel are described in chapter IV. Chapter V gives a description of the kinetics of two radiolabels after injection of in vitro formed complexes consisting of purified, 125 I-radiolabelled antithrombin III and various 35 S-radiolabelled heparin fractions. (Auth.)
2009-01-01
A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....
Mojtaba Ahmadi
2016-11-01
Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.
Peters, A.M.; Lavender, J.P.; Saverymuttu, S.H.
1985-01-01
By using density gradient materials enriched with autologous plasma, the authors have been able to isolate granulocutes from other cellular elements and label them with In-111 without separation from a plasma environment. The kinetic behavior of these cells suggests that phenomena attributed to granulocyte activation are greatly reduced by this labeling. Here, they review their study of granulocyte kinetics in health and disease in hope of quantifying sites of margination and identifying principal sites of destruction. The three principle headings of the paper are distribution, life-span, and destruction
Kreuzer, Hans Jürgen
1986-01-01
This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...
Colombino, A.; Mosiello, R.; Norelli, F.; Jorio, V.M.; Pacilio, N.
1975-01-01
A nuclear system kinetics is formulated according to a stochastic approach. The detailed probability balance equations are written for the probability of finding the mixed population of neutrons and detected neutrons, i.e. detectrons, at a given level for a given instant of time. Equations are integrated in search of a probability profile: a series of cases is analyzed through a progressive criterium. It tends to take into account an increasing number of physical processes within the chosen model. The most important contribution is that solutions interpret analytically experimental conditions of equilibrium (moise analysis) and non equilibrium (pulsed neutron measurements, source drop technique, start up procedures)
Hicks, D.R.; Kraml, M.; Cayen, M.N.; Dubuc, J.; Ryder, S.; Dvornik, D.
1984-01-01
The kinetics of tolrestat, a potent inhibitor of aldose reductase, were examined. Serum concentrations of tolrestat and of total 14 C were measured after dosing normal subjects and subjects with diabetes with 14 C-labeled tolrestat. In normal subjects, tolrestat was rapidly absorbed and disappearance from serum was biphasic. Distribution and elimination t 1/2s were approximately 2 and 10 to 12 hr, respectively, after single and multiple doses. Unchanged tolrestat accounted for the major portion of 14 C in serum. Radioactivity was rapidly and completely excreted in urine and feces in an approximate ratio of 2:1. Findings were much the same in subjects with diabetes. In normal subjects, the kinetics of oral tolrestat were independent of dose in the 10 to 800 mg range. Repetitive dosing did not result in unexpected cumulation. Tolrestat was more than 99% bound to serum protein; it did not compete with warfarin for binding sites but was displaced to some extent by high concentrations of tolbutamide or salicylate
Cesium removal and kinetics equilibrium: Precipitation kinetics
Barnes, M.J.
1999-01-01
This task consisted of both non-radioactive and radioactive (tracer) tests examining the influence of potentially significant variables on cesium tetraphenylborate precipitation kinetics. The work investigated the time required to reach cesium decontamination and the conditions that affect the cesium precipitation kinetics
Elliott, J.A.
1993-01-01
Plasma kinetic theory is discussed and a comparison made with the kinetic theory of gases. The plasma is described by a modified set of fluid equations and it is shown how these fluid equations can be derived. (UK)
Principles of chemical kinetics
House, James E
2007-01-01
James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela
Introduction to chemical kinetics
Soustelle, Michel
2013-01-01
This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re
Kinetic equation solution by inverse kinetic method
Salas, G.
1983-01-01
We propose a computer program (CAMU) which permits to solve the inverse kinetic equation. The CAMU code is written in HPL language for a HP 982 A microcomputer with a peripheral interface HP 9876 A ''thermal graphic printer''. The CAMU code solves the inverse kinetic equation by taking as data entry the output of the ionization chambers and integrating the equation with the help of the Simpson method. With this program we calculate the evolution of the reactivity in time for a given disturbance
Kinetics in radiation chemistry
Hummel, A.
1987-01-01
In this chapter the authors first briefly review the kinetics of first- and second-order processes for continuous and pulsed irradiation, without taking the effects of nonhomogeneous formation of the species into consideration. They also discuss diffusion controlled reactions under conditions where interactions of more than two particles can be neglected, first the kinetics of the diffusion-controlled reaction of randomly generated species (homogeneous reaction) and then that of isolated pairs of reactants. The latter is often called geminate kinetics when dealing with pairs of oppositely charged species; they shall use this term for the kinetics of isolated pairs in general. In the last section they discuss briefly the kinetics of groups of more than two reactants
Non-kinetic capabilities: complementing the kinetic prevalence to targeting
Ducheine, P.
2014-01-01
Targeting is used in military doctrine to describe a military operational way, using (military) means to influence a target (or addressee) in order to achieve designated political and/or military goals. The four factors italicized are used to analyse non-kinetic targeting, complementing our knowledge and understanding of the kinetic prevalence. Paradoxically, non-kinetic targeting is not recognized as a separate concept: kinetic and non-kinetic are intertwined facets of targeting. Kinetic tar...
Kinetics of phase transformations
Thompson, M.O.; Aziz, M.J.; Stephenson, G.B.
1992-01-01
This volume contains papers presented at the Materials Research Society symposium on Kinetics of Phase Transformations held in Boston, Massachusetts from November 26-29, 1990. The symposium provided a forum for research results in an exceptionally broad and interdisciplinary field. Presentations covered nearly every major class of transformations including solid-solid, liquid-solid, transport phenomena and kinetics modeling. Papers involving amorphous Si, a dominant topic at the symposium, are collected in the first section followed by sections on four major areas of transformation kinetics. The symposium opened with joint sessions on ion and electron beam induced transformations in conjunction with the Surface Chemistry and Beam-Solid Interactions: symposium. Subsequent sessions focused on the areas of ordering and nonlinear diffusion kinetics, solid state reactions and amorphization, kinetics and defects of amorphous silicon, and kinetics of melting and solidification. Seven internationally recognized invited speakers reviewed many of the important problems and recent results in these areas, including defects in amorphous Si, crystal to glass transformations, ordering kinetics, solid-state amorphization, computer modeling, and liquid/solid transformations
Irreversible processes kinetic theory
Brush, Stephen G
2013-01-01
Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s
SHORT COMMUNICATION CATALYTIC KINETIC ...
IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of ...
Relativistic Chiral Kinetic Theory
Stephanov, Mikhail
2016-01-01
This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi: (10.1103/PhysRevLett.113.182302); J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: (10.1103/PhysRevLett.115.021601); M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: (10.1103/PhysRevLett.116.122302)].
Relativistic Chiral Kinetic Theory
Stephanov, Mikhail
2016-12-15
This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi: (10.1103/PhysRevLett.113.182302); J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: (10.1103/PhysRevLett.115.021601); M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: (10.1103/PhysRevLett.116.122302)].
Erbium hydride decomposition kinetics.
Ferrizz, Robert Matthew
2006-11-01
Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.
Vereshchagin, Gregory V.; Aksenov, Alexey G.
2017-02-01
Preface; Acknowledgements; Acronyms and definitions; Introduction; Part I. Theoretical Foundations: 1. Basic concepts; 2. Kinetic equation; 3. Averaging; 4. Conservation laws and equilibrium; 5. Relativistic BBGKY hierarchy; 6. Basic parameters in gases and plasmas; Part II. Numerical Methods: 7. The basics of computational physics; 8. Direct integration of Boltzmann equations; 9. Multidimensional hydrodynamics; Part III. Applications: 10. Wave dispersion in relativistic plasma; 11. Thermalization in relativistic plasma; 12. Kinetics of particles in strong fields; 13. Compton scattering in astrophysics and cosmology; 14. Self-gravitating systems; 15. Neutrinos, gravitational collapse and supernovae; Appendices; Bibliography; Index.
Bonitz, Michael
2016-01-01
This book presents quantum kinetic theory in a comprehensive way. The focus is on density operator methods and on non-equilibrium Green functions. The theory allows to rigorously treat nonequilibrium dynamics in quantum many-body systems. Of particular interest are ultrafast processes in plasmas, condensed matter and trapped atoms that are stimulated by rapidly developing experiments with short pulse lasers and free electron lasers. To describe these experiments theoretically, the most powerful approach is given by non-Markovian quantum kinetic equations that are discussed in detail, including computational aspects.
Oxidative desulfurization: kinetic modelling.
Dhir, S; Uppaluri, R; Purkait, M K
2009-01-30
Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.
Oxidative desulfurization: Kinetic modelling
Dhir, S.; Uppaluri, R.; Purkait, M.K.
2009-01-01
Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H 2 O 2 over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel
Modeling chemical kinetics graphically
Heck, A.
2012-01-01
In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could
CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...
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acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...
Abstract. This paper presents the detailed turbulent kinetic energy budget and higher order statistics of flow behind a surface-mounted rib with and without superimposed acoustic excitation. Pattern recognition technique is used to determine the large-scale structure magnitude. It is observed that most of the turbulence ...
Kimpland, R.H.
1996-01-01
A normalized form of the point kinetics equations, a prompt jump approximation, and the Nordheim-Fuchs model are used to model nuclear systems. Reactivity feedback mechanisms considered include volumetric expansion, thermal neutron temperature effect, Doppler effect and void formation. A sample problem of an excursion occurring in a plutonium solution accidentally formed in a glovebox is presented
LLNL Chemical Kinetics Modeling Group
Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J
2008-09-24
The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.
Bricmont, R.J.; Hamilton, P.A.; Ming Long Ting, R.
1981-01-01
Reactors, fuel processing plants etc incorporate pipes and conduits for fluids under high pressure. Fractures, particularly adjacent to conduit elbows, produce a jet of liquid which whips the broken conduit at an extremely high velocity. An enormous impact load would be applied to any stationary object in the conduit's path. The design of cellular, corrugated metal impact pads to absorb the kinetic energy of the high velocity conduits is given. (U.K.)
Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.
2016-12-01
A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral
Kinetics of tetrataenite disordering
Dos Santos, E.; Gattacceca, J.; Rochette, P.; Fillion, G.; Scorzelli, R.B.
2015-01-01
Tetrataenite is a chemically ordered L1 0 -type Fe 50 Ni 50 alloy detected for the first time in 1977 by 57 Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L 10 superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites
Augusiak, R; Cucchietti, F M; Lewenstein, M; Haake, F
2010-01-01
In this paper, we introduce a quantum generalization of classical kinetic Ising models (KIM), described by a certain class of quantum many-body master equations. Similarly to KIMs with detailed balance that are equivalent to certain Hamiltonian systems, our models reduce to a set of Hamiltonian systems determining the dynamics of the elements of the many-body density matrix. The ground states of these Hamiltonians are well described by the matrix product, or pair entangled projected states. We discuss critical properties of such Hamiltonians, as well as entanglement properties of their low-energy states.
Seery, D.J.; Freihaut, J.D.; Proscia, W.M. (United Technologies Research Center, East Hartford, CT (USA)); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. (Massachusetts Inst. of Tech., Cambridge, MA (USA)); Jenkins, R.; Mallin, J.; Espindola-Merin, B. (Pennsylvania State Univ., University Park, PA (USA)); Essenhigh, R.; Misra, M.K. (Ohio State Univ., Columbus, OH (USA))
1989-07-01
This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.
Thames, H.D.
1989-01-01
Monoexponential repair kinetics is based on the assumption of a single, dose-independent rate of repair of sublethal injury in the target cells for tissue injury after exposure to ionizing radiation. Descriptions of the available data based on this assumption have proved fairly successful for both acutely responding (skin, lip mucosa, gut) and late-responding (lung, spinal cord) normal tissues. There are indications of biphasic exponential repair in both categories, however. Unfortunately, the data usually lack sufficient resolution to permit unambiguous determination of the repair rates. There are also indications that repair kinetics may depend on the size of the dose. The data are conflicting on this account, however, with suggestions of both faster and slower repair after larger doses. Indeed, experiments that have been explicitly designed to test this hypothesis show either no effect (gut, spinal cord), faster repair after higher doses (lung, kidney), or slower repair after higher doses (skin). Monoexponential repair appears to be a fairly accurate description that provides an approximation to a more complicated picture, the elucidation of whose details will, however, require very careful and extensive experimental study. (author). 30 refs.; 1 fig
Diffusion Influenced Adsorption Kinetics.
Miura, Toshiaki; Seki, Kazuhiko
2015-08-27
When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.
Chemical kinetics and reaction mechanism
Jung, Ou Sik; Park, Youn Yeol
1996-12-01
This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.
Chemical kinetics of gas reactions
Kondrat'Ev, V N
2013-01-01
Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema
Adsorption analysis equilibria and kinetics
Do, Duong D
1998-01-01
This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such
Ruan, Zhongyuan; Iñiguez, Gerardo; Karsai, Márton; Kertész, János
2015-11-01
Diffusion of information, behavioral patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of "immune" nodes who never adopt, and a perpetual flow of external information. While any constant, nonzero rate of dynamically introduced spontaneous adopters leads to global spreading, the kinetics by which the asymptotic state is approached shows rich behavior. In particular, we find that, as a function of the immune node density, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of network fragmentation, and has its origin in the competition between cascading behavior induced by adopters and blocking due to immune nodes. This change is accompanied by a percolation transition of the induced clusters.
The temperature hydration kinetics
Mircea Oroian
2017-07-01
Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.
Kinetic theory of Jeans instability
Trigger, S.A.; Ershkovic, A.I.; Heijst, van G.J.F.; Schram, P.P.J.M.
2004-01-01
Kinetic treatment of the Jeans gravitational instability, with collisions taken into account, is presented. The initial-value problem for the distribution function which obeys the kinetic equation, with the collision integral conserving the number of particles, is solved. Dispersion relation is
Inada, Mitsuo; Nishikawa, Mitsushige; Naito, Kimikazu; Ishii, Hitoshi; Tanaka, Kiyoshi
1980-01-01
Kinetics of thyroid hormones were outlined, and recent progress in metabolism of these hormones was also described. Recently, not only T 4 and T 3 but also rT 3 , 3,3'-T 2 , 3',5'-T 2 , and 3,5-T 2 can be measured by RIA. To clarify metabolic pathways of these hormones, metabolic clearance rate and production rate of these hormones were calculated. As single-compartment analysis was insufficient to clarify disappearance curves of thyroid hormones in blood such as T 3 and T 2 of which metabolic speed was so fast, multi-compartment analysis or non-compartment analysis were also performed. Thyroid hormones seemed to be measured more precisely by constant infusion method. At the first step of T 4 metabolism, T 3 was formed by 5'-monodeiodination of T 4 , and rT 3 was formed by 5-monodeiodination of T 4 . As metabolic pathways of T 3 and rT 3 , conversion of them to 3,3'-T 2 or to 3',5'-T 2 and 3,5-T 2 was supposed. This subject will be an interesting research theme in future. (Tsunoda, M.)
Kinetic effects on magnetohydrodynamic phenomena
Naito, Hiroshi; Matsumoto, Taro
2001-01-01
Resistive and ideal magnetohydrodynamic (MHD) theories are insufficient to adequately explain MHD phenomena in the high-temperature plasma. Recent progress in numerical simulations concerning kinetic effects on magnetohydrodynamic phenomena is summarized. The following three topics are studied using various models treating extended-MHD phenomena. (1) Kinetic modifications of internal kink modes in tokamaks with normal and reversed magnetic shear configurations. (2) Temporal evolution of the toroidal Alfven eigenmode and fishbone mode in tokamaks with energetic ions. (3) Kinetic stabilization of a title mode in field-reversed configurations by means of anchoring ions and beam ions. (author)
Bicarbonate kinetics in Indian males
Madhu
ized kinetics of bicarbonate using a three-compartment model, to assess which compartmental fluxes changed dur- .... total VCO2 was < 3 % and the average respiratory quotient ..... a part of the nonrespiratory losses of 13CO2 occur to this.
Kinetic equations in dirty superconductors
Kraehenbuehl, Y.
1981-01-01
Kinetic equations for superconductors in the dirty limit are derived using a method developed for superfluid systems, which allows a systematic expansion in small parameters; exact charge conservation is obeyed. (orig.)
Cell kinetics and therapeutic efficiency
Andreeff, M.; Abenhardt, W.; Gruner, B.; Stoffner, D.; Mainz Univ.
1976-01-01
The study shows that cell kinetics effects correlate with the effects of cytostatic drugs in the tumour model investigated here. It should, however, be noted that even genetically related tumour cell types may react differently to the same cytostatic drug, and that the cell kinetics effects, due to the changes in the cell cycle, cannot be predicted but should be followed with a very fast method, e.g. sequential flan fluorescence cytophotometry, for optimal therapeutic results. (orig./GSE) [de
Kinetic parameters from thermogravimetric analysis
Kiefer, Richard L.
1993-01-01
High performance polymeric materials are finding increased use in aerospace applications. Proposed high speed aircraft will require materials to withstand high temperatures in an oxidative atmosphere for long periods of time. It is essential that accurate estimates be made of the performance of these materials at the given conditions of temperature and time. Temperatures of 350 F (177 C) and times of 60,000 to 100,000 hours are anticipated. In order to survey a large number of high performance polymeric materials on a reasonable time scale, some form of accelerated testing must be performed. A knowledge of the rate of a process can be used to predict the lifetime of that process. Thermogravimetric analysis (TGA) has frequently been used to determine kinetic information for degradation reactions in polymeric materials. Flynn and Wall studied a number of methods for using TGA experiments to determine kinetic information in polymer reactions. Kinetic parameters, such as the apparent activation energy and the frequency factor, can be determined in such experiments. Recently, researchers at the McDonnell Douglas Research Laboratory suggested that a graph of the logarithm of the frequency factor against the apparent activation energy can be used to predict long-term thermo-oxidative stability for polymeric materials. Such a graph has been called a kinetic map. In this study, thermogravimetric analyses were performed in air to study the thermo-oxidative degradation of several high performance polymers and to plot their kinetic parameters on a kinetic map.
Gyrocenter-gauge kinetic theory
Qin, H.; Tang, W.M.; Lee, W.W.
2000-01-01
Gyrocenter-gauge kinetic theory is developed as an extension of the existing gyrokinetic theories. In essence, the formalism introduced here is a kinetic description of magnetized plasmas in the gyrocenter coordinates which is fully equivalent to the Vlasov-Maxwell system in the particle coordinates. In particular, provided the gyroradius is smaller than the scale-length of the magnetic field, it can treat high frequency range as well as the usual low frequency range normally associated with gyrokinetic approaches. A significant advantage of this formalism is that it enables the direct particle-in-cell simulations of compressional Alfven waves for MHD applications and of RF waves relevant to plasma heating in space and laboratory plasmas. The gyrocenter-gauge kinetic susceptibility for arbitrary wavelength and arbitrary frequency electromagnetic perturbations in a homogeneous magnetized plasma is shown to recover exactly the classical result obtained by integrating the Vlasov-Maxwell system in the particle coordinates. This demonstrates that all the waves supported by the Vlasov-Maxwell system can be studied using the gyrocenter-gauge kinetic model in the gyrocenter coordinates. This theoretical approach is so named to distinguish it from the existing gyrokinetic theory, which has been successfully developed and applied to many important low-frequency and long parallel wavelength problems, where the conventional meaning of gyrokinetic has been standardized. Besides the usual gyrokinetic distribution function, the gyrocenter-gauge kinetic theory emphasizes as well the gyrocenter-gauge distribution function, which sometimes contains all the physics of the problems being studied, and whose importance has not been realized previously. The gyrocenter-gauge distribution function enters Maxwell's equations through the pull-back transformation of the gyrocenter transformation, which depends on the perturbed fields. The efficacy of the gyrocenter-gauge kinetic approach is
Crystallization Kinetics within a Generic Modelling Framework
Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist
2013-01-01
An existing generic modelling framework has been expanded with tools for kinetic model analysis. The analysis of kinetics is carried out within the framework where kinetic constitutive models are collected, analysed and utilized for the simulation of crystallization operations. A modelling...... procedure is proposed to gain the information of crystallization operation kinetic model analysis and utilize this for faster evaluation of crystallization operations....
Transformation kinetics for nucleus clusters
Villa, Elena; Rios, Paulo R.
2009-01-01
A rigorous mathematical approach based on stochastic geometry concepts is presented to extend previous Johnson-Mehl, Avrami, Kolmogorov treatment of transformation kinetics to situations in which nuclei are not homogeneously located in space but are located in clusters. An exact analytical solution is presented here for the first time assuming that nucleation sites follow a Matern cluster process. The influence of Matern cluster process parameters on subsequent growth kinetics and the microstructural path are illustrated by means of numerical examples. Moreover, using the superposition principle, exact analytical solutions are also obtained when nucleation takes place by a combination of a Matern cluster process and an inhomogeneous Poisson point process. The new solutions presented here significantly increase the number of exactly solvable cases available to formal kinetics.
Chapter 22. Cell population kinetics
Tubiana, M.
1975-01-01
The main contribution of radioisotopes to the development of a new discipline, cell population kinetics, was shown. The aim of this science is to establish, for each tissue of the organism, the life span of its component cells and the mechanisms governing its growth, its differentiation and its homeostasis with respect to outside attacks. Labelling techniques have been used to follow the cells during these various processes. The case of non-dividing cells was considered first, taking as example, the red blood cells of which the lifetime was studied, after which the case of proliferating cells was examined using 14 C- or tritium-labelled thymidine. The methods used to measure the cell cycle parameters were described: labelled-mitosis curve method, double-labelling and continuous labelling methods, proliferation coefficient measurement. Cell kinetics were shown to allow an interpretation of radiobiological data. Finally the practical value of cell kinetics research was shown [fr
Kinetic theory and transport phenomena
Soto, Rodrigo
2016-01-01
This textbook presents kinetic theory, which is a systematic approach to describing nonequilibrium systems. The text is balanced between the fundamental concepts of kinetic theory (irreversibility, transport processes, separation of time scales, conservations, coarse graining, distribution functions, etc.) and the results and predictions of the theory, where the relevant properties of different systems are computed. The book is organised in thematic chapters where different paradigmatic systems are studied. The specific features of these systems are described, building and analysing the appropriate kinetic equations. Specifically, the book considers the classical transport of charges, the dynamics of classical gases, Brownian motion, plasmas, and self-gravitating systems, quantum gases, the electronic transport in solids and, finally, semiconductors. Besides these systems that are studied in detail, concepts are applied to some modern examples including the quark–gluon plasma, the motion of bacterial suspen...
Selected readings in chemical kinetics
Back, Margaret H
2013-01-01
Selected Readings in Chemical Kinetics covers excerpts from 12 papers in the field of general and gas-phase kinetics. The book discusses papers on the laws of connexion between the conditions of a chemical change and its amount; on the reaction velocity of the inversion of the cane sugar by acids; and the calculation in absolute measure of velocity constants and equilibrium constants in gaseous systems. The text then tackles papers on simple gas reactions; on the absolute rate of reactions in condensed phases; on the radiation theory of chemical action; and on the theory of unimolecular reacti
Chemical kinetics and reaction dynamics
Houston, Paul L
2006-01-01
This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications.Each chapter is self-contained and features an introduction that identifies its basic goals, their significance, and a general plan for their achievement. This text's important aims are to demonstrate that the basic kinetic principles are essential to the solution of modern chemical problems, and to show how the underlying qu
Chemical kinetics and combustion modeling
Miller, J.A. [Sandia National Laboratories, Livermore, CA (United States)
1993-12-01
The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.
Deuteration kinetics of the graphene
Nefedov, Alexei; Woell, Christof [KIT, Leopoldshafen (Germany); Paris, Alessio; Calliari, Lucia [FBK-CMM, Trento (Italy); Verbitskiy, Nikolay [MSU, Moscow (Russian Federation); University of Vienna, Vienna (Austria); Wang, Ying; Irle, Stephan [Nagoya University, Nagoya (Japan); Fedorov, Alexander [IFW Dresden, Dresden (Germany); St. Petersburg University, St. Petersburg (Russian Federation); Haberer, Danny; Knupfer, Martin; Buechner, Bernd [IFW Dresden, Dresden (Germany); Oetzelt, Martin [BESSY II, Berlin (Germany); Petaccia, Luca [Elettra, Trieste (Italy); Usachov, Dmitry [St. Petersburg University, St. Petersburg (Russian Federation); Vyalikh, Denis [St. Petersburg University, St. Petersburg (Russian Federation); TU Dresden, Dresden (Germany); Sagdev, Hermann [MPI fuer Polymerforschung, Mainz (Germany); Yashina, Lada [MSU, Moscow (Russian Federation); Grueneis, Alexander [IFW Dresden, Dresden (Germany); University of Vienna, Vienna (Austria)
2013-07-01
The kinetics of the hydrogenation/deuteration reaction of graphene was studied by time-dependent x-ray photoemission spectroscopy (XPS). The graphene layer was then exposed to hydrogen or deuterium atomic gas beams, obtained by thermal cracking in a tungsten capillary at T=3000 K. After each step XPS of the C1s line was performed in order to measure H/C and D/C ratios. We have observed a strong kinetic isotope effect for the hydrogenation/deuteration reaction leading to substantially faster adsorption and higher maximum D/C ratios as compared to H/C (D/C 35% vs. H/C 25%).
Vlasov simulations of Kinetic Alfven Waves at proton kinetic scales
C.L. Vasconez; F. Valentini (Francesco); E. Camporeale (Enrico); P. Veltri
2014-01-01
htmlabstractKinetic Alfv ́en waves represent an important subject in space plasma physics, since they are thought to play a crucial role in the development of the turbulent energy cascade in the solar wind plasma at short wavelengths (of the order of the proton inertial length d p and beyond). A
Elements of plasma kinetic theory
Guasp, J.
1976-01-01
The physical foundations of plasma kinetic equations are exposed inside a series of seminars on plasma and fusion physics. The Vlasov and collisional equations with its application range have been discussed. The momenta equations for the macroscopic magnitudes and the more usual approximations have been obtained: two fluid equations for cold and warm plasmas, magnetohydrodynamic equations and the double-adiabatic theory. (author)
Kinetic studies on leucite precursors
Mrázová, M.; Kloužková, A.; Kohoutková, Martina
2009-01-01
Roč. 7, č. 2 (2009), s. 205-210 ISSN 1895-1066 R&D Projects: GA MPO 2A-1TP1/063 Institutional research plan: CEZ:AV0Z40320502 Keywords : leucite * crystallization kinetics * hydrothermal Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass Impact factor: 1.065, year: 2009
Some parameters of radionuclide kinetics
Prokof'ev, O.N.; Smirnov, V.A.; Belen'kij, E.I.
1978-01-01
Numerical values of the rates of radionuclide absorption into, and elimination from, bovine organs were determined. Kinetic rate constants of radionuclides such as 89 Sr, 99 Mo, 131 I, 132 Tl, and 140 Be were calculated. The calculations were done for muscle, liver, and kidney
Solving Simple Kinetics without Integrals
de la Pen~a, Lisandro Herna´ndez
2016-01-01
The solution of simple kinetic equations is analyzed without referencing any topic from differential equations or integral calculus. Guided by the physical meaning of the rate equation, a systematic procedure is used to generate an approximate solution that converges uniformly to the exact solution in the case of zero, first, and second order…
Robustness Analysis of Kinetic Structures
Kirkegaard, Poul Henning; Sørensen, John Dalsgaard
2009-01-01
Kinetic structures in architecture follows a new trend which is emerging in responsive architecture coined by Nicholas Negroponte when he proposed that architecture may benefit from the integration of computing power into built spaces and structures, and that better performing, more rational...
Villadsen, John
2015-01-01
his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...
Resonance transport and kinetic entropy
Ivanov, Yu.B.; Knoll, J.; Voskresensky, D.N.
2000-01-01
We continue the description of the dynamics of unstable particles within the real-time formulation of nonequilibrium field theory initiated in a previous paper . There we suggest to use Baym's PHI-functional method in order to achieve approximation schemes with 'built in' consistency with respect to conservation laws and thermodynamics even in the case of particles with finite damping width. Starting from Kadanoff-Baym equations we discuss a consistent first order gradient approach to transport which preserves the PHI-derivable properties. The validity conditions for the resulting quantum four-phase-space kinetic theory are discussed under the perspective to treat particles with broad damping widths. This non-equilibrium dynamics naturally includes all those quantum features already inherent in the corresponding equilibrium limit (e.g. Matsubara formalism) at the same level of PHI-derivable approximation. Various collision-term diagrams are discussed including those of higher order which lead to memory effects. As an important novel part we derive a generalized nonequilibrium expression for the kinetic entropy flow, which includes contributions from fluctuations and mass-width effects. In special cases an H-theorem is derived implying that the entropy can only increase with time. Memory effects in the kinetic terms provide contributions to the kinetic entropy flow that in the equilibrium limit recover the famous bosonic type T 3 lnT correction to the specific heat in the case of Fermi liquids like Helium-3
Some Aspects of Extended Kinetic Equation
Dilip Kumar
2015-09-01
Full Text Available Motivated by the pathway model of Mathai introduced in 2005 [Linear Algebra and Its Applications, 396, 317–328] we extend the standard kinetic equations. Connection of the extended kinetic equation with fractional calculus operator is established. The solution of the general form of the fractional kinetic equation is obtained through Laplace transform. The results for the standard kinetic equation are obtained as the limiting case.
Holographic kinetic k-essence model
Cruz, Norman [Departamento de Fisica, Facultad de Ciencia, Universidad de Santiago de Chile, Casilla 307, Santiago (Chile)], E-mail: ncruz@lauca.usach.cl; Gonzalez-Diaz, Pedro F.; Rozas-Fernandez, Alberto [Colina de los Chopos, Instituto de Fisica Fundamental, Consejo Superior de Investigaciones Cientificas, Serrano 121, 28006 Madrid (Spain)], E-mail: a.rozas@cfmac.csic.es; Sanchez, Guillermo [Departamento de Matematica y Ciencia de la Computacion, Facultad de Ciencia, Universidad de Santiago de Chile, Casilla 307, Santiago (Chile)], E-mail: gsanchez@usach.cl
2009-08-31
We consider a connection between the holographic dark energy density and the kinetic k-essence energy density in a flat FRW universe. With the choice c{>=}1, the holographic dark energy can be described by a kinetic k-essence scalar field in a certain way. In this Letter we show this kinetic k-essential description of the holographic dark energy with c{>=}1 and reconstruct the kinetic k-essence function F(X)
Kinetic modelling of enzymatic starch hydrolysis
Bednarska, K.A.
2015-01-01
Kinetic modelling of enzymatic starch hydrolysis – a summary
K.A. Bednarska
The dissertation entitled ‘Kinetic modelling of enzymatic starch hydrolysis’ describes the enzymatic hydrolysis and kinetic modelling of liquefaction and saccharification of wheat starch.
Morphogenesis of Kinetic Reciprocal Frames
Parigi, Dario; Sassone, Mario
2011-01-01
Kinetic structures in civil engineering and architecture gained considerable more attention in the very recent years as a practical solution to face time dependant performances. Realized projects are mostly bridges, retractable roofs, while in architecture the trend follows the category of intera......Kinetic structures in civil engineering and architecture gained considerable more attention in the very recent years as a practical solution to face time dependant performances. Realized projects are mostly bridges, retractable roofs, while in architecture the trend follows the category...... (RF) were studied in the past as a practical solution to span distances with shorter elements. Leonardo da Vinci discovered interesting RF patterns and studied three dimensional arch structures for bridges. RF are generally defined as structures that forms closed circuits of forces, and where elements...
Kinetic approach to relativistic dissipation
Gabbana, A.; Mendoza, M.; Succi, S.; Tripiccione, R.
2017-08-01
Despite a long record of intense effort, the basic mechanisms by which dissipation emerges from the microscopic dynamics of a relativistic fluid still elude complete understanding. In particular, several details must still be finalized in the pathway from kinetic theory to hydrodynamics mainly in the derivation of the values of the transport coefficients. In this paper, we approach the problem by matching data from lattice-kinetic simulations with analytical predictions. Our numerical results provide neat evidence in favor of the Chapman-Enskog [The Mathematical Theory of Non-Uniform Gases, 3rd ed. (Cambridge University Press, Cambridge, U.K., 1970)] procedure as suggested by recent theoretical analyses along with qualitative hints at the basic reasons why the Chapman-Enskog expansion might be better suited than Grad's method [Commun. Pure Appl. Math. 2, 331 (1949), 10.1002/cpa.3160020403] to capture the emergence of dissipative effects in relativistic fluids.
Kinetic theory of tearing instability
Hazeltine, R.D.; Dobrott, D.; Wang, T.S.
1975-01-01
The guiding-center kinetic equation with Fokker-Planck collision term is used to study, in cylindrical geometry, a class of dissipative instabilities of which the classical tearing mode is an archetype. Variational solution of the kinetic equation obviates the use of an approximate Ohm's law or adiabatic assumption, as used in previous studies, and it provides a dispersive relation which is uniformly valid for any ratio of wave frequency to collision frequency. One result of using the rigorous collision operator is the prediction of a new instability. This instability, driven by the electron temperature gradient, is predicted to occur under the long mean-free path conditions of present tokamak experiments, and has significant features in common with the kink-like oscillations observed in such experiments
Kinetics of cadmium hydroxide precipitation
Patterson, J.W.; Marani, D.; Luo, B.; Swenson, P.
1987-01-01
This paper presents some preliminary results on the kinetics of Cd(OH)/sub 2/ precipitation, both in the absence and the presence of citric acid as an inhibiting agent. Batch and continuous stirred tank reactor (CSTR) precipitation studies are performed by mixing equal volumes of NaOH and Cd(NO/sub 3/)/sub 2/ solutions, in order to avoid localized supersaturation conditions. The rate of metal removal from the soluble phase is calculated from the mass balance for the CSTR precipitation tests. In addition, precipitation kinetics are studied in terms of nucleation and crystal growth rates, by means of a particle counter that allows a population balance analysis for the precipitation reactor at steady state conditions
Art Engineering and Kinetic Art
Barış Yılmaz
2014-12-01
Full Text Available Performing an art, either by painting or by sculpturing, requires to be interdisciplinary. When an artist creates his/her work of art, the process he/she realizes is supported by different engineering disciplines. Therefore, especially modern artists need to understand engineering science and this results in transforming artists into engineers. Opportunities provided by technology and science enable artists to expand his/her vision and to improve his/her works. Especially kinetic art has become an approach that combines art with engineering. Kinetic art, which is nourished with varied disciplines, is an excellent example to prove that art is interdisciplinary and to show the relationship between artist/art and engineering.
Modeling the isochronal crystallization kinetics
Sahay, S.S.; Krishnan, Karthik
2004-01-01
The classical Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, originally formulated for the isothermal condition, is often used in conjunction with additivity principle for modeling the non-isothermal crystallization kinetics. This approach at times results in significant differences between the model prediction and experimental data. In this article, a modification to this approach has been imposed via an additional functional relationship between the activation energy and heating rate. The methodology has been validated with experimental isochronal crystallization kinetic data in Se 71 Te 20 Sb 9 glass and Ge 20 Te 80 systems. It has been shown that the functional relationship between heating rate and activation energy, ascribed to the reduction in apparent activation energy due to increasing non-isothermality, provides better phenomenological description and therefore improves the prediction capability of the JMAK model under isochronal condition
Muscular Oxygen Uptake Kinetics in Aged Adults.
Koschate, J; Drescher, U; Baum, K; Eichberg, S; Schiffer, T; Latsch, J; Brixius, K; Hoffmann, U
2016-06-01
Pulmonary oxygen uptake (V˙O2) kinetics and heart rate kinetics are influenced by age and fitness. Muscular V˙O2 kinetics can be estimated from heart rate and pulmonary V˙O2. In this study the applicability of a test using pseudo-random binary sequences in combination with a model to estimate muscular V˙O2 kinetics was tested. Muscular V˙O2 kinetics were expected to be faster than pulmonary V˙O2 kinetics, slowed in aged subjects and correlated with maximum V˙O2 and heart rate kinetics. 27 elderly subjects (73±3 years; 81.1±8.2 kg; 175±4.7 cm) participated. Cardiorespiratory kinetics were assessed using the maximum of cross-correlation functions, higher maxima implying faster kinetics. Muscular V˙O2 kinetics were faster than pulmonary V˙O2 kinetics (0.31±0.1 vs. 0.29±0.1 s; p=0.004). Heart rate kinetics were not correlated with muscular or pulmonary V˙O2 kinetics or maximum V˙O2. Muscular V˙O2 kinetics correlated with maximum V˙O2 (r=0.35; p=0.033). This suggests, that muscular V˙O2 kinetics are faster than estimates from pulmonary V˙O2 and related to maximum V˙O2 in aged subjects. In the future this experimental approach may help to characterize alterations in muscular V˙O2 under various conditions independent of motivation and maximal effort. © Georg Thieme Verlag KG Stuttgart · New York.
Bumetanide kinetics in renal failure
Pentikaeinen, P.J.P.; Pasternack, A.; Lampainen, E.; Neuvonen, P.J.; Penttilae, A.
1985-01-01
To study the effects of renal failure on bumetanide kinetics, the authors administered single intravenous doses of 1.0 mg/3.08 microCi 14 C-bumetanide to six healthy subjects and 22 patients with variable degrees of renal failure. The kinetics of 14 C-bumetanide and total 14 C were adequately described by a two-compartment open model in the control subjects and in the patients. The volume of the central compartment and the distribution t1/2 were of the same order in both groups, whereas the mean (+/- SE) volume at steady state was larger (22.1 +/- 1.6 and 16.9 +/- 1.0 L) and the elimination t1/2 was longer (1.9 +/- 0.2 and 1.4 +/- 0.1 hours) in patients with renal failure than in healthy controls. Bumetanide renal clearance was lower (10 +/- 3 and 90 +/- 13 ml/min) in patients than in subjects and correlated with creatinine clearance (r = 0.784) and log serum creatinine level (r = -0.843), whereas nonrenal clearance was significantly higher in the patients (153 +/- 14 and 99 +/- 6 ml/min). Bumetanide total plasma clearance did not significantly change. The non-protein-bound, free fraction of bumetanide was higher in patients and correlated with plasma albumin levels (r = -0.777). The kinetics of total 14 C showed similar but greater changes than those of 14C-bumetanide. Thus the most important changes in bumetanide kinetics in patients with renal failure are low renal clearance and a high free fraction, with a consequent increase in nonrenal clearance, volume of distribution, and elimination t1/2
Production kinetics of zirconium tetrachloride
Sudjoko, D.; Masduki, B.; Sunardjo; Sulistyo, B.
1996-01-01
This research was intended to study the kinetics of zirconium tetrachloride production. The process was carried out in semi continuous reactor, equipped with heater, temperature controller, sublimator and scrubber. The variables investigated were time, temperature and the pellet forming pressure. Within the range of variables studied, the expression of the process in the chemical reaction controller region and diffusion controller region were both presented. (author)
Lombard, R.J.; Mas, D.; Moszkowski, S.A.
1991-01-01
We discuss two expressions for the density of kinetic energy which differ by an integration by parts. Using the Wigner transform we shown that the arithmetic mean of these two terms is closely analogous to the classical value. Harmonic oscillator wavefunctions are used to illustrate the radial dependence of these expressions. We study the differences they induce through effective mass terms when performing self-consistent calculations. (author)
Ristic, M.M.
1962-01-01
Detailed conclusions related to the UO 2 sintering can be drawn from investigating the kinetics of the sintering process. This report gives an thorough analysis of the the data concerned with sintering available in the literature taking into account the Jander and Arrhenius laws. This analysis completes the study of influence of the O/U ratio and the atmosphere on the sintering. Results presented are fundamentals of future theoretical and experimental work related to characterisation of the UO 2 sintering process
KINETIC ALGORITHMS FOR HARBOUR MANAGEMENT
C. M. Gold
2012-07-01
Full Text Available Modern harbour management for a busy port needs to resolve a variety of simultaneous problems. Harbour traffic may be busy and the waterways congested, both by the major shipping and by the attendant harbour tugs. The harbour channel may be narrow and tortuous, and rapidly changing tides may require frequent course adjustments. Navigation aids must be clearly specified and immediately identifiable, in order to permit safe passage for the vessels. This requires a GIS with attributes not easily available with traditional products. The GeoVS system is a kinetic GIS with full three-dimensional visualisation, so that ships, bathymetry and landscape may be viewed in a form that is immediately understandable to both harbour pilots and the harbour authority. The system is kinetic because the data structures used to preserve the topological relationships between ships, seafloor and coastline are able to be maintained on a real-time basis, taking account of ship movement recorded on the compulsory AIS (Automatic Information System beacons. Maintenance of this real-time topology allows for easy detection of potential collisions, as well as real-time bathymetric estimations, necessary to prevent ship grounding in highly tidal environments. The system, based on previous research into kinetic Voronoi diagrams, as well as development of a completely new graphical engine, is now in commercial production, where its advantages over simpler twodimensional models without automatic collision and grounding detection are becoming evident. Other applications are readily envisaged, and will be addressed in the near future.
Oxidation kinetics of corium pool
Sulatsky, A.A., E-mail: andrei314@mail.ru [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Smirnov, S.A. [D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St. Petersburg (Russian Federation); Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu. [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Fischer, M.; Hellmann, S. [AREVA NP GmbH, Erlangen (Germany); Tromm, W.; Miassoedov, A. [Forschungzentrum Karlsruhe (FZK), Karlsruhe (Germany); Bottomley, D. [EUROPÄISCHE KOMMISSION, Joint Research Centre Institut für Transurane (ITU), Karlsruhe (Germany); Piluso, P. [CEA Cadarache-DEN/DTN/STRI, St.Paul-lez-Durance (France); Barrachin, M. [Institut de Radioprotection et Sûreté Nucléaire, St.Paul-lez-Durance (France)
2013-09-15
Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations.
Oxidation kinetics of corium pool
Sulatsky, A.A.; Smirnov, S.A.; Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu.; Fischer, M.; Hellmann, S.; Tromm, W.; Miassoedov, A.; Bottomley, D.; Piluso, P.; Barrachin, M.
2013-01-01
Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations
Aluminum corrosion product release kinetics
Edwards, Matt, E-mail: Matthew.Edwards@cnl.ca; Semmler, Jaleh; Guzonas, Dave; Chen, Hui Qun; Toor, Arshad; Hoendermis, Seanna
2015-07-15
Highlights: • Release of Al corrosion product was measured in simulated post-LOCA sump solutions. • Increased boron was found to enhance Al release kinetics at similar pH. • Models of Al release as functions of time, temperature, and pH were developed. - Abstract: The kinetics of aluminum corrosion product release was examined in solutions representative of post-LOCA sump water for both pressurized water and pressurized heavy-water reactors. Coupons of AA 6061 T6 were exposed to solutions in the pH 7–11 range at 40, 60, 90 and 130 °C. Solution samples were analyzed by inductively coupled plasma atomic emission spectroscopy, and coupon samples were analyzed by secondary ion mass spectrometry. The results show a distinct “boron effect” on the release kinetics, expected to be caused by an increase in the solubility of the aluminum corrosion products. New models were developed to describe both sets of data as functions of temperature, time, and pH (where applicable)
Nonlinear Kinetics on Lattices Based on the Kinetic Interaction Principle
Giorgio Kaniadakis
2018-06-01
Full Text Available Master equations define the dynamics that govern the time evolution of various physical processes on lattices. In the continuum limit, master equations lead to Fokker–Planck partial differential equations that represent the dynamics of physical systems in continuous spaces. Over the last few decades, nonlinear Fokker–Planck equations have become very popular in condensed matter physics and in statistical physics. Numerical solutions of these equations require the use of discretization schemes. However, the discrete evolution equation obtained by the discretization of a Fokker–Planck partial differential equation depends on the specific discretization scheme. In general, the discretized form is different from the master equation that has generated the respective Fokker–Planck equation in the continuum limit. Therefore, the knowledge of the master equation associated with a given Fokker–Planck equation is extremely important for the correct numerical integration of the latter, since it provides a unique, physically motivated discretization scheme. This paper shows that the Kinetic Interaction Principle (KIP that governs the particle kinetics of many body systems, introduced in G. Kaniadakis, Physica A 296, 405 (2001, univocally defines a very simple master equation that in the continuum limit yields the nonlinear Fokker–Planck equation in its most general form.
A kinetics database and scripts for PHREEQC
Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.
2017-12-01
Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.
Thermodynamic basis for cluster kinetics
Hu, Lina; Bian, Xiufang; Qin, Xubo
2006-01-01
Due to the inaccessibility of the supercooled region of marginal metallic glasses (MMGs) within the experimental time window, we study the cluster kinetics above the liquidus temperature, Tl, to acquire information on the fragility of the MMG systems. Thermodynamic basis for the stability...... of locally ordered structure in the MMG liquids is discussed in terms of the two-order-parameter model. It is found that the Arrhenius activation energy of clusters, h, is proportional to the chemical mixing enthalpy of alloys, Hchem. Fragility of the MMG forming liquids can be described by the ratio...
Kinetics of heterogeneous catalytic reactions
Boudart, Michel
2014-01-01
This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc
Kinetic equations with pairing correlations
Fauser, R.
1995-12-01
The Gorkov equations are derived for a general non-equilibrium system. The Gorkov factorization is generalized by the cumulant expansion of the 2-particle correlation and by a generalized Wick theorem in the case of a perturbation expansion. A stationary solution for the Green functions in the Schwinger-Keldysh formalism is presented taking into account pairing correlations. Especially the effects of collisional broadening on the spectral functions and Green functions is discussed. Kinetic equations are derived in the quasi-particle approximation and in the case of particles with width. Explicit expressions for the self-energies are given. (orig.)
Kinetic theory of radiation effects
Mansur, L.K.
1987-01-01
To help achieve the quantitative and mechanistic understanding of these processes, the kinetic theory of radiation effects has been developed in the DOE basic energy sciences radiation effects and fusion reactor materials programs, as well as in corresponding efforts in other countries. This discipline grapples with a very wide range of phenomena and draws on numerous sub-fields of theory such as defect physics, diffusion, elasticity, chemical reaction rates, phase transformations and thermodynamics. The theory is cast in a mathematical framework of continuum dynamics. Issues particularly relevant to the present inquiry can be viewed from the standpoints of applications of the theory and areas requiring further progress
A kinetic model for hydrodesulfurisation
Sau, M.; Narasimhan, C.S.L.; Verma, R.P. [Indian Oil Corporation Limited, Research and Development Centre, Faridabad (India)
1997-07-01
Due to stringent environmental considerations and related insistence on low sulfur fuels, hydrodesulfurisation has emerged as an important component of any refining scheme globally. The process is used ranging from Naphta/Kerosine hydrotreating to heavy oil hydrotreating. Processes such as Deep gas oil desulfurisation aiming at reduction of sulfur levels to less than 500 ppm have emerged as major players in the scenario. Hydrodesulfurisation (HDS) involves parallel desulfurisation of different organo-sulfur compounds present in the complex petroleum mixtures. In order to design, monitor, optimise and control the HDS reactor, it is necessary to have a detailed, yet simple model which follows the reaction chemistry accurately. In the present paper, a kinetic model is presented for HDS using continuum theory of lumping. The sulfur distribution in the reaction mixture is treated as continuum and parallel reaction networks are devised for kinetic modelling using continuum theory of lumping approach. The model based on the above approach follows the HDS chemistry reasonably well and hence the model parameters are almost feed invariant. Methods are also devised to incorporate heat and pressure effects into the model. The model has been validated based on commercial kero-HDS data. It is found that the model predictions agree with the experimental/commercial data. 17 refs.
Kinetic Profiles in NSTX Plasmas
Bell, R.E.; LeBlanc, B.P.; Bourdelle, C.; Ernst, D.R.; Fredrickson, E.D.; Gates, D.A.; Hosea, J.C.; Johnson, D.W.; Kaye, S.M.; Maingi, R.; Medley, S.; Menard, J.E.; Mueller, D.; Ono, M.; Paoletti, F.; Peng, M.; Sabbagh, S.A.; Stutman, D.; Swain, D.W.; Synakowski, E.J.; Wilson, J.R.
2001-01-01
The National Spherical Torus Experiment (NSTX) is a low aspect ratio (R/a approximately 1.3) device with auxiliary heating from neutral-beam injection (NBI) and high-harmonic fast-wave heating (HHFW). Typical NSTX parameters are R(subscript ''0'') = 85 cm, a = 67 cm, I(subscript ''p'') = 0.7-1.4 MA, B(subscript ''phi'') = 0.25-0.45 T. Three co-directed deuterium neutral-beam sources have injected P(subscript ''NB'') less than or equal to 4.7 MW. HHFW plasmas typically have delivered P(subscript ''RF'') less than or equal to 3 MW. Important to the understanding of NSTX confinement are the new kinetic profile diagnostics: a multi-pulse Thomson scattering system (MPTS) and a charge-exchange recombination spectroscopy (CHERS) system. The MPTS diagnostic currently measures electron density and temperature profiles at 30 Hz at ten spatial locations. The CHERS system has recently become available to measure carbon ion temperature and toroidal flow at 17 radial positions spanning the outer half of the minor radius with 20 msec time resolution during NBI. Experiments conducted during the last year have produced a wide range of kinetic profiles in NSTX. Some interesting examples are presented below
Conformational kinetics of aliphatic tails
Ferrarini, Alberta; Moro, Giorgio; Nordio, Pier Luigi
The master equation describing the random walk between sites identified with the stable conformers of a chain molecule, represents the extension to the time domain of the Rotational Isomeric State model. The asymptotic analysis of the multidimensional diffusion equation in the continuous torsional variables subjected to the configurational potential, provides a rigorous justification for the discrete models, and it supplies, without resorting to phenomenological parameters, molecular definitions of the kinetic rates for the conformational transitions occurring at each segment of the chain. The coupling between the torsional variables is fully taken into account, giving rise to cooperative effects. A complete calculation of the specific correlation functions which describe the time evolution of the angular functions probed by N.M.R. and dielectric relaxation measurements, has been performed for alkyl chains attached to a massive core. The resulting behaviour has been compared with the decay of trans and gauche populations of specific bonds, expressed in terms of suitable correlation functions whose time integrals lead quite naturally to the definition of effective kinetic constants for the conformational transitions.
Skrable, K.W.; Chabot, G.E.; French, C.S.; Wrenn, M.E.; Lipsztein, J.; Sasso, T.L.; Durbin, P.W.
1980-01-01
Exact and approximate kinetics equations relating to the transfer and elimination of radionuclides from the blood and various organs in the body are presented. These expressions may be used to estimate the instantaneous activity or the total number of disintegrations of a radionuclide in the blood or various organs of reference in the body, hence, also the respective dose rates and doses. The exact kinetics equations may be used to relate measurements of radionuclides in excreta to burdens in the body. They do give better results for exposure intervals long compared to the effective mean lives of the radionuclide in the various organs of reference, and they yield the exact steady state expressions. Fortunately, this condition is often satisfied for the relatively long standard exposure interval of 50 years that is applied to occupational exposure. In addition, the steady state expressions may be used along with metabolic data of the distribution of elements in the body, diet and excreta to estimate values of the rate constants used in both the exact and approximate expressions. A comparison of the exact and approximate expressions is given for the uranium metabolic model of Wrenn et al. and a comparison is made with current ICRP models. (author)
Combustion kinetics and reaction pathways
Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)
1993-12-01
This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.
Numerical Simulation of the Kinetic Critical Nucleus
Sanada, Masaaki; Nishioka, Kazumi; Okada, Masahumi; Maksimov, Igor, L.
1997-01-01
Our main interest is to see whether the number density indicates a peak at the kinetically stable critical nucleus due to its kinetical stability. We have numerically calculated the time evolution of the number densities of clusters in the case of water vapor nucleation. We employ the condition in which the difference between the size of the thermodynamic crtitical nucleus and that of the kinetic one is appreciable. The results show that the peak does not appear in the number densities of clu...
Drug-Target Kinetics in Drug Discovery.
Tonge, Peter J
2018-01-17
The development of therapies for the treatment of neurological cancer faces a number of major challenges including the synthesis of small molecule agents that can penetrate the blood-brain barrier (BBB). Given the likelihood that in many cases drug exposure will be lower in the CNS than in systemic circulation, it follows that strategies should be employed that can sustain target engagement at low drug concentration. Time dependent target occupancy is a function of both the drug and target concentration as well as the thermodynamic and kinetic parameters that describe the binding reaction coordinate, and sustained target occupancy can be achieved through structural modifications that increase target (re)binding and/or that decrease the rate of drug dissociation. The discovery and deployment of compounds with optimized kinetic effects requires information on the structure-kinetic relationships that modulate the kinetics of binding, and the molecular factors that control the translation of drug-target kinetics to time-dependent drug activity in the disease state. This Review first introduces the potential benefits of drug-target kinetics, such as the ability to delineate both thermodynamic and kinetic selectivity, and then describes factors, such as target vulnerability, that impact the utility of kinetic selectivity. The Review concludes with a description of a mechanistic PK/PD model that integrates drug-target kinetics into predictions of drug activity.
Tantalum high-temperature oxidation kinetics
Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.
1981-01-01
Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru
Disordering kinetics in surface overlayers
Jesina, A.; Tringides, M.C.
1993-01-01
The disordering kinetics of the O/W(110)-p(2x1)+p(2x2) overlayer, prepared initially in a well-ordered state, are studied with low-energy electron diffraction profile analysis. The decay of the peak intensity, used as a measure of the growing disorder, cannot be fitted to a power law as in the case of ordering processes. The full width at half maximum of the time-dependent structure factor S(q,t) is constant with time, which suggests that the average size remains constant. Diffusion activation energy extracted for the temperature dependence of the disordering is 1.0±0.05 eV, which is different from the value of 0.6 eV measured in ordering processes. The difference can be explained by the adsorbate-adsorbate interactions, which contribute differently to the diffusion barrier, in the two experiments
Analysis of kinetic reaction mechanisms
Turányi, Tamás
2014-01-01
Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.
Nuclear reactor kinetics and control
Lewins, J.
1978-01-01
A consistent, integrated account of modern developments in the study of nuclear reactor kinetics and the problem of their efficient and safe control. It aims to prepare the student for advanced study and research or practical work in the field. Special features include treatments of noise theory, reliability theory and safety related studies. It covers all aspects of the operation and control of nuclear reactors, power and research and is complete in providing physical data methods of calculation and solution including questions of equipment reliability. The work uses illustrations of the main types of reactors in use in the UK, USA and Europe. Each chapter contains problems and worked examples suitable for course work and study. The subject is covered in chapters, entitled: introductory review; neutron and precursor equations; elementary solutions at low power; linear reactor process dynamics with feedback; power reactor control systems; fluctuations and reactor noise; safety and reliability; nonlinear systems (safety and control); analogue computing. (author)
Method of molybdenum kinetic determination
Krejngol'd, S.U.; Dzotsenidze, N.E.; Ruseishviyai, T.G.; Nelen', I.M.
1980-01-01
The method molybdenum kinetic determination according to oxidation of pyrogallol with bromate in the medium of 0.05-0.15 M perchloric or sulphuric acids is presented. 1 mg of Ni, Co, Mn, Mg, Zn, Cr(3); 100 μg of Ca, Al, Cu, 10 μg of Cr(4), W; 10 μg of Fe in the presence of 22x10 - 4 M solution of EDTA, as well as 10 - 4 M solutions of chlorides and fluorides, 10 - 5 M solutions of bromides do not interfere with molybdenum determination using the given method. The method is rather simple, it takes 30 min to carry out the analysis. Determination limit of molybdenum constitutes 0.01 μg/ml
Quantum-statistical kinetic equations
Loss, D.; Schoeller, H.
1989-01-01
Considering a homogeneous normal quantum fluid consisting of identical interacting fermions or bosons, the authors derive an exact quantum-statistical generalized kinetic equation with a collision operator given as explicit cluster series where exchange effects are included through renormalized Liouville operators. This new result is obtained by applying a recently developed superoperator formalism (Liouville operators, cluster expansions, symmetrized projectors, P q -rule, etc.) to nonequilibrium systems described by a density operator ρ(t) which obeys the von Neumann equation. By means of this formalism a factorization theorem is proven (being essential for obtaining closed equations), and partial resummations (leading to renormalized quantities) are performed. As an illustrative application, the quantum-statistical versions (including exchange effects due to Fermi-Dirac or Bose-Einstein statistics) of the homogeneous Boltzmann (binary collisions) and Choh-Uhlenbeck (triple collisions) equations are derived
Growth kinetics in multicomponent fluids
Chen, S.; Lookman, T.
1995-01-01
The hydrodynamic effects on the late-stage kinetics in spinodal decomposition of multicomponent fluids are examined using a lattice Boltzmann scheme with stochastic fluctuations in the fluid and at the interface. In two dimensions, the three- and four-component immiscible fluid mixture (with a 1024 2 lattice) behaves like an off-critical binary fluid with an estimated domain growth of t 0.4 +/= 0.03 rather than t 1/3 as previously estimated, showing the significant influence of hydrodynamics. In three dimensions (with a 256 3 lattice), we estimate the growth as t 0.96 +/= 0.05 for both critical and off-critical quenches, in agreement with phenomenological theory
Al-Chalabi, R.M.; Turinsky, P.J.; Faure, F.-X.; Sarsour, H.N.; Engrand, P.R.
1993-01-01
The NESTLE nodal kinetics code has been developed for utilization as a stand-alone code for steady-state and transient reactor neutronic analysis and for incorporation into system transient codes, such as TRAC and RELAP. The latter is desirable to increase the simulation fidelity over that obtained from currently employed zero- and one-dimensional neutronic models and now feasible due to advances in computer performance and efficiency of nodal methods. As a stand-alone code, requirements are that it operate on a range of computing platforms from memory-limited personal computers (PCs) to supercomputers with vector processors. This paper summarizes the features of NESTLE that reflect the utilization and requirements just noted
Kinetics model for lutate dosimetry
Lima, M.F.; Mesquita, C.H.
2013-01-01
The use of compartmental analysis to predict the behavior of drugs in the organism is considered the better option among numerous methods employed in pharmacodynamics. A six compartments model was developed to determinate the kinetic constants of 177Lu-DOTATATO biodistribution using data from one published study with 67 patients treated by PRRT (Peptide receptor radionuclide therapy) and followed by CT during 68,25 hours. The compartmental analysis was made using the software AnaComp®. The influence of the time pos-injection over the dose assessment was studied taking into account the renal excretion management by aminoacid coinfusion, whose direct effects persist in the first day. The biodistribution curve was split in five sectors: 0-0.25h; 0-3.25h; 3.25-24.25h; 24.25-68.25h and 3.25-68.25h. After the examination of that influence, the study was concentrated in separate the biodistribution curve in two phases. Phase 1: governed by uptake from the blood, considering the time pos-injection until 3.25h and phase 2: governed by renal excretion, considering the time pos-injection from 3.25h to 68.25h. The model considered the organs and tissues superposition in the CT image acquisition by sampling parameters as the contribution of the the activity concentration in blood and relation between the sizes of the whole body and measured organs. The kinetic constants obtained from each phase (1 and 2) were used in dose assessment to patients in 26 organs and tissues described by MIRD. Dosimetry results were in agreement with the available results from literature, restrict to whole body, kidneys, bone marrow, spleen and liver. The advantage of the proposed model is the compartmental method quickness and power to estimate dose in organs and tissues, including tumor that, in the most part, were not discriminate by voxels of phantoms built using CT images. (author)
Nanoparticle shape, thermodynamics and kinetics
Marks, L D; Peng, L
2016-01-01
Nanoparticles can be beautiful, as in stained glass windows, or they can be ugly as in wear and corrosion debris from implants. We estimate that there will be about 70 000 papers in 2015 with nanoparticles as a keyword, but only one in thirteen uses the nanoparticle shape as an additional keyword and research focus, and only one in two hundred has thermodynamics. Methods for synthesizing nanoparticles have exploded over the last decade, but our understanding of how and why they take their forms has not progressed as fast. This topical review attempts to take a critical snapshot of the current understanding, focusing more on methods to predict than a purely synthetic or descriptive approach. We look at models and themes which are largely independent of the exact synthetic method whether it is deposition, gas-phase condensation, solution based or hydrothermal synthesis. Elements are old dating back to the beginning of the 20th century—some of the pioneering models developed then are still relevant today. Others are newer, a merging of older concepts such as kinetic-Wulff constructions with methods to understand minimum energy shapes for particles with twins. Overall we find that while there are still many unknowns, the broad framework of understanding and predicting the structure of nanoparticles via diverse Wulff constructions, either thermodynamic, local minima or kinetic has been exceedingly successful. However, the field is still developing and there remain many unknowns and new avenues for research, a few of these being suggested towards the end of the review. (topical review)
Kinetics model for lutate dosimetry
Lima, M.F.; Mesquita, C.H., E-mail: mflima@ipen.br, E-mail: chmesqui@ipen.br [Instituto de Pesquisas Energeticas (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)
2013-11-01
The use of compartmental analysis to predict the behavior of drugs in the organism is considered the better option among numerous methods employed in pharmacodynamics. A six compartments model was developed to determinate the kinetic constants of 177Lu-DOTATATO biodistribution using data from one published study with 67 patients treated by PRRT (Peptide receptor radionuclide therapy) and followed by CT during 68,25 hours. The compartmental analysis was made using the software AnaComp Registered-Sign . The influence of the time pos-injection over the dose assessment was studied taking into account the renal excretion management by aminoacid coinfusion, whose direct effects persist in the first day. The biodistribution curve was split in five sectors: 0-0.25h; 0-3.25h; 3.25-24.25h; 24.25-68.25h and 3.25-68.25h. After the examination of that influence, the study was concentrated in separate the biodistribution curve in two phases. Phase 1: governed by uptake from the blood, considering the time pos-injection until 3.25h and phase 2: governed by renal excretion, considering the time pos-injection from 3.25h to 68.25h. The model considered the organs and tissues superposition in the CT image acquisition by sampling parameters as the contribution of the the activity concentration in blood and relation between the sizes of the whole body and measured organs. The kinetic constants obtained from each phase (1 and 2) were used in dose assessment to patients in 26 organs and tissues described by MIRD. Dosimetry results were in agreement with the available results from literature, restrict to whole body, kidneys, bone marrow, spleen and liver. The advantage of the proposed model is the compartmental method quickness and power to estimate dose in organs and tissues, including tumor that, in the most part, were not discriminate by voxels of phantoms built using CT images. (author)
Conformational Diffusion and Helix Formation Kinetics
Hummer, Gerhard; Garcia, Angel E.; Garde, Shekhar
2000-01-01
The time, temperature, and sequence dependences of helix formation kinetics of fully atomistic peptide models in explicit solvent are described quantitatively by a diffusive search within the coil state with barrierless transitions into the helical state. Conformational diffusion leads to nonexponential kinetics and jump-width dependences in temperature jump experiments. (c) 2000 The American Physical Society
Towards Free-Form Kinetic Structures
Parigi, Dario; Kirkegaard, Poul Henning
2012-01-01
of pin-slot paths starting from the local displacements of element [2] [3]. In the design of kinetic structures, in particular when complex three dimensional and non regular configurations are involved, the functionality is frequently related to a global displacement capability of the assembly rather...... for the generation of free-form kinetic structures....
Modeling composting kinetics: A review of approaches
Hamelers, H.V.M.
2004-01-01
Composting kinetics modeling is necessary to design and operate composting facilities that comply with strict market demands and tight environmental legislation. Current composting kinetics modeling can be characterized as inductive, i.e. the data are the starting point of the modeling process and
Saffman-Taylor fingers with kinetic undercooling
Gardiner, Bennett P. J.
2015-02-23
© 2015 American Physical Society. The mathematical model of a steadily propagating Saffman-Taylor finger in a Hele-Shaw channel has applications to two-dimensional interacting streamer discharges which are aligned in a periodic array. In the streamer context, the relevant regularization on the interface is not provided by surface tension but instead has been postulated to involve a mechanism equivalent to kinetic undercooling, which acts to penalize high velocities and prevent blow-up of the unregularized solution. Previous asymptotic results for the Hele-Shaw finger problem with kinetic undercooling suggest that for a given value of the kinetic undercooling parameter, there is a discrete set of possible finger shapes, each analytic at the nose and occupying a different fraction of the channel width. In the limit in which the kinetic undercooling parameter vanishes, the fraction for each family approaches 1/2, suggesting that this "selection" of 1/2 by kinetic undercooling is qualitatively similar to the well-known analog with surface tension. We treat the numerical problem of computing these Saffman-Taylor fingers with kinetic undercooling, which turns out to be more subtle than the analog with surface tension, since kinetic undercooling permits finger shapes which are corner-free but not analytic. We provide numerical evidence for the selection mechanism by setting up a problem with both kinetic undercooling and surface tension and numerically taking the limit that the surface tension vanishes.
Chemical kinetics and oil shale process design
Burnham, A.K.
1993-07-01
Oil shale processes are reviewed with the goal of showing how chemical kinetics influences the design and operation of different processes for different types of oil shale. Reaction kinetics are presented for organic pyrolysis, carbon combustion, carbonate decomposition, and sulfur and nitrogen reactions.
A Comprehensive Enzyme Kinetic Exercise for Biochemistry
Barton, Janice S.
2011-01-01
This article describes a comprehensive treatment of experimental enzyme kinetics strongly coupled to electronic data acquisition and use of spreadsheets to organize data and perform linear and nonlinear least-squares analyses, all in a manner that promotes development of important reasoning skills. Kinetic parameters are obtained for the stable…
Kinetic equations for the collisional plasma model
Rij, W.I. Van; Meier, H.K.; Beasley, C.O. Jr.; McCune, J.E.
1977-01-01
Using the Collisional Plasma Model (CPM) representation, expressions are derived for the Vlasov operator, both in its general form and in the drift-kinetic approximation following the recursive derivation by Hazeltine. The expressions for the operators give easily calculated couplings between neighbouring components of the CPM representation. Expressions for various macroscopic observables in the drift-kinetics approximation are also given. (author)
Chemistry and reaction kinetics of biowaste torrefaction
Stelt, van der M.J.C.
2011-01-01
This thesis addresses the question of how the chemistry and reaction kinetics of torrefaction are influenced by reaction conditions and the effects occuring during the reaction. This research question can be specified by questions such as, what controls their kinetics during torrefaction and what
Determination of the kinetics of ethene epoxidation
Schouten, E.P.S.; Schouten, E.P.S.; Borman, P.C.; Borman, P.C.; Westerterp, K.R.
1996-01-01
Several problems and pitfalls in the use of laboratory reactors for the determination of the kinetics of ethene epoxidation over industrial silver on α-alumina catalyst are discussed. Also, commonly used methodologies for kinetic studies are dealt with because of the general nature of some problems.
Kinetic spectrophotometric determination of some fluoroquinolone ...
A simple and sensitive kinetic spectrophotometric method was developed for the determination of some fluoroquinolonea antibiotics; gemifloxacin mesylate, moxifloxacin hydrochloride and gatifloxacin in bulk and in pharmaceutical preparations. The method is based upon a kinetic investigation of the oxidation reaction of ...
Saffman-Taylor fingers with kinetic undercooling
Gardiner, Bennett P. J.; McCue, Scott W.; Dallaston, Michael C.; Moroney, Timothy J.
2015-01-01
© 2015 American Physical Society. The mathematical model of a steadily propagating Saffman-Taylor finger in a Hele-Shaw channel has applications to two-dimensional interacting streamer discharges which are aligned in a periodic array. In the streamer context, the relevant regularization on the interface is not provided by surface tension but instead has been postulated to involve a mechanism equivalent to kinetic undercooling, which acts to penalize high velocities and prevent blow-up of the unregularized solution. Previous asymptotic results for the Hele-Shaw finger problem with kinetic undercooling suggest that for a given value of the kinetic undercooling parameter, there is a discrete set of possible finger shapes, each analytic at the nose and occupying a different fraction of the channel width. In the limit in which the kinetic undercooling parameter vanishes, the fraction for each family approaches 1/2, suggesting that this "selection" of 1/2 by kinetic undercooling is qualitatively similar to the well-known analog with surface tension. We treat the numerical problem of computing these Saffman-Taylor fingers with kinetic undercooling, which turns out to be more subtle than the analog with surface tension, since kinetic undercooling permits finger shapes which are corner-free but not analytic. We provide numerical evidence for the selection mechanism by setting up a problem with both kinetic undercooling and surface tension and numerically taking the limit that the surface tension vanishes.
Concepts of radial and angular kinetic energies
Dahl, Jens Peder; Schleich, W.P.
2002-01-01
We consider a general central-field system in D dimensions and show that the division of the kinetic energy into radial and angular parts proceeds differently in the wave-function picture and the Weyl-Wigner phase-space picture, Thus, the radial and angular kinetic energies are different quantities...
Conformational Diffusion and Helix Formation Kinetics
Hummer, Gerhard [Laboratory of Chemical Physics, Building 5, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, Maryland 20892-0520 (United States); Garcia, Angel E. [Theoretical Biology and Biophysics Group T-10, MS K710, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Garde, Shekhar [Department of Chemical Engineering, Rensselaer Polytechnic Institute, 110 8th Street, Troy, New York 12180 (United States)
2000-09-18
The time, temperature, and sequence dependences of helix formation kinetics of fully atomistic peptide models in explicit solvent are described quantitatively by a diffusive search within the coil state with barrierless transitions into the helical state. Conformational diffusion leads to nonexponential kinetics and jump-width dependences in temperature jump experiments. (c) 2000 The American Physical Society.
Inflation Rates, Car Devaluation, and Chemical Kinetics.
Pogliani, Lionello; Berberan-Santos, Mario N.
1996-01-01
Describes the inflation rate problem and offers an interesting analogy with chemical kinetics. Presents and solves the car devaluation problem as a normal chemical kinetic problem where the order of the rate law and the value of the rate constant are derived. (JRH)
Kinetic theory of gases and plasmas
Schram, P.P.J.M.
1991-01-01
Kinetic theory provides the link between the non-equilibrium statistical mechanics of many-particle systems and macroscopic or phenomenological physics. This volume deals with the derivation of kinetic equations, their limitations and generalizations,and with the applications of kinetic theory to physical phenomena and the calculation of transport coefficients. This book is divided in 12 chapters which discuss a wide range of topics such as balanced equations, the Klimontovich, Vlasov-Maxwell, and Boltzmann equations, Chapman-Enskog theory, the kinetic theory of plasmas, B.G.K. models, linear response theory, Brownian motion and renormalized kinetic theory. Each chapter is concluded with exercises, which not only enable the readers to test their understanding of the theory, but also present additional examples which complement the text. 151 refs.; 35 figs.; 5 tabs
Crystallization Kinetics within a Generic Modeling Framework
Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist V.
2014-01-01
of employing a well-structured model library for storage, use/reuse, and analysis of the kinetic models are highlighted. Examples illustrating the application of the modeling framework for kinetic model discrimination related to simulation of specific crystallization scenarios and for kinetic model parameter......A new and extended version of a generic modeling framework for analysis and design of crystallization operations is presented. The new features of this framework are described, with focus on development, implementation, identification, and analysis of crystallization kinetic models. Issues related...... to the modeling of various kinetic phenomena like nucleation, growth, agglomeration, and breakage are discussed in terms of model forms, model parameters, their availability and/or estimation, and their selection and application for specific crystallization operational scenarios under study. The advantages...
Hydrogen electrode reaction: A complete kinetic description
Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.
2007-01-01
The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed
Kinetic advantage of controlled intermediate nuclear fusion
Guo Xiaoming
2012-01-01
The dominated process of controlled fusion is to let nuclei gain enough kinetic energy to overcome Coulomb barrier. As a result, a fusion scheme can consider two factors in its design: to increase kinetic energy of nuclei and to alter the Coulomb barrier. Cold Fusion and Hot fusion are all one-factor schemes while Intermediate Fusion is a twofactors scheme. This made CINF kinetically superior. Cold Fusion reduces deuteron-deuteron distance, addressing Coulomb barrier, and Hot Fusion heat up plasma into extreme high temperature, addressing kinetic energy. Without enough kinetic energy made Cold Fusion skeptical. Extreme high temperature made Hot Fusion very difficult to engineer. Because CIFN addresses both factors, CIFN is a more promising technique to be industrialized.
Kinetics of solid state phase transformations: Measurement and ...
Administrator
heating or cooling rate can also exert a crucial influence on the kinetic outcome is stressed. The kinetic ... A simple and general modelling methodology for understanding the kinetics of ... state is of interest on both basic and applied grounds.
Kinetic theory of tearing instabilities
Drake, J.F.; Lee, Y.C.
1977-01-01
The transition of the tearing instability from the collisional to the collisionless regime is investigated kinetically using a Fokker--Planck collision operator to represent electron-ion collisions. As a function of the collisionality of the plasma, the tearing instability falls into three regions, which are referred to as collisionless, semi-collisional, and collisional. The width Δ of the singular layer around kxB 0 =0 is limited by electron thermal motion along B 0 in the collisional and semi-collisional regimes and is typically smaller than rho/sub i/, the ion Larmor radius. Previously accepted theories, which are based on the assumption Δvery-much-greater-thanrho/sub i/, are found to be valid only in the collisional regime. The effects of density and temperature gradients on the instabilities are also studied. The tearing instability is only driven by the temperature gradient in the collisional and semi-collisional regimes. Numerical calculations indicate that the semi-collisional tearing instability is particularly relevant to present day high temperature tokamak discharges
Kinetics of DNA tile dimerization.
Jiang, Shuoxing; Yan, Hao; Liu, Yan
2014-06-24
Investigating how individual molecular components interact with one another within DNA nanoarchitectures, both in terms of their spatial and temporal interactions, is fundamentally important for a better understanding of their physical behaviors. This will provide researchers with valuable insight for designing more complex higher-order structures that can be assembled more efficiently. In this report, we examined several spatial factors that affect the kinetics of bivalent, double-helical (DH) tile dimerization, including the orientation and number of sticky ends (SEs), the flexibility of the double helical domains, and the size of the tiles. The rate constants we obtained confirm our hypothesis that increased nucleation opportunities and well-aligned SEs accelerate tile-tile dimerization. Increased flexibility in the tiles causes slower dimerization rates, an effect that can be reversed by introducing restrictions to the tile flexibility. The higher dimerization rates of more rigid tiles results from the opposing effects of higher activation energies and higher pre-exponential factors from the Arrhenius equation, where the pre-exponential factor dominates. We believe that the results presented here will assist in improved implementation of DNA tile based algorithmic self-assembly, DNA based molecular robotics, and other specific nucleic acid systems, and will provide guidance to design and assembly processes to improve overall yield and efficiency.
Kinetics of vein graft hyperplasia
Zwolak, R.M.; Adams, M.C.; Clowes, A.W.
1986-01-01
Human aortocoronary vein grafts fail due to accelerated occlusive disease. The possibility that this is related to cellular hyperplasia was investigated in a rabbit model where kinetics of vein graft thickening, endothelial (EC) repair, and smooth muscle cell (SMC) proliferation were measured from 2 days to 24 weeks after implanting jugular vein segments in the carotid artery. Immediately after graft placement focal EC denudation was observed. These defects were repaired within 1 week and did not recur. By 4 weeks intimal area had increased 30 fold from 0.028 +/- 0.004 to 0.705 +/- 0.021 mm 2 , and a 24 weeks was 0.93 +/- 0.21 mm 2 . This response did not produce a reduction in graft lumen area. EC and SMC thymidine-labeling index were measured by en face and cross-section autoradiography after injection of 3 H-thymidine and perfusion fixation. Despite rapid EC surface repair EC labeling index remained elevated and only returned to normal levels at 12 weeks; SMC labeling was 10 fold greater than baseline even at 24 weeks (0.22% vs 0.02%). SMC mass demonstrated morphometrically increased between 2 and 12 weeks. Intimal thickening in vein grafts is due to SMC proliferation and develops after the EC layer has been restored. In contrast, intimal SMC proliferate in damaged arteries when the EC layer is absent and cease when the EC layer is regenerated
Azo compound degradation kinetics and halonitromethane formation kinetics during chlorination.
Fu, Jing; Wang, Xiaomao; Bai, Weiliang; Yang, Hongwei; Xie, Yuefeng F
2017-05-01
The chlorination of azo compounds can produce halonitromethanes (HNMs), which have attracted increasing concern due to their high genotoxicity. By impacting the speciation of chlorine and azo compounds, pH impacts apparent second-order rate constants of Methyl Orange (MO, 27.5-1.4 × 10 3 M -1 s -1 ), Acid Orange II (AO, 16.7-99.3 M -1 s -1 ), and Acid Red 1 (AR 1, 3.7-72.5 M -1 s -1 ) (pH range 6.3-9.0). The two-compartment first-order model successfully described the chloropicrin (TCNM) formation kinetics, suggesting that both fast- and slow-reacting precursors of TCNM are generated from the chlorination of azo compounds. The ratios between fast and slow formation rate constants for MO and AO were 15.6-5.4 × 10 2 , while that of AR 1 was 9.8-19.4 (pH range 6.5-9.0). The fraction of the fast-reacting TCNM precursors decreased with increasing pH for MO and AO; while that for AR 1 decreased when pH increased from 6.5 to 8.0, and then increased when pH increased from 8.0 to 9.0. The impact of pH on TCNM formation was also precursor-specific. The highest molar yields of TCNM predicted from the model in this study were 2.4%, 2.5%, and 1.5% for MO, AO, and AR 1, respectively. The study demonstrates that azo compounds are important HNM precursors, and pose a potential threat to drinking water safety. Copyright © 2017 Elsevier Ltd. All rights reserved.
Chemical Kinetic Modeling of 2-Methylhexane Combustion
Mohamed, Samah Y.
2015-03-30
Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important for investigating the combustion behavior of diesel, gasoline, and aviation fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values and rate rules. These update provides a better agreement with rapid compression machine measurements of ignition delay time, while also strengthening the fundamental basis of the model.
Nuclear reactor kinetics and plant control
Oka, Yoshiaki
2013-01-01
Understanding time-dependent behaviors of nuclear reactors and the methods of their control is essential to the operation and safety of nuclear power plants. This book provides graduate students, researchers, and engineers in nuclear engineering comprehensive information on both the fundamental theory of nuclear reactor kinetics and control and the state-of-the-art practice in actual plants, as well as the idea of how to bridge the two. The first part focuses on understanding fundamental nuclear kinetics. It introduces delayed neutrons, fission chain reactions, point kinetics theory, reactivit
Research in chemical kinetics, v.2
1994-01-01
This is the second volume in a new series, which aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the c
Isoconversional kinetics of thermally stimulated processes
Vyazovkin, Sergey
2015-01-01
The use of isoconversional kinetic methods for analysis of thermogravimetric and calorimetric data on thermally stimulated processes is quickly growing in popularity. The purpose of this book is to create the first comprehensive resource on the theory and applications of isoconversional methodology. The book introduces the reader to the kinetics of physical and chemical condensed phase processes that occur as a result of changing temperature and discusses how isoconversional analysis can provide important kinetic insights into them. The book will help the readers to develop a better understanding of the methodology, and promote its efficient usage and successful development.
Research in Chemical Kinetics, v.3
2012-01-01
This series of volumes aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the contributions and their top
Liquefaction chemistry and kinetics: Hydrogen utilization studies
Rothenberger, K.S.; Warzinski, R.P.; Cugini, A.V. [Pittsburgh Energy Technology Center, PA (United States)] [and others
1995-12-31
The objectives of this project are to investigate the chemistry and kinetics that occur in the initial stages of coal liquefaction and to determine the effects of hydrogen pressure, catalyst activity, and solvent type on the quantity and quality of the products produced. The project comprises three tasks: (1) preconversion chemistry and kinetics, (2) hydrogen utilization studies, and (3) assessment of kinetic models for liquefaction. The hydrogen utilization studies work will be the main topic of this report. However, the other tasks are briefly described.
Progress in antenna coupled kinetic inductance detectors
Baryshev, A.; Baselmans, J.J.A.; Freni, A.; Gerini, G.; Hoevers, H.F.C.; Iacono, A.; Neto, A.
2011-01-01
This paper describes the combined Dutch efforts toward the development of large wideband focal plane array receivers based on kinetic inductance detectors (KIDs). Taking into account strict electromagnetic and detector sensitivity requirements for future ground and space based observatories, this
A mathematical model for iodine kinetics
Silva, E.A.T. da.
1976-01-01
A mathematical model for the iodine kinetics in thyroid is presented followed by its analytical solution. An eletroanalogical model is also developed for a simplified stage and another is proposed for the main case [pt
Kinetic Study of Curcumin on Modal Fabric
Abu Naser Md. Ahsanul Haque
2018-03-01
Full Text Available A kinetic study of curcumin on modal fabric was carried out using an initial dye concentration of 1 g/L at three different temperatures, 70 °C, 85 °C and 100 °C, at pH 7 and an material to liquor ratio of 1:20. Pseudo first-order and pseudo second-order kinetics were applied, and it was found that the adsorption kinetics of curcumin on modal fabric matched the pseudo second-order kinetic model. The activation energy was found to be equal to 71.14 kJ/mol, while the enthalpy and entropy of activation were 68.16 kJ/mol and –66.02 J/molK respectively.
Kinetic Model of Growth of Arthropoda Populations
Ershov, Yu. A.; Kuznetsov, M. A.
2018-05-01
Kinetic equations were derived for calculating the growth of crustacean populations ( Crustacea) based on the biological growth model suggested earlier using shrimp ( Caridea) populations as an example. The development cycle of successive stages for populations can be represented in the form of quasi-chemical equations. The kinetic equations that describe the development cycle of crustaceans allow quantitative prediction of the development of populations depending on conditions. In contrast to extrapolation-simulation models, in the developed kinetic model of biological growth the kinetic parameters are the experimental characteristics of population growth. Verification and parametric identification of the developed model on the basis of the experimental data showed agreement with experiment within the error of the measurement technique.
Kinetic investigation on enantioselective hydrolytic resolution of ...
Kinetic investigation on enantioselective hydrolytic resolution of epichlorohydrin by crude epoxide hydrolase from domestic duck liver. X Ling, D Lu, J Wang, J Chen, L Ding, J Chen, H Chai, P Ouyang ...
Chemical Kinetic Modeling of 2-Methylhexane Combustion
Mohamed, Samah Y.; Sarathy, Mani
2015-01-01
necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values
Kinetics of oxidic phase dissolution in acids
Gorichev, I.G.; Kipriyanov, N.A.
1981-01-01
The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru
Thermodynamic, kinetic and mechanistic investigations of ...
with respect to the rate determining step and the thermodynamic quantities with respect to the equilibrium steps were evaluated and ... are, (1) to establish a rate law through kinetic measure- ments, (2) to ..... second and third equilibrium steps.
Kinetic Theory of the Inner Magnetospheric Plasma
Khazanov, George V
2011-01-01
This book provides a broad introduction to the kinetic theory of space plasma physics with the major focus on the inner magnetospheric plasma. It is designed to provide a comprehensive description of the different kinds of transport equations for both plasma particles and waves with an emphasis on the applicability and limitations of each set of equations. The major topics are: Kinetic Theory of Superthermal Electrons, Kinetic Foundation of the Hydrodynamic Description of Space Plasmas (including wave-particle interaction processes), and Kinetic Theory of the Terrestrial Ring Current. Distinguishable features of this book are the analytical solutions of simplified transport equations. Approximate analytic solutions of transport phenomena are very useful because they help us gain physical insight into how the system responds to varying sources of mass, momentum and energy and also to various external boundary conditions. They also provide us a convenient method to test the validity of complicated numerical mod...
Plasma heating by kinetic Alfven wave
Assis, A.S. de.
1982-01-01
The heating of a nonuniform plasma (electron-ion) due to the resonant excitation of the shear Alfven wave in the low β regime is studied using initially the ideal MHD model and posteriorly using the kinetic model. The Vlasov equation for ions and the drift kinetic equation for electrons have been used. Through the ideal MHD model, it is concluded that the energy absorption is due to the continuous spectrum (phase mixing) which the shear Alfven wave has in a nonuniform plasma. An explicit expression for the energy absorption is derived. Through the kinetic model it is concluded that the energy absorption is due to a resonant mode convertion of the incident wave into the kinetic Alfven wave which propagates away from the resonant region. Its electron Landau damping has been observed. There has been a concordance with the MHD calculations. (Author) [pt
Kinetics from Replica Exchange Molecular Dynamics Simulations.
Stelzl, Lukas S; Hummer, Gerhard
2017-08-08
Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.
Fundamental aspects of plasma chemical physics kinetics
Capitelli, Mario; Colonna, Gianpiero; Esposito, Fabrizio; Gorse, Claudine; Hassouni, Khaled; Laricchiuta, Annarita; Longo, Savino
2016-01-01
Describing non-equilibrium "cold" plasmas through a chemical physics approach, this book uses the state-to-state plasma kinetics, which considers each internal state as a new species with its own cross sections. Extended atomic and molecular master equations are coupled with Boltzmann and Monte Carlo methods to solve the electron energy distribution function. Selected examples in different applied fields, such as microelectronics, fusion, and aerospace, are presented and discussed including the self-consistent kinetics in RF parallel plate reactors, the optimization of negative ion sources and the expansion of high enthalpy flows through nozzles of different geometries. The book will cover the main aspects of the state-to-state kinetic approach for the description of nonequilibrium cold plasmas, illustrating the more recent achievements in the development of kinetic models including the self-consistent coupling of master equations and Boltzmann equation for electron dynamics. To give a complete portrayal, the...
Practical steady-state enzyme kinetics.
Lorsch, Jon R
2014-01-01
Enzymes are key components of most biological processes. Characterization of enzymes is therefore frequently required during the study of biological systems. Steady-state kinetics provides a simple and rapid means of assessing the substrate specificity of an enzyme. When combined with site-directed mutagenesis (see Site-Directed Mutagenesis), it can be used to probe the roles of particular amino acids in the enzyme in substrate recognition and catalysis. Effects of interaction partners and posttranslational modifications can also be assessed using steady-state kinetics. This overview explains the general principles of steady-state enzyme kinetics experiments in a practical, rather than theoretical, way. Any biochemistry textbook will have a section on the theory of Michaelis-Menten kinetics, including derivations of the relevant equations. No specific enzymatic assay is described here, although a method for monitoring product formation or substrate consumption over time (an assay) is required to perform the experiments described. © 2014 Elsevier Inc. All rights reserved.
Some concepts in condensed phase chemical kinetics
Adelman, S.A.
1986-01-01
Some concepts in condensed phase chemical kinetics which have emerged from a recent rigorous statistical mechanical treatment of condensed phase chemical reaction dynamics (S.A. Adelman, Adv. Chem. Phys.53:61 (1983)) are discussed in simple physical terms
MBS Analysis Of Kinetic Structures Using ADAMS
Kirkegaard, Poul Henning; Nielsen, Søren R.K.
2009-01-01
The present paper considers multibody system (MBS) analysis of kinetic structures using the software package ADAMS. Deployable, foldable, expandable and reconfigurable kinetic structures can provide a change in the geometric morphology of the envelope by contributing to making it adaptable to e.......g. changing external climate factors, in order to improve the indoor climate performance of the building. The derivation of equations of motion for such spatial mechanical systems is a challenging issue in scientific community. However, with new symbolic tools one can automatically derive equations in so......-called multibody system (MBS) formalism. The present paper considers MBS modeling of kinetic architectural structures using the software packages ADAMS. As a result, it is found that symbolic MBS simulation tools facilitate a useful evaluation environment for MBS users during a design phase of responsive kinetic...
Kinetic Theory of Granular Gases
Trizac, Emmanuel [Center of Theoretical Biological Physics, UC San Diego, La Jolla, CA 92093-0374 (United States); Laboratoire de Physique Theorique et Modeles Statistiques, Campus Universitaire, 91405 Orsay (France)
2005-11-25
Granular gases are composed of macroscopic bodies kept in motion by an external energy source such as a violent shaking. The behaviour of such systems is quantitatively different from that of ordinary molecular gases: due to the size of the constituents, external fields have a stronger effect on the dynamics and, more importantly, the kinetic energy of the gas is no longer a conserved quantity. The key role of the inelasticity of collisions has been correctly appreciated for about fifteen years, and the ensuing consequences in terms of phase behaviour or transport properties studied in an increasing and now vast body of literature. The purpose of this book is to help the newcomer to the field in acquiring the essential theoretical tools together with some numerical techniques. As emphasized by the authors-who were among the pioneers in the domain- the content could be covered in a one semester course for advanced undergraduates, or it could be incorporated in a more general course dealing with the statistical mechanics of dissipative systems. The book is self-contained, clear, and avoids mathematical complications. In order to elucidate the main physical ideas, heuristic points of views are sometimes preferred to a more rigorous route that would lead to a longer discussion. The 28 chapters are short; they offer exercises and worked examples, solved at the end of the book. Each part is supplemented with a relevant foreword and a useful summary including take-home messages. The editorial work is of good quality, with very few typographical errors. In spite of the title, kinetic theory stricto sensu is not the crux of the matter covered. The authors discuss the consequences of the molecular chaos assumption both at the individual particle level and in terms of collective behaviour. The first part of the book addresses the mechanics of grain collisions. It is emphasized that considering the coefficient of restitution {epsilon} -a central quantity governing the
Kinetic Theory of Granular Gases
Trizac, Emmanuel
2005-01-01
Granular gases are composed of macroscopic bodies kept in motion by an external energy source such as a violent shaking. The behaviour of such systems is quantitatively different from that of ordinary molecular gases: due to the size of the constituents, external fields have a stronger effect on the dynamics and, more importantly, the kinetic energy of the gas is no longer a conserved quantity. The key role of the inelasticity of collisions has been correctly appreciated for about fifteen years, and the ensuing consequences in terms of phase behaviour or transport properties studied in an increasing and now vast body of literature. The purpose of this book is to help the newcomer to the field in acquiring the essential theoretical tools together with some numerical techniques. As emphasized by the authors-who were among the pioneers in the domain- the content could be covered in a one semester course for advanced undergraduates, or it could be incorporated in a more general course dealing with the statistical mechanics of dissipative systems. The book is self-contained, clear, and avoids mathematical complications. In order to elucidate the main physical ideas, heuristic points of views are sometimes preferred to a more rigorous route that would lead to a longer discussion. The 28 chapters are short; they offer exercises and worked examples, solved at the end of the book. Each part is supplemented with a relevant foreword and a useful summary including take-home messages. The editorial work is of good quality, with very few typographical errors. In spite of the title, kinetic theory stricto sensu is not the crux of the matter covered. The authors discuss the consequences of the molecular chaos assumption both at the individual particle level and in terms of collective behaviour. The first part of the book addresses the mechanics of grain collisions. It is emphasized that considering the coefficient of restitution ε -a central quantity governing the inelasticity of
Thermal physics kinetic theory and thermodynamics
Singh, Devraj; Yadav, Raja Ram
2016-01-01
THERMAL PHYSICS: Kinetic Theory and Thermodynamics is designed for undergraduate course in Thermal Physics and Thermodynamics. The book provides thorough understanding of the fundamental principles of the concepts in Thermal Physics. The book begins with kinetic theory, then moves on liquefaction, transport phenomena, the zeroth, first, second and third laws, thermodynamics relations and thermal conduction. The book concluded with radiation phenomenon. KEY FEATURES: * Include exercises * Short Answer Type Questions * Long Answer Type Questions * Numerical Problems * Multiple Choice Questions
NLTE4 Plasma Population Kinetics Database
SRD 159 NLTE4 Plasma Population Kinetics Database (Web database for purchase) This database contains benchmark results for simulation of plasma population kinetics and emission spectra. The data were contributed by the participants of the 4th Non-LTE Code Comparison Workshop who have unrestricted access to the database. The only limitation for other users is in hidden labeling of the output results. Guest users can proceed to the database entry page without entering userid and password.
Hamiltonian kinetic theory of plasma ponderomotive processes
McDonald, S.W.; Kaufman, A.N.
1982-01-01
The nonlinear nonresonant interaction of plasma waves and particles is formulated in Hamiltonian kinetic theory which treats the wave-action and particle distributions on an equal footing, thereby displaying reciprocity relations. In the quasistatic limit, a nonlinear wave-kinetic equation is obtained. The generality of the formalism allows for applications to arbitrary geometry, with the nonlinear effects expressed in terms of the linear susceptibility
Thermal decomposition kinetics of ammonium uranyl carbonate
Kim, E.H.; Park, J.J.; Park, J.H.; Chang, I.S.; Choi, C.S.; Kim, S.D.
1994-01-01
The thermal decomposition kinetics of AUC [ammonium uranyl carbonate; (NH 4 ) 4 UO 2 (CO 3 ) 3 [ in an isothermal thermogravimetric (TG) reactor under N 2 atmosphere has been determined. The kinetic data can be represented by the two-dimensional nucleation and growth model. The reaction rate increases and activation energy decreases with increasing particle size and precipitation time which appears in the particle size larger than 30 μm in the mechano-chemical phenomena. (orig.)
Preventing Corrosion by Controlling Cathodic Reaction Kinetics
2016-03-25
3. DATES COVERED (From - To) 09/23/15 - 04/22/16 4. TITLE AND SUBTITLE Sa. CONTRACT NUMBER Preventing Corrosion by Controlling Cathodic Reaction...Preventing corrosion by controlling cathodic reaction kinetics Progress Report for Period: 1 SEP 2015-31 MAR 2016 John Keith Department of...25 March 2016 Preventing corrosion by controlling cathodic reaction kinetics Annual Summary Report: FY16 PI: John Keith, 412-624-7016,jakeith
Hamiltonian kinetic theory of plasma ponderomotive processes
McDonald, S.W.; Kaufman, A.N.
1981-12-01
The nonlinear nonresonant interaction of plasma waves and particles is formulated in a Hamiltonian kinetic theory which treats the wave-action and particle distributions on an equal footing, thereby displaying reciprocity relations. In the quasistatic limit, a nonlinear wave-kinetic equation is obtained. The generality of the formalism allows for applications to arbitrary geometry, with the nonlinear effects expressed in terms of the linear susceptibility
Ozone mass transfer and kinetics experiments
Bollyky, L.J.; Beary, M.M.
1981-12-01
Experiments were conducted at the Hanford Site to determine the most efficient pH and temperature levels for the destruction of complexants in Hanford high-level defense waste. These complexants enhance migration of radionuclides in the soil and inhibit the growth of crystals in the evaporator-crystallizer. Ozone mass transfer and kinetics tests have been outlined for the determination of critical mass transfer and kinetics parameters of the ozone-complexant reaction
Spatial neutron kinetic module of ROSA code
Cherezov, A.L.; Shchukin, N.V.
2009-01-01
A spatial neutron kinetic module was developed for computer code ROSA. The paper describes a numerical scheme used in the module for resolving neutron kinetic equations. Analytical integration for delayed neutrons emitters method and direct numerical integration method (Gear's method) were analyzed. The two methods were compared on their efficiency and accuracy. Both methods were verified with test problems. The results obtained in the verification studies were presented [ru
Kinetic mixing and the supersymmetric gauge hierarchy
Dienes, K.R.; Kolda, C.; March-Russell, J.
1997-01-01
The most general Lagrangian for a model with two U(1) gauge symmetries contains a renormalizable operator which mixes their gauge kinetic terms. Such kinetic mixing can be generated at arbitrarily high scales but will not be suppressed by large masses. In models whose supersymmetry (SUSY)-breaking hidden sectors contain U(1) gauge factors, we show that such terms will generically arise and communicate SUSY breaking to the visible sector through mixing with hypercharge. In the context of the usual supergravity- or gauge-mediated communication scenarios with D-terms of order the fundamental scale of SUSY breaking, this effect can destabilize the gauge hierarchy. Even in models for which kinetic mixing is suppressed or the D-terms are arranged to be small, this effect is a potentially large correction to the soft scalar masses and therefore introduces a new measurable low-energy parameter. We calculate the size of kinetic mixing both in field theory and in string theory, and argue that appreciable kinetic mixing is a generic feature of string models. We conclude that the possibility of kinetic mixing effects cannot be ignored in model building and in phenomenological studies of the low-energy SUSY spectra. (orig.)
Neutron inverse kinetics via Gaussian Processes
Picca, Paolo; Furfaro, Roberto
2012-01-01
Highlights: ► A novel technique for the interpretation of experiments in ADS is presented. ► The technique is based on Bayesian regression, implemented via Gaussian Processes. ► GPs overcome the limits of classical methods, based on PK approximation. ► Results compares GPs and ANN performance, underlining similarities and differences. - Abstract: The paper introduces the application of Gaussian Processes (GPs) to determine the subcriticality level in accelerator-driven systems (ADSs) through the interpretation of pulsed experiment data. ADSs have peculiar kinetic properties due to their special core design. For this reason, classical – inversion techniques based on point kinetic (PK) generally fail to generate an accurate estimate of reactor subcriticality. Similarly to Artificial Neural Networks (ANNs), Gaussian Processes can be successfully trained to learn the underlying inverse neutron kinetic model and, as such, they are not limited to the model choice. Importantly, GPs are strongly rooted into the Bayes’ theorem which makes them a powerful tool for statistical inference. Here, GPs have been designed and trained on a set of kinetics models (e.g. point kinetics and multi-point kinetics) for homogeneous and heterogeneous settings. The results presented in the paper show that GPs are very efficient and accurate in predicting the reactivity for ADS-like systems. The variance computed via GPs may provide an indication on how to generate additional data as function of the desired accuracy.
Kinetic partitioning mechanism of HDV ribozyme folding
Chen, Jiawen; Gong, Sha; Wang, Yujie; Zhang, Wenbing, E-mail: wbzhang@whu.edu.cn [Department of Physics, Wuhan University, Wuhan, Hubei 430072 (China)
2014-01-14
RNA folding kinetics is directly tied to RNA biological functions. We introduce here a new approach for predicting the folding kinetics of RNA secondary structure with pseudoknots. This approach is based on our previous established helix-based method for predicting the folding kinetics of RNA secondary structure. In this approach, the transition rates for an elementary step: (1) formation, (2) disruption of a helix stem, and (3) helix formation with concomitant partial melting of an incompatible helix, are calculated with the free energy landscape. The folding kinetics of the Hepatitis delta virus (HDV) ribozyme and the mutated sequences are studied with this method. The folding pathways are identified by recursive searching the states with high net flux-in(out) population starting from the native state. The theory results are in good agreement with that of the experiments. The results indicate that the bi-phasic folding kinetics for the wt HDV sequence is ascribed to the kinetic partitioning mechanism: Part of the population will quickly fold to the native state along the fast pathway, while another part of the population will fold along the slow pathway, in which the population is trapped in a non-native state. Single mutation not only changes the folding rate but also the folding pathway.
Dual kinetic curves in reversible electrochemical systems.
Michael J Hankins
Full Text Available We introduce dual kinetic chronoamperometry, in which reciprocal relations are established between the kinetic curves of electrochemical reactions that start from symmetrical initial conditions. We have performed numerical and experimental studies in which the kinetic curves of the electron-transfer processes are analyzed for a reversible first order reaction. Experimental tests were done with the ferrocyanide/ferricyanide system in which the concentrations of each component could be measured separately using the platinum disk/gold ring electrode. It is shown that the proper ratio of the transient kinetic curves obtained from cathodic and anodic mass transfer limited regions give thermodynamic time invariances related to the reaction quotient of the bulk concentrations. Therefore, thermodynamic time invariances can be observed at any time using the dual kinetic curves for reversible reactions. The technique provides a unique possibility to extract the non-steady state trajectory starting from one initial condition based only on the equilibrium constant and the trajectory which starts from the symmetrical initial condition. The results could impact battery technology by predicting the concentrations and currents of the underlying non-steady state processes in a wide domain from thermodynamic principles and limited kinetic information.
Variational estimates of point-kinetics parameters
Favorite, J.A.; Stacey, W.M. Jr.
1995-01-01
Variational estimates of the effect of flux shifts on the integral reactivity parameter of the point-kinetics equations and on regional power fractions were calculated for a variety of localized perturbations in two light water reactor (LWR) model problems representing a small, tightly coupled core and a large, loosely coupled core. For the small core, the flux shifts resulting from even relatively large localized reactivity changes (∼600 pcm) were small, and the standard point-kinetics approximation estimates of reactivity were in error by only ∼10% or less, while the variational estimates were accurate to within ∼1%. For the larger core, significant (>50%) flux shifts occurred in response to local perturbations, leading to errors of the same magnitude in the standard point-kinetics approximation of the reactivity worth. For positive reactivity, the error in the variational estimate of reactivity was only a few percent in the larger core, and the resulting transient power prediction was 1 to 2 orders of magnitude more accurate than with the standard point-kinetics approximation. For a large, local negative reactivity insertion resulting in a large flux shift, the accuracy of the variational estimate broke down. The variational estimate of the effect of flux shifts on reactivity in point-kinetics calculations of transients in LWR cores was found to generally result in greatly improved accuracy, relative to the standard point-kinetics approximation, the exception being for large negative reactivity insertions with large flux shifts in large, loosely coupled cores
Decomposition kinetics of plutonium hydride
Haschke, J.M.; Stakebake, J.L.
1979-01-01
Kinetic data for decomposition of PuH/sub 1/ /sub 95/ provides insight into a possible mechanism for the hydriding and dehydriding reactions of plutonium. The fact that the rate of the hydriding reaction, K/sub H/, is proportional to P/sup 1/2/ and the rate of the dehydriding process, K/sub D/, is inversely proportional to P/sup 1/2/ suggests that the forward and reverse reactions proceed by opposite paths of the same mechanism. The P/sup 1/2/ dependence of hydrogen solubility in metals is characteristic of the dissociative absorption of hydrogen; i.e., the reactive species is atomic hydrogen. It is reasonable to assume that the rates of the forward and reverse reactions are controlled by the surface concentration of atomic hydrogen, (H/sub s/), that K/sub H/ = c'(H/sub s/), and that K/sub D/ = c/(H/sub s/), where c' and c are proportionality constants. For this surface model, the pressure dependence of K/sub D/ is related to (H/sub s/) by the reaction (H/sub s/) reversible 1/2H/sub 2/(g) and by its equilibrium constant K/sub e/ = (H/sub 2/)/sup 1/2//(H/sub s/). In the pressure range of ideal gas behavior, (H/sub s/) = K/sub e//sup -1/(RT)/sup -1/2/ and the decomposition rate is given by K/sub D/ = cK/sub e/(RT)/sup -1/2/P/sup 1/2/. For an analogous treatment of the hydriding process with this model, it can be readily shown that K/sub H/ = c'K/sub e//sup -1/(RT)/sup -1/2/P/sup 1/2/. The inverse pressure dependence and direct temperature dependence of the decomposition rate are correctly predicted by this mechanism which is most consistent with the observed behavior of the Pu--H system.
Thermal dehydration kinetics of phosphogypsum
López, F. A.
2015-09-01
Full Text Available Phsophogypsum is a by-product from the processing phosphate rock. Before the use of it in cement industry such as setting regulator is necessary a study of dehydration reaction of phosphogypsum to avoid the false setting during the milling. The aim is to study the thermal behavior of two different phosphogypsum sources (Spain and Tunisia under non-isothermal conditions in argon atmosphere by using Thermo-Gravimetriy, Differential Thermal Analysis (TG-DTA and Differential Scanning Calorimetry (DSC. DSC experiments were carried out at temperatures ranging from ambient to 350 °C at different heating rates. The temperatures of conversion from gypsum to hemihydrate and anhydrite states and heat of dehydration were determined. Various methods were used to analyze the DSC data for reaction kinetics determination. The activation energy and frequency factor were calculated for dehydration of phosphogypsum. Activation energy values of the main dehydration reaction of phosphogypsum were calculated to be approximately 61–118 kJ/mol.El fosfoyeso es un subproducto procedente del procesado de la roca fosfato. Una de las posibles vías de reutilización y revalorización es su uso como regulador del fraguado en la industria cementera. Debido a los posibles problemas de falso fraguado asociado a los procesos de deshidratación que tienen lugar durante la molienda del cemento, esta investigación estudió el comportamiento térmico, bajo condiciones no-isotérmicas en atmósfera de argón, de dos fosfoyesos, mediante TG-DTA y DSC. Los ensayos de DSC se realizaron hasta los 350 °C a diferentes velocidades de calentamiento. La temperatura de conversión del yeso a las formas de hemihidrato y anhidrita y el calor de hidratación fueron determinados. Las cinéticas de reacción fueron obtenidas analizando los datos de DSC mediante varios métodos. Se calculó la energía de activación y el factor de frecuencia para las reacciones de deshidratación del
Stochastic theory of interfacial enzyme kinetics: A kinetic Monte Carlo study
Das, Biswajit; Gangopadhyay, Gautam
2012-01-01
Graphical abstract: Stochastic theory of interfacial enzyme kinetics is formulated. Numerical results of macroscopic phenomenon of lag-burst kinetics is obtained by using a kinetic Monte Carlo approach to single enzyme activity. Highlights: ► An enzyme is attached with the fluid state phospholipid molecules on the Langmuir monolayer. ► Through the diffusion, the enzyme molecule reaches the gel–fluid interface. ► After hydrolysing a phospholipid molecule it predominantly leaves the surface in the lag phase. ► The enzyme is strictly attached to the surface with scooting mode of motion and the burst phase appears. - Abstract: In the spirit of Gillespie’s stochastic approach we have formulated a theory to explore the advancement of the interfacial enzyme kinetics at the single enzyme level which is ultimately utilized to obtain the ensemble average macroscopic feature, lag-burst kinetics. We have provided a theory of the transition from the lag phase to the burst phase kinetics by considering the gradual development of electrostatic interaction among the positively charged enzyme and negatively charged product molecules deposited on the phospholipid surface. It is shown that the different diffusion time scales of the enzyme over the fluid and product regions are responsible for the memory effect in the correlation of successive turnover events of the hopping mode in the single trajectory analysis which again is reflected on the non-Gaussian distribution of turnover times on the macroscopic kinetics in the lag phase unlike the burst phase kinetics.
The Application of Biomimicry in Kinetic Facades
Wijdan Deyaa Abdul Jalil
2016-10-01
Full Text Available Biomimicry, as a way of thinking to go back to nature for inspiration, has its impact on many contemporary technological achievements. Some of them are used to design and construct kinetic facades in architecture, because of the importance role of facades in reducing sun radiation, that enter the building through using shading systems and components. In light of this, research problem is determined: "Do technologies which are inspired by biomimicry effect shading in kinetic facades through its characteristics in materials and the mechanics. So the research identifies its goal as: "To identify the types of kinetic facades in buildings and their characteristics as materials and shading mechanism associated with the biomimicry. The research explains the basic types of kinetic facades depending on the technology and materials used to provide the possibility of reducing solar radiation that enters the building. It also compares the case studies which have been chosen in their inspiration concept from biological world, which reflect on the system used of protecting against sun and reducing energy consumption as the designer teams suggest. The research concluded that kinetic façade which is depending on smart materials is self-responding and don't need energy to operate, so it is better in reducing consumption of energy.
Modeling the degradation kinetics of ascorbic acid.
Peleg, Micha; Normand, Mark D; Dixon, William R; Goulette, Timothy R
2018-06-13
Most published reports on ascorbic acid (AA) degradation during food storage and heat preservation suggest that it follows first-order kinetics. Deviations from this pattern include Weibullian decay, and exponential drop approaching finite nonzero retention. Almost invariably, the degradation rate constant's temperature-dependence followed the Arrhenius equation, and hence the simpler exponential model too. A formula and freely downloadable interactive Wolfram Demonstration to convert the Arrhenius model's energy of activation, E a , to the exponential model's c parameter, or vice versa, are provided. The AA's isothermal and non-isothermal degradation can be simulated with freely downloadable interactive Wolfram Demonstrations in which the model's parameters can be entered and modified by moving sliders on the screen. Where the degradation is known a priori to follow first or other fixed order kinetics, one can use the endpoints method, and in principle the successive points method too, to estimate the reaction's kinetic parameters from considerably fewer AA concentration determinations than in the traditional manner. Freeware to do the calculations by either method has been recently made available on the Internet. Once obtained in this way, the kinetic parameters can be used to reconstruct the entire degradation curves and predict those at different temperature profiles, isothermal or dynamic. Comparison of the predicted concentration ratios with experimental ones offers a way to validate or refute the kinetic model and the assumptions on which it is based.
Kinetic parameters for source driven systems
Dulla, S.; Ravetto, P.; Carta, M.; D'Angelo, A.
2006-01-01
The definition of the characteristic kinetic parameters of a subcritical source-driven system constitutes an interesting problem in reactor physics with important consequences for practical applications. Consistent and physically meaningful values of the parameters allow to obtain accurate results from kinetic simulation tools and to correctly interpret kinetic experiments. For subcritical systems a preliminary problem arises for the adoption of a suitable weighting function to be used in the projection procedure to derive a point model. The present work illustrates a consistent factorization-projection procedure which leads to the definition of the kinetic parameters in a straightforward manner. The reactivity term is introduced coherently with the generalized perturbation theory applied to the source multiplication factor ks, which is thus given a physical role in the kinetic model. The effective prompt lifetime is introduced on the assumption that a neutron generation can be initiated by both the fission process and the source emission. Results are presented for simplified configurations to fully comprehend the physical features and for a more complicated highly decoupled system treated in transport theory. (authors)
Nonlocal kinetic-energy-density functionals
Garcia-Gonzalez, P.; Alvarellos, J.E.; Chacon, E.
1996-01-01
In this paper we present nonlocal kinetic-energy functionals T[n] within the average density approximation (ADA) framework, which do not require any extra input when applied to any electron system and recover the exact kinetic energy and the linear response function of a homogeneous system. In contrast with previous ADA functionals, these present good behavior of the long-range tail of the exact weight function. The averaging procedure for the kinetic functional (averaging the Fermi momentum of the electron gas, instead of averaging the electron density) leads to a functional without numerical difficulties in the calculation of extended systems, and it gives excellent results when applied to atoms and jellium surfaces. copyright 1996 The American Physical Society
Kinetics model of bainitic transformation with stress
Zhou, Mingxing; Xu, Guang; Hu, Haijiang; Yuan, Qing; Tian, Junyu
2018-01-01
Thermal simulations were conducted on a Gleeble 3800 simulator. The main purpose is to investigate the effects of stress on the kinetics of bainitic transformation in a Fe-C-Mn-Si advanced high strength bainitic steel. Previous studies on modeling the kinetics of stress affected bainitic transformation only considered the stress below the yield strength of prior austenite. In the present study, the stress above the yield strength of prior austenite is taken into account. A new kinetics model of bainitic transformation dependent on the stress (including the stresses below and above the yield strength of prior austenite) and the transformation temperature is proposed. The new model presents a good agreement with experimental results. In addition, it is found that the acceleration degree of stress on bainitic transformation increases with the stress whether its magnitude is below or above the yield strength of austenite, but the increasing rate gradually slows down when the stress is above the yield strength of austenite.
Kinetic mechanism for modeling of electrochemical reactions.
Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil
2012-04-01
We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.
Sulfide toxicity kinetics of a uasb reactor
D. R. Paula Jr.
2009-12-01
Full Text Available The effect of sulfide toxicity on kinetic parameters of anaerobic organic matter removal in a UASB (up-flow anaerobic sludge blanket reactor is presented. Two lab-scale UASB reactors (10.5 L were operated continuously during 12 months. The reactors were fed with synthetic wastes prepared daily using glucose, ammonium acetate, methanol and nutrient solution. One of the reactors also received increasing concentrations of sodium sulfide. For both reactors, the flow rate of 16 L.d-1 was held constant throughout the experiment, corresponding to a hydraulic retention time of 15.6 hours. The classic model for non-competitive sulfide inhibition was applied to the experimental data for determining the overall kinetic parameter of specific substrate utilization (q and the sulfide inhibition coefficient (Ki. The application of the kinetic parameters determined allows prediction of methanogenesis inhibition and thus the adoption of operating parameters to minimize sulfide toxicity in UASB reactors.
Kinetic study of solid-state processes
Malek, Jiri; Mitsuhashi, Takefumi
2003-01-01
A simple method for kinetic analysis of solid-state processes has been developed and the criteria capable of classifying different processes are explored. They provide a useful tool for the determination of the most suitable kinetic model. The method has been applied to the analysis of calorimetric data corresponding to the crystallization processes in amorphous ZrO 2 . It is found that the crystallization kinetics of amorphous powder sample exhibits a complex behavior under non-isothermal conditions. A two-parameter model provides a satisfactory description of the crystallization process for isothermal and non-isothermal conditions. This enables better control of crystallization extent in fine ZrO 2 powders that is important for preparation of zirconia ceramics with defined properties. (author)
Kinetic chain abnormalities in the athletic shoulder.
Sciascia, Aaron; Thigpen, Charles; Namdari, Surena; Baldwin, Keith
2012-03-01
Overhead activities require the shoulder to be exposed to and sustain repetitive loads. The segmental activation of the body's links, known as the kinetic chain, allows this to occur effectively. Proper muscle activation is achieved through generation of energy from the central segment or core, which then transfers the energy to the terminal links of the shoulder, elbow, and hand. The kinetic chain is best characterized by 3 components: optimized anatomy, reproducible efficient motor patterns, and the sequential generation of forces. However, tissue injury and anatomic deficits such as weakness and/or tightness in the leg, pelvic core, or scapular musculature can lead to overuse shoulder injuries. These injuries can be prevented and maladaptations can be detected with a thorough understanding of biomechanics of the kinetic chain as it relates to overhead activity.
Kinetics and spectroscopy of low temperature plasmas
Loureiro, Jorge
2016-01-01
This is a comprehensive textbook designed for graduate and advanced undergraduate students. Both authors rely on more than 20 years of teaching experience in renowned Physics Engineering courses to write this book addressing the students’ needs. Kinetics and Spectroscopy of Low Temperature Plasmas derives in a full self-consistent way the electron kinetic theory used to describe low temperature plasmas created in the laboratory with an electrical discharge, and presents the main optical spectroscopic diagnostics used to characterize such plasmas. The chapters with the theoretical contents make use of a deductive approach in which the electron kinetic theory applied to plasmas with basis on the electron Boltzmann equation is derived from the basic concepts of Statistical and Plasma Physics. On the other hand, the main optical spectroscopy diagnostics used to characterize experimentally such plasmas are presented and justified from the point of view of the Atomic and Molecular Physics. Low temperature plasmas...
Transient processes in cell proliferation kinetics
Yakovlev, Andrej Yu
1989-01-01
A mathematician who has taken the romantic decision to devote himself to biology will doubtlessly look upon cell kinetics as the most simple and natural field of application for his knowledge and skills. Indeed, the thesaurus he is to master is not so complicated as, say, in molecular biology, the structural elements of the system, i. e. ceils, have been segregated by Nature itself, simple considerations of balance may be used for deducing basic equations, and numerous analogies in other areas of science also superficial add to one"s confidence. Generally speaking, this number of impression is correct, as evidenced by the very great theoretical studies on population kinetics, unmatched in other branches of mathematical biology. This, however, does not mean that mathematical theory of cell systems has traversed in its development a pathway free of difficulties or errors. The seeming ease of formalizing the phenomena of cell kinetics not infrequently led to the appearance of mathematical models lacking in adequ...
Kinetics and thermodynamics of living copolymerization processes.
Gaspard, Pierre
2016-11-13
Theoretical advances are reported on the kinetics and thermodynamics of free and template-directed living copolymerizations. Until recently, the kinetic theory of these processes had only been established in the fully irreversible regime, in which the attachment rates are only considered. However, the entropy production is infinite in this regime and the approach to thermodynamic equilibrium cannot be investigated. For this purpose, the detachment rates should also be included. Inspite of this complication, the kinetics can be exactly solved in the regimes of steady growth and depolymerization. In this way, analytical expressions are obtained for the mean growth velocity, the statistical properties of the copolymer sequences, as well as the thermodynamic entropy production. The results apply to DNA replication, transcription and translation, allowing us to understand important aspects of molecular evolution.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).
Redox kinetics and mechanism in silicate melts
Cochain, B.
2009-12-01
This work contributes to better understand iron redox reactions and mechanisms in silicate melts. It was conducted on compositions in both Na 2 O-B 2 O 3 -SiO 2 -FeO and Na 2 O-Al 2 O 3 -SiO 2 -FeO systems. The influence of boron-sodium and aluminum-sodium substitutions and iron content on properties and structure of glasses and on the iron redox kinetics has been studied by Raman, Moessbauer and XANES spectroscopies at the B and Fe K-edges. In borosilicate glasses, an increase in iron content or in the Fe 3+ /ΣFe redox state implies a structural rearrangement of the BO 4 species in the glass network whereas the BO 3 and BO 4 relative proportions remain nearly constant. In all studied glasses and melts, Fe 3+ is a network former in tetrahedral coordination, unless for aluminosilicates of ratio Al/Na≥1 where Fe 3+ is a network modifier in five-fold coordination. Near Tg, diffusion of network modifying cations controls the iron redox kinetics along with a flux of electron holes. At liquidus temperatures, oxygen diffusion is considered to be the mechanism that governs redox reactions. This study shows the role played by the silicate network polymerization on the redox kinetics. In borosilicate melts, iron redox kinetics depends on the boron speciation between BO 3 and BO 4 that depends itself on the sodium content. Furthermore, an increase in the network-former/network-modifier ratio implies a decrease in oxygen diffusion that results in a slowing down of the redox kinetics. The obtained results allow a description of the iron redox kinetics for more complex compositions as natural lavas or nuclear waste model glasses. (author)
Relaxation and kinetics in scalar field theories
Boyanovsky, D.; Lawrie, I.D.; Lee, D.
1996-01-01
A new approach to the dynamics of relaxation and kinetics of thermalization in a scalar field theory is presented that incorporates the relevant time scales through the resummation of hard thermal loops. An alternative derivation of the kinetic equations for the open-quote open-quote quasiparticle close-quote close-quote distribution functions is obtained that allows a clear understanding of the different open-quote open-quote coarse-graining close-quote close-quote approximations usually involved in a kinetic description. This method leads to a systematic perturbative expansion to obtain the kinetic equations including hard thermal loop resummation and to an improvement including renormalization, off-shell effects, and contributions that change chemical equilibrium on short time scales. As a by-product of these methods we establish the equivalence between the relaxation time scale in the linearized equation of motion of the quasiparticles and the thermalization time scale of the quasiparticle distribution function in the open-quote open-quote relaxation time approximation close-quote close-quote including hard thermal loop effects. Hard thermal loop resummation dramatically modifies the scattering rate for long wavelength modes as compared to the usual (semi)classical estimate. Relaxation and kinetics are studied both in the unbroken and broken symmetry phases of the theory. The broken symmetry phase also provides the setting to obtain the contribution to the kinetic equations from processes that involve decay of a heavy scalar into light scalar particles in the medium. copyright 1996 The American Physical Society
Exercise: Kinetic considerations for gas exchange.
Rossiter, Harry B
2011-01-01
The activities of daily living typically occur at metabolic rates below the maximum rate of aerobic energy production. Such activity is characteristic of the nonsteady state, where energy demands, and consequential physiological responses, are in constant flux. The dynamics of the integrated physiological processes during these activities determine the degree to which exercise can be supported through rates of O₂ utilization and CO₂ clearance appropriate for their demands and, as such, provide a physiological framework for the notion of exercise intensity. The rate at which O₂ exchange responds to meet the changing energy demands of exercise--its kinetics--is dependent on the ability of the pulmonary, circulatory, and muscle bioenergetic systems to respond appropriately. Slow response kinetics in pulmonary O₂ uptake predispose toward a greater necessity for substrate-level energy supply, processes that are limited in their capacity, challenge system homeostasis and hence contribute to exercise intolerance. This review provides a physiological systems perspective of pulmonary gas exchange kinetics: from an integrative view on the control of muscle oxygen consumption kinetics to the dissociation of cellular respiration from its pulmonary expression by the circulatory dynamics and the gas capacitance of the lungs, blood, and tissues. The intensity dependence of gas exchange kinetics is discussed in relation to constant, intermittent, and ramped work rate changes. The influence of heterogeneity in the kinetic matching of O₂ delivery to utilization is presented in reference to exercise tolerance in endurance-trained athletes, the elderly, and patients with chronic heart or lung disease. © 2011 American Physiological Society.
The coke drum thermal kinetic effects
Aldescu, Maria M.; Romero, Sim; Larson, Mel [KBC Advanced Technologies plc, Surrey (United Kingdom)
2012-07-01
The coke drum thermal kinetic dynamics fundamentally affect the coker unit yields as well as the coke product properties and unit reliability. In the drum the thermal cracking and polymerization or condensation reactions take place in a semi-batch environment. Understanding the fundamentals of the foaming kinetics that occur in the coke drums is key to avoiding a foam-over that could result in a unit shutdown for several months. Although the most dynamic changes with time occur during drum filling, other dynamics of the coker process will be discussed as well. KBC has contributed towards uncovering and modelling the complexities of heavy oil thermal dynamics. (author)
Kinetic Parameters of Thermal Degradation of Polymers
朱新生; 程嘉祺
2003-01-01
The derivative expressions between activation energy (E) and the temperature at the maximum mass loss rate(Tmax) and between activation energy (E) and exponent (N) were deduced in the light of Arrhenius theory. It was found that the increase of activation energy results in the decrease of exponent and the increase of Tmax. The kinetic parameters were involved in the analysis of the thermal degradation of several polymers. The degradation kinetics of these polymers well complied with the prediction of the derivative expressions for the polymer degradation with single mechanism dominated.
Calmodulin-lanthanide ion exchange kinetics
Buccigross, J.; O'Donnell, C.; Nelson, D.
1985-01-01
A flow dialysis apparatus suitable for the study of high affinity metal binding proteins has been utilized to study calmodulin-metal exchange kinetics. Calmodulin labeled with Eu-155 and Gd-153 was dialyzed against buffer containing various competing metal ions. The rate of metal exchange was monitored by a gamma-ray scintillation detector. The kinetics of exchange are first order, and the rates fall into two categories: Ca (II) and CD (II) in one, and the lanthanides Eu (III), Gd (III), and La (III) in the other
Unified kinetic theory in toroidal systems
Hitchcock, D.A.; Hazeltine, R.D.
1980-12-01
The kinetic theory of toroidal systems has been characterized by two approaches: neoclassical theory which ignores instabilities and quasilinear theory which ignores collisions. In this paper we construct a kinetic theory for toroidal systems which includes both effects. This yields a pair of evolution equations; one for the spectrum and one for the distribution function. In addition, this theory yields a toroidal generalization of the usual collision operator which is shown to have many similar properties - conservation laws, H theorem - to the usual collision operator
Catalytic Kinetic Resolution of Biaryl Compounds.
Ma, Gaoyuan; Sibi, Mukund P
2015-08-10
Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds. © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.
Alternative kinetic energy metrics for Lagrangian systems
Sarlet, W.; Prince, G.
2010-11-01
We examine Lagrangian systems on \\ {R}^n with standard kinetic energy terms for the possibility of additional, alternative Lagrangians with kinetic energy metrics different to the Euclidean one. Using the techniques of the inverse problem in the calculus of variations we find necessary and sufficient conditions for the existence of such Lagrangians. We illustrate the problem in two and three dimensions with quadratic and cubic potentials. As an aside we show that the well-known anomalous Lagrangians for the Coulomb problem can be removed by switching on a magnetic field, providing an appealing resolution of the ambiguous quantizations of the hydrogen atom.
Kinetic studies of elementary chemical reactions
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.
Supercritical kinetic analysis in simplified system of fuel debris using integral kinetic model
Tuya, Delgersaikhan; Obara, Toru
2016-01-01
Highlights: • Kinetic analysis in simplified weakly coupled fuel debris system was performed. • The integral kinetic model was used to simulate criticality accidents. • The fission power and released energy during simulated accident were obtained. • Coupling between debris regions and its effect on the fission power was obtained. - Abstract: Preliminary prompt supercritical kinetic analyses in a simplified coupled system of fuel debris designed to roughly resemble a melted core of a nuclear reactor were performed using an integral kinetic model. The integral kinetic model, which can describe region- and time-dependent fission rate in a coupled system of arbitrary geometry, was used because the fuel debris system is weakly coupled in terms of neutronics. The results revealed some important characteristics of coupled systems, such as the coupling between debris regions and the effect of the coupling on the fission rate and released energy in each debris region during the simulated criticality accident. In brief, this study showed that the integral kinetic model can be applied to supercritical kinetic analysis in fuel debris systems and also that it can be a useful tool for investigating the effect of the coupling on consequences of a supercritical accident.
Kinetic theory of nonideal gases and nonideal plasmas
Klimontovich, Yu L
2013-01-01
Kinetic Theory of Nonideal Gases and Nonideal Plasmas presents the fundamental aspects of the kinetic theory of gases and plasmas. The book consists of three parts, which attempts to present some of the ideas, methods and applications in the study of the kinetic processes in nonideal gases and plasmas. The first part focuses on the classical kinetic theory of nonideal gases. The second part discusses the classical kinetic theory of fully ionized plasmas. The last part is devoted to the quantum kinetic theory of nonideal gases and plasmas. A concluding chapter is included, which presents a shor
Kinetics of fibrilar aggregation of food proteins
Arnaudov, L.N.
2005-01-01
In this thesis we study the kinetics of fibrilar aggregation of two model proteins widely used in the food industry -b-lactoglobulin (b-lg) and hen
Thermodynamics, Kinetics and Microstructural Evolution during Nitrocarburising
Somers, Marcel A.J.; Du, Hong
2000-01-01
The evolution of the phase distribution, the composition and the growth kinetics of the compound layer is described for nitrocarburising experiments at well defined combinations of nitriding and carburising potentials in the gaseous environment. Initially, the compound layer development is associ...
Kinetic equation of heterogeneous catalytic isotope exchange
Trokhimets, A I [AN Belorusskoj SSR, Minsk. Inst. Fiziko-Organicheskoj Khimii
1979-12-01
A kinetic equation is derived for the bimolecular isotope exchange reaction between AXsub(n)sup(*) and BXsub(m)sup(o), all atoms of element X in each molecule being equivalent. The equation can be generalized for homogeneous and heterogeneous catalytic isotope exchange.
Application of dhurrin for kinetics and thermodynamic ...
The entropy change (ΔS) increased with enzyme purity from 0.588 J/mol.deg. to 1.4625Jmol degree. The enthalpy change KJ/mol followed the same pattern whereby increases influenced by enzyme purity ranged from 1892 KJ/mol to 13104KJ/mol. Keywords: kinetics, thermodynamic, characterization, dhurrin, genetically ...
Microstructure and transformation kinetics in bainitic steels
Luzginova, N.V.
2008-01-01
With the aim of reaching a better understanding of the microstructure evolution and the overall phase transformation kinetics in hyper-eutectoid steels a commercial SAE 52100 bearing steel and 7 model alloys with different concentrations of chromium, cobalt and aluminum have been studied in this
Some remarks concerning relativistic kinetic theory
Schroeter, J.
1990-01-01
The starting point of our investigation is a classical kinetic theory which includes correlational effects as well as the complete electromagnetic interaction. Also classical gravitation can be incorporated. The relativistic version of this theory is written down using some heuristic arguments. Its essential feature is the difference between terms representing gravitational interaction and the metric tensor representing geometrical properties. (author)
Rehydration kinetics of freeze-dried carrots
Vergeldt, F.J.; Dalen, van G.; Duijster, A.J.; Voda, A.; Khalloufi, S.; Vliet, van L.J.; As, van H.; Duynhoven, van J.P.M.; Sman, van der R.G.M.
2014-01-01
Rehydration kinetics by two modes of imbibition is studied in pieces of freeze-dried winter carrot, after different thermal pre-treatments. Water ingress at room temperature is measured in real time by in situ MRI and NMR relaxometry. Blanched samples rehydrate substantially faster compared to
Deposition kinetics of nanocolloidal gold particles
Brouwer, E.A.M.; Kooij, Ernst S.; Hakbijl, Mark; Wormeester, Herbert; Poelsema, Bene
2005-01-01
The deposition kinetics of the irreversible adsorption of citrate-stabilized, nanocolloidal gold particles on Si/SiO2 surfaces, derivatized with (aminopropyl)triethoxysilane (APTES), is investigated in situ using single wavelength optical reflectometry. A well-defined flow of colloids towards the
CHEMSIMUL: A simulator for chemical kinetics
Kirkegaard, P.; Bjergbakke, E.
1999-01-01
CHEMSIMUL is a computer program system for numerical simulation of chemical reaction systems. It can be used for modeling complex kinetics in many contexts, in particular radiolytic processes. It contains a translator module and a module for solving theresulting coupled nonlinear ordinary...
Kinetic modeling of reactions in Foods
Boekel, van M.A.J.S.
2008-01-01
The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to
COMPARATIVE ANALYSIS OF SOME EXISTING KINETIC MODELS ...
The biosorption of three heavy metal ions namely; Zn2+, Cu2+ and Mn2+ using five microorganisms namely; Bacillus circulans, Pseudomonas aeruginosa, Staphylococcus xylosus, Streptomyces rimosus and Yeast (Saccharomyces sp.) were studied. In this paper, the effectiveness of six existing and two proposed kinetic ...
Free-Form Kinetic Reciprocal System
Parigi, Dario; Sassone, Mario
2011-01-01
Kinetic Reciprocal System (KRS) are innovative moveable structures based on the principle of reciprocity [1] with internal pin-slot constraints [2]. The analysis of KRS kinematic and static determinacy is developed through the construction of kinematic matrices, accordingly with [3] and a discuss...
Trapped particle stability for the kinetic stabilizer
Berk, H. L.; Pratt, J.
2011-08-01
A kinetically stabilized axially symmetric tandem mirror (KSTM) uses the momentum flux of low-energy, unconfined particles that sample only the outer end-regions of the mirror plugs, where large favourable field-line curvature exists. The window of operation is determined for achieving magnetohydrodynamic (MHD) stability with tolerable energy drain from the kinetic stabilizer. Then MHD stable systems are analysed for stability of the trapped particle mode. This mode is characterized by the detachment of the central-cell plasma from the kinetic-stabilizer region without inducing field-line bending. Stability of the trapped particle mode is sensitive to the electron connection between the stabilizer and the end plug. It is found that the stability condition for the trapped particle mode is more constraining than the stability condition for the MHD mode, and it is challenging to satisfy the required power constraint. Furthermore, a severe power drain may arise from the necessary connection of low-energy electrons in the kinetic stabilizer to the central region.
Non-equilibrium thermodynamics and physical kinetics
Bikkin, Halid
2014-01-01
This graduate textbook covers contemporary directions of non-equilibrium statistical mechanics as well as classical methods of kinetics. With one of the main propositions being to avoid terms such as "obviously" and "it is easy to show", this treatise is an easy-to-read introduction into this traditional, yet vibrant field.
Temperatures of fragment kinetic energy spectra
Bauer, W.
1995-01-01
Multifragmentation reactions without large compression in the initial state (proton-induced reactions, reverse kinematics, projectile fragmentation) are examined, and it is verified quantitatively that the high temperatures obtained from fragment kinetic energy spectra and lower temperatures obtained from observables such as level population or isotope ratios can be understood in a common framework
Kinetics of Oxidation of Fe–6Si
Lashin, Abdel Rahman; Schneeweiss, Oldřich; Svoboda, Milan
2008-01-01
Roč. 69, č. 5-6 (2008), s. 359-374 ISSN 0030-770X R&D Projects: GA AV ČR IAA1041404 Institutional research plan: CEZ:AV0Z20410507 Keywords : iron silicon * Mössbauer spectroscopy * XRD * iron oxides * oxidation kinetics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.359, year: 2008
Combustion Kinetic Studies of Gasolines and Surrogates
Javed, Tamour
2016-01-01
. These measurements were performed in shock tubes and rapid compression machines over a wide range of experimental conditions (650 – 1250 K, 10 – 40 bar) relevant to internal combustion engines. Using the measured the data and chemical kinetic analyses, the surrogate
Copper laser diagnostics and kinetics support
1981-12-01
In the effort MSNW participated with the LINL copper-Vapor Laser Program by providing a useful plasma diagnostic for interpretation of Copper-vapor laser kinetics. MSNW developed and delivered a pulsed interferometric diagnostic package to LLNL. Moreover MSNW provided personal services at the request and direction of LLL in the implementation of the diagnostic and interpretation of the data
An Inversion Recovery NMR Kinetics Experiment
Williams, Travis J.; Kershaw, Allan D.; Li, Vincent; Wu, Xinping
2011-01-01
A convenient laboratory experiment is described in which NMR magnetization transfer by inversion recovery is used to measure the kinetics and thermochemistry of amide bond rotation. The experiment utilizes Varian spectrometers with the VNMRJ 2.3 software, but can be easily adapted to any NMR platform. The procedures and sample data sets in this…
A kinetic equation for irreversible aggregation
Zanette, D.H.
1990-09-01
We introduce a kinetic equation for describing irreversible aggregation in the ballistic regime, including velocity distributions. The associated evolution for the macroscopic quantities is studied, and the general solution for Maxwell interaction models is obtained in the Fourier representation. (author). 23 refs
The kinetic theory of open systems
Klimontovich, Yu.L.
2001-01-01
This paper begins with a survey of recently obtained results in the statistical theory of open systems, including quantum open systems. Then the definition of the thermal flux in the kinetic theory is considered, further the collision nature of the Landau damping. Finally the Lamb shift and Bethe's formula are analyzed. (orig.)
The kinetically dominated quasar 3C 418
Punsly, Brian; Kharb, Preeti
2017-06-01
The existence of quasars that are kinetically dominated, where the jet kinetic luminosity, Q, is larger than the total (infrared to X-ray) thermal luminosity of the accretion flow, Lbol, provides a strong constraint on the fundamental physics of relativistic jet formation. Since quasars have high values of Lbol by definition, only ˜10 kinetically dominated quasars (with \\overline{Q}/L_{bol}>1) have been found, where \\overline{Q} is the long-term time-averaged jet power. We use low-frequency (151 MHz-1.66 GHz) observations of the quasar 3C 418 to determine \\overline{Q}≈ 5.5 ± 1.3 × 10^{46} {erg s^{-1}}. Analysis of the rest-frame ultraviolet spectrum indicates that this equates to 0.57 ± 0.28 times the Eddington luminosity of the central supermassive black hole and \\overline{Q}/L_{bol} ≈ 4.8 ± 3.1, making 3C 418 one of the most kinetically dominated quasars found to date. It is shown that this maximal \\overline{Q}/L_{bol} is consistent with models of magnetically arrested accretion of jet production in which the jet production reproduces the observed trend of a decrement in the extreme ultraviolet continuum as the jet power increases. This maximal condition corresponds to an almost complete saturation of the inner accretion flow with vertical large-scale magnetic flux (maximum saturation).
KINETICS AND MECHANISM OF REACTION OF ACIDIC ...
The kinetics and mechanism of the oxidation of two phenoxazine dyes namely Nile blue (7-amino-3-diethylamino-8,9-benzo phenoxazine chloride, NB+) and Meldola\\'s blue (3- dimethylamino-8,9-benzo phenoxazine chloride, MB+) with acidic chlorite and hypochlorous acid have been investigated using a UV-visible and a ...
Development and Application of Kinetic Spectrophotometric Method ...
Purpose: To develop an improved kinetic-spectrophotometric procedure for the determination of metronidazole (MNZ) in pharmaceutical formulations. Methods: The method is based on oxidation reaction of MNZ by hydrogen peroxide in the presence of Fe(II) ions at pH 4.5 (acetate buffer). The reaction was monitored ...
Kinetics of carbon dioxide during cardiopulmonary resuscitation
Wiklund, L; Söderberg, D; Henneberg, S
1986-01-01
CO2 kinetics during CPR was investigated in 15 anesthetized piglets. BP, blood gases, and acid-base balance were monitored through catheters in the carotid artery and a central vein, as well as in cerebrospinal fluid. Cardiac arrest was induced by a transthoracic direct current shock. CPR was beg...
Antioxidant Capacity, Radical Scavenging Kinetics and Phenolic ...
Antioxidant Capacity, Radical Scavenging Kinetics and Phenolic Profile of Methanol Extracts of Wild Plants of Southern Sonora, Mexico. EF Moran-Palacio, LA Zamora-Álvarez, NA Stephens-Camacho, GA Yáñez- Farías, A Virgen-Ortiz, O Martínez-Cruz, JA Rosas-Rodríguez ...
Flash pyrolysis kinetics of pine wood
Wagenaar, B.M.; Prins, W.; van Swaaij, Willibrordus Petrus Maria
1993-01-01
The kinetics of sawdust pyrolysis in the temperature range from 300 to 600 °C has been measured. A thermogravimetric analyser was applied for the temperature range from 300 to 450 °C while for measurements in the temperature range from 450 to 600 °C, an entrained flow reactor has been used. The
Production of a sterile species: Quantum kinetics
Boyanovsky, D.; Ho, C. M.
2007-10-01
Production of a sterile species is studied within an effective model of active-sterile neutrino mixing in a medium in thermal equilibrium. The quantum kinetic equations for the distribution functions and coherences are obtained from two independent methods: the effective action and the quantum master equation. The decoherence time scale for active-sterile oscillations is τdec=2/Γaa, but the evolution of the distribution functions is determined by the two different time scales associated with the damping rates of the quasiparticle modes in the medium: Γ1=Γaacos2θm; Γ2=Γaasin2θm where Γaa is the interaction rate of the active species in the absence of mixing and θm the mixing angle in the medium. These two time scales are widely different away from Mikheyev-Smirnov-Wolfenstein resonances and preclude the kinetic description of active-sterile production in terms of a simple rate equation. We give the complete set of quantum kinetic equations for the active and sterile populations and coherences and discuss in detail the various approximations. A generalization of the active-sterile transition probability in a medium is provided via the quantum master equation. We derive explicitly the usual quantum kinetic equations in terms of the “polarization vector” and show their equivalence to those obtained from the quantum master equation and effective action.
Reaction kinetics of polybutylene terephthalate polycondensation reaction
Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.
2005-01-01
The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl
Lithium hydride hydrolysis: experimental and kinetic study
Charton, S.; Maupoix, C.; Brevet, A.; Delaunay, F.; Heintz, O.; Saviot, L.
2006-01-01
In this work has been studied the contribution of various analyses techniques in the framework, on the one hand of revealing the mechanisms implied in lithium hydride hydrolysis, and on the other hand of studying the kinetics of hydrogen production. Among the methods recently investigated, Raman spectroscopy, XPS and SIMS seem to be particularly attractive. (O.M.)
Platelet kinetics: the state of the art
Heyns, A. duP
1984-01-01
In this paper an overview of the state of the art of platelet kinetics 1982 is presented. The subjects considered include a discussion of the advantages and disadvantages of some of the many radionuclide platelet labels, viz 51 Cr, 111 In, focussing briefly on models for analysis of platelets survival. (Auth.)
A MODEL FOR POSTRADIATION STEM CELL KINETICS,
In polycythemic rats observed for 17 days postradiation (300 R, 250 KVP X-rays) it was noted that stem cell release diminished to 8 percent of the...correlate these findings with a kinetic model of erythropoiesis. It was suggested that the initial depression in stem cell release might be due to cellular
Enzyme kinetic characterization of protein tyrosine phosphatases
Peters, Günther H.J.; Branner, S.; Møller, K. B.
2003-01-01
Protein tyrosine phosphatases (PTPs) play a central role in cellular signaling processes, resulting in an increased interest in modulating the activities of PTPs. We therefore decided to undertake a detailed enzyme kinetic evaluation of various transmembrane and cytosolic PTPs (PTPalpha, PTPbeta...
Genesis and kinetics of peritoneal macrophages
Wacker, H.H.
1982-01-01
The author intended to develop an experimental model for investigations of the proliferation kinetics of tissue macrophages, using the example of peritoneal macrophages. To get a suitable cell population, a blood cell population was labelled with 3 H-thymidine and transferred in a parabiotic test. (orig./MG) [de
Kinetics of infrared stimulated luminescence from feldspars
Jain, Mayank; Sohbati, Reza; Guralnik, Benny
2015-01-01
thermal and optical, of the infrared stimulated luminescence signal from feldspar. Based on the application of this model, it is concluded that different infra-red stimulated luminescence emissions (UV, blue, yellow and far-red) follow the same kinetics, and, therefore, involve participation of the same...
Norepinephrine kinetics during insulin-induced hypoglycemia
Hilsted, J; Christensen, N J; Larsen, S
1985-01-01
Norepinephrine (NE) kinetics (plasma appearance rate, clearance, and forearm extraction) were measured during insulin-induced hypoglycemia in six healthy subjects. NE clearance did not change during hypoglycemia, indicating that the increase in plasma NE during hypoglycemia is due to an increased...
Aircraft Measurements of Atmospheric Kinetic Energy Spectra
Lundtang Petersen, Erik; Lilly, D. K.
1983-01-01
Wind velocity data obtained from a jet airliner are used to construct kinetic energy spectra over the range of wavelengths from 2.5 to 2500 km. The spectra exhibit an approximate -5/3 slope for wavelengths of less than about 150 km, steepening to about -2.2 at larger scales. These results support...
Thermodynamic and kinetic modelling: creep resistant materials
Hald, John; Korcakova, L.; Danielsen, Hilmar Kjartansson
2008-01-01
The use of thermodynamic and kinetic modelling of microstructure evolution in materials exposed to high temperatures in power plants is demonstrated with two examples. Precipitate stability in martensitic 9–12%Cr steels is modelled including equilibrium phase stability, growth of Laves phase part...
KINETICS OF THE OXIDATION OF VITAMIN C
Sitti Rahmawati
2012-12-01
Full Text Available Vitamin C or ascorbic acid is needed by the human body but it is already damaged by the rise in temperature due to be oxidized to L-dehydroascorbic acid. This research aims to determine the kinetics of oxidation of ascorbic acid due to an increase if temperature (40-80 °C and to design an ascorbic acid oxidation reaction laboratory module to be applied in the senior high school reaction kinetics curriculum. The determination of the kinetics of the oxidation of ascorbic acid applies the integral and half-change time methods, while the concentration of the remained ascorbic acid in sixty minute intervals is determined by iodimetric titration method. Decomposition of ascorbic acid was measured at 40, 50, 60, 70 and 80 °C. The results of this research indicate that at 40, 50, 60, 70 and 80 °C the kinetics of the oxidation of ascorbic acid is a first-order reaction with rate constants of 4.55 x 10-4, 5.85 x 10-4, 8.4 x 10-4, 1.1 x 10-3 and 1.015 x 10-3 min-1, respectively. Pre-exponential factor or the frequency of collisions is a factor which is a measure of the collision rate. The activation energy and the pre-exponential factor for the oxidation of ascorbic acid were found to be 20.73 kJ.mol-1 and 1.372 min-1. The procedure used in this study was modified into a laboratory module will be applied in the teaching of reaction kinetics at the senior high school level.
Reflected kinetics model for nuclear space reactor kinetics and control scoping calculations
Washington, K.E.
1986-05-01
The objective of this research is to develop a model that offers an alternative to the point kinetics (PK) modelling approach in the analysis of space reactor kinetics and control studies. Modelling effort will focus on the explicit treatment of control drums as reactivity input devices so that the transition to automatic control can be smoothly done. The proposed model is developed for the specific integration of automatic control and the solution of the servo mechanism problem. The integration of the kinetics model with an automatic controller will provide a useful tool for performing space reactor scoping studies for different designs and configurations. Such a tool should prove to be invaluable in the design phase of a space nuclear system from the point of view of kinetics and control limitations.
Reflected kinetics model for nuclear space reactor kinetics and control scoping calculations
Washington, K.E.
1986-05-01
The objective of this research is to develop a model that offers an alternative to the point kinetics (PK) modelling approach in the analysis of space reactor kinetics and control studies. Modelling effort will focus on the explicit treatment of control drums as reactivity input devices so that the transition to automatic control can be smoothly done. The proposed model is developed for the specific integration of automatic control and the solution of the servo mechanism problem. The integration of the kinetics model with an automatic controller will provide a useful tool for performing space reactor scoping studies for different designs and configurations. Such a tool should prove to be invaluable in the design phase of a space nuclear system from the point of view of kinetics and control limitations
Fluorescence kinetics and positron annihilation kinetics investigations in cadmium sulfide crystals
Grillot, E; Bancie-Grillot, M; Egee, M [Reims Univ., 51 (France)
1976-03-01
Fluorescence kinetics and positrons annihilation kinetics investigations on CdS crystals, either very pure or with increasing contents of Ag-ions, led to similar and complementary results. Ag-ions mainly fill the cadmium vacancies of the lattice, building red emission luminogene centres, while green 'edge-emission' ones are destroyed. These latter, which involve an excited level active for high energy series fluorescence, seems actually related to cadmium vacancies.
New Methods for Processing and Quantifying VO2 Kinetics to Steady State: VO2 Onset Kinetics
Craig R. McNulty
2017-09-01
Full Text Available Current methods of oxygen uptake (VO2 kinetics data handling may be too simplistic for the complex physiology involved in the underlying physiological processes. Therefore, the aim of this study was to quantify the VO2 kinetics to steady state across the full range of sub-ventilatory threshold work rates, with a particular focus on the VO2 onset kinetics. Ten healthy, moderately trained males participated in five bouts of cycling. Each bout involved 10 min at a percentage of the subject's ventilation threshold (30, 45, 60, 75, 90% from unloaded cycling. The VO2 kinetics was quantified using the conventional mono-exponential time constant (tau, τ, as well as the new methods for VO2 onset kinetics. Compared to linear modeling, non-linear modeling caused a deterioration of goodness of fit (main effect, p < 0.001 across all exercise intensities. Remainder kinetics were also improved using a modified application of the mono-exponential model (main effect, p < 0.001. Interestingly, the slope from the linear regression of the onset kinetics data is similar across all subjects and absolute exercise intensities, and thereby independent of subject fitness and τ. This could indicate that there are no functional limitations between subjects during this onset phase, with limitations occurring for the latter transition to steady state. Finally, the continuing use of mono-exponential modeling could mask important underlying physiology of more instantaneous VO2 responses to steady state. Consequently, further research should be conducted on this new approach to VO2 onset kinetics.
Kinetic modelling of the Maillard reaction between proteins and sugars
Brands, C.M.J.
2002-01-01
Keywords: Maillard reaction, sugar isomerisation, kinetics, multiresponse modelling, brown colour formation, lysine damage, mutagenicity, casein, monosaccharides, disaccharides, aldoses, ketoses
The aim of this thesis was to determine the kinetics of the Maillard reaction between
Relativistic thermodynamics and kinetic theory, with applications to cosmology
Stewart, J.M.
1973-01-01
The discussion of relativistic thermodynamics and kinetic theory with applications to cosmology also covers the fundamentals and nonequilibrium relativistic kinetic theory and applications to cosmology and astrophysics. (U.S.)
Alkylation of Chlorobenzene. An Experiment Illustrating Kinetic versus Thermodynamic Control.
Kolb, Kenneth; And Others
1988-01-01
Describes an experiment which illustrates the kinetic versus thermodynamic control of chemical reactions for organic chemistry students. Considers the laboratory procedures including the isolation of both the kinetic and thermodynamic products. (CW)
Kinetics of molybdenite oxidizing leaching in alkali medium by ozone
Medvedev, A.S.; Sokratova, N.B.; Litman, I.V.; Zelikman, A.N.
1985-01-01
On the basis of investigation of the process kinetics proposed is a model of oxidizing leaching of molybdenite in alkali medium while ozonization of the solution by ozoneair mixture. A kinetic equation is derived, that describes experimental data satisfactorily
Kinetic simulations in plasmas: a general view and some applications
Alves, Maria Virginia [Instituto Nacional de Pesquisas Espaciais (INPE), Sao Jose dos Campos, SP (Brazil). Lab. Associado de Plasma]. E-mail: alves@plasma.inpe.br
1999-07-01
In these lecture notes we talk about kinetic simulations plasma physics. We present a general view of the different approach that can be given to kinetic plasmas depending on the physical problem to be investigated. Some applications of kinetic simulations to space plasma phenomena and Pierce electrodes are introduced. (author)
Kinetic simulations in plasmas: a general view and some applications
Alves, Maria Virginia
1999-01-01
In these lecture notes we talk about kinetic simulations plasma physics. We present a general view of the different approach that can be given to kinetic plasmas depending on the physical problem to be investigated. Some applications of kinetic simulations to space plasma phenomena and Pierce electrodes are introduced. (author)
Kinetics of Pressurized Water Reactors with Hot or Cold Moderators
Norinder, O
1960-11-15
The set of neutron kinetic equations developed in this report permits the use of long integration steps during stepwise integration. Thermal relations which describe the transfer of heat from fuel to coolant are derived. The influence upon the kinetic behavior of the reactor of a number of parameters is studied. A comparison of the kinetic properties of the hot and cold moderators is given.
Stochastic optimization-based study of dimerization kinetics
To this end, we study dimerization kinetics of protein as a model system. We follow the dimerization kinetics using a stochastic simulation algorithm and ... optimization; dimerization kinetics; sensitivity analysis; stochastic simulation ... tion in large molecules and clusters, or the design ..... An unbiased strategy of allocating.
Kinetic aspects of the Maillard reaction: a critical review
Boekel, van M.A.J.S.
2001-01-01
The literature concerning the kinetics of the Maillard reaction was critically discussed according to the initial, intermediate and advanced stages, as this is the way the Maillard reaction is traditionally analysed. For each stage, a division is made between simple kinetics and complex kinetics.
Energy transfer and kinetics in mechanochemistry.
Chen, Zhiliang; Lu, Shengyong; Mao, Qiongjing; Buekens, Alfons; Wang, Yuting; Yan, Jianhua
2017-11-01
Mechanochemistry (MC) exerts extraordinary degradation and decomposition effects on many chlorinated, brominated, and even fluorinated persistent organic pollutants (POPs). However, its application is still limited by inadequate study of its reaction kinetic aspects. In the present work, the ball motion and energy transfer in planetary ball mill are investigated in some detail. Almost all milling parameters are summarised in a single factor-total effective impact energy. Furthermore, the MC kinetic between calcium oxide/Al and hexachlorobenzene is well established and modelled. The results indicate that total effective impact energy and reagent ratio are the two factors sufficient for describing the MC degradation degree of POPs. The reaction rate constant only depends on the chemical properties of reactants, so it could be used as an important index to appraise the quality of MC additives. This model successfully predicts the reaction rate for different operating conditions, indicating that it could be suitably applied for conducting MC reactions in other reactors.
Processes of aggression described by kinetic method
Aristov, V. V.; Ilyin, O.
2014-12-01
In the last decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France and USSR based on the kinetic theory. We model this process with the Cauchy boundary problem for the two-element kinetic equations with spatial initial conditions. The solution of the problem is given in the form of traveling wave. The propagation velocity of a frontline depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the frontline velocities are complied with the historical data.
Processes of aggression described by kinetic method
Aristov, V. V.; Ilyin, O.
2014-01-01
In the last decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France and USSR based on the kinetic theory. We model this process with the Cauchy boundary problem for the two-element kinetic equations with spatial initial conditions. The solution of the problem is given in the form of traveling wave. The propagation velocity of a frontline depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the frontline velocities are complied with the historical data
A KINETIC DATABASE FOR ASTROCHEMISTRY (KIDA)
Wakelam, V.; Pavone, B.; Hébrard, E.; Hersant, F.; Herbst, E.; Loison, J.-C.; Chandrasekaran, V.; Bergeat, A.; Smith, I. W. M.; Adams, N. G.; Bacchus-Montabonel, M.-C.; Béroff, K.; Bierbaum, V. M.; Chabot, M.; Dalgarno, A.; Van Dishoeck, E. F.; Faure, A.; Geppert, W. D.; Gerlich, D.; Galli, D.
2012-01-01
We present a novel chemical database for gas-phase astrochemistry. Named the KInetic Database for Astrochemistry (KIDA), this database consists of gas-phase reactions with rate coefficients and uncertainties that will be vetted to the greatest extent possible. Submissions of measured and calculated rate coefficients are welcome, and will be studied by experts before inclusion into the database. Besides providing kinetic information for the interstellar medium, KIDA is planned to contain such data for planetary atmospheres and for circumstellar envelopes. Each year, a subset of the reactions in the database (kida.uva) will be provided as a network for the simulation of the chemistry of dense interstellar clouds with temperatures between 10 K and 300 K. We also provide a code, named Nahoon, to study the time-dependent gas-phase chemistry of zero-dimensional and one-dimensional interstellar sources.
Adsorption kinetics of surfactants on activated carbon
Arnelli; Aditama, WP; Fikriani, Z.; Astuti, Y.
2018-04-01
A study on the adsorption of both cationic and anionic surfactants using activated carbon as well as the investigation of the adsorption isotherms and adsorption kinetics has been conducted. The results showed that the adsorption of sodium lauryl sulfate (SLS) by activated carbon was Langmuir’s adsorption isotherm while its adsorption kinetics showed pseudo-second order with an adsorption rate constant of 2.23 x 103 g mg-1 hour-1. Meanwhile, the adsorption of HDTMA-Br by activated carbon showed that the isotherm adsorption tended to follow Freundlich’s isotherm and was pseudo-second order with an adsorption rate constant of 89.39 g mg-1 hour-1.
Reactor kinetics - pulse and steady state
Estes, B F; Morris, F M [Sandia Laboratories (United States)
1974-07-01
An analytical model has been developed which couples the nuclear and thermal characteristics of the Annular Core Pulse Reactor (ACPR) into a solution which describes both the neutron kinetics of the reactor and the temperature behavior of a fuel-moderator element. The model describes both pulse and steady state operations. This paper describes the important aspects of the reactor, the fuel- moderator elements, the neutron kinetic equations of the reactor, and the time-temperature behavior of a fuel-moderator element that is being subjected to the maximum power density in the core. The parameters which are utilized in the equations are divided into two classes, those that can be measured directly and those that are assumed to be known (each is described briefly). Some of the solutions which demonstrate the versatility of the analytical model are described. (author)
Physics and kinetics of TRIGA reactor
Boeck, H.; Villa, M.
2007-01-01
This training module is written as an introduction to reactor physics for reactor operators. It assumes the reader has a basic, fundamental knowledge of physics, materials and mathematics. The objective is to provide enough reactor theory knowledge to safely operate a typical research reactor. At this level, it does not necessarily provide enough information to evaluate the safety aspects of experiment or non-standard operation reviews. The material provides a survey of basic reactor physics and kinetics of TRIGA type reactors. Subjects such as the multiplication factor, reactivity, temperature coefficients, poisoning, delayed neutrons and criticality are discussed in such a manner that even someone not familiar with reactor physics and kinetics can easily follow. A minimum of equations are used and several tables and graphs illustrate the text. (author)
Kinetic Titration Series with Biolayer Interferometry
Frenzel, Daniel; Willbold, Dieter
2014-01-01
Biolayer interferometry is a method to analyze protein interactions in real-time. In this study, we illustrate the usefulness to quantitatively analyze high affinity protein ligand interactions employing a kinetic titration series for characterizing the interactions between two pairs of interaction patterns, in particular immunoglobulin G and protein G B1 as well as scFv IC16 and amyloid beta (1–42). Kinetic titration series are commonly used in surface plasmon resonance and involve sequential injections of analyte over a desired concentration range on a single ligand coated sensor chip without waiting for complete dissociation between the injections. We show that applying this method to biolayer interferometry is straightforward and i) circumvents problems in data evaluation caused by unavoidable sensor differences, ii) saves resources and iii) increases throughput if screening a multitude of different analyte/ligand combinations. PMID:25229647
Reaction kinetics of bond rotations in graphene
Skowron, Stephen T.; Koroteev, Victor O.; Baldoni, Matteo; Lopatin, Sergei; Zurutuza, Amaia; Chuvilin, Andrey; Besley, Elena
2016-01-01
The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.
Engineering kinetic barriers in copper metallization
Huang Hanchen; Wei, H.L.; Woo, C.H.; Zhang, X.X.
2002-01-01
In metallization processes of integrated circuits, it is desirable to deposit the metal lines (aluminum or copper) fast and at low temperatures. However, the lines (films) usually consist of undesirable columns and voids, because of the absence of sufficient diffusion--a direct result of large kinetic barriers. Following the proposal and realization of the three-dimensional Ehrlich-Schwoebel (3D ES) barrier, we present here a method to engineer this kinetic barrier so as to improve quality of deposited copper films. We deposit copper films by magnetron sputtering, characterize the film structure and texture by using the scanning electron microscope and the x-ray diffraction, respectively. Taking indium as surfactant during copper deposition, we have achieved much better density and bottom coverage of copper filled trenches. The characterizations show that the improvement is the result of the 3D ES barrier reduction caused by indium addition. Engineering the 3D ES barrier therefore leads to improved film quality
Kinetic Line Voronoi Operations and Their Reversibility
Mioc, Darka; Anton, François; Gold, Christopher
2010-01-01
In Geographic Information Systems the reversibility of map update operations has not been explored yet. In this paper we are using the Voronoi based Quad-edge data structure to define reversible map update operations. The reversibility of the map operations has been formalised at the lowest level...... mechanisms and dynamic map visualisations. In order to use the reversibility within the kinetic Voronoi diagram of points and open oriented line segments, we need to assure that reversing the map commands will produce exactly the changes in the map equivalent to the previous map states. To prove...... that reversing the map update operations produces the exact reverse changes, we show an isomorphism between the set of complex operations on the kinetic Voronoi diagram of points and open oriented line segments and the sets of numbers of new / deleted Voronoi regions induced by these operations, and its...
Athermal kinetics in low alloy steels
Leiva, Jorge A Vega; Valencia Morales, Eduardo; Villar Cociña, Ernesto; Hernández Ruiz, Jesús; Donis, Carlos
2008-01-01
Athermic analyses for the kinetic study of the reactions in the solid state are preferred because they consume much less experimental work time than the isothermal tests, and lead to more accurate calculations of the energies of activation of reactions that have occurred. In the present work are required conditions where you can apply the equation of speed of an athermal reaction in a low alloy in solid steel. From records of steel (AISI 1050) dilatometric triples were calculated kinetics (E, Ko, n) that characterize the reactions that occurred during the tempering of samples using different methods of iso conversion, one of which is a new modification of the method of Friedman. Also, has shown that during the formation of carbide Epsilon in the first stage of the tempering has occurred a saturation of sites, which validates the use of some methods. Finally, the orders of the reactions occurred during tempering of steel studied treatment are calculated.
Hypocoercivity for linear kinetic equations conserving mass
Dolbeault, Jean; Mouhot, Clé ment; Schmeiser, Christian
2015-01-01
We develop a new method for proving hypocoercivity for a large class of linear kinetic equations with only one conservation law. Local mass conservation is assumed at the level of the collision kernel, while transport involves a confining potential, so that the solution relaxes towards a unique equilibrium state. Our goal is to evaluate in an appropriately weighted $ L^2$ norm the exponential rate of convergence to the equilibrium. The method covers various models, ranging from diffusive kinetic equations like Vlasov-Fokker-Planck equations, to scattering models or models with time relaxation collision kernels corresponding to polytropic Gibbs equilibria, including the case of the linear Boltzmann model. In this last case and in the case of Vlasov-Fokker-Planck equations, any linear or superlinear growth of the potential is allowed. - See more at: http://www.ams.org/journals/tran/2015-367-06/S0002-9947-2015-06012-7/#sthash.ChjyK6rc.dpuf
Positron kinetics in an idealized PET environment
Robson, R. E.; Brunger, M. J.; Buckman, S. J.; Garcia, G.; Petrović, Z. Lj.; White, R. D.
2015-08-01
The kinetic theory of non-relativistic positrons in an idealized positron emission tomography PET environment is developed by solving the Boltzmann equation, allowing for coherent and incoherent elastic, inelastic, ionizing and annihilating collisions through positronium formation. An analytic expression is obtained for the positronium formation rate, as a function of distance from a spherical source, in terms of the solutions of the general kinetic eigenvalue problem. Numerical estimates of the positron range - a fundamental limitation on the accuracy of PET, are given for positrons in a model of liquid water, a surrogate for human tissue. Comparisons are made with the ‘gas-phase’ assumption used in current models in which coherent scattering is suppressed. Our results show that this assumption leads to an error of the order of a factor of approximately 2, emphasizing the need to accurately account for the structure of the medium in PET simulations.
On the kinetic theory of quantum systems
Calkoen, C.J.
1986-01-01
The contents of this thesis which deals with transport phenomena of specific gases, plasmas and fluids, can be separated into two distinct parts. In the first part a statistical way is suggested to estimate the neutrino mass. Herefore use is made of the fact that massive neutrinos possess a non-zero volume viscosity in contrast with massless neutrinos. The second part deals with kinetic theory of strongly condensed quantum systems of which examples in nature are: liquid Helium, heavy nuclei, electrons in a metal and the interior of stars. In degenerate systems fermions in general interact strongly so that ordinary kinetic theory is not directly applicable. For such cases Landau-Fermi-liquid theory, in which the strongly interacting particles are replaced by much weaker interacting quasiparticles, proved to be very useful. A method is developed in this theory to calculate transport coefficients. Applications of this method on liquid 3 Helium yield surprisingly good agreement with experimental results for thermal conductivities. (Auth.)
The nonextensive gas: a kinetic approach
Lima, J.A.S.; Silva, R.
2005-01-01
We discuss a kinetic nonextensive generalization of the Maxwellian ideal gas. The analysis rests on two basic assumptions: (i) instead of the standard Gaussian form, the q-gas is described by a power-law velocity distribution as suggested in the nonextensive Tsallis' framework (ii) the q-nonextensive generalization of the Boltzmann entropy formula governs the behavior of the q-gas. In this context, we show that the pressure and the internal energy are kinetically modified, but the general equation of state, PV=2U/3, remains valid. The adiabatic index is now a function of the nonextensive parameter, γ=C p /C V =5/3q. However, the standard expression relating the specific heats (at constant pressure and volume) with the coefficient of expansion and the isothermal compressibility, C P -C V =TVα 2 /κ T , is not modified
Kinetic study on Iranian furfural extract hydrocracking
Zarkesh, J.; Akbarnejad, M. M. [NIOC Research Institute of Petroleum Industry, Tehran (Iran, Islamic Republic of); Khorasheh, F. [Sharif Univ. of Technology, Tehran (Iran, Islamic Republic of); Badakhshan, A. [Calgary Univ., AB (Canada)
1998-05-01
Upgrading heavy crude oil to light crude oil is one of the most important refining processes. Familiarity with the kinetics and related kinetic models is one of the important aspects of developing expertise in this field. This joint study between the NIOC Institute of Research of the Petroleum Industry and Sharif University was undertaken to determine the most appropriate upgrading process for Iranian heavy feed stock and to predict the conversion and product distribution in commercial hydrocracking units. The study involved the evaluation of stoichiometry of the hydrocracking process, focusing on the catalytic hydrocracking of furfural extract (a by-product of the lubricating oil plant) of the Tehran refinery. A pilot plant reactor was used. Good correspondence between model predictions and theoretical values was obtained.
Kinetics of molybdenum and chlorine interaction
Zelikman, A.N.; Nazarov, Yu.N.; Sarkarov, T.Eh.; Tulyakov, N.V.
1977-01-01
The kinetics is studied of molybdenite chlorination with gaseous chlorine. The time dependences of the depth and degree of molybdenite chlorination are given along with the dependence on chlorine concentration of molybdenite chlorination rate. Active interaction is shown to take place at 450-470 deg C. At 350-435 deg C, chlorination occurs in the kinetic range, the apparent activation energy being equal to 22.2 kcal/mole and the order of reaction by chlorine to 0.77. At 435-610 deg C, the process takes place in the diffusion range and is restricted by dissipation of the reaction products (activation energy - 4.05 kcal/mole; order of reaction by chlorine - 0.6)
Chemical kinetic functional sensitivity analysis: Elementary sensitivities
Demiralp, M.; Rabitz, H.
1981-01-01
Sensitivity analysis is considered for kinetics problems defined in the space--time domain. This extends an earlier temporal Green's function method to handle calculations of elementary functional sensitivities deltau/sub i//deltaα/sub j/ where u/sub i/ is the ith species concentration and α/sub j/ is the jth system parameter. The system parameters include rate constants, diffusion coefficients, initial conditions, boundary conditions, or any other well-defined variables in the kinetic equations. These parameters are generally considered to be functions of position and/or time. Derivation of the governing equations for the sensitivities and the Green's funciton are presented. The physical interpretation of the Green's function and sensitivities is given along with a discussion of the relation of this work to earlier research
Hypocoercivity for linear kinetic equations conserving mass
Dolbeault, Jean
2015-02-03
We develop a new method for proving hypocoercivity for a large class of linear kinetic equations with only one conservation law. Local mass conservation is assumed at the level of the collision kernel, while transport involves a confining potential, so that the solution relaxes towards a unique equilibrium state. Our goal is to evaluate in an appropriately weighted $ L^2$ norm the exponential rate of convergence to the equilibrium. The method covers various models, ranging from diffusive kinetic equations like Vlasov-Fokker-Planck equations, to scattering models or models with time relaxation collision kernels corresponding to polytropic Gibbs equilibria, including the case of the linear Boltzmann model. In this last case and in the case of Vlasov-Fokker-Planck equations, any linear or superlinear growth of the potential is allowed. - See more at: http://www.ams.org/journals/tran/2015-367-06/S0002-9947-2015-06012-7/#sthash.ChjyK6rc.dpuf
Kinetics of the chiral phase transition
Hees, Hendrik van [Johann-Wolfgang-Goethe-Universitaet Frankfurt, Institut fuer Theoretische Physik, Frankfurt (Germany); Frankfurt Institute for Advanced Studies (FIAS), Frankfurt (Germany); Wesp, Christian; Meistrenko, Alex; Greiner, Carsten [Johann-Wolfgang-Goethe-Universitaet Frankfurt, Institut fuer Theoretische Physik, Frankfurt (Germany)
2016-07-01
We simulate the kinetics of the chiral phase transition in hot and dense strongly interacting matter within a novel kinetic-theory approach. Employing an effective linear σ model for quarks, σ mesons, and pions we treat the quarks within a test-particle ansatz for solving the Boltzmann transport equation and the mesons in terms of classical fields. The decay-recombination processes like σ <-> anti q+q are treated using a kind of wave-particle dualism using the exact conservation of energy and momentum. After demonstrating the correct thermodynamic limit for particles and fields in a ''box calculation'' we apply the simulation to the dynamics of an expanding fireball similar to the medium created in ultrarelativistic heavy-ion collisions.
Global kinetic theory of astrophysical jets
Chang, T.
1989-01-01
We suggest that an astrophysical plasma stream flowing outward from a central object aling an open magnetic field line with decreasing field strength generally will have anisotropic velocity distributions. I particular, the electron distribution function of this type of plasma streams will contain a 'thermally populated' region and a stretche out high energy tail (or 'jet-like') region collimated in the utward direction of the magnetic field line. Our argument is based on a global, collisional, kinetic theory. Because the 'kinetic jets' are always pointed aling the outward direction of the field lines, thy are automatically collimated and will assume whatever the peculiar geometries dictated by the magnetic field. This result should be useful in the understanding of the basic structures of such diverse astrophysical objects as the extragalactic radio jets, stellar winds, the solar wind, planetary polar winds, and galactic jets. (author). 8 refs.; 2 figs
Thermodynamics, kinetics and process control of nitriding
Mittemeijer, Eric J.; Somers, Marcel A. J.
1999-01-01
As a prerequisite for predictability of properties obtained by a nitriding treatment of iron-based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present (even) the description of thermodynamic equilibrium...... of pure iron-nitrogen phases has not been achieved fully. It has been shown that taking into account ordering of nitrogen in the epsilon and gamma' iron-nitride phases, leads to an improved understanding of the Fe-N phase diagram. Although thermodynamics indicate the state the system strives for......, the nitriding result is determined largely by the kinetics of the process. The nitriding kinetics have been shown to be characterised by the occurring local near-equilibria and stationary states at surfaces and interfaces, and the diffusion coefficient of nitrogen in the various phases, for which new data have...
Luminescence kinetics of porous silicon: fluctuation approach
Bondarev, V N
2001-01-01
Theoretical interpretation of the kinetics of the photoluminescence (PL), caused by the tunnel radiative recombination of the photoexcited electron and hole, localized on the crystallite/matrix interface, is given on the basis of the notions on the porous silicon structure as an incidental totality of the Si nanodimensional crystallites, submerged into the SiO sub 2 matrix. The relatively slow (by the stretched exponential type) time drop in the PL intensity is the results of averaging the intensity in each PL elementary act by the electron and hole mutual disposition and by the crystallite dimensions. The good quantitative description of the low-temperature experiments may be obtained through the proposed approach both by the PL kinetics and time evolution of the porous silicon PL spectrum
Processes of aggression described by kinetic method
Aristov, V. V.; Ilyin, O. [Dorodnicyn Computing Centre of Russian Academy of Sciences, Vavilova str. 40, Moscow, 119333 (Russian Federation)
2014-12-09
In the last decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France and USSR based on the kinetic theory. We model this process with the Cauchy boundary problem for the two-element kinetic equations with spatial initial conditions. The solution of the problem is given in the form of traveling wave. The propagation velocity of a frontline depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the frontline velocities are complied with the historical data.
Kinetic modeling in PET imaging of hypoxia
Li, Fan; Joergensen, Jesper T; Hansen, Anders E; Kjaer, Andreas
2014-01-01
Tumor hypoxia is associated with increased therapeutic resistance leading to poor treatment outcome. Therefore the ability to detect and quantify intratumoral oxygenation could play an important role in future individual personalized treatment strategies. Positron Emission Tomography (PET) can be used for non-invasive mapping of tissue oxygenation in vivo and several hypoxia specific PET tracers have been developed. Evaluation of PET data in the clinic is commonly based on visual assessment together with semiquantitative measurements e.g. standard uptake value (SUV). However, dynamic PET contains additional valuable information on the temporal changes in tracer distribution. Kinetic modeling can be used to extract relevant pharmacokinetic parameters of tracer behavior in vivo that reflects relevant physiological processes. In this paper, we review the potential contribution of kinetic analysis for PET imaging of hypoxia. PMID:25250200
Reaction kinetics of bond rotations in graphene
Skowron, Stephen T.
2016-04-12
The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.
The kinetics of denitrification in permeable sediments
Evrard, Victor; Glud, Ronnie N.; Cook, Perran L. M.
2013-01-01
Permeable sediments comprise the majority of shelf sediments, yet the rates of denitrification remain highly uncertain in these environments. Computational models are increasingly being used to understand the dynamics of denitrification in permeable sediments, which are complex environments...... on sediments taken from six shallow coastal sites in Port Phillip Bay, Victoria, Australia. The results showed that denitrification commenced rapidly (within 30 min) after the onset of anoxia and the kinetics could be well described by Michaelis-Menten kinetics with half saturation constants (apparent K...... in cohesive sediments despite organic carbon contents one order of magnitude lower for the sediments studied here. The ratio of sediment O-2 consumption to V-max was in the range of 0.02-0.09, and was on average much lower than the theoretical ratio of 0.8. As a consequence, models implemented...
Relativistic charged fluids: hydrodynamic and kinetic approaches
Debbasch, F.; Bonnaud, G.
1991-10-01
This report gives a rigorous and consistent hydrodynamic and kinetic description of a charged fluid and the basis equations, in a relativistic context. This study should lead to a reliable model, as much analytical as numerical, of relativistic plasmas which will appear in the interaction of a strong laser field with a plasma. For simplicity, we limited our study to a perfect fluid or, in other words, we disregarded the energy dissipation processes inside the fluid [fr
Reduced kinetic equations: An influence functional approach
Wio, H.S.
1985-01-01
The author discusses a scheme for obtaining reduced descriptions of multivariate kinetic equations based on the 'influence functional' method of Feynmann. It is applied to the case of Fokker-Planck equations showing the form that results for the reduced equation. The possibility of Markovian or non-Markovian reduced description is discussed. As a particular example, the reduction of the Kramers equation to the Smoluchwski equation in the limit of high friction is also discussed
Chemical Kinetic Models for Advanced Engine Combustion
Pitz, William J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehl, Marco [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Westbrook, Charles K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
2014-10-22
The objectives for this project are as follows: Develop detailed chemical kinetic models for fuel components used in surrogate fuels for compression ignition (CI), homogeneous charge compression ignition (HCCI) and reactivity-controlled compression-ignition (RCCI) engines; and Combine component models into surrogate fuel models to represent real transportation fuels. Use them to model low-temperature combustion strategies in HCCI, RCCI, and CI engines that lead to low emissions and high efficiency.
Kinetic stability of internal kink mode
Romanelli, F.; Fogaccia, G.
1993-01-01
With reference to studies of the attainment of ignited operations on devices like ITER (International Thermonuclear Experimental Reactor), the stability of the internal kink mode is re-investigated by taking into account the contribution of perpendicular compressibility, obtained by solving the drift kinetic equation. The resulting stability condition yields threshold values typically larger than the conventional Bussac criterion. For the case of ultra-flat safety factor profiles, the mode can be stable also in the absence of line-bending
The Balescu kinetic equation with exchange interaction
Belyi, V V; Kukharenko, Yu A
2009-01-01
Starting with the quantum BBGKY hierarchy for the distribution functions, we have obtained the quantum kinetic equation including the dynamical screening of the interaction potential, which exactly takes into account the exchange scattering in the plasma. The collision integral is expressed in terms of the Green function of the linearized Hartree–Fock equation. The potential energy takes into account the polarization and exchange interaction too
Kinetics model development of cocoa bean fermentation
Kresnowati, M. T. A. P.; Gunawan, Agus Yodi; Muliyadini, Winny
2015-12-01
Although Indonesia is one of the biggest cocoa beans producers in the world, Indonesian cocoa beans are oftenly of low quality and thereby frequently priced low in the world market. In order to improve the quality, adequate post-harvest cocoa processing techniques are required. Fermentation is the vital stage in series of cocoa beans post harvest processing which could improve the quality of cocoa beans, in particular taste, aroma, and colours. During the fermentation process, combination of microbes grow producing metabolites that serve as the precursors for cocoa beans flavour. Microbial composition and thereby their activities will affect the fermentation performance and influence the properties of cocoa beans. The correlation could be reviewed using a kinetic model that includes unstructured microbial growth, substrate utilization and metabolic product formation. The developed kinetic model could be further used to design cocoa bean fermentation process to meet the expected quality. Further the development of kinetic model of cocoa bean fermentation also serve as a good case study of mixed culture solid state fermentation, that has rarely been studied. This paper presents the development of a kinetic model for solid-state cocoa beans fermentation using an empirical approach. Series of lab scale cocoa bean fermentations, either natural fermentations without starter addition or fermentations with mixed yeast and lactic acid bacteria starter addition, were used for model parameters estimation. The results showed that cocoa beans fermentation can be modelled mathematically and the best model included substrate utilization, microbial growth, metabolites production and its transport. Although the developed model still can not explain the dynamics in microbial population, this model can sufficiently explained the observed changes in sugar concentration as well as metabolic products in the cocoa bean pulp.
Nanostructured energy devices equilibrium concepts and kinetics
Bisquert, Juan
2014-01-01
Due to the pressing needs of society, low cost materials for energy devices have experienced an outstanding development in recent times. In this highly multidisciplinary area, chemistry, material science, physics, and electrochemistry meet to develop new materials and devices that perform required energy conversion and storage processes with high efficiency, adequate capabilities for required applications, and low production cost. Nanostructured Energy Devices: Equilibrium Concepts and Kinetics introduces the main physicochemical principles that govern the operation of energy devices. It inclu
Kinetics of catalytic reactions solutions manual
Vannice, M Albert
2005-01-01
Including countless exercises and worked examples, this advanced reference work and textbook will be extremely useful for the work of many industrial scientists. It teaches readers to design kinetic experiments involving heterogeneous catalysts, to characterize these catalysts, to acquire rate data, to find heat and mass transfer limitations in these data, to select reaction models, to derive rate expressions based on these models, and to assess the consistency of these rate equations.
Uncertainty quantification for hyperbolic and kinetic equations
Pareschi, Lorenzo
2017-01-01
This book explores recent advances in uncertainty quantification for hyperbolic, kinetic, and related problems. The contributions address a range of different aspects, including: polynomial chaos expansions, perturbation methods, multi-level Monte Carlo methods, importance sampling, and moment methods. The interest in these topics is rapidly growing, as their applications have now expanded to many areas in engineering, physics, biology and the social sciences. Accordingly, the book provides the scientific community with a topical overview of the latest research efforts.
Phenylalanine kinetics in human adipose tissue.
Coppack, S W; Persson, M; Miles, J M
1996-01-01
Very little is known about the regulation of protein metabolism in adipose tissue. In this study systemic, adipose tissue, and forearm phenylalanine kinetics were determined in healthy postabsorptive volunteers before and during a 2-h glucose infusion (7 mg.kg-1.min-1). [3H]Phenylalanine was infused and blood was sampled from a radial artery, a subcutaneous abdominal vein, and a deep forearm vein. Adipose tissue and forearm blood flow were measured with 133Xe and plethysmography, respectively...
An Inversion Recovery NMR Kinetics Experiment
Williams, Travis J.; Kershaw, Allan D.; Li, Vincent; Wu, Xinping
2011-01-01
A convenient laboratory experiment is described in which NMR magnetization transfer by inversion recovery is used to measure the kinetics and thermochemistry of amide bond rotation. The experiment utilizes Varian spectrometers with the VNMRJ 2.3 software, but can be easily adapted to any NMR platform. The procedures and sample data sets in this article will enable instructors to use inversion recovery as a laboratory activity in applied NMR classes and provide research students with a conveni...
Thallium kinetics in rat cardiac transplant rejection
Barak, J.H.; LaRaia, P.J.; Boucher, C.A.; Fallon, J.T.; Buckley, M.J.
1988-01-01
Cardiac transplant rejection is a very complex process involving both cellular and vascular injury. Recently, thallium imaging has been used to assess acute transplant rejection. It has been suggested that changes in thallium kinetics might be a sensitive indicator of transplant rejection. Accordingly, thallium kinetics were assessed in vivo in acute untreated rat heterotopic (cervical) transplant rejection. Male Lewis rats weighing 225-250 g received heterotopic heart transplants from syngeneic Lewis rats (group A; n = 13), or allogeneic Brown Norway rats (group B; n = 11). Rats were imaged serially on the 2nd and the 7th postoperative days. Serial cardiac thallium content was determined utilizing data collected every 150 sec for 2 hr. The data were fit to a monoexponential curve and the decay rate constant (/sec) derived. By day 7 all group B hearts had histological evidence of severe acute rejection, and demonstrated decreased global contraction. Group A hearts showed normal histology and contractility. However, thallium uptakes and washout of the two groups were the same. Peak thallium uptake of group B was +/- 3758 1166 counts compared with 3553 +/- 950 counts in the control group A (P = 0.6395); The 2-hr percentage of washout was 12.1 +/- 1.04 compared with 12.1 +/- 9.3 (P = 1.0000); and the decay constant was -0.00002065 +/- 0.00001799 compared with -0.00002202 +/- 0.00001508 (P = 0.8409). These data indicate that in vivo global thallium kinetics are preserved during mild-to-severe acute transplant rejection. These findings suggest that the complex cellular and extracellular processes of acute rejection limit the usefulness of thallium kinetics in the detection of acute transplant rejection
Kinetic catalytic studies of scorpion's hemocyanin
Queinnec, E.; Vuillaume, M.; Gardes-Albert, M.; Ferradini, C.; Ducancel, F.
1991-01-01
Hemocyanins are copper proteins which function as oxygen carriers in the haemolymph of Molluscs and Arthropods. They possess enzymatic properties: peroxidatic and catalatic activities, although they have neither iron nor porphyrin ring at the active site. The kinetics of the catalytic reaction is described. The reaction of superoxide anion with hemocyanin has been studied using pulse radiolysis at pH 9. The catalytic rate constant is 3.5 X 10 7 mol -1 .l.s -1 [fr
Epinephrine kinetics in humans: Radiotracer methodology
Rosen, S.G.; Linares, O.A.; Sanfield, J.A.; Zech, L.A.; Lizzio, V.P.; Halter, J.B.
1989-01-01
The use of the plasma epinephrine (EPI) level as an index of adrenomedullary activity in humans is complicated by the rapid removal of EPI from plasma by many tissues. To determine whether the kinetics of distribution and metabolism of EPI could be best quantified using the isotope dilution method or a mathematical modeling technique, eight human subjects received a [ 3 H]EPI infusion for 50-60 min. Analysis of the steady state arterialized plasma levels of EPI and [ 3 H]EPI using the isotope dilution technique showed that the basal plasma EPI appearance rate is 0.87 ± 0.11 nmol/m2.min, and the basal plasma EPI clearance rate is 1.63 ± 0.14 L/min.m2. Mathematical modeling of the [ 3 H]EPI levels revealed that a biexponential curve fit was superior to monoexponential and triexponential curve fits. A two-compartment model was the minimal compartment model that accurately described EPI kinetics. The basal plasma EPI appearance (0.82 ± 0.16 nmol/m2.min) and EPI clearance (1.67 ± 0.15 L/min.m2) rates that were estimated from this two-compartment model are similar to the results derived from the isotope dilution method. Mathematical modeling revealed a large extravascular mass of EPI. We conclude that the isotope dilution and mathematical modeling techniques similarly describe plasma EPI kinetics in humans. Kinetic analysis using mathematical modeling provides new insights into adrenomedullary function in humans
Kinetics of enzymatic hydrolysis of methyl ricinoleate
Neeharika, T. S.V.R.; Lokesh, P.; Prasanna Rani, K. N.; Prathap Kumar, T.; Prasad, R. B.N.
2015-01-01
Ricinoleic acid is an unsaturated hydroxy fatty acid that naturally occurs in castor oil in proportions of up to 85–90%. Ricinoleic acid is a potential raw material and finds several applications in coatings, lubricant formulations and pharmaceutical areas. Enzymatic hydrolysis of castor oil is preferred over conventional hydrolysis for the preparation of ricinoleic acid to avoid estolide formation. A kinetics analysis of the enzymatic hydrolysis of Methyl Ricinoleate in the presence of Candi...
Kinetics of strontium sorption in calcium phosphate
Bacic, S.; Komarov, V.F.; Vukovic, Z.
1989-01-01
Kinetics of strontium sorption by highly dispersed solids: tricalcium phosphate (Ca 3 (PO 4 ) 2 , TCP) and hydroxyapatite (Ca 5 (PO 4 ) 3 )H, HAP) were investigated. Analysis of sorption data was made taking into consideration composition and morphology of ultra micro particles. Conclusion is that the isomorphous strontium impurity is structurally sensitive element for calcium phosphate. It was determined that the beginning of strontium desorption corresponds to the beginning of transformation of the TCP - HAP (author)
A stochastic model of enzyme kinetics
Stefanini, Marianne; Newman, Timothy; McKane, Alan
2003-10-01
Enzyme kinetics is generally modeled by deterministic rate equations, and in the simplest case leads to the well-known Michaelis-Menten equation. It is plausible that stochastic effects will play an important role at low enzyme concentrations. We have addressed this by constructing a simple stochastic model which can be exactly solved in the steady-state. Throughout a wide range of parameter values Michaelis-Menten dynamics is replaced by a new and simple theoretical result.
Kinetic simulation on collisional bounded plasma
Zhu, S.P.; Sato, Tetsuya; Tomita, Yukihiro; Hatori, Tadatsugu
1998-01-01
A self-consistent kinetic simulation model on collisional bounded plasma is presented. The electric field is given by solving Poisson equation and collisions among particles (including charged particles and neutral particles) are included. The excitation and ionization of neutral particle, and recombination are also contained in the present model. The formation of potential structure near a boundary for a discharge system was used as an application of this model. (author)
Kinetics of the subtransition in dipalmitoylphosphatidylcholine
Tristram-Nagle, S.; Wiener, M.C.; Yang, C.P.; Nagle, J.F.
1987-01-01
The kinetics of the interconversions of the subgel and gel phases in dipalmitoylphosphatidylcholine have been studied by using differential dilatometry, differential scanning calorimetry (DSC), and neutral buoyancy centrifugation as a function of incubation temperature and deuteriation of the solvent. As seen by others, DSC scans show two peaks in the subgel transition region for incubation temperatures below 1 0 C. After incubation at 0.1 0 C, the DSC peak that occurs at the lower scanning temperature appears with an incubation half-time of 0.5 day and eventually converts into a peak at higher scanning temperature with an incubation half-time of 18 days. By varying the scanning rate, the authors show that these two peaks merge into one at slow scanning rates with a common equilibrium transition temperature of 13.8 0 C, in agreement with equilibrium calorimetry and dilatometry. For incubation temperatures above 4.6 0 C, only one peak appears in both scanning dilatometry and calorimetry. While the initial rate of subgel conversion is smaller at the higher incubation temperatures, after 300 h a higher percentage of the sample has converted to subgel than at the lower incubation temperatures. They suggest that higher incubation temperatures (near 5 0 C) are preferable for forming the stable subgel phase, and they present a colliding domain picture that indicates why this may be so. The results in D 2 O and the similarity of the kinetics of volume decrease with the kinetics of wide-angle diffraction lines also support the suggestion that the partial loss of interlamellar water plays a kinetic role in subgel formation
Kinetics of the subtransition in dipalmitoylphosphatidylcholine.
Tristram-Nagle, S; Wiener, M C; Yang, C P; Nagle, J F
1987-07-14
The kinetics of the interconversions of the subgel and gel phases in dipalmitoylphosphatidylcholine have been studied by using differential dilatometry, differential scanning calorimetry (DSC), and neutral buoyancy centrifugation as a function of incubation temperature and deuteriation of the solvent. As seen by others, DSC scans show two peaks in the subgel transition region for incubation temperatures below 1 degree C. After incubation at 0.1 degree C, the DSC peak that occurs at the lower scanning temperature appears with an incubation half-time of 0.5 day and eventually converts into a peak at higher scanning temperature with an incubation half-time of 18 days. By varying the scanning rate, we show that these two peaks merge into one at slow scanning rates with a common equilibrium transition temperature of 13.8 degrees C, in agreement with equilibrium calorimetry and dilatometry (delta V = 0.017 +/- 0.001 mL/g). For incubation temperatures above 4.6 degrees C, only one peak appears in both scanning dilatometry and calorimetry. While the initial rate of subgel conversion is smaller at the higher incubation temperatures, after 300 h a higher percentage of the sample has converted to subgel than at the lower incubation temperatures. We suggest that higher incubation temperatures (near 5 degrees C) are preferable for forming the stable subgel phase, and we present a colliding domain picture that indicates why this may be so. Our results in D2O and the similarity of the kinetics of volume decrease with the kinetics of wide-angle diffraction lines also support the suggestion that the partial loss of interlamellar water plays a kinetic role in subgel formation.
A kinetic model for chemical neurotransmission
Ramirez-Santiago, Guillermo; Martinez-Valencia, Alejandro; Fernandez de Miguel, Francisco
Recent experimental observations in presynaptic terminals at the neuromuscular junction indicate that there are stereotyped patterns of cooperativeness in the fusion of adjacent vesicles. That is, a vesicle in hemifusion process appears on the side of a fused vesicle and which is followed by another vesicle in a priming state while the next one is in a docking state. In this talk we present a kinetic model for this morphological pattern in which each vesicle state previous to the exocytosis is represented by a kinetic state. This chain states kinetic model can be analyzed by means of a Master equation whose solution is simulated with the stochastic Gillespie algorithm. With this approach we have reproduced the responses to the basal release in the absence of stimulation evoked by the electrical activity and the phenomena of facilitation and depression of neuromuscular synapses. This model offers new perspectives to understand the underlying phenomena in chemical neurotransmission based on molecular interactions that result in the cooperativity between vesicles during neurotransmitter release. DGAPA Grants IN118410 and IN200914 and Conacyt Grant 130031.
Fast kinetics of calcium dissociation from calsequestrin
MARIANELA BELTRÁN
2006-01-01
Full Text Available We measured the kinetics of calcium dissociation from calsequestrin in solution or forming part of isolated junctional sarcoplasmic reticulum membranes by mixing calsequestrin equilibrated with calcium with calcium-free solutions in a stopped-flow system. In parallel, we measured the kinetics of the intrinsic fluorescence changes that take place following calcium dissociation from calsequestrin. We found that at 25ºC calcium dissociation was 10-fold faster for calsequestrin attached to junctional membranes (k = 109 s-1 than in solution. These results imply that calcium dissociation from calsequestrin in vivo is not rate limiting during excitation-contraction coupling. In addition, we found that the intrinsic fluorescence decrease for calsequestrin in solution or forming part of junctional membranes was significantly slower than the rates of calcium dissociation. The kinetics of intrinsic fluorescence changes had two components for calsequestrin associated to junctional membranes and only one for calsequestrin in solution; the faster component was 8-fold faster (k = 54.1 s-1 than the slower component (k = 6.9 s-1, which had the same k value as for calsequestrin in solution. These combined results suggest that the presence of calsequestrin at high concentrations in a restricted space, such as when bound to the junctional membrane, accelerates calcium dissociation and the resulting structural changes, presumably as a result of cooperative molecular interactions.
Cell cycle kinetics and radiation therapy
Mendelsohn, M.L.
1975-01-01
Radiation therapy as currently practiced involves the subtle largely empirical art of balancing the recurrence of cancer due to undertreatment against severe damage to local tissues due to overtreatment. Therapeutic results too often fall short of desired success rates; yet, the therapist is continually tantalized to the likelihood that a slight shift of therapeutic ratio favoring normal tissue over cancer would have a profoundly beneficial effect. The application of cell cycle kinetics to radiation therapy is one hope for improving the therapeutic ratio; but, as I will try to show, kinetic approaches are complex, poorly understood, and presently too elusive to elicit confidence or to be used clinically. Their promise lies in their diversity and in the magnitude of our ignorance about how they work and how they should be used. Potentially useful kinetic approaches to therapy can be grouped into three classes. The first class takes advantage of intracyclic differential sensitivity, an effect involving the metabolism and biology of the cell cycle; its strategies are based on synchronization of cells over intervals of hours to days. The second class involves the distinction between cycling and noncycling cells; its strategies are based on the resistance of noncycling cells to cycle-linked radiation sensitizers and chemotherapeutic agents. The third class uses cell repopulation between fractions; its strategies are based on the relative growth rates of tumor and relevant normal tissue before and after perturbation
Imperfect dark energy from kinetic gravity braiding
Deffayet, Cédric [AstroParticule and Cosmologie, UMR7164-CNRS, Université Denis Diderot-Paris 7, CEA, Observatoire de Paris, 10 rue Alice Domon et Léonie Duquet, F-75205 Paris Cedex 13 (France); Pujolàs, Oriol [CERN, Theory Division, CH-1211 Geneva 23 (Switzerland); Sawicki, Ignacy; Vikman, Alexander, E-mail: deffayet@iap.fr, E-mail: oriol.pujolas@cern.ch, E-mail: ignacy.sawicki@nyu.edu, E-mail: alexander.vikman@nyu.edu [Center for Cosmology and Particle Physics, New York University, New York, NY 10003 (United States)
2010-10-01
We introduce a large class of scalar-tensor models with interactions containing the second derivatives of the scalar field but not leading to additional degrees of freedom. These models exhibit peculiar features, such as an essential mixing of scalar and tensor kinetic terms, which we have named kinetic braiding. This braiding causes the scalar stress tensor to deviate from the perfect-fluid form. Cosmology in these models possesses a rich phenomenology, even in the limit where the scalar is an exact Goldstone boson. Generically, there are attractor solutions where the scalar monitors the behaviour of external matter. Because of the kinetic braiding, the position of the attractor depends both on the form of the Lagrangian and on the external energy density. The late-time asymptotic of these cosmologies is a de Sitter state. The scalar can exhibit phantom behaviour and is able to cross the phantom divide with neither ghosts nor gradient instabilities. These features provide a new class of models for Dark Energy. As an example, we study in detail a simple one-parameter model. The possible observational signatures of this model include a sizeable Early Dark Energy and a specific equation of state evolving into the final de-Sitter state from a healthy phantom regime.
Imperfect dark energy from kinetic gravity braiding
Deffayet, Cédric; Pujolàs, Oriol; Sawicki, Ignacy; Vikman, Alexander
2010-01-01
We introduce a large class of scalar-tensor models with interactions containing the second derivatives of the scalar field but not leading to additional degrees of freedom. These models exhibit peculiar features, such as an essential mixing of scalar and tensor kinetic terms, which we have named kinetic braiding. This braiding causes the scalar stress tensor to deviate from the perfect-fluid form. Cosmology in these models possesses a rich phenomenology, even in the limit where the scalar is an exact Goldstone boson. Generically, there are attractor solutions where the scalar monitors the behaviour of external matter. Because of the kinetic braiding, the position of the attractor depends both on the form of the Lagrangian and on the external energy density. The late-time asymptotic of these cosmologies is a de Sitter state. The scalar can exhibit phantom behaviour and is able to cross the phantom divide with neither ghosts nor gradient instabilities. These features provide a new class of models for Dark Energy. As an example, we study in detail a simple one-parameter model. The possible observational signatures of this model include a sizeable Early Dark Energy and a specific equation of state evolving into the final de-Sitter state from a healthy phantom regime
Imperfect Dark Energy from Kinetic Gravity Braiding
Deffayet, Cedric; Sawicki, Ignacy; Vikman, Alexander
2010-01-01
We introduce a large class of scalar-tensor models with interactions containing the second derivatives of the scalar field but not leading to additional degrees of freedom. These models exhibit peculiar features, such as an essential mixing of scalar and tensor kinetic terms, which we have named kinetic braiding. This braiding causes the scalar stress tensor to deviate from the perfect-fluid form. Cosmology in these models possesses a rich phenomenology, even in the limit where the scalar is an exact Goldstone boson. Generically, there are attractor solutions where the scalar monitors the behaviour of external matter. Because of the kinetic braiding, the position of the attractor depends both on the form of the Lagrangian and on the external energy density. The late-time asymptotic of these cosmologies is a de Sitter state. The scalar can exhibit phantom behaviour and is able to cross the phantom divide with neither ghosts nor gradient instabilities. These features provide a new class of models for Dark Energ...
Kinetics of saccharose fermentation by Kombucha
Lončar Eva S.
2014-01-01
Full Text Available Kinetics of saccharose fermentation by Kombucha is not yet well defined due to lack of knowledge of reaction mechanisms taking place during this process. In this research kinetics of saccharose fermentation by Kombucha was analysed using the suggested empirical model. The data were obtained on 1.5 g L-1 of black tea, with 66.47 g L-1 of saccharose and using 10% (v/v or 15% (v/v of Kombucha. Total number of viable cells was as follows: approximately 5x105 of yeast cells per mL of the inoculum and approximately 2x106 of bacteria cells per mL of the inoculum. The samples were analysed after 0, 3, 4, 5, 6, 7 and 10 days. Their pH values and contents of saccharose, glucose, fructose, total acids and ethanol were determined. A saccharose concentration model was defined as sigmoidal function at 22oC and 30oC, and with 10% (v/v and 15% (v/v of inoculum quantity. Determination coefficients of the functions were very high (R2>0.99. Reaction rates were calculated as first derivatives of Boltzmann’s functions. No simple correlation between rate of reaction and independent variables (temperature and inoculum concentration was found. Analysis of empirical model indicated that saccharose fermentation by Kombucha occurred according to very complex kinetics. [Projekat Ministarstva nauke Republike Srbije, br. III 46009
Carbochlorination kinetics of tantalum and niobium pentoxides
Allain, E.; Gaballah, I.; Garcia, F.; Ferreira, S.; Ayala, J. N.; Hernandez, A.
1999-01-01
The carbochlorination kinetics of pure Nb 2 O 5 and Ta 2 O 5 by gas mixture (CL 2 +CO+N 2 ) between 380 and 1,000 degree centigree is studied. A calculation of the standard free energy of the carbochlorination reactions is made. A diagram of the phases stability is drawn. The influence of the gas flow, temperature and the partial pressure of Cl 2 and Co at temperatures below 650 degree centigree on the reaction rate is studied. The apparent activation energy is approximately 75 and 110 kJ/mol for Nb 2 O 5 and Ta 2 O 5 , respectively. At temperatures above 650 degree centigree the Arrhenius diagram presents and anomaly which may be attributed to the decomposition of the COCL 2 formed in situ. The apparent reaction order of the carbochlorination of these oxides against Cl 2 +CO is approximately 2. The carbochlorination rates of these oxides are much greater than those of chlorination by Cl 2 +N 2 . The carbochlorination kinetics of tin furnace slag leaching concentrates containing tantalum and niobium compounds are also studied and compared with the carbochlorination kinetics of the pure oxides. (Author) 14 refs
Kinetic mechanism of DNA polymerase I (Klenow)
Kuchta, R.D.; Mizrahi, V.; Benkovic, P.A.; Johnson, K.A.; Benkovic, S.J.
1987-01-01
The minimal kinetic scheme for DNA polymerization catalyzed by the Klenow fragment of DNA polymerase I (KF) from Escherichia coli has been determined with short DNA oligomers of defined sequence, labeled with [ 32 P]-nucleotides. A key feature of this scheme is a minimal two-step sequence that interconverts the ternary KF-DNA/sub n/-dNTP and KF-DNA/sub n+1/-PP/sub i/ complexes. The rate is not limited by the actual polymerization but by a separate step, possibly important in ensuring fidelity. Evidence for this sequence is supplied by the observation of biphasic kinetics in single-turnover pyrophosphorolysis experiments (the microscopic reverse of polymerization). Data analysis then provides an estimate of the internal equilibrium constant. The dissociations of DNA, dNTP, and PP/sub i/ from the various binary and ternary complexes were measured by partitioning (isotope-trapping) experiments. The rate constant for DNA dissociation from KF is sequence dependent and is rate limiting during nonprocessive DNA synthesis. The combination of single-turnover (both directions) and isotope-trapping experiments provides sufficient information to permit a quantitative evaluation of the kinetic scheme for specific DNA sequences
Chemical kinetics and modeling of planetary atmospheres
Yung, Yuk L.
1990-01-01
A unified overview is presented for chemical kinetics and chemical modeling in planetary atmospheres. The recent major advances in the understanding of the chemistry of the terrestrial atmosphere make the study of planets more interesting and relevant. A deeper understanding suggests that the important chemical cycles have a universal character that connects the different planets and ultimately link together the origin and evolution of the solar system. The completeness (or incompleteness) of the data base for chemical kinetics in planetary atmospheres will always be judged by comparison with that for the terrestrial atmosphere. In the latter case, the chemistry of H, O, N, and Cl species is well understood. S chemistry is poorly understood. In the atmospheres of Jovian planets and Titan, the C-H chemistry of simple species (containing 2 or less C atoms) is fairly well understood. The chemistry of higher hydrocarbons and the C-N, P-N chemistry is much less understood. In the atmosphere of Venus, the dominant chemistry is that of chlorine and sulfur, and very little is known about C1-S coupled chemistry. A new frontier for chemical kinetics both in the Earth and planetary atmospheres is the study of heterogeneous reactions. The formation of the ozone hole on Earth, the ubiquitous photochemical haze on Venus and in the Jovian planets and Titan all testify to the importance of heterogeneous reactions. It remains a challenge to connect the gas phase chemistry to the production of aerosols.
Drainage and Stratification Kinetics of Foam Films
Zhang, Yiran; Sharma, Vivek
2014-03-01
Baking bread, brewing cappuccino, pouring beer, washing dishes, shaving, shampooing, whipping eggs and blowing bubbles all involve creation of aqueous foam films. Foam lifetime, drainage kinetics and stability are strongly influenced by surfactant type (ionic vs non-ionic), and added proteins, particles or polymers modify typical responses. The rate at which fluid drains out from a foam film, i.e. drainage kinetics, is determined in the last stages primarily by molecular interactions and capillarity. Interestingly, for certain low molecular weight surfactants, colloids and polyelectrolyte-surfactant mixtures, a layered ordering of molecules, micelles or particles inside the foam films leads to a stepwise thinning phenomena called stratification. Though stratification is observed in many confined systems including foam films containing particles or polyelectrolytes, films containing globular proteins seem not to show this behavior. Using a Scheludko-type cell, we experimentally study the drainage and stratification kinetics of horizontal foam films formed by protein-surfactant mixtures, and carefully determine how the presence of proteins influences the hydrodynamics and thermodynamics of foam films.
MODELING STYRENE HYDROGENATION KINETICS USING PALLADIUM CATALYSTS
G. T. Justino
Full Text Available Abstract The high octane number of pyrolysis gasoline (PYGAS explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.
Measuring kinetic drivers of pneumolysin pore structure.
Gilbert, Robert J C; Sonnen, Andreas F-P
2016-05-01
Most membrane attack complex-perforin/cholesterol-dependent cytolysin (MACPF/CDC) proteins are thought to form pores in target membranes by assembling into pre-pore oligomers before undergoing a pre-pore to pore transition. Assembly during pore formation is into both full rings of subunits and incomplete rings (arcs). The balance between arcs and full rings is determined by a mechanism dependent on protein concentration in which arc pores arise due to kinetic trapping of the pre-pore forms by the depletion of free protein subunits during oligomerization. Here we describe the use of a kinetic assay to study pore formation in red blood cells by the MACPF/CDC pneumolysin from Streptococcus pneumoniae. We show that cell lysis displays two kinds of dependence on protein concentration. At lower concentrations, it is dependent on the pre-pore to pore transition of arc oligomers, which we show to be a cooperative process. At higher concentrations, it is dependent on the amount of pneumolysin bound to the membrane and reflects the affinity of the protein for its receptor, cholesterol. A lag occurs before cell lysis begins; this is dependent on oligomerization of pneumolysin. Kinetic dissection of cell lysis by pneumolysin demonstrates the capacity of MACPF/CDCs to generate pore-forming oligomeric structures of variable size with, most likely, different functional roles in biology.
Kinetics and hybrid kinetic-fluid models for nonequilibrium gas and plasmas
Crouseilles, N.
2004-12-01
For a few decades, the application of the physics of plasmas has appeared in different fields like laser-matter interaction, astrophysics or thermonuclear fusion. In this thesis, we are interested in the modeling and the numerical study of nonequilibrium gas and plasmas. To describe such systems, two ways are usually used: the fluid description and the kinetic description. When we study a nonequilibrium system, fluid models are not sufficient and a kinetic description have to be used. However, solving a kinetic model requires the discretization of a large number of variables, which is quite expensive from a numerical point of view. The aim of this work is to propose a hybrid kinetic-fluid model thanks to a domain decomposition method in the velocity space. The derivation of the hybrid model is done in two different contexts: the rarefied gas context and the more complicated plasmas context. The derivation partly relies on Levermore's entropy minimization approach. The so-obtained model is then discretized and validated on various numerical test cases. In a second stage, a numerical study of a fully kinetic model is presented. A collisional plasma constituted of electrons and ions is considered through the Vlasov-Poisson-Fokker-Planck-Landau equation. Then, a numerical scheme which preserves total mass and total energy is presented. This discretization permits in particular a numerical study of the Landau damping. (author)
Vlasov simulations of kinetic Alfvén waves at proton kinetic scales
Vásconez, C. L. [Dipartimento di Fisica, Università della Calabria, I-87036 Cosenza (Italy); Observatorio Astronómico de Quito, Escuela Politécnica Nacional, Quito (Ecuador); Valentini, F.; Veltri, P. [Dipartimento di Fisica, Università della Calabria, I-87036 Cosenza (Italy); Camporeale, E. [Centrum Wiskunde and Informatica, Amsterdam (Netherlands)
2014-11-15
Kinetic Alfvén waves represent an important subject in space plasma physics, since they are thought to play a crucial role in the development of the turbulent energy cascade in the solar wind plasma at short wavelengths (of the order of the proton gyro radius ρ{sub p} and/or inertial length d{sub p} and beyond). A full understanding of the physical mechanisms which govern the kinetic plasma dynamics at these scales can provide important clues on the problem of the turbulent dissipation and heating in collisionless systems. In this paper, hybrid Vlasov-Maxwell simulations are employed to analyze in detail the features of the kinetic Alfvén waves at proton kinetic scales, in typical conditions of the solar wind environment (proton plasma beta β{sub p} = 1). In particular, linear and nonlinear regimes of propagation of these fluctuations have been investigated in a single-wave situation, focusing on the physical processes of collisionless Landau damping and wave-particle resonant interaction. Interestingly, since for wavelengths close to d{sub p} and β{sub p} ≃ 1 (for which ρ{sub p} ≃ d{sub p}) the kinetic Alfvén waves have small phase speed compared to the proton thermal velocity, wave-particle interaction processes produce significant deformations in the core of the particle velocity distribution, appearing as phase space vortices and resulting in flat-top velocity profiles. Moreover, as the Eulerian hybrid Vlasov-Maxwell algorithm allows for a clean almost noise-free description of the velocity space, three-dimensional plots of the proton velocity distribution help to emphasize how the plasma departs from the Maxwellian configuration of thermodynamic equilibrium due to nonlinear kinetic effects.
Energy Conservation Tests of a Coupled Kinetic-kinetic Plasma-neutral Transport Code
Stotler, D. P.; Chang, C. S.; Ku, S. H.; Lang, J.; Park, G.
2012-08-29
A Monte Carlo neutral transport routine, based on DEGAS2, has been coupled to the guiding center ion-electron-neutral neoclassical PIC code XGC0 to provide a realistic treatment of neutral atoms and molecules in the tokamak edge plasma. The DEGAS2 routine allows detailed atomic physics and plasma-material interaction processes to be incorporated into these simulations. The spatial pro le of the neutral particle source used in the DEGAS2 routine is determined from the uxes of XGC0 ions to the material surfaces. The kinetic-kinetic plasma-neutral transport capability is demonstrated with example pedestal fueling simulations.
A critical look at the kinetic models of thermoluminescence-II. Non-first order kinetics
Sunta, C M; Ayta, W E F; Chubaci, J F D; Watanabe, S
2005-01-01
Non-first order (FO) kinetics models are of three types; second order (SO), general order (GO) and mixed order (MO). It is shown that all three of these have constraints in their energy level schemes and their applicable parameter values. In nature such restrictions are not expected to exist. The thermoluminescence (TL) glow peaks produced by these models shift their position and change their shape as the trap occupancies change. Such characteristics are very unlike those found in samples of real materials. In these models, in general, retrapping predominates over recombination. It is shown that the quasi-equilibrium (QE) assumption implied in the derivation of the TL equation of these models is quite valid, thus disproving earlier workers' conclusion that QE cannot be held under retrapping dominant conditions. However notwithstanding their validity, they suffer from the shortcomings as stated above and have certain lacunae. For example, the kinetic order (KO) parameter and the pre-exponential factor which are assumed to be the constant parameters of the GO kinetics expression turn out to be variables when this expression is applied to plausible physical models. Further, in glow peak characterization using the GO expression, the quality of fit is found to deteriorate when the best fitted value of KO parameter is different from 1 and 2. This means that the found value of the basic parameter, namely the activation energy, becomes subject to error. In the MO kinetics model, the value of the KO parameter α would change with dose, and thus in this model also, as in the GO model, no single value of KO can be assigned to a given glow peak. The paper discusses TL of real materials having characteristics typically like those of FO kinetics. Theoretically too, a plausible physical model of TL emission produces glow peaks which have characteristics of FO kinetics under a wide variety of parametric combinations. In the background of the above findings, it is suggested that
Jegou, Ch.; Gin, St.; Advocat, Th.; Vernaz, E.
1997-01-01
Work carried out since the early 1980's to predict the long-term behavior of nuclear containment glasses has revealed the inadequacy of existing models, notably in accounting for the fundamental mechanisms involved in some complex systems (e.g. glass-water-clay), inciting us to examine and discuss the theoretical basis for the hypotheses generally assumed in our models. This paper discusses the theoretical basis for the Aagaard-Helgeson law and its application to nuclear glasses. The contribution of other types of kinetic laws is also considered to describe the alteration kinetics of nuclear glasses. (authors)
Biodegradation kinetics for pesticide exposure assessment.
Wolt, J D; Nelson, H P; Cleveland, C B; van Wesenbeeck, I J
2001-01-01
Understanding pesticide risks requires characterizing pesticide exposure within the environment in a manner that can be broadly generalized across widely varied conditions of use. The coupled processes of sorption and soil degradation are especially important for understanding the potential environmental exposure of pesticides. The data obtained from degradation studies are inherently variable and, when limited in extent, lend uncertainty to exposure characterization and risk assessment. Pesticide decline in soils reflects dynamically coupled processes of sorption and degradation that add complexity to the treatment of soil biodegradation data from a kinetic perspective. Additional complexity arises from study design limitations that may not fully account for the decline in microbial activity of test systems, or that may be inadequate for considerations of all potential dissipation routes for a given pesticide. Accordingly, kinetic treatment of data must accommodate a variety of differing approaches starting with very simple assumptions as to reaction dynamics and extending to more involved treatments if warranted by the available experimental data. Selection of the appropriate kinetic model to describe pesticide degradation should rely on statistical evaluation of the data fit to ensure that the models used are not overparameterized. Recognizing the effects of experimental conditions and methods for kinetic treatment of degradation data is critical for making appropriate comparisons among pesticide biodegradation data sets. Assessment of variability in soil half-life among soils is uncertain because for many pesticides the data on soil degradation rate are limited to one or two soils. Reasonable upper-bound estimates of soil half-life are necessary in risk assessment so that estimated environmental concentrations can be developed from exposure models. Thus, an understanding of the variable and uncertain distribution of soil half-lives in the environment is
Keizer, K.; Batist, P.A.; Schuit, G.C.A.
1969-01-01
The kinetics of oxidn. of 1-butene with O on three types of bismuth molybdate catalysts were investigated in pulse expts. For all the catalysts mentioned the kinetics can be expressed by a first-order dependency on the butene pressure and a zero-order dependency on the O pressure. A slight deviation
Quantifying human vitamin kinetics using AMS
Hillegonds, D; Dueker, S; Ognibene, T; Buchholz, B; Lin, Y; Vogel, J; Clifford, A
2004-02-19
Tracing vitamin kinetics at physiologic concentrations has been hampered by a lack of quantitative sensitivity for chemically equivalent tracers that could be used safely in healthy people. Instead, elderly or ill volunteers were sought for studies involving pharmacologic doses with radioisotopic labels. These studies fail to be relevant in two ways: vitamins are inherently micronutrients, whose biochemical paths are saturated and distorted by pharmacological doses; and while vitamins remain important for health in the elderly or ill, their greatest effects may be in preventing slow and cumulative diseases by proper consumption throughout youth and adulthood. Neither the target dose nor the target population are available for nutrient metabolic studies through decay counting of radioisotopes at high levels. Stable isotopic labels are quantified by isotope ratio mass spectrometry at levels that trace physiologic vitamin doses, but the natural background of stable isotopes severely limits the time span over which the tracer is distinguishable. Indeed, study periods seldom ranged over a single biological mean life of the labeled nutrients, failing to provide data on the important final elimination phase of the compound. Kinetic data for the absorption phase is similarly rare in micronutrient research because the phase is rapid, requiring many consecutive plasma samples for accurate representation. However, repeated blood samples of sufficient volume for precise stable or radio-isotope quantitations consume an indefensible amount of the volunteer's blood over a short period. Thus, vitamin pharmacokinetics in humans has often relied on compartmental modeling based upon assumptions and tested only for the short period of maximal blood circulation, a period that poorly reflects absorption or final elimination kinetics except for the most simple models.
Kinetics of niobium carbide precipitation in ferrite
Gendt, D.
2001-01-01
The aim of this study is to develop a NbC precipitation modelling in ferrite. This theoretical study is motivated by the fact it considers a ternary system and focus on the concurrence of two different diffusion mechanisms. An experimental study with TEP, SANS and Vickers micro-hardening measurements allows a description of the NbC precipitation kinetics. The mean radius of the precipitates is characterized by TEM observations. To focus on the nucleation stage, we use the Tomographic Atom Probe that analyses, at an atomistic scale, the position of the solute atoms in the matrix. A first model based on the classical nucleation theory and the diffusion-limited growth describes the precipitation of spherical precipitates. To solve the set of equations, we use a numerical algorithm that furnishes an evaluation of the precipitated fraction, the mean radius and the whole size distribution of the particles. The parameters that are the interface energy, the solubility product and the diffusion coefficients are fitted with the data available in the literature and our experimental results. It allows a satisfactory agreement as regards to the simplicity of the model. Monte Carlo simulations are used to describe the evolution of a ternary alloy Fe-Nb-C on a cubic centred rigid lattice with vacancy and interstitial mechanisms. This is realized with an atomistic description of the atoms jumps and their related frequencies. The model parameters are fitted with phase diagrams and diffusion coefficients. For the sake of simplicity, we consider that the precipitation of NbC is totally coherent and we neglect any elastic strain effect. We can observe different kinetic paths: for low supersaturations, we find an expected precipitation of NbC but for higher supersaturations, the very fast diffusivity of carbon atoms conducts to the nucleation of iron carbide particles. We establish that the occurrence of this second phenomenon depends on the vacancy arrival kinetics and can be related
Kinetic Analysis of Horizontal Plyometric Exercise Intensity.
Kossow, Andrew J; Ebben, William P
2018-05-01
Kossow, AJ, DeChiara, TG, Neahous, SM, and Ebben, WP. Kinetic analysis of horizontal plyometric exercise intensity. J Strength Cond Res 32(5): 1222-1229, 2018-Plyometric exercises are frequently performed as part of a strength and conditioning program. Most studies assessed the kinetics of plyometric exercises primarily performed in the vertical plane. The purpose of this study was to evaluate the multiplanar kinetic characteristics of a variety of plyometric exercises, which have a significant horizontal component. This study also sought to assess sex differences in the intensity progression of these exercises. Ten men and 10 women served as subjects. The subjects performed a variety of plyometric exercises including the double-leg hop, standing long jump, single-leg standing long jump, bounding, skipping, power skipping, cone hops, and 45.72-cm hurdle hops. Subjects also performed the countermovement jump for comparison. All plyometric exercises were evaluated using a force platform. Dependent variables included the landing rate of force development and landing ground reaction forces for each exercise in the vertical, frontal, and sagittal planes. A 2-way mixed analysis of variance with repeated-measures for plyometric exercise type demonstrated main effects for exercise type for all dependent variables (p ≤ 0.001). There was no significant interaction between plyometric exercise type and sex for any of the variable assessed. Bonferroni-adjusted pairwise comparisons identified a number of differences between the plyometric exercises for the dependent variables assessed (p ≤ 0.05). These findings should be used to guide practitioners in the progression of plyometric exercise intensity, and thus program design, for those who require significant horizontal power in their sport.
Group-kinetic theory of turbulence
Tchen, C. M.
1986-01-01
The two phases are governed by two coupled systems of Navier-Stokes equations. The couplings are nonlinear. These equations describe the microdynamical state of turbulence, and are transformed into a master equation. By scaling, a kinetic hierarchy is generated in the form of groups, representing the spectral evolution, the diffusivity and the relaxation. The loss of memory in formulating the relaxation yields the closure. The network of sub-distributions that participates in the relaxation is simulated by a self-consistent porous medium, so that the average effect on the diffusivity is to make it approach equilibrium. The kinetic equation of turbulence is derived. The method of moments reverts it to the continuum. The equation of spectral evolution is obtained and the transport properties are calculated. In inertia turbulence, the Kolmogoroff law for weak coupling and the spectrum for the strong coupling are found. As the fluid analog, the nonlinear Schrodinger equation has a driving force in the form of emission of solitons by velocity fluctuations, and is used to describe the microdynamical state of turbulence. In order for the emission together with the modulation to participate in the transport processes, the non-homogeneous Schrodinger equation is transformed into a homogeneous master equation. By group-scaling, the master equation is decomposed into a system of transport equations, replacing the Bogoliubov system of equations of many-particle distributions. It is in the relaxation that the memory is lost when the ensemble of higher-order distributions is simulated by an effective porous medium. The closure is thus found. The kinetic equation is derived and transformed into the equation of spectral flow.
Spectroscopy and reaction kinetics of HCO
Guo, Yili.
1989-01-01
The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ν 1 band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ν 1 data with previous microwave and FIR LMR measurements. A new set of spectroscopic constants for the (1, 0, 0) state, the equilibrium rotational constants, and the orientation of the transition dipole moment are also reported. The kinetics and product branching ratios of the HCO + NO 2 reaction have been studied using visible and infrared laser flash kinetic spectroscopy. The rate constant for the disappearance of HCO radical at 296 K is (5.7 +- 0.9) /times/ 10/sup /minus/11/ cm 3 molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF 6 buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO 2 . The product channel, H + CO 2 + NO, is responsible for 52% of the reaction. HONO has been observed, though not quantitatively, as a reaction product corresponding to the HONO + CO channel. 51 refs., 21 figs., 8 tabs
High-temperature spreading kinetics of metals
Rauch, N.
2005-05-15
In this PhD work a drop transfer setup combined with high speed photography has been used to analyze the spreading of Ag on polished polycrystalline Mo and single crystalline Mo (110) and (100) substrates. The objective of this work was to unveil the basic phenomena controlling spreading in metal-metal systems. The observed spreading kinetics were compared with current theories of low and high temperature spreading such as a molecular kinetic model and a fluid flow model. Analyses of the data reveal that the molecular model does describe the fastest velocity data well for all the investigated systems. Therefore, the energy which is dissipated during the spreading process is a dissipation at the triple line rather than dissipation due to the viscosity in the liquid. A comparison of the determined free activation energy for wetting of {delta}G95{approx}145kJ/mol with literature values allows the statement that the rate determining step seems to be a surface diffusion of the Ag atoms along the triple line. In order to investigate possible ridge formation, due to local atomic diffusion of atoms of the substrate at the triple during the spreading process, grooving experiments of the polycrystalline Mo were performed to calculate the surface diffusities that will control ridge evolution. The analyses of this work showed that a ridge formation at the fastest reported wetting velocities was not possible if there is no initial perturbation for a ridge. If there was an initial perturbation for a ridge the ridge had to be much smaller than 1 nm in order to be able to move with the liquid font. Therefore ridge formation does not influence the spreading kinetics for the studied system and the chosen conditions. SEM, AFM and TEM investigations of the triple line showed that ridge formation does also not occur at the end of the wetting experiment when the drop is close to equilibrium and the wetting velocity is slow. (orig.)
Kinetic theory for strongly coupled Coulomb systems
Dufty, James; Wrighton, Jeffrey
2018-01-01
The calculation of dynamical properties for matter under extreme conditions is a challenging task. The popular Kubo-Greenwood model exploits elements from equilibrium density-functional theory (DFT) that allow a detailed treatment of electron correlations, but its origin is largely phenomenological; traditional kinetic theories have a more secure foundation but are limited to weak ion-electron interactions. The objective here is to show how a combination of the two evolves naturally from the short-time limit for the generator of the effective single-electron dynamics governing time correlation functions without such limitations. This provides a theoretical context for the current DFT-related approach, the Kubo-Greenwood model, while showing the nature of its corrections. The method is to calculate the short-time dynamics in the single-electron subspace for a given configuration of the ions. This differs from the usual kinetic theory approach in which an average over the ions is performed as well. In this way the effective ion-electron interaction includes strong Coulomb coupling and is shown to be determined from DFT. The correlation functions have the form of the random-phase approximation for an inhomogeneous system but with renormalized ion-electron and electron-electron potentials. The dynamic structure function, density response function, and electrical conductivity are calculated as examples. The static local field corrections in the dielectric function are identified in this way. The current analysis is limited to semiclassical electrons (quantum statistical potentials), so important quantum conditions are excluded. However, a quantization of the kinetic theory is identified for broader application while awaiting its detailed derivation.
Thermodynamics and kinetics of vesicles formation processes.
Guida, Vincenzo
2010-12-15
Vesicles are hollow aggregates, composed of bilayers of amphiphilic molecules, dispersed into and filled with a liquid solvent. These aggregates can be formed either as equilibrium or as out of equilibrium meta-stable structures and they exhibit a rich variety of different morphologies. The surprising richness of structures, the vast range of industrial applications and the presence of vesicles in a number of biological systems have attracted the interest of numerous researchers and scientists. In this article, we review both the thermodynamics and the kinetics aspects of the phenomena of formation of vesicles. We start presenting the thermodynamics of bilayer membranes formation and deformation, with the aim of deriving the conditions for the existence of equilibrium vesicles. Specifically, we use the results from continuum thermodynamics to discuss the possibility of formation of stable equilibrium vesicles, from both mixed amphiphiles and single component systems. We also link the bilayer membrane properties to the molecular structure of the starting amphiphiles. In the second part of this article, we focus on the dynamics and kinetics of vesiculation. We review the process of vesicles formation both from planar lamellar phase under shear and from isotropic micelles. In order to clarify the physical mechanisms of vesicles formation, we continuously draw a parallel between emulsification and vesiculation processes. Specifically, we compare the experimental results, the driving forces and the relative scaling laws identified for the two processes. Describing the dynamics of vesicles formation, we also discuss why non equilibrium vesicles can be formed by kinetics control and why they are meta-stable. Understanding how to control the properties, the stability and the formation process of vesicles is of fundamental importance for a vast number of industrial applications. Copyright © 2009. Published by Elsevier B.V.
ENZYMATIC KINETIC STUDY HYDROLASE FROM CITRUS
Israel Hernández
2015-09-01
Full Text Available In this paper the degrading activity of enzymes derived from orange peels (Citrus x sinensis, grapefruit (Citrus paradise and pineapple (Ananas comosus on the organic matter in wastewater is evaluated. This activity is measured indirectly by quantifying the biochemical oxygen demand (COD before and after degradation process based on a period of time using the HACH DR / 2010, and then the kinetic study was performed by the differential method and integral with the experimental data, obtaining a reaction order of 1 to pectinase (orange, and order 2 for bromelain (pineapple.
Kinetic theory of free electron lasers
Hafizi, B. [Naval Research Lab., Washington, DC (United States); Roberson, C.W. [Office of Naval Research, Arlington, VA (United States)
1995-12-31
We have developed a relativistic kinetic theory of free electron lasers (FELs). The growth rate, efficiency, filling factor and radius of curvature of the radiation wave fronts are determined. We have used the theory to examine the effects of beam compression on growth rate. The theory has been extended to include self field effects on FEL operation. These effects are particularly important in compact, low voltage FELs. The surprising result is that the self field contribution to the beam quality is opposite to the emittance contribution. Hence self fields can improve beam quality, particularly in compact, low voltage FELs.
Kinetic analysis of dynamic PET data
Knittel, B.
1983-12-01
Our goal is to quantify regional physiological processes such as blood flow and metabolism by means of tracer kinetic modeling and positron emission tomography (PET). Compartmental models are one way of characterizing the behavior of tracers in physiological systems. This paper describes a general method of estimating compartmental model rate constants from measurements of the concentration of tracers in blood and tissue, taken at multiple time intervals. A computer program which applies the method is described, and examples are shown for simulated and actual data acquired from the Donner 280-Crystal Positron Tomograph.
Kinetic electron model for plasma thruster plumes
Merino, Mario; Mauriño, Javier; Ahedo, Eduardo
2018-03-01
A paraxial model of an unmagnetized, collisionless plasma plume expanding into vacuum is presented. Electrons are treated kinetically, relying on the adiabatic invariance of their radial action integral for the integration of Vlasov's equation, whereas ions are treated as a cold species. The quasi-2D plasma density, self-consistent electric potential, and electron pressure, temperature, and heat fluxes are analyzed. In particular, the model yields the collisionless cooling of electrons, which differs from the Boltzmann relation and the simple polytropic laws usually employed in fluid and hybrid PIC/fluid plume codes.
Decomposition kinetics of aminoborane in aqueous solutions
Shvets, I.B.; Erusalimchik, I.G.
1984-01-01
Kinetics of aminoborane hydrolysis has been studied using the method of polarization galvanostatical curves on a platinum electrode in buffer solutions at pH 3; 5; 7. The supposition that the reaction of aminoborane hydrolysis is the reaction of the first order by aminoborane is proved. The rate constant of aminoborane decomposition in the solution with pH 5 is equal to: K=2.5x10 -5 s -1 and with pH 3 it equals K=1.12x10 -4 s -1
Reactor kinetics methods development. Final report
Hansen, K.F.; Henry, A.F.
1978-01-01
This report is a qualitative summary of research conducted at MIT from 1967 to 1977 in the area of reactor kinetics methods. The objectives of the research were to find methods of integration of various mathematical models of nuclear reactor transients. From the beginning the work was aimed at numerical integration methods. Specific areas of research, discussed in more detail following, included: integration of multigroup diffusion theory models by finite difference and finite element methods; response matrix and nodal methods; coarse-mesh homogenization; and special treatment of boundary conditions
Reaction kinetic analysis of reactor surveillance data
Yoshiie, T., E-mail: yoshiie@rri.kyoto-u.ac.jp [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Kinomura, A. [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Nagai, Y. [The Oarai Center, Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan)
2017-02-15
In the reactor pressure vessel surveillance data of a European-type pressurized water reactor (low-Cu steel), it was found that the concentration of matrix defects was very high, and a large number of precipitates existed. In this study, defect structure evolution obtained from surveillance data was simulated by reaction kinetic analysis using 15 rate equations. The saturation of precipitation and the growth of loops were simulated, but it was not possible to explain the increase in DBTT on the basis of the defect structures. The sub-grain boundary segregation of solutes was discussed for the origin of the DBTT increase.
CHEMSIMUL: A simulator for chemical kinetics
Kirkegaard, P.; Bjergbakke, E.
1999-01-01
CHEMSIMUL is a computer program system for numerical simulation of chemical reaction systems. It can be used for modeling complex kinetics in many contexts, in particular radiolytic processes. It contains a translator module and a module for solving the resulting coupled nonlinear ordinary differential equations. An overview of the program system is given, and its use is illustrated by examples. A number of special features are described, in particular a method for verifying the mass balance. Moreover, the document contains a complete User's Guide for running CHEMSIMUL on a PC or another computer. Finally, the mathematical implementation is discussed. (au)
Kinetic coefficients in isotopically disordered crystals
Zhernov, Arkadii P; Inyushkin, Alexander V
2002-01-01
Peculiarities of the behavior of kinetic coefficients, like thermal conductivity, electric conductivity, and thermoelectric power, in isotopically disordered materials are reviewed in detail. New experimental and theoretical results on the isotope effects in the thermal conductivity of diamond, Ge, and Si semiconductors are presented. The suppression effect of phonon-drag thermopower in the isotopically disordered Ge crystals is discussed. The influence of dynamic and static crystal lattice deformations on the electric conductivity of metals as well as on the ordinary phonon spectrum deformations is considered. (reviews of topical problems)
The Kinetics Human Action Video Dataset
Kay, Will; Carreira, Joao; Simonyan, Karen; Zhang, Brian; Hillier, Chloe; Vijayanarasimhan, Sudheendra; Viola, Fabio; Green, Tim; Back, Trevor; Natsev, Paul; Suleyman, Mustafa; Zisserman, Andrew
2017-01-01
We describe the DeepMind Kinetics human action video dataset. The dataset contains 400 human action classes, with at least 400 video clips for each action. Each clip lasts around 10s and is taken from a different YouTube video. The actions are human focussed and cover a broad range of classes including human-object interactions such as playing instruments, as well as human-human interactions such as shaking hands. We describe the statistics of the dataset, how it was collected, and give some ...
Stress enhanced calcium kinetics in a neuron.
Kant, Aayush; Bhandakkar, Tanmay K; Medhekar, Nikhil V
2018-02-01
Accurate modeling of the mechanobiological response of a Traumatic Brain Injury is beneficial toward its effective clinical examination, treatment and prevention. Here, we present a stress history-dependent non-spatial kinetic model to predict the microscale phenomena of secondary insults due to accumulation of excess calcium ions (Ca[Formula: see text]) induced by the macroscale primary injuries. The model is able to capture the experimentally observed increase and subsequent partial recovery of intracellular Ca[Formula: see text] concentration in response to various types of mechanical impulses. We further establish the accuracy of the model by comparing our predictions with key experimental observations.
Kinetics of steel corrosion in water
Vettegren', V.I.; Bashkarev, A.Ya.; Danchukov, K.G.; Morozov, G.I.
2003-01-01
Kinetics of corrosion damage accumulation in steels of different composition (Cr-Ni-Mo-Ti, Cr-Ni-Mn-N-V, Cr-Ni-N-Mn-Mo, Cr-Ni-Nb, Cr-Ni-Ti, Cr-Mn-Ni, Mn-Al-Nb-Si, Mn-Cr-Al-Si and Mn-Al-Si) in NaCl solution and in sea water was studied. It is shown that degree of corrosion damage relates to time according to the first order reaction expression. The values of corrosion activation energy and of parameter characterizing protection properties of corrosion film are determined [ru
Kinetic Boltzmann, Vlasov and Related Equations
Sinitsyn, Alexander; Vedenyapin, Victor
2011-01-01
Boltzmann and Vlasov equations played a great role in the past and still play an important role in modern natural sciences, technique and even philosophy of science. Classical Boltzmann equation derived in 1872 became a cornerstone for the molecular-kinetic theory, the second law of thermodynamics (increasing entropy) and derivation of the basic hydrodynamic equations. After modifications, the fields and numbers of its applications have increased to include diluted gas, radiation, neutral particles transportation, atmosphere optics and nuclear reactor modelling. Vlasov equation was obtained in
The kinetic stabilizer: Issues and opportunities
Post, R.F.
2002-01-01
Five decades of fusion research have resulted in a solid base of understanding of the physics of plasma confinement by magnetic fields, including documentation of the role of the topology of the magnetic fields, i.e., 'open' or 'closed' field lines, in determining the confinement. Without known exception, closed systems, such as tokamaks, stellarators, or reversed-field pinches, have confinement times that are dominated by turbulence. As a result, to produce net fusion power, closed systems must be so large in size as to raise questions as to their practicality. By contrast, there are examples of open (mirror-based) systems where turbulence, if present at all, was at such low levels as to have a negligible influence on the confinement. Specifically, members of a subset of open systems, those with axisymmetric fields, have demonstrated cross-field transport rates that agree with classical predictions, opening up the possibility of fusion power systems that would be much smaller than their closed-field counterparts. Standing in the way of implementing axisymmetric mirror-based fusion systems is the MHD-unstable nature of their equilibria. The kinetic stabilizer represents a proposed way to overcome this difficulty, one based on theory that has been confirmed in the gas dynamic trap (GDT) axisymmetric mirror experiment in Novosibirsk, Russia. MHD-stabilization in the GDT arises from the presence of a sufficient density of effluent plasma on the outwardly expanding field lines outside the mirrors. However, in those mirror-based fusion systems, such as tandem-mirrors, that would operate at lower plasma collisionalities than the GDT, the effluent plasma density would be too low for this stabilization method to be effective. The kinetic stabilizer overcomes this difficulty by using ion beams injected from ion sources located far out on the expanding field lines beyond the outer mirror. These ion beams, aimed at small angles to the field lines, are compressed, stagnated
Kinetics and mechanism of hydrolysis of benzimidazolylcarbamates
Norberto, F. P.; Santos, S. P.; Iley, J.; Silva, D. B.; Corte Real, M.
2007-01-01
Synthesis of new 2-aminobenzimidazole-1-carbamates was accomplished by carbamoylation of 2-aminobenzimidazole using different substituted phenyl chloroformates. The aqueous hydrolysis of the new compounds was examined in the pH range 1-13 at 25 ºC. The evaluated kinetic parameters led to the conclusion that up to pH 4 reaction proceeds by a bimolecular attack of water to the N-protonated substrate. This is the first time this behavior is described for carbamates, and can be ascribed to the hi...
Kinetics of glucose transport in rat muscle
Ploug, Thorkil; Galbo, Henrik; Vinten, Jørgen
1987-01-01
The effects of insulin and prior muscle contractions, respectively, on 3-O-methylglucose (3-O-MG) transport in skeletal muscle were studied in the perfused rat hindquarter. Initial rates of entry of 3-O-MG in red gastrocnemius, soleus, and white gastrocnemius muscles as a function of perfusate 3-O-MG...... concentration exhibited Michaelis-Menten kinetics. Uptake by simple diffusion could not be detected. The maximum 3-O-MG transport velocity (Vmax) was increased more by maximum isometric contractions (10- to 40-fold, depending on fiber type) than by insulin (20,000 microU/ml; 3- to 20-fold) in both red and white...
Kinetic analysis of dynamic PET data
Knittel, B.
1983-12-01
Our goal is to quantify regional physiological processes such as blood flow and metabolism by means of tracer kinetic modeling and positron emission tomography (PET). Compartmental models are one way of characterizing the behavior of tracers in physiological systems. This paper describes a general method of estimating compartmental model rate constants from measurements of the concentration of tracers in blood and tissue, taken at multiple time intervals. A computer program which applies the method is described, and examples are shown for simulated and actual data acquired from the Donner 280-Crystal Positron Tomograph
Generalized slow roll for noncanonical kinetic terms
Hu, Wayne
2011-01-01
We show that the generalized slow roll approach for calculating the power spectrum where the inflationary slow roll parameters are neither small nor slowly varying can be readily extended to models with noncanonical kinetic terms in the inflaton action. For example, rapid sound speed variations can arise in Dirac-Born-Infeld models with features in the warp factor leading to features in the power spectrum. Nonetheless there remains a single source function for deviations that is simply related to the power spectrum. Empirical constraints on this source function can be readily interpreted in the context of features in the inflaton potential or sound speed.
Kinetics of fragmentation-annihilation processes
Filipe, JAN; Rodgers, GJ
1996-01-01
We investigate the kinetics of systems in which particles of one species undergo binary fragmentation and pair annihilation. In the latter, nonlinear process, fragments react at collision to produce an inert species, causing loss of mass. We analyze these systems in the reaction-limited regime by solving a continuous model within the mean-field approximation. The rate of fragmentation for a particle of mass x to break into fragments of masses y and x-y has the form x(lambda-1) (lambda > 0), a...
Studies of combustion kinetics and mechanisms
Gutman, D. [Catholic Univ. of America, Washington, DC (United States)
1993-12-01
The objective of the current research is to gain new quantitative knowledge of the kinetics and mechanisms of polyatomic free radicals which are important in hydrocarbon combustion processes. The special facility designed and built for these (which includes a heatable tubular reactor coupled to a photoionization mass spectrometer) is continually being improved. Where possible, these experimental studies are coupled with theoretical ones, sometimes conducted in collaboration with others, to obtain an improved understanding of the factors determining reactivity. The decomposition of acetyl radicals, isopropyl radicals, and n-propyl radicals have been studied as well as the oxidation of methylpropargyl radicals.
Kinetic coefficients for quark-antiquark plasma
Czyz, W.; Florkowski, W.
1986-03-01
The quark-antiquark plasma near equilibrium is studied. The results are based on the Heinz kinetic equations with the Boltzmann collision operator approximated by a relaxation term with the relaxation time, τ, treated as a small parameter. Linear in τ solutions of these equations are used to calculate the transport coefficients: the non-abelian version of Ohm's law, and the shear and volume viscosities. We introduce new chemical potentials which determine the color density matrix of quarks (antiquarks). Gradients of these potentials generate color currents. 12 refs. (author)
Slow VO2 off-kinetics in skeletal muscle is associated with fast PCr off-kinetics--and inversely.
Korzeniewski, Bernard; Zoladz, Jerzy A
2013-09-01
The computer model of the bioenergetic system in skeletal muscle, developed previously, was used to study the effect of the characteristic decay time of the parallel activation of oxidative phosphorylation [τ(OFF)] during muscle recovery on the muscle oxygen consumption rate (Vo2) and phosphocreatine (PCr) work-to-rest transition (off)-kinetics and on the relationship between the Vo2 and PCr rest-to-work transition (on)- and off-kinetics in moderate and heavy exercise. An increase in τ(OFF) slows down the initial phase of the muscle Vo2 off-kinetics and accelerates the PCr off-kinetics. As a result, the relationship between the initial phase of the Vo2 off-kinetics (lasting approximately 3-60 s in computer simulations) and the PCr off-kinetics is inverse: the slower the former, the faster the latter. A faster initial phase of the Vo2 off-kinetics is associated with a slower late phase of the Vo2 off-kinetics, and as a result, the integral of Vo2 above baseline during recovery, representing the oxygen debt, is identical in all cases [values of τ(OFF)] for a given PCr decrease. Depending on τ(OFF), the muscle Vo2 on-kinetics was either equally fast or slower than the Vo2 off-kinetics in moderate exercise and always slower in heavy exercise. PCr on-kinetics was always faster than PCr off-kinetics. This study clearly demonstrates that τ(OFF) has a pronounced impact on the mutual relations between the muscle Vo2 and PCr on- and off-kinetics.
Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method
Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung
1978-09-01
The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.
Wang, Zhandong; Zhao, Long; Wang, Yu; Bian, Huiting; Zhang, Lidong; Zhang, Feng; Li, Yuyang; Sarathy, Mani; Qi, Fei
2015-01-01
species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high
Analysis of a kinetic multi-segment foot model part II: kinetics and clinical implications.
Bruening, Dustin A; Cooney, Kevin M; Buczek, Frank L
2012-04-01
Kinematic multi-segment foot models have seen increased use in clinical and research settings, but the addition of kinetics has been limited and hampered by measurement limitations and modeling assumptions. In this second of two companion papers, we complete the presentation and analysis of a three segment kinetic foot model by incorporating kinetic parameters and calculating joint moments and powers. The model was tested on 17 pediatric subjects (ages 7-18 years) during normal gait. Ground reaction forces were measured using two adjacent force platforms, requiring targeted walking and the creation of two sub-models to analyze ankle, midtarsal, and 1st metatarsophalangeal joints. Targeted walking resulted in only minimal kinematic and kinetic differences compared with walking at self selected speeds. Joint moments and powers were calculated and ensemble averages are presented as a normative database for comparison purposes. Ankle joint powers are shown to be overestimated when using a traditional single-segment foot model, as substantial angular velocities are attributed to the mid-tarsal joint. Power transfer is apparent between the 1st metatarsophalangeal and mid-tarsal joints in terminal stance/pre-swing. While the measurement approach presented here is limited to clinical populations with only minimal impairments, some elements of the model can also be incorporated into routine clinical gait analysis. Copyright © 2011 Elsevier B.V. All rights reserved.
Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi
2018-08-01
The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.
Asadi, Z.; Zeinali, A.; Dušek, Michal; Eigner, Václav
2014-01-01
Roč. 46, č. 12 (2014), s. 718-729 ISSN 0538-8066 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl * Schiff base * kinetics * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.517, year: 2014
Modeling in applied sciences a kinetic theory approach
Pulvirenti, Mario
2000-01-01
Modeling complex biological, chemical, and physical systems, in the context of spatially heterogeneous mediums, is a challenging task for scientists and engineers using traditional methods of analysis Modeling in Applied Sciences is a comprehensive survey of modeling large systems using kinetic equations, and in particular the Boltzmann equation and its generalizations An interdisciplinary group of leading authorities carefully develop the foundations of kinetic models and discuss the connections and interactions between model theories, qualitative and computational analysis and real-world applications This book provides a thoroughly accessible and lucid overview of the different aspects, models, computations, and methodology for the kinetic-theory modeling process Topics and Features * Integrated modeling perspective utilized in all chapters * Fluid dynamics of reacting gases * Self-contained introduction to kinetic models * Becker–Doring equations * Nonlinear kinetic models with chemical reactions * Kinet...
Kinetics of laser irradiated nanoparticles cloud
Mishra, S. K.; Upadhyay Kahaly, M.; Misra, Shikha
2018-02-01
A comprehensive kinetic model describing the complex kinetics of a laser irradiated nanoparticle ensemble has been developed. The absorbed laser radiation here serves dual purpose, viz., photoenhanced thermionic emission via rise in its temperature and direct photoemission of electrons. On the basis of mean charge theory along with the equations for particle (electron) and energy flux balance over the nanoparticles, the transient processes of charge/temperature evolution over its surface and mass diminution on account of the sublimation (phase change) process have been elucidated. Using this formulation phenomenon of nanoparticle charging, its temperature rise to the sublimation point, mass ablation, and cloud disintegration have been investigated; afterwards, typical timescales of disintegration, sublimation and complete evaporation in reference to a graphite nanoparticle cloud (as an illustrative case) have been parametrically investigated. Based on a numerical analysis, an adequate parameter space describing the nanoparticle operation below the sublimation temperature, in terms of laser intensity, wavelength and nanoparticle material work function, has been identified. The cloud disintegration is found to be sensitive to the nanoparticle charging through photoemission; as a consequence, it illustrates that radiation operating below the photoemission threshold causes disintegration in the phase change state, while above the threshold, it occurs with the onset of surface heating.
Kinetic Simulations of Dense Plasma Focus Breakdown
Schmidt, A.; Higginson, D. P.; Jiang, S.; Link, A.; Povilus, A.; Sears, J.; Bennett, N.; Rose, D. V.; Welch, D. R.
2015-11-01
A dense plasma focus (DPF) device is a type of plasma gun that drives current through a set of coaxial electrodes to assemble gas inside the device and then implode that gas on axis to form a Z-pinch. This implosion drives hydrodynamic and kinetic instabilities that generate strong electric fields, which produces a short intense pulse of x-rays, high-energy (>100 keV) electrons and ions, and (in deuterium gas) neutrons. A strong factor in pinch performance is the initial breakdown and ionization of the gas along the insulator surface separating the two electrodes. The smoothness and isotropy of this ionized sheath are imprinted on the current sheath that travels along the electrodes, thus making it an important portion of the DPF to both understand and optimize. Here we use kinetic simulations in the Particle-in-cell code LSP to model the breakdown. Simulations are initiated with neutral gas and the breakdown modeled self-consistently as driven by a charged capacitor system. We also investigate novel geometries for the insulator and electrodes to attempt to control the electric field profile. The initial ionization fraction of gas is explored computationally to gauge possible advantages of pre-ionization which could be created experimentally via lasers or a glow-discharge. Prepared by LLNL under Contract DE-AC52-07NA27344.
Kinetic Inductance Parametric Up-Converter
Kher, A.; Day, P. K.; Eom, B. H.; Zmuidzinas, J.; Leduc, H. G.
2016-07-01
We describe a novel class of devices based on the nonlinearity of the kinetic inductance of a superconducting thin film. By placing a current-dependent inductance in a microwave resonator, small currents can be measured through their effect on the resonator's frequency. By using a high-resistivity material for the film and nanowires as kinetic inductors, we can achieve a large coefficient of nonlinearity to improve device sensitivity. We demonstrate a current sensitivity of 8{ {pA/}}√{{ {Hz}}}, making this device useful for transition-edge sensor (TES) readout and other cutting-edge applications. An advantage of these devices is their natural ability to be multiplexed in the frequency domain, enabling large detector arrays for TES-based instruments. A traveling-wave version of the device, consisting of a thin-film microwave transmission line, is also sensitive to small currents as they change the phase length of the line due to their effect on its inductance. We demonstrate a current sensitivity of 5{ {pA/}}√{{ {Hz}}} for this version of the device, making it also suitable for TES readout as well as other current-detection applications. It has the advantage of multi-GHz bandwidth and greater dynamic range, offering a different approach to the resonator version of the device.
Tandem mass spectrometry at low kinetic energy
Cooks, R.G.; Hand, O.W.
1987-01-01
Recent progress in mass spectrometry, as applied to molecular analysis, is reviewed with emphasis on tandem mass spectrometry. Tandem instruments use multiple analyzers (sector magnets, quadrupole mass filters and time-of-flight devices) to select particular molecules in ionic form, react them in the gas-phase and then record the mass, momenta or kinetic energies of their products. The capabilities of tandem mass spectrometry for identification of individual molecules or particular classes of compounds in complex mixtures are illustrated. Several different types of experiments can be run using a tandem mass spectrometer; all share the feature of sifting the molecular mixture being analyzed on the basis of chemical properties expressed in terms of ionic mass, kinetic energy or charge state. Applications of mass spectrometry to biological problems often depend upon desorption methods of ionization in which samples are bombarded with particle beams. Evaporation of preformed charged species from the condensed phase into the vacuum is a particularly effective method of ionization. It is suggested that the use of accelerator mass spectrometers be extended to include problems of molecular analysis. In such experiments, low energy tandem mass spectrometry conducted in the eV or keV range of energies, would be followed by further characterization of the production ion beam using high selective MeV collision processes
Optimal Bayesian Experimental Design for Combustion Kinetics
Huan, Xun
2011-01-04
Experimental diagnostics play an essential role in the development and refinement of chemical kinetic models, whether for the combustion of common complex hydrocarbons or of emerging alternative fuels. Questions of experimental design—e.g., which variables or species to interrogate, at what resolution and under what conditions—are extremely important in this context, particularly when experimental resources are limited. This paper attempts to answer such questions in a rigorous and systematic way. We propose a Bayesian framework for optimal experimental design with nonlinear simulation-based models. While the framework is broadly applicable, we use it to infer rate parameters in a combustion system with detailed kinetics. The framework introduces a utility function that reflects the expected information gain from a particular experiment. Straightforward evaluation (and maximization) of this utility function requires Monte Carlo sampling, which is infeasible with computationally intensive models. Instead, we construct a polynomial surrogate for the dependence of experimental observables on model parameters and design conditions, with the help of dimension-adaptive sparse quadrature. Results demonstrate the efficiency and accuracy of the surrogate, as well as the considerable effectiveness of the experimental design framework in choosing informative experimental conditions.
Hydrogen atom kinetics in capacitively coupled plasmas
Nunomura, Shota; Katayama, Hirotaka; Yoshida, Isao
2017-05-01
Hydrogen (H) atom kinetics has been investigated in capacitively coupled very high frequency (VHF) discharges at powers of 16-780 mW cm-2 and H2 gas pressures of 0.1-2 Torr. The H atom density has been measured using vacuum ultra violet absorption spectroscopy (VUVAS) with a micro-discharge hollow cathode lamp as a VUV light source. The measurements have been performed in two different electrode configurations of discharges: conventional parallel-plate diode and triode with an intermediate mesh electrode. We find that in the triode configuration, the H atom density is strongly reduced across the mesh electrode. The H atom density varies from ˜1012 cm-3 to ˜1010 cm-3 by crossing the mesh with 0.2 mm in thickness and 36% in aperture ratio. The fluid model simulations for VHF discharge plasmas have been performed to study the H atom generation, diffusion and recombination kinetics. The simulations suggest that H atoms are generated in the bulk plasma, by the electron impact dissociation (e + H2 \\to e + 2H) and the ion-molecule reaction (H2 + + H2 \\to {{{H}}}3+ + H). The diffusion of H atoms is strongly limited by a mesh electrode, and thus the mesh geometry influences the spatial distribution of the H atoms. The loss of H atoms is dominated by the surface recombination.
Kinetic studies on the hafnium nad deuterium
Bing Wenzeng; Long Xinggui; Zhu Zuliang
2009-04-01
Through the method of reaction rate analysis in a constant volume reactor, the time dependence of the pressure drop of the hafnium deuteride formation are studied over a temperature range 573-873 K on a metal hydride thermodynamic and kinetic parameters measuring apparatus. The rate constants of the hafnium deuteride formation, which are 0.0530 s -1 , 0.0452 s -1 , 0.0319 s -1 , 0.0261 s -1 , are calculated at a serial temperatures of 573 K, 673 K, 773 K, 873 K and the initial pressure of 13 kPa. The activation energy of the reaction is (-10.1±1.5) kJ·mol -1 . Comparing the above results with those of titanium deuteride formation on the same measuring apparatus, the kinetic mechanism of the deuteride formation of hafnium and titanium is considered different. It is concluded that the reaction rate of hafnium absorbing deuterium may be controlled by phase transformation and surface oxidation. (authors)
Designing Antibacterial Peptides with Enhanced Killing Kinetics
Faiza H. Waghu
2018-02-01
Full Text Available Antimicrobial peptides (AMPs are gaining attention as substitutes for antibiotics in order to combat the risk posed by multi-drug resistant pathogens. Several research groups are engaged in design of potent anti-infective agents using natural AMPs as templates. In this study, a library of peptides with high sequence similarity to Myeloid Antimicrobial Peptide (MAP family were screened using popular online prediction algorithms. These peptide variants were designed in a manner to retain the conserved residues within the MAP family. The prediction algorithms were found to effectively classify peptides based on their antimicrobial nature. In order to improve the activity of the identified peptides, molecular dynamics (MD simulations, using bilayer and micellar systems could be used to design and predict effect of residue substitution on membranes of microbial and mammalian cells. The inference from MD simulation studies well corroborated with the wet-lab observations indicating that MD-guided rational design could lead to discovery of potent AMPs. The effect of the residue substitution on membrane activity was studied in greater detail using killing kinetic analysis. Killing kinetics studies on Gram-positive, negative and human erythrocytes indicated that a single residue change has a drastic effect on the potency of AMPs. An interesting outcome was a switch from monophasic to biphasic death rate constant of Staphylococcus aureus due to a single residue mutation in the peptide.
Analysis of lipid peroxidation kinetics. I
Doktorov, Alexander B.; Lukzen, Nikita N.; Pedersen, Jørgen Boiden
2008-01-01
concentrations of reactants or diﬀerent ways of initiating the re- action. Nor has it been possible to predict the time dependence of the products. The reason for these problems is the complicated structure of the kinetic scheme, which includes a chain reaction. In this work we perform an in depth analysis...... The kinetics of the lipid peroxidation reaction is only partly under- stood. Although the set of reactions constituting the overall reaction is believed to be known, it has not been possible to predict how the reaction will respond to a change of one or more of the parameters, e.g. initial...... of the importance of the individual reaction steps and we introduce a new quasi-stationary concentration method based on the assumption that one or more concentrations vary much slower than the others. We show that it is justiﬁed to use a quasi-stationary concentration approximation for the alkyl radical L...
Nonlinear oxidation kinetics of nickel cermets
Galinski, Henning; Bieberle-Huetter, Anja; Rupp, Jennifer L.M.; Gauckler, Ludwig J.
2011-01-01
The oxidation of a cermet of screen-printed nickel (Ni) and gadolinia-doped ceria (CGO) with an approximate median porosity of 50 vol.% has been studied via in situ X-ray diffraction and focused ion beam nanotomography in the temperature range 773-848 K. The oxidation kinetics of Ni to NiO is found to be highly nonlinear with an apparent activation energy of 2.8(2) eV in this temperature range. The nonlinear oxidation kinetics found is in good agreement with theoretical works on oxide growth driven by nonlinear inbuilt fields. Stress-induced Kirkendall void formation has been identified as the physical process that enhances the oxidation of Ni/CGO cermets. Compressive stresses within the Ni matrix result from the thermal expansion mismatch of Ni and CGO and cause plastic deformation as they exceed the yield stress of the Ni matrix. The pore size distribution of Kirkendall voids formed has been measured by FIB nanotomography and shows a significant temperature dependence. It is shown that even one cycle of reoxidation changes irreversibly the microstructure of the cermet which can be interpreted as the onset and main contribution to the mechanical degradation of the cermet.
Kinetics of elementary atom and radical reactions
Gordon, R.J.
1990-06-01
During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B ( 1 Σ + ) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O( 3 P) + H 2 . In this work we measured the rate constant for the reaction O( 3 P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections
Detailed Chemical Kinetic Modeling of Hydrazine Decomposition
Meagher, Nancy E.; Bates, Kami R.
2000-01-01
The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.
Kinetics of Scheelite Conversion in Sulfuric Acid
Shen, Leiting; Li, Xiaobin; Zhou, Qiusheng; Peng, Zhihong; Liu, Guihua; Qi, Tiangui; Taskinen, Pekka
2018-02-01
Complete conversion of scheelite in H2SO4 solution plays a key role in exploration of cleaner technology for producing ammonium paratungstate. In this work, the factors influencing scheelite conversion were investigated experimentally to model its kinetics. The results indicated that the conversion rate increases with increasing temperature and reducing particle size, but is almost independent of stirring speed. Moreover, although the conversion rate increases with increasing initial H2SO4 concentration (≤ 1.25 mol/L), it decreases rapidly at 1.5 mol/L H2SO4 after 10 min due to formation of a H2WO4 layer. The experimental data agree quite well with the shrinking core model under chemical reaction control in ≤ 1.25 mol/L H2SO4 solution, and the kinetic equation was established as: 1- ( 1- α )^{ 1 / 3} = 2 2 2 5 4 6. 6\\cdot C_{{{H}_{ 2} {SO}_{ 4} }}^{ 1. 2 2 6} \\cdot r_{ 0}^{ - 1} \\cdot e^{{ - 3 9 2 6 0/RT}} \\cdot t (t, min). This work could contribute to better understanding of scheelite conversion in H2SO4 solution and development of a new route for ammonium paratungstate production.
Vortex lattice melting, pinning and kinetics
Doniach, S.; Ryu, S.; Kapitulnik, A.
1994-01-01
The phenomenology of the high T c superconductors is discussed both at the level of the thermodynamics of melting of the Abrikosov flux lattice and in terms of the melting and kinetics of the flux lattice for a pinned system. The authors review results on 3D melting obtained by a Monte Carlo simulation approach in which the 2D open-quotes pancakeclose quotes vortices are treated as statistical variables. The authors discuss pinning in the context of the strong pinning regime in which the vortex density given in terms of the applied field B is small compared to that represented by an effective field B pin measuring the pinning center density. The authors introduce a new criterion for the unfreezing of a vortex glass on increase of magnetic field or temperature, in the strong pinning, small field unit. The authors model this limit in terms of a single flux line interacting with a columnar pin. This model is studied both analytically and by computer simulation. By applying a tilt potential, the authors study the kinetics of the vortex motion in an external current and show that the resulting current-voltage characteristic follows a basic vortex glass-like scaling relation in the vicinity of the depinning transition
Acceleration transforms and statistical kinetic models
LuValle, M.J.; Welsher, T.L.; Svoboda, K.
1988-01-01
For a restricted class of problems a mathematical model of microscopic degradation processes, statistical kinetics, is developed and linked through acceleration transforms to the information which can be obtained from a system in which the only observable sign of degradation is sudden and catastrophic failure. The acceleration transforms were developed in accelerated life testing applications as a tool for extrapolating from the observable results of an accelerated life test to the dynamics of the underlying degradation processes. A particular concern of a physicist attempting to interpreted the results of an analysis based on acceleration transforms is determining the physical species involved in the degradation process. These species may be (a) relatively abundant or (b) relatively rare. The main results of this paper are a theorem showing that for an important subclass of statistical kinetic models, acceleration transforms cannot be used to distinguish between cases a and b, and an example showing that in some cases falling outside the restrictions of the theorem, cases a and b can be distinguished by their acceleration transforms
Cellular Kinetics of Perivascular MSC Precursors
William C. W. Chen
2013-01-01
Full Text Available Mesenchymal stem/stromal cells (MSCs and MSC-like multipotent stem/progenitor cells have been widely investigated for regenerative medicine and deemed promising in clinical applications. In order to further improve MSC-based stem cell therapeutics, it is important to understand the cellular kinetics and functional roles of MSCs in the dynamic regenerative processes. However, due to the heterogeneous nature of typical MSC cultures, their native identity and anatomical localization in the body have remained unclear, making it difficult to decipher the existence of distinct cell subsets within the MSC entity. Recent studies have shown that several blood-vessel-derived precursor cell populations, purified by flow cytometry from multiple human organs, give rise to bona fide MSCs, suggesting that the vasculature serves as a systemic reservoir of MSC-like stem/progenitor cells. Using individually purified MSC-like precursor cell subsets, we and other researchers have been able to investigate the differential phenotypes and regenerative capacities of these contributing cellular constituents in the MSC pool. In this review, we will discuss the identification and characterization of perivascular MSC precursors, including pericytes and adventitial cells, and focus on their cellular kinetics: cell adhesion, migration, engraftment, homing, and intercellular cross-talk during tissue repair and regeneration.
Kinetics and Thermodynamics of Membrane Protein Folding
Ernesto A. Roman
2014-03-01
Full Text Available Understanding protein folding has been one of the great challenges in biochemistry and molecular biophysics. Over the past 50 years, many thermodynamic and kinetic studies have been performed addressing the stability of globular proteins. In comparison, advances in the membrane protein folding field lag far behind. Although membrane proteins constitute about a third of the proteins encoded in known genomes, stability studies on membrane proteins have been impaired due to experimental limitations. Furthermore, no systematic experimental strategies are available for folding these biomolecules in vitro. Common denaturing agents such as chaotropes usually do not work on helical membrane proteins, and ionic detergents have been successful denaturants only in few cases. Refolding a membrane protein seems to be a craftsman work, which is relatively straightforward for transmembrane β-barrel proteins but challenging for α-helical membrane proteins. Additional complexities emerge in multidomain membrane proteins, data interpretation being one of the most critical. In this review, we will describe some recent efforts in understanding the folding mechanism of membrane proteins that have been reversibly refolded allowing both thermodynamic and kinetic analysis. This information will be discussed in the context of current paradigms in the protein folding field.
Ozone kinetics in low-pressure discharges
Guerra, Vasco; Marinov, Daniil; Guaitella, Olivier; Rousseau, Antoine
2012-10-01
Ozone kinetics is quite well established at atmospheric pressure, due to the importance of ozone in atmospheric chemistry and to the development of industrial ozone reactors. However, as the pressure is decreased and the dominant three-body reactions lose importance, the main mechanisms involved in the creation and destruction of ozone are still surrounded by important uncertainties. In this work we develop a self-consistent model for a pulsed discharge and its afterglow operating in a Pyrex reactor with inner radius 1 cm, at pressures in the range 1-5 Torr and discharge currents of 40-120 mA. The model couples the electron Boltzmann equation with a system of equations for the time evolution of the heavy particles. The calculations are compared with time-dependent measurements of ozone and atomic oxygen. Parametric studies are performed in order to clarify the role of vibrationally excited ozone in the overall kinetics and to establish the conditions where ozone production on the surface may become important. It is shown that vibrationally excited ozone does play a significant role, by increasing the time constants of ozone formation. Moreover, an upper limit for the ozone formation at the wall in these conditions is set at 10(-4).
The Kinetics of Swinging a Baseball Bat.
Crisco, Joseph J; Osvalds, Nikolas J; Rainbow, Michael J
2018-04-13
The purpose of this study was to compute the three-dimensional kinetics required to swing three youth baseball bats of varying moments of inertia (MOI). 306 swings by 22 male players (13-18 yrs.) were analyzed. Inverse dynamics with respect to the batter's hands were computed given the known kinematics and physical properties of the bats. We found that peak force increased with larger bat MOI and was strongly correlated with bat tip speed. In contrast, peak moments were weakly correlated with bat MOI and bat tip speed. Throughout the swing, the force applied to the bat was dominated by a component aligned with the long axis of the bat and directed away from the bat knob, while the moment applied to the bat was minimal until just prior to ball impact. These results indicate that players act to mostly "pull" the bat during their swing until just prior to ball impact, at which point they rapidly increase the moment on the bat. This kinetic analysis provides novel insight into the forces and moments used to swing baseball bats.
Kinetics of particle deposition at heterogeneous surfaces
Stojiljković, D. Lj.; Vrhovac, S. B.
2017-12-01
The random sequential adsorption (RSA) approach is used to analyze adsorption of spherical particles of fixed diameter d0 on nonuniform surfaces covered by square cells arranged in a square lattice pattern. To characterize such pattern two dimensionless parameters are used: the cell size α and the cell-cell separation β, measured in terms of the particle diameter d0. Adsorption is assumed to occur if the particle (projected) center lies within a cell area. We focus on the kinetics of deposition process in the case when no more than a single disk can be placed onto any square cell (α deposition process is not consistent with the power law behavior. However, if the geometry of the pattern approaches towards ;noninteracting conditions; (β > 1), when adsorption on each cell can be decoupled, approach of the coverage fraction θ(t) to θJ becomes closer to the exponential law. Consequently, changing the pattern parameters in the present model allows to interpolate the deposition kinetics between the continuum limit and the lattice-like behavior. Structural properties of the jammed-state coverings are studied in terms of the radial distribution function g(r) and spatial distribution of particles inside the cell. Various, non-trivial spatial distributions are observed depending on the geometry of the pattern.
Glucose kinetics in infants of diabetic mothers
Cowett, R.M.; Susa, J.B.; Giletti, B.; Oh, W.; Schwartz, R.
1983-01-01
Glucose kinetic studies were performed to define the glucose turnover rate with 78% enriched D-[U-13C] glucose by the prime constant infusion technique at less than or equal to 6 hours of age in nine infants of diabetic mothers (four insulin-dependent and five chemical diabetic patients) at term. Five normal infants were studied as control subjects. All infants received 0.9% saline intravenously during the study with the tracer. Fasting plasma glucose, insulin, and glucose13/12C ratios were measured during the steady state, and the glucose turnover rate was derived. The average plasma glucose concentration was similar during the steady state in the infants of the diabetic mothers and in the control infants, and the glucose turnover rate was not significantly different among the groups: 2.3 +/- 0.6 mg . kg-1 min-1 in infants of insulin-dependent diabetic patients; 2.4 +/- 0.4 mg . kg-1 min-1 in infants of chemical diabetic patients; and 3.2 +/- 0.3 mg . kg-1 min-1 in the control subjects. Good control of maternal diabetes evidenced by the normal maternal hemoglobin A1c and plasma glucose concentration at delivery and cord plasma glucose concentration resulted in glucose kinetic values in the infants of diabetic mothers that were indistinguishable from those of control subjects. The data further support the importance of good control of the diabetic state in the pregnant woman to minimize or prevent neonatal hypoglycemia
Kinetics of the maintenance of the epidermis
Zhdanov, Vladimir P.; Cho, Nam-Joon
2013-08-01
The epidermis is the outermost layer of skin. It is comprised of keratin-containing cells called keratinocytes. Functionally, the epidermis serves as a physical barrier that can prevent infection and regulate body hydration. Maintenance and repair of the epidermis are important for human health. Mechanistically, these processes occur primarily via proliferation and differentiation of stem cells located in the basal monolayer. These processes are believed to depend on cell-cell communication and spatial constraints but existing kinetic models focus mainly on proliferation and differentiation. To address this issue, we present a mean-field kinetic model that takes these additional factors into account and describes the epidermis at a biosystem level. The corresponding equations operate with the populations of stem cells and differentiated cells in the basal layer. The keratinocytes located above the basal layer are treated at a more coarse-grained level by considering the thickness of the epidermis. The model clarifies the likely role of various negative feedbacks that may control the epidermis and, accordingly, provides insight into the cellular mechanisms underlying complex biological phenomena such as wound healing.
The Kinetics of Carrier Transport Inhibition
Rosenberg, T.; Wilbrandt, Robert Walter
1962-01-01
The kinetical treatment of enzymatic carrier transports as given in previous communications has been extended to conditions of inhibition. Various possible types of inhibitors have been considered differing in the site of attack (enzyme or carrier), in the mode of action (competing with the subst......The kinetical treatment of enzymatic carrier transports as given in previous communications has been extended to conditions of inhibition. Various possible types of inhibitors have been considered differing in the site of attack (enzyme or carrier), in the mode of action (competing...... with the substrate for the enzyme or the carrier or for both, competing with the carrier for the enzyme, or non-competitive) and in the ability of penetrating the membrane. Experiments are reported on the inhibition of glucose and fructose transport across the human red cell membrane by phlorizine, phloretine...... and polyphloretinephosphate. The results of the analysis for these inhibitors indicate a substrate competitive mode of action. The effect of reversing the transport direction by interchanging the substrate concentration has been treated for the case of a non-penetrating substrate competitive inhibitor in the external medium...
Neutral particle kinetics in fusion devices
Tendler, M.; Heifetz, D.
1986-05-01
The theory of neutral particle kinetics treats the transport of mass, momentum, and energy in a plasma due to neutral particles which themselves are unaffected by magnetic fields. This transport affects the global power and particle balances in fusion devices, as well as profile control and plasma confinement quality, particle and energy fluxes onto device components, performance of pumping systems, and the design of diagnostics and the interpretation of their measurements. This paper reviews the development of analytic, numerical, and Monte Carlo methods of solving the time-independent Boltzmann equation describing neutral kinetics. These models for neutral particle behavior typically use adaptations of techniques developed originally for computing neutron transport, due to the analogy between the two phenomena, where charge-exchange corresponds to scattering and ionization to absorption. Progress in the field depends on developing multidimensional analytic methods, and obtaining experimental data for the physical processes of wall reflection, the neutral/plasma interaction, and for processes in fusion devices which are directly related to neutral transport, such as H/sub α/ emission rates, plenum pressures, and charge-exchange emission spectra
Neutral particle kinetics in fusion devices
Tendler, M.; Heifetz, D.
1986-05-01
The theory of neutral particle kinetics treats the transport of mass, momentum, and energy in a plasma due to neutral particles which themselves are unaffected by magnetic fields. This transport affects the global power and particle balances in fusion devices, as well as profile control and plasma confinement quality, particle and energy fluxes onto device components, performance of pumping systems, and the design of diagnostics and the interpretation of their measurements. This paper reviews the development of analytic, numerical, and Monte Carlo methods of solving the time-independent Boltzmann equation describing neutral kinetics. These models for neutral particle behavior typically use adaptations of techniques developed originally for computing neutron transport, due to the analogy between the two phenomena, where charge-exchange corresponds to scattering and ionization to absorption. Progress in the field depends on developing multidimensional analytic methods, and obtaining experimental data for the physical processes of wall reflection, the neutral/plasma interaction, and for processes in fusion devices which are directly related to neutral transport, such as H/sub ..cap alpha../ emission rates, plenum pressures, and charge-exchange emission spectra.
Space-time reactor kinetics for heterogeneous reactor structure
Raisic, N [Boris Kidric Institute of nuclear sciences Vinca, Belgrade (Yugoslavia)
1969-11-15
An attempt is made to formulate time dependent diffusion equation based on Feinberg-Galanin theory in the from analogue to the classical reactor kinetic equation. Parameters of these equations could be calculated using the existing codes for static reactor calculation based on the heterogeneous reactor theory. The obtained kinetic equation could be analogues in form to the nodal kinetic equation. Space-time distribution of neutron flux in the reactor can be obtained by solving these equations using standard methods.
A discontinuous Galerkin method on kinetic flocking models
Tan, Changhui
2014-01-01
We study kinetic representations of flocking models. They arise from agent-based models for self-organized dynamics, such as Cucker-Smale and Motsch-Tadmor models. We prove flocking behavior for the kinetic descriptions of flocking systems, which indicates a concentration in velocity variable in infinite time. We propose a discontinuous Galerkin method to treat the asymptotic $\\delta$-singularity, and construct high order positive preserving scheme to solve kinetic flocking systems.
Treatment of polymer surfaces in plasma Part I. Kinetic model
Tabaliov, N A; Svirachev, D M
2006-01-01
The surface tension of the polymer materials depends on functional groups over its surface. As a result from the plasma treatment the kind and concentration of the functional groups can be changed. In the present work, the possible kinetic reactions are defined. They describe the interaction between the plasma and the polymer surface of polyethylene terephthalate (PET). Basing on these reactions, the systems of differential kinetic equations are suggested. The solutions are obtained analytically for the system kinetic equations at defined circumstances
Stochastic chemical kinetics theory and (mostly) systems biological applications
Érdi, Péter; Lente, Gabor
2014-01-01
This volume reviews the theory and simulation methods of stochastic kinetics by integrating historical and recent perspectives, presents applications, mostly in the context of systems biology and also in combustion theory. In recent years, due to the development in experimental techniques, such as optical imaging, single cell analysis, and fluorescence spectroscopy, biochemical kinetic data inside single living cells have increasingly been available. The emergence of systems biology brought renaissance in the application of stochastic kinetic methods.
Wang, Zhandong
2015-07-01
Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high temperature pyrolysis and oxidation was developed and validated against the pyrolysis and flame data performed in this work. Further validation of the kinetic model is presented against literature data including species concentrations in jet-stirred reactor oxidation, ignition delay times in a shock tube, and laminar flame speeds at various pressures and equivalence ratios. The model well predicts the consumption of ECH, the growth of aromatics, and the global combustion properties. Reaction flux and sensitivity analysis were utilized to elucidate chemical kinetic features of ECH combustion under various reaction conditions. © 2015 The Combustion Institute.
Introduction to the neutron kinetics of nuclear power reactors
Tyror, J G; Grant, P J
2013-01-01
An Introduction to the Neutron Kinetics of Nuclear Power Reactors introduces the reader to the neutron kinetics of nuclear power reactors. Topics covered include the neutron physics of reactor kinetics, feedback effects, water-moderated reactors, fast reactors, and methods of plant control. The reactor transients following faults are also discussed, along with the use of computers in the study of power reactor kinetics. This book is comprised of eight chapters and begins with an overview of the reactor physics characteristics of a nuclear power reactor and their influence on system design and
A balance principle approach for modeling phase transformation kinetics
Lusk, M.; Krauss, G.; Jou, H.J.
1995-01-01
A balance principle is offered to model volume fraction kinetics of phase transformation kinetics at a continuum level. This microbalance provides a differential equation for transformation kinetics which is coupled to the differential equations governing the mechanical and thermal aspects of the process. Application here is restricted to diffusive transformations for the sake of clarity, although the principle is discussed for martensitic phase transitions as well. Avrami-type kinetics are shown to result from a special class of energy functions. An illustrative example using a 0.5% C Chromium steel demonstrates how TTT and CCT curves can be generated using a particularly simple effective energy function. (orig.)
Study of internal oxidation kinetics of molybdenum base alloys
Krushinskij, Yu.Yu.; Belyakov, B.G.; Belomyttsev, M.Yu.
1989-01-01
Metallographic and microdurometric method as well as new technique were used to study kinetics of internal oxidation (IO). It is shown that study of IO kinetics on the base of metallographic measurements of layers depth is not correct because it is related with insufficient sensitivity of the method. IO kinetics under conditions of formation of molybdenum oxide layer on saturated material surface as well as IO of alloy with high carbon content were investigated. Oxide film formation does not affect the IO kinetics; decarburization observed along with oxidation increases the apparent activation energy and K exponent on time dependence of diffusion layer depth
MODELLING OF KINETICS OF FLUORINE ADSORPTION ONTO MODIFIED DIATOMITE
VEACESLAV ZELENTSOV
2017-03-01
Full Text Available The paper presents kinetics modelling of adsorption of fluorine onto modified diatomite, its fundamental characteristics and mathematical derivations. Three models of defluoridation kinetics were used to fit the experimental results on adsorption fluorine onto diatomite: the pseudo-first order model Lagergren, the pseudo-second order model G. McKay and H.S. Ho and intraparticle diffusion model of W.J. Weber and J.C. Morris. Kinetics studies revealed that the adsorption of fluorine followed second-order rate model, complimented by intraparticle diffusion kinetics. The adsorption mechanism of fluorine involved three stages – external surface adsorption, intraparticle diffusion and the stage of equilibrium.
Reduced Chemical Kinetic Mechanisms for JP-8 Combustion
Montgomery, Christopher J; Cannon, S. M; Mawid, M. A; Sekar, B
2002-01-01
Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, six different reduced chemical kinetic mechanisms for JP-8 combustion have been generated...
ZareNezhad, Bahman; Varaminian, Farshad
2013-01-01
Highlights: • A unified kinetic model for description of promoted and non-promoted gas hydrate formation processes is presented. • Effects of impeller speed, promoter concentration and different kinetic promoters are investigated. • A unique region of gas hydrate formation is identified regarding gas hydrate formation processes. • The proposed model is useful for understanding the behavior of gas hydrate formation processes and design of GTH converters. - Abstract: The kinetic promoters have found wide applications in enhancing the rate of energy conversion and storage via gas hydrate formation processes. Effects of different kinetic promoters such as anionic surfactants sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBSA), and sodium dodecyl benzene sulfonate (SDBS); cationic surfactants, Cetyl trimethyl ammonium bromide (CTAB), dodecyl trimethyl ammonium bromide (DTAB) and non-ionic surfactants, alkylpolyglucoside (APG), dodecyl polysaccharide glycoside (DPG), TritonX-100 (TX100) on methane (CH 4 ), ethane (C 2 H 6 ) and propane (C 3 H 8 ) gas hydrate formation processes are investigated in this work. A macroscopic kinetic model based on the time variations of reaction chemical potential is also presented for global description of gas hydrate formation processes. Experimental gas hydrate formation data are employed to validate the proposed kinetic model. Effects of promoter’s concentrations and agitation intensities on the gas consumption profiles are also investigated. A universal correlation and a unified kinetic map have been proposed for macroscopic description of gas hydrate formation kinetics in the presence or absence of kinetic promoters. According to the presented unified kinetic map, a unique region of gas hydrate formation is identified for the first time. For negligible amounts of kinetic promoters, the presented region disappears and approaches to a unique path at high agitation intensities. The presented unified approach is
Kinetics and mechanism of DNA repair
Meldrum, R.A.; Wharton, C.W.; Shall, S.
1990-01-01
Experiments are described in which the feasibility of using caged dideoxy and other nucleoside triphosphate analogues for trapping breaks induced by u.v. radiation damage to mammalian cell DNA is evaluated. These nucleotide analogues that have a photolabile 1-(2-nitrophenyl)ethyl-protecting group attached to the γ-phosphate are placed in situ by permeabilizing cells by exposure to hypo-osmotic medium. The nucleoside triphosphate is released by a 351 nm u.v. laser pulse whence it may incorporate in the growing chain of DNA induced by the excision-repair process and terminate chain elongation. If the photoreleased dideoxynucleoside trisphosphate is isotopically labelled in the α-phosphate position the break is trapped and labelled. Incorporation of radioactivity into trichloroacetic acid insoluble material in these experiments confirms their potential for use in studies of the kinetics of mammalian cell DNA repair. (author)
Kinetic equation for spin-polarized plasmas
Cowley, S.C.; Kulsrud, R.M.; Valeo, E.
1984-07-01
The usual kinetic description of a plasma is extended to include variables to describe the spin. The distribution function, over phase-space and the new spin variables, provides a sufficient description of a spin-polarized plasma. The evolution equation for the distribution function is given. The equations derived are used to calculate depolarization due to four processes, inhomogeneous fields, collisions, collisions in inhomogeneous fields, and waves. It is found that depolarization by field inhomogeneity on scales large compared with the gyroradius is totally negligible. The same is true for collisional depolarization. Collisions in inhomogeneous fields yield a depolarization rate of order 10 -4 S -1 for deuterons and a negligible rate for tritons in a typical fusion reactor design. This is still sufficiently small on reactor time scales. However, small amplitude magnetic fluctuations (of order one gauss) resonant with the spin precession frequency can lead to significant depolarization (depolarises triton in ten seconds and deuteron in a hundred seconds.)
The Imperfect Fluid behind Kinetic Gravity Braiding
Pujolas, Oriol; Vikman, Alexander
2011-01-01
We present a standard hydrodynamical description for non-canonical scalar field theories with kinetic gravity braiding. In particular, this picture applies to the simplest galileons and k-essence. The fluid variables not only have a clear physical meaning but also drastically simplify the analysis of the system. The fluid carries charges corresponding to shifts in field space. This shift-charge current contains a spatial part responsible for diffusion of the charges. Moreover, in the incompressible limit, the equation of motion becomes the standard diffusion equation. The fluid is indeed imperfect because the energy flows neither along the field gradient nor along the shift current. The fluid has zero vorticity and is not dissipative: there is no entropy production, the energy-momentum is exactly conserved, the temperature vanishes and there is no shear viscosity. Still, in an expansion around a perfect fluid one can identify terms which correct the pressure in the manner of bulk viscosity. We close by formul...
Recent results in muonium solution kinetics
Jean, Y.C.; Ito, Y.; Stadlbauer, J.M.; Ng, B.W.; Walker, D.C.
1983-06-01
Using muonium spin rotation (MSR) techniques the aqueous solution kinetics of several muonium addition reactions and spin conversion interactions have been studied. The addition reactions show both diffusion and activation-controlled reaction rates with isotope effects between 1 and 3 for diffusion-control and between 7 and 31 for activation-control reactions. Barrier energies are typically approximately 15 kJ/mole and approximately 30 kJ/mole, respectively, for these processes in water. Spin-conversion interactions involving Ni +2 (aq) and Ni(cyclam) +2 complexes showed that spin-conversion of 'triplet' Mu by a paramagnetic solute occurs at or near the diffusion-controlled limit while the chemical reaction with the diamagnetic configuration of Ni(cyclam) +2 occurred some 100 times slower at ksub(M) 18 M -1 s -1
Logarithmic Exchange Kinetics in Monodisperse Copolymeric Micelles
García Daza, Fabián A.; Bonet Avalos, Josep; Mackie, Allan D.
2017-06-01
Experimental measurements of the relaxation kinetics of copolymeric surfactant exchange for micellar systems unexpectedly show a peculiar logarithmic decay. Several authors use polydispersity as an explanation for this behavior. However, in coarse-grained simulations that preserve microscopic details of the surfactants, we find evidence of the same logarithmic behavior. Since we use a strictly monodisperse distribution of chain lengths such a relaxation process cannot be attributed to polydispersity, but has to be caused by an inherent physical process characteristic of this type of system. This is supported by the fact that the decay is specifically logarithmic and not a power law with an exponent inherited from the particular polydispersity distribution of the sample. We suggest that the degeneracy of the energy states of the hydrophobic block in the core, which is broken on leaving the micelle, can qualitatively explain the broad distribution of energy barriers, which gives rise to the observed nonexponential relaxation.
Crystallization kinetics of phase change materials
Klein, Michael; Sontheimer, Tobias; Wuttig, Matthias [I. Physikalisches Institut (1A), RWTH Aachen (Germany)
2008-07-01
Phase change materials are fascinating materials. They can be rapidly switched between two metastable states, the amorphous and crystalline phase, which show pronounced contrast in their optical and electrical properties. They are already widely used as the active layer in rewritable optical media and are expected to be used in the upcoming phase change random access memory (PRAM). Here we show measurements of the crystallization kinetics of chalcogenide materials that lead to a deeper understanding of these processes. This work focuses mainly on the Ge-Sb-Te system but also includes Ag-In-Te materials. The crystallization behaviour of these materials was investigated with an ex-situ annealing method employing the precise oven of a differential scanning calorimeter and imaging techniques employing atomic force microscopy and optical microscopy.
Mandl, A.; Klimek, D.; Parks, J.H.
1984-01-01
A series of measurements characterizing an e beam pumped KrF* laser was carried out using a 200-nsec e-beam pulse having a rise time of 25 nsec at current densities up to 50 A/cm 2 . These pump conditions are relevent for inertial confinement fusion laser drivers. The measurements include fluorescence efficiency, sidelight suppression of the fluorescence during lasing, and laser energy output over a wide range of laser parameters including: total density 0.5--2.0 amagats, temperature 300--400 K, fluorine density 0.15%--0.5%, current density 38--50 A/cm 2 and various mirror transmissions. This data was used to verify and refine a model of KrF* kinetics which was then used to estimate the performance of an angular multiplexed power amplifier suitable for laser fusion applications
Kinetics of current formation in molecular diode
Petrov, Eh.G.; Leonov, V.A.; Shevchenko, E.V.
2012-01-01
Based on the kinetic theory of election transfer in low-dimensional molecular systems, the formation of transient and stationary currents in a system 'electrode l-molecule-electrode 2' (molecular diode) is studied for different regimes of charge transmission. In the framework of the HOMO-LUMO molecular model, a situation is considered where the current formation is initiated either by molecule photoexcitation or by change of interelectrode voltage bias. It is found that the distant (tunnel) inelastic electron transfer plays a crucial role in changing molecular electronic states and, as a result, in generating transmission channels for hopping (sequential) and distant (direct) current components. The effect of inelastic tunneling is especially pronounced in the condition of resonant electron transmission.
Fractional superstatistics from a kinetic approach
Ourabah, Kamel; Tribeche, Mouloud
2018-03-01
Through a kinetic approach, in which temperature fluctuations are taken into account, we obtain generalized fractional statistics interpolating between Fermi-Dirac and Bose-Einstein statistics. The latter correspond to the superstatistical analogues of the Polychronakos and Haldane-Wu statistics. The virial coefficients corresponding to these statistics are worked out and compared to those of an ideal two-dimensional anyon gas. It is shown that the obtained statistics reproduce correctly the second and third virial coefficients of an anyon gas. On this basis, a link is established between the statistical parameter and the strength of fluctuations. A further generalization is suggested by allowing the statistical parameter to fluctuate. As a by-product, superstatistics of ewkons, introduced recently to deal with dark energy [Phys. Rev. E 94, 062115 (2016), 10.1103/PhysRevE.94.062115], are also obtained within the same method.
Kinetics of actinide reduction by hydroxylamine
Koltunov, V.S.; Zhuravleva, G.I.; Shapovalov, M.P.
1981-01-01
The kinetics of Pu(6) reduction to Pu(5) with hydroxylamine in perchloric acid solution at the ionic force of μ=3 in the temperature range of 40-68 deg C is studied. The reaction rate is described with the equation d[Pu(6)]/dt=k 1 [Pu(6)]x[NH 3 OH + ]/[H + ], where k 1 =4.22+-0.12 min -1 at 60 deg C. The energy and entropy of activation constitute 78+-2 kJ/mol-10 entropy units respectively. At [H + ]> approximately 0.5 mol/l the reaction is accelerated autocatalytically at the expense of PuO 2 2+ and Pu 3+ -ion interaction with subsequent rapid transition of Pu(4) to Pu(3) as a result of reaction with hydroxylamine. The reaction mechanism is discussed [ru
Dynamics of asymmetric kinetic Ising systems revisited
Huang, Haiping; Kabashima, Yoshiyuki
2014-01-01
The dynamics of an asymmetric kinetic Ising model is studied. Two schemes for improving the existing mean-field description are proposed. In the first scheme, we derive the formulas for instantaneous magnetization, equal-time correlation, and time-delayed correlation, considering the correlation between different local fields. To derive the time-delayed correlation, we emphasize that the small-correlation assumption adopted in previous work (Mézard and Sakellariou, 2011 J. Stat. Mech. L07001) is in fact not required. To confirm the prediction efficiency of our method, we perform extensive simulations on single instances with either temporally constant external driving fields or sinusoidal external fields. In the second scheme, we develop an improved mean-field theory for instantaneous magnetization prediction utilizing the notion of the cavity system in conjunction with a perturbative expansion approach. Its efficiency is numerically confirmed by comparison with the existing mean-field theory when partially asymmetric couplings are present. (paper)
Domain growth kinetics in stratifying foam films
Zhang, Yiran; Sharma, Vivek
2015-11-01
Baking bread, brewing cappuccino, pouring beer, washing dishes, shaving, shampooing, whipping eggs and blowing bubbles all involve creation of aqueous foam films. Typical foam films consist of two surfactant-laden surfaces that are ~ 5 nm - 10 micron apart. Sandwiched between these interfacial layers is a fluid that drains primarily under the influence of viscous and interfacial forces, including disjoining pressure. Interestingly, a layered ordering of micelles inside the foam films (thickness characteristic scaling laws. Though several studies have focused on the expansion dynamics of isolated domains that exhibit a diffusion-like scaling, the change in expansion kinetics observed after domains contact with the Plateau border has not been reported and analyzed before.
Aggregation kinetics and structure of cryoimmunoglobulins clusters
De Spirito, M; Bassi, F A; Di Stasio, E; Giardina, B; Arcovito, G
2002-01-01
Cryoimmunoglobulins are pathological antibodies characterized by a temperature-dependent reversible insolubility. Rheumatoid factors (RF) are immunoglobulins possessing anti-immunoglobulin activity and usually consist of an IgM antibody that recognizes IgG as antigen. These proteins are present in sera of patients affected by a large variety of different pathologies, such as HCV infection, neoplastic and autoimmune diseases. Aggregation and precipitation of cryoimmunoglobulins, leading to vasculiti, are physical phenomena behind such pathologies. A deep knowledge of the physico-chemical mechanisms regulating such phenomena plays a fundamental role in biological and clinical applications. In this work, a preliminary investigation of the aggregation kinetics and of the final macro- molecular structure of the aggregates is presented. Through static light scattering techniques, the gyration radius R/sub g/ and the fractal dimension D/sub m/ of the growing clusters have been determined. However, while the initial ...
Hydrocarbon fermentation: kinetics of microbial cell growth
Goma, G [Institut National des Sciences Appliquees, Toulouse; Ribot, D
1978-11-01
Modeling of microbial growth using nonmiscible substrate is studied when kinetics of substrate dissolution is rate limiting. When the substrate concentration is low, the growth rate is described by an analytical relation that can be identified as a Contois relationship. If the substrate concentration is greater than a critical value S/sub crit/, the potentially useful hydrocarbon S* concentration is described by S* = S/sub crit//(1 + S/sub crit//S). A relationship was found between S/sub crit/ and the biomass concentration X. When X increased, S/sub crit/ decreased. The cell growth rate is related to a relation ..mu.. = ..mu../sub m/(A(X/S/sub crit/)(1 + S/sub crit//S) + 1)/sup -1/. This model describes the evolution of the growth rate when exponential or linear growth occurs, which is related to physico-chemical properties and hydrodynamic fermentation conditions. Experimental data to support the model are presented.
Kinetics of a gas adsorption compressor
Chan, C. K.; Tward, E.; Elleman, D. D.
1984-01-01
Chan (1981) has suggested that a process based on gas adsorption could be used as a means to drive a Joule-Thomson (J-T) device. The resulting system has several advantages. It is heat powered, it has no sealing, there are no mechanical moving parts, and no active control is required. In the present investigation, a two-phase model is used to analyze the transients of a gas adsorption compressor. The modeling of the adsorption process is based on a consideration of complete thermal and mechanical equilibrium between the gaseous phase and the adsorbed gas phase. The experimental arrangement for two sets of kinetic tests is discussed, and data regarding the experimental results are presented in graphs. For a theoretical study, a two-phase model was developed to predict the transient behavior of the compressor. A computer code was written to solve the governing equations with the aid of a standard forward marching predictor-corrector method.
Hydrogen peroxide decomposition kinetics in aquaculture water
Arvin, Erik; Pedersen, Lars-Flemming
2015-01-01
during the HP decomposition. The model assumes that the enzyme decay is controlled by an inactivation stoichiometry related to the HP decomposition. In order to make the model easily applicable, it is furthermore assumed that the COD is a proxy of the active biomass concentration of the water and thereby......Hydrogen peroxide (HP) is used in aquaculture systems where preventive or curative water treatments occasionally are required. Use of chemical agents can be challenging in recirculating aquaculture systems (RAS) due to extended water retention time and because the agents must not damage the fish...... reared or the nitrifying bacteria in the biofilters at concentrations required to eliminating pathogens. This calls for quantitative insight into the fate of the disinfectant residuals during water treatment. This paper presents a kinetic model that describes the HP decomposition in aquaculture water...
Investigation into kinetics of decomposition of nitrates
Belov, B.A.; Gorozhankin, Eh.V.; Efremov, V.N.; Sal'nikova, N.S.; Suris, A.L.
1985-01-01
Using the method of thermogravimetry, the decomposition of nitrates, Cd(NO 3 ) 2 x4H 2 O, La(NO 3 ) 2 x6H 2 O, Sr(NO 3 ) 2 , ZrO(NO 3 ) 2 x2H 2 O, Y(NO 3 ) 3 x6H 2 O, in particular, is studied in the 20-1000 deg C range. It is shown, that gaseous pyrolysis, products, remaining in the material, hamper greatly the heat transfer required for the decomposition which reduces the reaction order. An effective activation energy of the process is in a satisfactory agreement with the characteristic temperature of the last endotherm. Kinetic parameters are calculated by the minimization method using a computer
Kinetics of sintering of uranium dioxide
Soni, N.C.; Moorthy, V.K.
1978-01-01
The kinetics of sintering of UO 2 powders derived from ADU route and calcined at different temperatures was studied. The activation energy for sintering was found to depend on the calcination temperature, the density chosen and the sintering temperature range. The motive force for sintering is the excess free energy in the particle system. This exists in the powder compact in the form of surface energy and the excess lattice energy due to defects. The defects which can be eliminated at the operating temperature are responsible for the mobility and hence sintering. This concept of the motive force for sintering has been used to explain the difference in the activation energies observed in the present study. This would also explain phenomena such as attainment of limiting density, presence of optimum sintering temperature and the influence of calcination treatments on the sintering behaviour of powders. (author)
Blood platelet kinetics and platelet transfusion.
Aster, Richard H
2013-11-01
The discovery of citrate anticoagulant in the 1920s and the development of plastic packs for blood collection in the 1960s laid the groundwork for platelet transfusion therapy on a scale not previously possible. A major limitation, however, was the finding that platelet concentrates prepared from blood anticoagulated with citrate were unsuitable for transfusion because of platelet clumping. We found that this could be prevented by simply reducing the pH of platelet-rich plasma to about 6.5 prior to centrifugation. We used this approach to characterize platelet kinetics and sites of platelet sequestration in normal and pathologic states and to define the influence of variables such as anticoagulant and ABO incompatibility on post-transfusion platelet recovery. The "acidification" approach enabled much wider use of platelet transfusion therapy until alternative means of producing concentrates suitable for transfusion became available.
Spectroscopy, Kinetics, and Dynamics of Combustion Radicals
Nesbitt, David J. [Research/Professor
2013-08-06
Spectroscopy, kinetics and dynamics of jet cooled hydrocarbon transients relevant to the DOE combustion mission have been explored, exploiting i) high resolution IR lasers, ii) slit discharge sources for formation of jet cooled radicals, and iii) high sensitivity detection with direct laser absorption methods and near the quantum shot noise limit. What makes this combination powerful is that such transients can be made under high concentrations and pressures characteristic of actual combustion conditions, and yet with the resulting species rapidly cooled (T ≈10-15K) in the slit supersonic expansion. Combined with the power of IR laser absorption methods, this provides novel access to spectral detection and study of many critical combustion species.
Kinetic stability analyses in a bumpy cylinder
Dominguez, R.R.; Berk, H.L.
1981-01-01
Recent interest in the ELMO Bumpy Torus (EBT) has prompted a number of stability analyses of both the hot electron rings and the toroidal plasma. Typically these works employ the local approximation, neglecting radial eigenmode structure and ballooning effects to perform the stability analysis. In the present work we develop a fully kinetic formalism for performing nonlocal stability analyses in a bumpy cylinder. We show that the Vlasov-Maxwell integral equations (with one ignorable coordinate) are self-adjoint and hence amenable to analysis using numerical techniques developed for self-adjoint systems of equations. The representation we obtain for the kernel of the Vlasov-Maxwell equations is a differential operator of arbitrarily high order. This form leads to a manifestly self-adjoint system of differential equations for long wavelength modes
Dehydration kinetics of a natural montmorillonite
Andreotti, G.; Loria, A.; Mazzega, E.; Valeri, S.
1978-01-01
The dehydration mass loss of samples of montmorillonite (a layered hydrated silicate) was measured in an environment at constant temperature and at constant undersatured water vapour content. The hydration curves were analyzed by assuming the model of thermally activated, monoenergetic and first-order process compatible with the experimental results. Two dehydration kinetics with activation energies (0.21+-0.02) eV and (0.34+-0.02) eV were found that can be related to the existence of two kinds of water (structured and nonstructured) in the hydrated silicate interlayers. The possibility of an icelike structure of a fraction of the adsorbed molecules is briefly discussed. The experimental results show, furthermore, that in the investigated hydration range (up to about 10% in mass) the fraction of structured water has a maximum when the hydration is about 6%. (author)
Skin pigmentation kinetics after UVB exposure
Ravnbak, M.H.; Philipsen, P.A.; Wiegell, S.R.
2008-01-01
There have been few previous studies of the kinetics of pigmentation following ultraviolet B (UVB) exposure, and these have included only fair-skinned persons. The current study investigated pigmentation increase to steady state and fading in 12 Scandinavians and 12 Indians/Pakistanis. Over...... a period of 3 weeks the subjects were UV-irradiated 6 times on the right side of the back and 12 times on the left side using a Solar Simulator and narrowband UVB with equal sub-Minimal Melanogenesis Doses (individually predetermined). Pigmentation was measured from skin remittance at 555 urn and 660 nm...... (allowing correction for erythema). The absolute pigmentation increase was independent of pre-exposure pigmentation, therefore the percentage pigmentation increase was higher in fair-skinned volunteers. The UV dose to minimal pigmentation was higher in darker-skinned persons for single and multiple UV...
U3O8 microspheres sintering kinetics
Godoy, A.L.E.
1986-01-01
U 3 O 8 microspheres sintering kinetics was determined using a hot-stage optical microscopy apparatus, able to reach temperature up to 1350 0 C in controlled atmospheres. The sintered material had its microstructure analysed by optical and electron microscopy. The microspheres were characterized initialy utilizing X-ray diffractometry and thermogravimetry. The equation which describes the microspheres shrinkage in function of the time was obtained using finite difference analysis X-ray diffractometry indicated hexagonal structure for the microspheres main starting material, ammonium diuranate thermogravimetric analysis showed reduction of this material to U 3 O 8 at 600 0 C. Ceramography results showed 5 hours sintered microspheres grain sizes G vary with the temperature. Sintered U 3 O 8 micrographs compared with published results for UO 2 , indicate similar homogeneity microstructural characteristics and suggest the processed micorspheres to be potentially useful as nuclear fuels. (Author) [pt
Crystallization kinetics of the borax decahydrate
Ceyhan, A. A.; Sahin, Ö.; Bulutcu, A. N.
2007-03-01
The growth and dissolution rates of borax decahydrate have been measured as a function of supersaturation for various particle sizes at different temperature ranges of 13 and 50 °C in a laboratory-scale fluidized bed crystallizer. The values of mass transfer coefficient, K, reaction rate constant, kr and reaction rate order, r were determined. The relative importances of diffusion and integration resistance were described by new terms named integration and diffusion concentration fraction. It was found that the overall growth rate of borax decahydrate is mainly controlled by integration (reaction) steps. It was also estimated that the dissolution region of borax decahydrate, apart from other materials, is controlled by diffusion and surface reaction. Increasing the temperature and particle size cause an increase in the values of kinetic parameters ( Kg, kr and K). The activation energies of overall, reaction and mass transfer steps were determined as 18.07, 18.79 and 8.26 kJmol -1, respectively.
Generic analysis of kinetically driven inflation
Saitou, Rio
2018-04-01
We perform a model-independent analysis of kinetically driven inflation (KDI) which (partially) includes generalized G-inflation and ghost inflation. We evaluate the background evolution splitting into the inflationary attractor and the perturbation around it. We also consider the quantum fluctuation of the scalar mode with a usual scaling and derive the spectral index, ignoring the contribution from the second-order products of slow-roll parameters. Using these formalisms, we find that within our generic framework the models of KDI which possess the shift symmetry of scalar field cannot create the quantum fluctuation consistent with the observation. Breaking the shift symmetry, we obtain a few essential conditions for viable models of KDI associated with the graceful exit.
Redistribution of Kinetic Energy in Turbulent Flows
Alain Pumir
2014-10-01
Full Text Available In statistically homogeneous turbulent flows, pressure forces provide the main mechanism to redistribute kinetic energy among fluid elements, without net contribution to the overall energy budget. This holds true in both two-dimensional (2D and three-dimensional (3D flows, which show fundamentally different physics. As we demonstrate here, pressure forces act on fluid elements very differently in these two cases. We find in numerical simulations that in 3D pressure forces strongly accelerate the fastest fluid elements, and that in 2D this effect is absent. In 3D turbulence, our findings put forward a mechanism for a possibly singular buildup of energy, and thus may shed new light on the smoothness problem of the solution of the Navier-Stokes equation in 3D.
Immune adherence: a quantitative and kinetic analysis
Sekine, T [National Cancer Center, Tokyo (Japan). Research Inst.
1978-09-01
Quantitative and kinetic analysis of the immune-adherence reaction (IA) between C3b fragments and IA receptors as an agglutination reaction is difficult. Analysis is possible, however, by use of radio-iodinated bovine serum albumin as antigen at low concentrations (less than 200 ng/ml) and optimal concentration of antibody to avoid precipitation of antigen-antibody complexes with human erythrocytes without participation of complement. Antigen and antibody are reacted at 37/sup 0/C, complement is added, the mixture incubated and human erythrocytes added; after further incubation, ice-cold EDTA containing buffer is added and the erythrocytes centrifuged and assayed for radioactivity. Control cells reacted with heated guinea pig serum retained less than 5% of the added radioactivity. The method facilitates measurement of IA reactivity and permits more detailed analysis of the mechanism underlying the reaction.
Kinetic neoclassical calculations of impurity radiation profiles
D.P. Stotler
2017-08-01
Full Text Available Modifications of the drift-kinetic transport code XGC0 to include the transport, ionization, and recombination of individual charge states, as well as the associated radiation, are described. The code is first applied to a simulation of an NSTX H-mode discharge with carbon impurity to demonstrate the approach to coronal equilibrium. The effects of neoclassical phenomena on the radiated power profile are examined sequentially through the activation of individual physics modules in the code. Orbit squeezing and the neoclassical inward pinch result in increased radiation for temperatures above a few hundred eV and changes to the ratios of charge state emissions at a given electron temperature. Analogous simulations with a neon impurity yield qualitatively similar results.
Synchronization of DNA array replication kinetics
Manturov, Alexey O.; Grigoryev, Anton V.
2016-04-01
In the present work we discuss the features of the DNA replication kinetics at the case of multiplicity of simultaneously elongated DNA fragments. The interaction between replicated DNA fragments is carried out by free protons that appears at the every nucleotide attachment at the free end of elongated DNA fragment. So there is feedback between free protons concentration and DNA-polymerase activity that appears as elongation rate dependence. We develop the numerical model based on a cellular automaton, which can simulate the elongation stage (growth of DNA strands) for DNA elongation process with conditions pointed above and we study the possibility of the DNA polymerases movement synchronization. The results obtained numerically can be useful for DNA polymerase movement detection and visualization of the elongation process in the case of massive DNA replication, eg, under PCR condition or for DNA "sequencing by synthesis" sequencing devices evaluation.
Neutralization kinetics of charged polymer surface
Mukherjee, S. [Surface Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Mukherjee, M. [Surface Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)], E-mail: manabendra.mukherjee@saha.ac.in
2008-04-15
In case of photoemission spectroscopy of an insulating material the data obtained from the charged surface are normally distorted due to differential charging. Recently, we have developed a controlled surface neutralization technique to study the kinetics of the surface charging. Using this technique and the associated data analysis scheme with an effective charging model, quantitative information from the apparently distorted photoemission data from PTFE surfaces were extracted. The surface charging was controlled by tuning the electron flood current as well as the X-ray intensity. The effective model was found to describe the charging consistently for both the cases. It was shown that the non-linear neutralization response of differential charging around a critical neutralizing electron flux or a critical X-ray emission current was due to percolation of equipotential surface domains. The obtained value of the critical percolation exponent {gamma} close to unity indicates a percolation similar to that of avalanche breakdown or chain reaction.
Popcorn polymerisation of chloroprene. A kinetic investigation
Brough, Neil
1997-01-01
The project was sponsored by Du Font Dow Elastomers Ltd (Maydown, N. Ireland), in whose neoprene plant the popcorn polymers are found. The material itself has no commercial value, but grows rapidly and has the ability to block pipes and halt production. Therefore the production equipment containing monomers is all scheduled for 'popcorn search' inspections at intervals that differ according to the prevailing temperatures and monomer concentrations; a process which adds to costs. Prior work within the Queen's University of Belfast has identified the factors which affect the initiation of chlorobutadiene popcorn polymers, but available published and unpublished kinetic studies are in conflict concerning their rate of growth, and there is no data on the dichlorobutadiene popcorn polymer. In consequence, current relief system design procedures are based on a worst case scenario about popcorn growth rates and thus the design may be unduly expensive. The research obtained reliable kinetic data to allow these 'popcorn search' schedules to be rationalised and relief system designs to be improved and as a result to reduce the company's expenditure and improve operational safety margins. The proposed research was to investigate the kinetic behaviour of chlorinated butadiene monomers in the formation of omega- or 'popcorn' polymers. The growth rates of the chloroprene popcorn polymer were investigated at various temperatures in the liquid phase in the pure chloroprene monomer, mixed with other monomers and diluted with toluene in what we term 'Korean' type experiments. In these experiments the growth of popcorn polymer was terminated in a set of identically prepared ampoules after a fixed time. The growth rates of popcorn polymer seeds were obtained over various time periods, namely 24, 43 and 54 hours, at temperatures ranging from 10 deg C to 60 deg C. It was observed that the results differ greatly from those obtained by J.Op.Li. In particular, in the present work it was
Comparing kinetic curves in liquid chromatography
Kurganov, A. A.; Kanat'eva, A. Yu.; Yakubenko, E. E.; Popova, T. P.; Shiryaeva, V. E.
2017-01-01
Five equations for kinetic curves which connect the number of theoretical plates N and time of analysis t 0 for five different versions of optimization, depending on the parameters being varied (e.g., mobile phase flow rate, pressure drop, sorbent grain size), are obtained by means of mathematical modeling. It is found that a method based on the optimization of a sorbent grain size at fixed pressure is most suitable for the optimization of rapid separations. It is noted that the advantages of the method are limited by an area of relatively low efficiency, and the advantage of optimization is transferred to a method based on the optimization of both the sorbent grain size and the drop in pressure across a column in the area of high efficiency.
SPQR: a Monte Carlo reactor kinetics code
Cramer, S.N.; Dodds, H.L.
1980-02-01
The SPQR Monte Carlo code has been developed to analyze fast reactor core accident problems where conventional methods are considered inadequate. The code is based on the adiabatic approximation of the quasi-static method. This initial version contains no automatic material motion or feedback. An existing Monte Carlo code is used to calculate the shape functions and the integral quantities needed in the kinetics module. Several sample problems have been devised and analyzed. Due to the large statistical uncertainty associated with the calculation of reactivity in accident simulations, the results, especially at later times, differ greatly from deterministic methods. It was also found that in large uncoupled systems, the Monte Carlo method has difficulty in handling asymmetric perturbations
Kinetics of protein unfolding at interfaces
Yano, Yohko F
2012-01-01
The conformation of protein molecules is determined by a balance of various forces, including van der Waals attraction, electrostatic interaction, hydrogen bonding, and conformational entropy. When protein molecules encounter an interface, they are often adsorbed on the interface. The conformation of an adsorbed protein molecule strongly depends on the interaction between the protein and the interface. Recent time-resolved investigations have revealed that protein conformation changes during the adsorption process due to the protein-protein interaction increasing with increasing interface coverage. External conditions also affect the protein conformation. This review considers recent dynamic observations of protein adsorption at various interfaces and their implications for the kinetics of protein unfolding at interfaces. (topical review)
Kinetic depletion model for pellet ablation
Kuteev, Boris V.
2001-11-01
A kinetic model for depletion effect, which determines pellet ablation when the pellet passes a rational magnetic surface, is formulated. The model predicts a moderate decrease of the ablation rate compared with the earlier considered monoenergy versions [1, 2]. For typical T-10 conditions the ablation rate reduces by a reactor of 2.5 when the 1-mm pellet penetrates through the plasma center. A substantial deceleration of pellets -about 15% per centimeter of low shire rational q region; is predicted. Penetration for Low Field Side and High Field Side injections is considered taking into account modification of the electron distribution function by toroidal magnetic field. It is shown that Shafranov shift and toroidal effects yield the penetration length for HFS injection higher by a factor of 1.5. This fact should be taken into account when plasma-shielding effects on penetration are considered. (author)
Kinetic slow mode-type solitons
K. Baumgärtel
2005-01-01
Full Text Available One-dimensional hybrid code simulations are presented, carried out in order both to study solitary waves of the slow mode branch in an isotropic, collisionless, medium-β plasma (βi=0.25 and to test the fluid based soliton interpretation of Cluster observed strong magnetic depressions (Stasiewicz et al., 2003; Stasiewicz, 2004 against kinetic theory. In the simulations, a variety of strongly oblique, large amplitude, solitons are seen, including solitons with Alfvenic polarization, similar to those predicted by the Hall-MHD theory, and robust, almost non-propagating, solitary structures of slow magnetosonic type with strong magnetic field depressions and perpendicular ion heating, which have no counterpart in fluid theory. The results support the soliton-based interpretation of the Cluster observations, but reveal substantial deficiencies of Hall-MHD theory in describing slow mode-type solitons in a plasma of moderate beta.
MATHEMATICAL MODELING OF ORANGE SEED DRYING KINETICS
Daniele Penteado Rosa
2015-06-01
Full Text Available Drying of orange seeds representing waste products from juice processing was studied in the temperatures of 40, 50, 60 and 70 °C and drying velocities of 0.6, 1.0 and 1.4 m/s. Experimental drying kinetics of orange seeds were obtained using a convective air forced dryer. Three thin-layer models: Page model, Lewis model, and the Henderson-Pabis model and the diffusive model were used to predict the drying curves. The Henderson-Pabis and the diffusive models show the best fitting performance and statistical evaluations. Moreover, the temperature dependence on the effective diffusivity followed an Arrhenius relationship, and the activation energies ranging from 16.174 to 16.842 kJ/mol
High temperature oxidation kinetics of dysprosium particles
Jaques, Brian J.; Butt, Darryl P., E-mail: DarrylButt@BoiseState.edu
2015-09-25
Highlights: • The oxidation behavior of dysprosium particles was studied from 500 to 1000 °C. • Activation energy in initial region found as 8–25 kJ/mol, depending on atmosphere. • Activation energy in intermediate region found as 80–95 kJ/mol. • The oxide grows at the metal–oxide interface. • Generally, the formed oxide behaved as a p-type semiconductor. - Abstract: Rare earth elements have been recognized as critical materials for the advancement of many strategic and green technologies. Recently, the United States Department of Energy has invested many millions of dollars to enhance, protect, and forecast their production and management. The work presented here attempts to clarify the limited and contradictory literature on the oxidation behavior of the rare earth metal, dysprosium. Dysprosium particles were isothermally oxidized from 500 to 1000 °C in N{sub 2}–(2%, 20%, and 50%) O{sub 2} and Ar–20% O{sub 2} using simultaneous thermal analysis techniques. Two distinct oxidation regions were identified at each isothermal temperature in each oxidizing atmosphere. Initially, the oxidation kinetics are very fast until the reaction enters a slower, intermediate region of oxidation. The two regions are defined and the kinetics of each are assessed to show an apparent activation energy of 8–25 kJ/mol in the initial region and 80–95 kJ/mol in the intermediate oxidation reaction region. The effects of varying the oxygen partial pressure on the reaction rate constant are used to show that dysprosium oxide (Dy{sub 2}O{sub 3}) generally acts as a p-type semiconductor in both regions of oxidation (with an exception above 750 °C in the intermediate region)
Kinetics and oxidation mechanisms of polycrystaline niobium
Paschoal, J.O.A.
1979-01-01
The oxidation kinetics of annealed niobium was determined by thermogravimetric analysis between 450 and 800 0 C and for oxygen pressures varying from 20 to 700 mmHg. The oxidation kinetics of cold worked and/or irradiated niobium for temperatures between 500 and 700 0 C, with oxygen pressures varying from 100 to 300 mmHg. Was also determined. Using X-ray diffraction it was found that the oxide formed in the range of temperature and oxygen pressure considered in this research is γ-Nb 2 O 5 . Optical and scanning eletronic microscopy showed that for annealed niobium oxidized under 600 0 C there was formation of non-uniform oxide layers, containing cracks and pores, presenting very irregular metal/pentoxide interface. The presence of sub-oxide NbOsub(z) platelets was observed in this interface. This sub-oxide platelets where not observed in annealed oxidized niobium samples over 600 0 C; the oxide layers formed were compact. At 800 0 C and the beginning at 700 0 C the interfaces were quite regular. Through microhardness measurements for the metal near the metal/pentoxide interface, the formation of oxygen solid solution was found and the oxygen diffusion coefficient was calculated. The results showed that at 600 0 C the oxygen diffusion coefficient in cold worked niobium is three times larger than the value obtained for annealed niobium. The results suggest that the reaction between annealed niobium and oxygen undaer 600 0 C is controlled by reaction in interface where the oxide layers are not compacted, parcially due to Nb sub(z) platelets formation.(Author) [pt
Kinetic quantification of plyometric exercise intensity.
Ebben, William P; Fauth, McKenzie L; Garceau, Luke R; Petushek, Erich J
2011-12-01
Ebben, WP, Fauth, ML, Garceau, LR, and Petushek, EJ. Kinetic quantification of plyometric exercise intensity. J Strength Cond Res 25(12): 3288-3298, 2011-Quantification of plyometric exercise intensity is necessary to understand the characteristics of these exercises and the proper progression of this mode of exercise. The purpose of this study was to assess the kinetic characteristics of a variety of plyometric exercises. This study also sought to assess gender differences in these variables. Twenty-six men and 23 women with previous experience in performing plyometric training served as subjects. The subjects performed a variety of plyometric exercises including line hops, 15.24-cm cone hops, squat jumps, tuck jumps, countermovement jumps (CMJs), loaded CMJs equal to 30% of 1 repetition maximum squat, depth jumps normalized to the subject's jump height (JH), and single leg jumps. All plyometric exercises were assessed with a force platform. Outcome variables associated with the takeoff, airborne, and landing phase of each plyometric exercise were evaluated. These variables included the peak vertical ground reaction force (GRF) during takeoff, the time to takeoff, flight time, JH, peak power, landing rate of force development, and peak vertical GRF during landing. A 2-way mixed analysis of variance with repeated measures for plyometric exercise type demonstrated main effects for exercise type and all outcome variables (p ≤ 0.05) and for the interaction between gender and peak vertical GRF during takeoff (p ≤ 0.05). Bonferroni-adjusted pairwise comparisons identified a number of differences between the plyometric exercises for the outcome variables assessed (p ≤ 0.05). These findings can be used to guide the progression of plyometric training by incorporating exercises of increasing intensity over the course of a program.
Kinetics of monomer biodegradation in soil.
Siotto, Michela; Sezenna, Elena; Saponaro, Sabrina; Innocenti, Francesco Degli; Tosin, Maurizio; Bonomo, Luca; Mezzanotte, Valeria
2012-01-01
In modern intensive agriculture, plastics are used in several applications (i.e. mulch films, drip irrigation tubes, string, clips, pots, etc.). Interest towards applying biodegradable plastics to replace the conventional plastics is promising. Ten monomers, which can be applied in the synthesis of potentially biodegradable polyesters, were tested according to ASTM 5988-96 (standard respirometric test to evaluate aerobic biodegradation in soil by measuring the carbon dioxide evolution): adipic acid, azelaic acid, 1,4-butanediol, 1,2-ethanediol, 1,6-hexanediol, lactic acid, glucose, sebacic acid, succinic acid and terephthalic acid. Eight replicates were carried out for each monomer for 27-45 days. The numerical code AQUASIM was applied to process the CO₂ experimental data in order to estimate values for the parameters describing the different mechanisms occurring to the monomers in soil: i) the first order solubilization kinetic constant, K(sol) (d⁻¹); ii) the first order biodegradation kinetic constant, K(b) (d⁻¹); iii) the lag time in biodegradation, t(lag) (d); and iv) the carbon fraction biodegraded but not transformed into CO₂, Y (-). The following range of values were obtained: [0.006 d⁻¹, 6.9 d⁻¹] for K(sol), [0.1 d⁻¹, 1.2 d⁻¹] for K(b), and [0.32-0.58] for Y; t(lag) was observed for azelaic acid, 1,2-ethanediol, and terephthalic acid, with estimated values between 3.0 e 4.9 d. Copyright © 2011 Elsevier Ltd. All rights reserved.
Kinetics of particle ensembles with variable charges
Ivlev, A. V.; Zhdanov, S.; Klumov, B.; Morfill, G.; Tsytovich, V. N.; Angelis, U. de
2005-01-01
One of the remarkable features distinguishing complex (dusty) plasmas from usual plasmas is that charges on the grains are not constant, but fluctuate in time around some equilibrium value which, in then, is some function of spatial coordinates. Generally, ensembles of particles with variable charges are non-Hamiltonian systems where the mutual collisions do not conserve energy. Therefore, the use of thermodynamic potentials to describe such systems is not really valid. An appropriate way to investigate their evolution is to employ the kinetic approach. We studied (both analytical and numerically) two cases: (a) inhomogeneous charge-it depends on the particle coordinate but does not change in time, and (b)fluctuating charge-it changes in time around the equilibrium value, which is constant in space. For both cases we used the Fokker-Planck approach to derive the collision integral which describes the momentum and energy transfer in mutual particle collisions as well as in the collisions with neutrals. We obtained that the mean particle energy grows in time when the neutral friction is below a certain threshold (as shown in Fig. 1). In case (a) the energy changes as ∞(t c r-t)''2, in case (b) it scales as ∞(t c r-t)''-1, exhibiting the explosion-like growth with t c r a critical time scale. The obtained solutions can be of significant importance for laboratory dusty plasmas as well as for space plasma environments, where inhomogeneous charge distributions are often present. For instance, the instability can cause dust heating in low-pressure complex plasma experiments, it can be responsible for the melting of plasma crystals, it might operate in protoplanetary disks and effect the kinetics of the planet formation, etc. (Author)
Fractional Bhatnagar-Gross-Krook kinetic equation
Goychuk, Igor
2017-11-01
The linear Boltzmann equation (LBE) approach is generalized to describe fractional superdiffusive transport of the Lévy walk type in external force fields. The time distribution between scattering events is assumed to have a finite mean value and infinite variance. It is completely characterized by the two scattering rates, one fractional and a normal one, which defines also the mean scattering rate. We formulate a general fractional LBE approach and exemplify it with a particularly simple case of the Bohm and Gross scattering integral leading to a fractional generalization of the Bhatnagar, Gross and Krook (BGK) kinetic equation. Here, at each scattering event the particle velocity is completely randomized and takes a value from equilibrium Maxwell distribution at a given fixed temperature. We show that the retardation effects are indispensable even in the limit of infinite mean scattering rate and argue that this novel fractional kinetic equation provides a viable alternative to the fractional Kramers-Fokker-Planck (KFP) equation by Barkai and Silbey and its generalization by Friedrich et al. based on the picture of divergent mean time between scattering events. The case of divergent mean time is also discussed at length and compared with the earlier results obtained within the fractional KFP. Also a phenomenological fractional BGK equation without retardation effects is proposed in the limit of infinite scattering rates. It cannot be, however, rigorously derived from a scattering model, being rather clever postulated. It this respect, this retardationless equation is similar to the fractional KFP by Barkai and Silbey. However, it corresponds to the opposite, much more physical limit and, therefore, also presents a viable alternative.
Kinetics of phosphomevalonate kinase from Saccharomyces cerevisiae.
David E Garcia
Full Text Available The mevalonate-based isoprenoid biosynthetic pathway is responsible for producing cholesterol in humans and is used commercially to produce drugs, chemicals, and fuels. Heterologous expression of this pathway in Escherichia coli has enabled high-level production of the antimalarial drug artemisinin and the proposed biofuel bisabolane. Understanding the kinetics of the enzymes in the biosynthetic pathway is critical to optimize the pathway for high flux. We have characterized the kinetic parameters of phosphomevalonate kinase (PMK, EC 2.7.4.2 from Saccharomyces cerevisiae, a previously unstudied enzyme. An E. coli codon-optimized version of the S. cerevisiae gene was cloned into pET-52b+, then the C-terminal 6X His-tagged protein was expressed in E. coli BL21(DE3 and purified on a Ni²⁺ column. The KM of the ATP binding site was determined to be 98.3 µM at 30°C, the optimal growth temperature for S. cerevisiae, and 74.3 µM at 37°C, the optimal growth temperature for E. coli. The K(M of the mevalonate-5-phosphate binding site was determined to be 885 µM at 30°C and 880 µM at 37°C. The V(max was determined to be 4.51 µmol/min/mg enzyme at 30°C and 5.33 µmol/min/mg enzyme at 37°C. PMK is Mg²⁺ dependent, with maximal activity achieved at concentrations of 10 mM or greater. Maximum activity was observed at pH = 7.2. PMK was not found to be substrate inhibited, nor feedback inhibited by FPP at concentrations up to 10 µM FPP.
Kinetic energy factors in evaluation of athletes.
Jones, Jason N; Priest, Joe W; Marble, Daniel K
2008-11-01
It is established that speed and agility are critical attributes of sports performance. Performance timing of runs during agility course testing can be used to estimate acceleration, speed, or quickness. The authors of this research effort also report the energy of motion, or kinetic energy of the athlete, which considers not only the speed but also the mass of the athlete. An electronic timer was used to determine total run times as well as split performance times during a new 60-yd "run-shuttle" test. This newly designed agility test takes advantage of the technological capabilities of a laser timing device. Separate times for each of four run segments were recorded and converted to average speeds (m x s(-1)) as well as a quantitative factor of merit defined as the "K-factor." The purpose of this study was to describe the effects of training and to compare athletes and teams using measures of time, speed, and kinetic energy. Results of the analysis of total time on the 60-yd run-shuttle provided evidence of the effectiveness of the training programs. Split times of segments within the 60-yd run-shuttle provided information not available from conventional agility tests. Average speeds and K-factors identified discriminating characteristics of otherwise similar athletes. Our findings support the conclusion that training programs and athletic performance may be evaluated using the 60-yd run-shuttle with laser timer system. Coaches and trainers may find practical application of this technology for American football, soccer, basketball, baseball/softball, track and field, and field hockey.
Nonlocal kinetic energy functionals by functional integration
Mi, Wenhui; Genova, Alessandro; Pavanello, Michele
2018-05-01
Since the seminal studies of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting kinetic energy, Ts[ρ], the subject of this work. The typical paradigm is to first approximate the energy functional and then take its functional derivative, δ/Ts[ρ ] δ ρ (r ) , yielding a potential that can be used in orbital-free DFT or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for Ts[ρ] is prescribed [which we dub Mi-Genova-Pavanello (MGP)] having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential is derived from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (body-centered cubic, face-centered cubic) and semiconducting (crystal diamond) phases of silicon as well as of III-V semiconductors. The MGP functional is found to be numerically stable typically reaching self-consistency within 12 iterations of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter nonlocal functional or any generalized gradient approximation functional.
Thermodynamically consistent model calibration in chemical kinetics
Goutsias John
2011-05-01
Full Text Available Abstract Background The dynamics of biochemical reaction systems are constrained by the fundamental laws of thermodynamics, which impose well-defined relationships among the reaction rate constants characterizing these systems. Constructing biochemical reaction systems from experimental observations often leads to parameter values that do not satisfy the necessary thermodynamic constraints. This can result in models that are not physically realizable and may lead to inaccurate, or even erroneous, descriptions of cellular function. Results We introduce a thermodynamically consistent model calibration (TCMC method that can be effectively used to provide thermodynamically feasible values for the parameters of an open biochemical reaction system. The proposed method formulates the model calibration problem as a constrained optimization problem that takes thermodynamic constraints (and, if desired, additional non-thermodynamic constraints into account. By calculating thermodynamically feasible values for the kinetic parameters of a well-known model of the EGF/ERK signaling cascade, we demonstrate the qualitative and quantitative significance of imposing thermodynamic constraints on these parameters and the effectiveness of our method for accomplishing this important task. MATLAB software, using the Systems Biology Toolbox 2.1, can be accessed from http://www.cis.jhu.edu/~goutsias/CSS lab/software.html. An SBML file containing the thermodynamically feasible EGF/ERK signaling cascade model can be found in the BioModels database. Conclusions TCMC is a simple and flexible method for obtaining physically plausible values for the kinetic parameters of open biochemical reaction systems. It can be effectively used to recalculate a thermodynamically consistent set of parameter values for existing thermodynamically infeasible biochemical reaction models of cellular function as well as to estimate thermodynamically feasible values for the parameters of new
Kinetic model of excess activated sludge thermohydrolysis.
Imbierowicz, Mirosław; Chacuk, Andrzej
2012-11-01
Thermal hydrolysis of excess activated sludge suspensions was carried at temperatures ranging from 423 K to 523 K and under pressure 0.2-4.0 MPa. Changes of total organic carbon (TOC) concentration in a solid and liquid phase were measured during these studies. At the temperature 423 K, after 2 h of the process, TOC concentration in the reaction mixture decreased by 15-18% of the initial value. At 473 K total organic carbon removal from activated sludge suspension increased to 30%. It was also found that the solubilisation of particulate organic matter strongly depended on the process temperature. At 423 K the transfer of TOC from solid particles into liquid phase after 1 h of the process reached 25% of the initial value, however, at the temperature of 523 K the conversion degree of 'solid' TOC attained 50% just after 15 min of the process. In the article a lumped kinetic model of the process of activated sludge thermohydrolysis has been proposed. It was assumed that during heating of the activated sludge suspension to a temperature in the range of 423-523 K two parallel reactions occurred. One, connected with thermal destruction of activated sludge particles, caused solubilisation of organic carbon and an increase of dissolved organic carbon concentration in the liquid phase (hydrolysate). The parallel reaction led to a new kind of unsolvable solid phase, which was further decomposed into gaseous products (CO(2)). The collected experimental data were used to identify unknown parameters of the model, i.e. activation energies and pre-exponential factors of elementary reactions. The mathematical model of activated sludge thermohydrolysis appropriately describes the kinetics of reactions occurring in the studied system. Copyright © 2012 Elsevier Ltd. All rights reserved.
On-rate based optimization of structure-kinetic relationship--surfing the kinetic map.
Schoop, Andreas; Dey, Fabian
2015-10-01
In the lead discovery process residence time has become an important parameter for the identification and characterization of the most efficacious compounds in vivo. To enable the success of compound optimization by medicinal chemistry toward a desired residence time the understanding of structure-kinetic relationship (SKR) is essential. This article reviews various approaches to monitor SKR and suggests using the on-rate as the key monitoring parameter. The literature is reviewed and examples of compound series with low variability as well as with significant changes in on-rates are highlighted. Furthermore, findings of kinetic on-rate changes are presented and potential underlying rationales are discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.
Uptake kinetics of arsenic by lettuce cultivars under hydroponics ...
Arsenic (As) uptake ability based on kinetic parameters by two lettuce cultivars; Sijibaiye (SJBY) and Texuanyanlingsun (TXYLS) was investigated in nutrient solution containing eight levels of arsenic (As). Depletion of As from solution was monitored over a period of 24 h at regular time to estimate As uptake kinetics of the ...
Kinetic mechanism of the decomposition of dimethyltin dichloride
Mol, van A.M.B.; Croon, de M.H.J.M.; Spee, C.I.M.A.; Schouten, J.C.
1999-01-01
Results are reported of a study of the intrinsic kinetics of gas phase reactions. For this purpose a reactor system is designed in such a way that concentration and temperature variations throughout the reactor can be neglected enabling investigation of intrinsic reaction kinetics. The gas phase
The kinetics of hydrolysis of acetylsalicylic acid (Aspirin) in different ...
The kinetics of hydrolysis of Acetylsalicylic acid (Aspirin) to salicylic acid was followed by the direct spectrophotometric measurement of the amount of salicylic acid produced with time. Salicylic acid was complexed with ferric ion giving a characteristic purple colour (λlm 523nm). The kinetics of hydrolysis was found to follow ...
The kinetics and thermodynamics of adsorption of heavy metal ions ...
Titanium-Pillared and Un-Pillared bentonite clays were studied in order to evaluate the thermodynamics and kinetics of heavy metal ion removal from aqueous solutions. The results showed that the maximum sorption of Cu, Cd, Hg and Pb ions occurred within 30 minutes. A pseudo-second order kinetic model was used to ...
Key factors of combustion from kinetics to gas dynamics
Rubtsov, Nikolai M
2017-01-01
This book summarizes the main advances in the mechanisms of combustion processes. It focuses on the analysis of kinetic mechanisms of gas combustion processes and experimental investigation into the interrelation of kinetics and gas dynamics in gas combustion. The book is complimentary to the one previously published, The Modes of Gaseous Combustion.
Satl model lesson in chemical kinetics | Nazir | African Journal of ...
Studies in order to pursue kinetics and mechanism of chemical reactions are a vital component of chemical literature. SATL literature is still not available for promoting this vital aspect of chemistry teaching. A lesson pertaining to this important issue has been developed and various parameters of kinetic studies are ...
Kinetic models in spin chemistry. 1. The hyperfine interaction
Mojaza, M.; Pedersen, J. B.
2012-01-01
Kinetic models for quantum systems are quite popular due to their simplicity, although they are difficult to justify. We show that the transformation from quantum to kinetic description can be done exactly for the hyperfine interaction of one nuclei with arbitrary spin; more spins are described w...... induced enhancement of the reaction yield. (C) 2012 Elsevier B.V. All rights reserved....
Kinetics and mechanism of oxidation of chloramphenicol by 1
Chloramphenicol (CAP) is an antibiotic drug having a wide spectrum of activity. The kinetics of oxidation of chloramphenicol by 1-chlorobenzotriazole (CBT) in HClO4 medium over the temperature range 293-323 K has been investigated. The reaction exhibits first-order kinetics with respect to [CBT]o and zero-order with ...
Kinetics of Oxidation of Aliphatic Alcohols by Potassium Dichromate ...
The kinetics of oxidation of four aliphatic alcohols in acidic aqueous and micellar media were investigated. The reaction was found to be first-order with respect to both alcohol and oxidant. Pseudo-first-order kinetics were found to be perfectly applicable with ethanol, 1-propanol and 2-propanol while deviation was observed ...
Application of Chemical Kinetics to Deterioration of Foods.
Labuza, T. P.
1984-01-01
Possible modes of food deterioration (such as microbial decay, nonenzymatic browning, senescence, lipid oxidation) are reviewed. A basic mathematical approach to the kinetics of food deterioration, kinetic approach to accelerating shelf-life deterioration, and shelf-life predictions are discussed. (JN)
Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks
Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.
2011-01-01
Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…
Kinetic Scale Structure of Low-frequency Waves and Fluctuations
López, Rodrigo A.; Yoon, Peter H. [Institute for Physical Science and Technology, University of Maryland, College Park, MD 20742 (United States); Viñas, Adolfo F. [NASA Goddard Space Flight Center, Heliophysics Science Division, Geospace Physics Laboratory, Mail Code 673, Greenbelt, MD 20771 (United States); Araneda, Jaime A., E-mail: rlopezh@umd.edu, E-mail: yoonp@umd.edu [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Concepción, Concepción (Chile)
2017-08-10
The dissipation of solar wind turbulence at kinetic scales is believed to be important for the heating of the corona and for accelerating the wind. The linear Vlasov kinetic theory is a useful tool for identifying various wave modes, including kinetic Alfvén, fast magnetosonic/whistler, and ion-acoustic (or kinetic slow), and their possible roles in the dissipation. However, the kinetic mode structure in the vicinity of ion-cyclotron modes is not clearly understood. The present paper aims to further elucidate the structure of these low-frequency waves by introducing discrete particle effects through hybrid simulations and Klimontovich formalism of spontaneous emission theory. The theory and simulation of spontaneously emitted low-frequency fluctuations are employed to identify and distinguish the detailed mode structures associated with ion-Bernstein modes versus quasi-modes. The spontaneous emission theory and simulation also confirm the findings of the Vlasov theory in that the kinetic Alfvén waves can be defined over a wide range of frequencies, including the proton cyclotron frequency and its harmonics, especially for high-beta plasmas. This implies that these low-frequency modes may play predominant roles even in the fully kinetic description of kinetic scale turbulence and dissipation despite the fact that cyclotron harmonic and Bernstein modes may also play important roles in wave–particle interactions.
In vitro studies of ante-mortem proliferation kinetics
McBride, W.H.; Withers, H.R.
1986-01-01
Using K562 human erythroblastoid cells, it was concluded that dose fractionation has no discrepant effect on the ante-mortem proliferation kinetics of doomed cells as opposed to clonogenic cell survival and that effects on ante-mortem proliferation kinetics cannot be solely responsible for the differences in fractionation response between early and late responding tissues. (UK)
Kinetic models of cell growth, substrate utilization and bio ...
Bio-decolorization kinetic studies of distillery effluent in a batch culture were conducted using Aspergillus fumigatus. A simple model was proposed using the Logistic Equation for the growth, Leudeking-Piret kinetics for bio-decolorization, and also for substrate utilization. The proposed models appeared to provide a suitable ...
Wang, Xun; Hu, Mian; Hu, Wanyong; Chen, Zhihua; Liu, Shiming; Hu, Zhiquan; Xiao, Bo
2016-11-01
Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)[-ln(1-α)](-0.0515), f(α)=(1-α)(1.0597)α(-0.6909)[-ln(1-α)](0.9026) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law. Copyright © 2016 Elsevier Ltd. All rights reserved.
Performance of neutron kinetics models for ADS transient analyses
Rineiski, A.; Maschek, W.; Rimpault, G.
2002-01-01
Within the framework of the SIMMER code development, neutron kinetics models for simulating transients and hypothetical accidents in advanced reactor systems, in particular in Accelerator Driven Systems (ADSs), have been developed at FZK/IKET in cooperation with CE Cadarache. SIMMER is a fluid-dynamics/thermal-hydraulics code, coupled with a structure model and a space-, time- and energy-dependent neutronics module for analyzing transients and accidents. The advanced kinetics models have also been implemented into KIN3D, a module of the VARIANT/TGV code (stand-alone neutron kinetics) for broadening application and for testing and benchmarking. In the paper, a short review of the SIMMER and KIN3D neutron kinetics models is given. Some typical transients related to ADS perturbations are analyzed. The general models of SIMMER and KIN3D are compared with more simple techniques developed in the context of this work to get a better understanding of the specifics of transients in subcritical systems and to estimate the performance of different kinetics options. These comparisons may also help in elaborating new kinetics models and extending existing computation tools for ADS transient analyses. The traditional point-kinetics model may give rather inaccurate transient reaction rate distributions in an ADS even if the material configuration does not change significantly. This inaccuracy is not related to the problem of choosing a 'right' weighting function: the point-kinetics model with any weighting function cannot take into account pronounced flux shape variations related to possible significant changes in the criticality level or to fast beam trips. To improve the accuracy of the point-kinetics option for slow transients, we have introduced a correction factor technique. The related analyses give a better understanding of 'long-timescale' kinetics phenomena in the subcritical domain and help to evaluate the performance of the quasi-static scheme in a particular case. One
Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas
2017-07-19
Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.
Simulation of ITG instabilities with fully kinetic ions and drift-kinetic electrons in tokamaks
Hu, Youjun; Chen, Yang; Parker, Scott
2017-10-01
A turbulence simulation model with fully kinetic ions and drift-kinetic electrons is being developed in the toroidal electromagnetic turbulence code GEM. This is motivated by the observation that gyrokinetic ions are not well justified in simulating turbulence in tokamak edges with steep density profile, where ρi / L is not small enough to be used a small parameter needed by the gyrokinetic ordering (here ρi is the gyro-radius of ions and L is the scale length of density profile). In this case, the fully kinetic ion model may be useful. Our model uses an implicit scheme to suppress high-frequency compressional Alfven waves and waves associated with the gyro-motion of ions. The ion orbits are advanced by using the well-known Boris scheme, which reproduces correct drift-motion even with large time-step comparable to the ion gyro-period. The field equation in this model is Ampere's law with the magnetic field eliminated by using an implicit scheme of Faraday's law. The current contributed by ions are computed by using an implicit δf method. A flux tube approximation is adopted, which makes the field equation much easier to solve. Numerical results of electromagnetic ITG obtained from this model will be presented and compared with the gyrokinetic results. This work is supported by U.S. Department of Energy, Office of Fusion Energy Sciences under Award No. DE-SC0008801.
Dsc cure kinetics of an unsaturated polyester resin using empirical kinetic model
Abdullah, I.
2015-01-01
In this paper, the kinetics of curing of unsaturated polyester resin initiated with benzoyl peroxide was studied. In case of unsaturated polyester (UP) resin, isothermal test alone could not predict correctly the curing time of UP resin. Therefore, isothermal kinetic analysis through isoconventional adjustment was used to correctly predict the curing time and temperature of UP resin. Isothermal kinetic analysis through isoconversional adjustment indicated that 97% of UP resin cures in 33 min at 120 degree C. Curing of UP resin through microwaves was also studied and found that 67% of UP resin cures in 1 min at 120 degree C. The crosslinking reaction of UP resin is so fast at 120 degree C that it becomes impossible to predict correctly the curing time of UP resin using isothermal test and the burial of C=C bonds in microgels makes it impossible to be fully cured by microwaves at 120 degree C. The rheological behaviour of unsaturated polyester resin was also studied to observe the change in viscosity with respect to time and temperature. (author)
Borén, Jan; Watts, Gerald F; Adiels, Martin; Söderlund, Sanni; Chan, Dick C; Hakkarainen, Antti; Lundbom, Nina; Matikainen, Niina; Kahri, Juhani; Vergès, Bruno; Barrett, P Hugh R; Taskinen, Marja-Riitta
2015-10-01
Patients with obesity and diabetes mellitus have increased risk of cardiovascular disease. A major cause is an atherogenic dyslipidemia related primarily to elevated plasma concentrations of triglyceride-rich lipoproteins. The aim of this study was to clarify determinants of plasma triglyceride concentration. We focused on factors that predict the kinetics of very-low density lipoprotein 1 (VLDL1) triglycerides. A multicenter study using dual stable isotopes (deuterated leucine and glycerol) and multicompartmental modeling was performed to elucidate the kinetics of triglycerides and apoB in VLDL1 in 46 subjects with abdominal obesity and additional cardiometabolic risk factors. Results showed that plasma triglyceride concentrations were dependent on both the secretion rate (r=0.44, Ptriglycerides and VLDL1-apoB. Liver fat mass was independently and directly associated with secretion rates of VLDL1-triglycerides (r=0.56, Ptriglycerides (r=0.48, Ptriglyceride concentrations in abdominal obesity are determined by the kinetics of VLDL1 subspecies, catabolism being mainly dependent on apoC-III concentration and secretion on liver fat content. Reduction in liver fat and targeting apoC-III may be an effective approach for correcting triglyceride metabolism atherogenic dyslipidemia in obesity. © 2015 American Heart Association, Inc.
The Einstein-Vlasov System/Kinetic Theory.
Andréasson, Håkan
2011-01-01
The main purpose of this article is to provide a guide to theorems on global properties of solutions to the Einstein-Vlasov system. This system couples Einstein's equations to a kinetic matter model. Kinetic theory has been an important field of research during several decades in which the main focus has been on non-relativistic and special relativistic physics, i.e., to model the dynamics of neutral gases, plasmas, and Newtonian self-gravitating systems. In 1990, Rendall and Rein initiated a mathematical study of the Einstein-Vlasov system. Since then many theorems on global properties of solutions to this system have been established. This paper gives introductions to kinetic theory in non-curved spacetimes and then the Einstein-Vlasov system is introduced. We believe that a good understanding of kinetic theory in non-curved spacetimes is fundamental to a good comprehension of kinetic theory in general relativity.
Fully kinetic simulations of megajoule-scale dense plasma focus
Schmidt, A.; Link, A.; Tang, V.; Halvorson, C.; May, M. [Lawrence Livermore National Laboratory, Livermore California 94550 (United States); Welch, D. [Voss Scientific, LLC, Albuquerque, New Mexico 87108 (United States); Meehan, B. T.; Hagen, E. C. [National Security Technologies, LLC, Las Vegas, Nevada 89030 (United States)
2014-10-15
Dense plasma focus (DPF) Z-pinch devices are sources of copious high energy electrons and ions, x-rays, and neutrons. Megajoule-scale DPFs can generate 10{sup 12} neutrons per pulse in deuterium gas through a combination of thermonuclear and beam-target fusion. However, the details of the neutron production are not fully understood and past optimization efforts of these devices have been largely empirical. Previously, we reported on the first fully kinetic simulations of a kilojoule-scale DPF and demonstrated that both kinetic ions and kinetic electrons are needed to reproduce experimentally observed features, such as charged-particle beam formation and anomalous resistivity. Here, we present the first fully kinetic simulation of a MegaJoule DPF, with predicted ion and neutron spectra, neutron anisotropy, neutron spot size, and time history of neutron production. The total yield predicted by the simulation is in agreement with measured values, validating the kinetic model in a second energy regime.
Empiricism or self-consistent theory in chemical kinetics?
Gutman, E.M.
2007-01-01
To give theoretical background for mechanochemical kinetics, we need first of all to find a possibility to predict the kinetic parameters for real chemical processes by determining rate constants and reaction orders without developing strictly specialized and, to a great extent, artificial models, i.e. to derive the kinetic law of mass action from 'first principles'. However, the kinetic law of mass action has had only an empirical basis from the first experiments of Gulberg and Waage until now, in contrast to the classical law of mass action for chemical equilibrium rigorously derived in chemical thermodynamics from equilibrium condition. Nevertheless, in this paper, an attempt to derive the kinetic law of mass action from 'first principles' is made in macroscopic formulation. It has turned out to be possible owing to the methods of thermodynamics of irreversible processes that were unknown in Gulberg and Waage's time
Deep subcritical levels measurements dependents upon kinetic distortion factors
Pan Shibiao; Li Xiang; Fu Guo'en; Huang Liyuan; Mu Keliang
2013-01-01
The measurement of deep subcritical levels, with the increase of subcriticality, showed that the results impact on the kinetic distortion effect, along with neutron flux strongly deteriorated. Using the diffusion theory, calculations have been carried out to quantify the kinetic distortion correction factors in subcritical systems, and these indicate that epithermal neutron distributions are strongly affected by kinetic distortion. Subcriticality measurements in four different rod-state combination at the zero power device was carried out. The test data analysis shows that, with increasing subcriticality, kinetic distortion effect correction factor gradually increases from 1.052 to 1.065, corresponding reactive correction amount of 0.78β eff ∼ 3.01β eff . Thus, it is necessary to consider the kinetic distortion effect in the deep subcritical reactivity measurements. (authors)
Kinetic modeling of cell metabolism for microbial production.
Costa, Rafael S; Hartmann, Andras; Vinga, Susana
2016-02-10
Kinetic models of cellular metabolism are important tools for the rational design of metabolic engineering strategies and to explain properties of complex biological systems. The recent developments in high-throughput experimental data are leading to new computational approaches for building kinetic models of metabolism. Herein, we briefly survey the available databases, standards and software tools that can be applied for kinetic models of metabolism. In addition, we give an overview about recently developed ordinary differential equations (ODE)-based kinetic models of metabolism and some of the main applications of such models are illustrated in guiding metabolic engineering design. Finally, we review the kinetic modeling approaches of large-scale networks that are emerging, discussing their main advantages, challenges and limitations. Copyright © 2015 Elsevier B.V. All rights reserved.
Lumping procedure for a kinetic model of catalytic naphtha reforming
H. M. Arani
2009-12-01
Full Text Available A lumping procedure is developed for obtaining kinetic and thermodynamic parameters of catalytic naphtha reforming. All kinetic and deactivation parameters are estimated from industrial data and thermodynamic parameters are calculated from derived mathematical expressions. The proposed model contains 17 lumps that include the C6 to C8+ hydrocarbon range and 15 reaction pathways. Hougen-Watson Langmuir-Hinshelwood type reaction rate expressions are used for kinetic simulation of catalytic reactions. The kinetic parameters are benchmarked with several sets of plant data and estimated by the SQP optimization method. After calculation of deactivation and kinetic parameters, plant data are compared with model predictions and only minor deviations between experimental and calculated data are generally observed.
A century of enzyme kinetic analysis, 1913 to 2013.
Johnson, Kenneth A
2013-09-02
This review traces the history and logical progression of methods for quantitative analysis of enzyme kinetics from the 1913 Michaelis and Menten paper to the application of modern computational methods today. Following a brief review of methods for fitting steady state kinetic data, modern methods are highlighted for fitting full progress curve kinetics based upon numerical integration of rate equations, including a re-analysis of the original Michaelis-Menten full time course kinetic data. Finally, several illustrations of modern transient state kinetic methods of analysis are shown which enable the elucidation of reactions occurring at the active sites of enzymes in order to relate structure and function. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.
Electron kinetics modeling in a weakly ionized gas
Boeuf, Jean-Pierre
1985-01-01
This work presents some features of electron kinetics in a weakly ionized gas. After a summary of the basis and recent developments of the kinetic theory, and a review of the most efficient numerical techniques for solving the Boltzmann equation, several aspects of electron motion in gases are analysed. Relaxation phenomena toward equilibrium under a uniform electric field, and the question of the existence of the hydrodynamic regime are first studied. The coupling between electron kinetics and chemical kinetics due to second kind collisions in Nitrogen is then analysed; a quantitative description of the evolution of the energy balance, accounting for electron-molecule as well as molecule-molecule energy transfer is also given. Finally, electron kinetics in space charge distorted, highly non uniform electric fields (glow discharges, streamers propagation) is investigated with microscopic numerical methods based on Boltzmann and Poisson equations. (author) [fr
Ise, Takeharu
1976-12-01
Review studies have been made on algorithms of numerical analysis and benchmark tests on point kinetics and quasistatic approximate kinetics computer codes to perform efficiently benchmark tests on space-dependent neutron kinetics codes. Point kinetics methods have now been improved since they can be directly applied to the factorization procedures. Methods based on Pade rational function give numerically stable solutions and methods on matrix-splitting are interested in the fact that they are applicable to the direct integration methods. An improved quasistatic (IQ) approximation is the best and the most practical method; it is numerically shown that the IQ method has a high stability and precision and the computation time which is about one tenth of that of the direct method. IQ method is applicable to thermal reactors as well as fast reactors and especially fitted for fast reactors to which many time steps are necessary. Two-dimensional diffusion kinetics codes are most practicable though there exist also three-dimensional diffusion kinetics code as well as two-dimensional transport kinetics code. On developing a space-dependent kinetics code, in any case, it is desirable to improve the method so as to have a high computing speed for solving static diffusion and transport equations. (auth.)
Compilation of kinetic data for geochemical calculations
Arthur, R.C.; Savage, D.; Sasamoto, Hiroshi; Shibata, Masahiro; Yui, Mikazu
2000-01-01
Kinetic data, including rate constants, reaction orders and activation energies, are compiled for 34 hydrolysis reactions involving feldspars, sheet silicates, zeolites, oxides, pyroxenes and amphiboles, and for similar reactions involving calcite and pyrite. The data are compatible with a rate law consistent with surface reaction control and transition-state theory, which is incorporated in the geochemical software package EQ3/6 and GWB. Kinetic data for the reactions noted above are strictly compatible with the transition-state rate law only under far-from-equilibrium conditions. It is possible that the data are conceptually consistent with this rate law under both far-from-equilibrium and near-to-equilibrium conditions, but this should be confirmed whenever possible through analysis of original experimental results. Due to limitations in the availability of kinetic data for mine-water reactions, and in order to simplify evaluations of geochemical models of groundwater evolution, it is convenient to assume local-equilibrium in such models whenever possible. To assess whether this assumption is reasonable, a modeling approach accounting for couple fluid flow and water-rock interaction is described that can be use to estimate spatial and temporal scale of local equilibrium. The approach is demonstrated for conditions involving groundwater flow in fractures at JNC's Kamaishi in-situ tests site, and is also used to estimate the travel time necessary for oxidizing surface waters to migrate to the level of a HLW repository in crystalline rock. The question of whether local equilibrium is a reasonable assumption must be addressed using an appropriate modeling approach. To be appropriate for conditions at the Kamaishi site using the modeling approach noted above, the fracture fill must closely approximate a porous mine, groundwater flow must be purely advective and diffusion of solutes across the fracture-host rock boundary must not occur. Moreover, the mineralogical and
Carbochlorination kinetics of tantalum and niobium pentoxides
Allain, E.
1999-08-01
Full Text Available The carbochlorination kinetics of pure Nb_{2}O_{5} and Ta_{2}O_{5} by gas mixture (C1_{2} + CO + N_{2} between 380 and 1,000 °C is studied. A calculation of the standard free energy of the carbochlorination reactions is made. A diagram of the phases stability is drawn. The influence of the gas flow, temperature and the pardal pressure of Cl_{2} and CO at temperatures below 650 °C on the reaction rate is studied. The apparent activation energy is approximately 75 and 110 kJ/mol for Nb_{2}Os and Ta_{2}O_{5}, respectively. At temperatures above 650°C the Arrhenius diagram presents an anomaly which may be attributed to the decomposition of the COCl_{2} formed in situ. The apparent reaction order of the carbochlorination of these oxides against Cl_{2}+CO is approximately 2. The carbochlorination rates of these oxides are much greater than those of chlorination by Cl_{2} + N_{2}. The carbochlorination kinetics of tin furnace slag leaching concentrates containing tantalum and niobium compounds are also studied and compared with the carbochlorination kinetics of the pure oxides.
En este trabajo se estudia la cinética de carbocloruración del Nb_{2}O_{5} y del Ta_{2}O_{5} por la mezcla de gases (Cl_{2} + CO + N_{2} entre 380 y 1000°C. Se hace un cálculo de la energía libre estándar de carbocloruración y se dibujan los diagramas de equilibrio de fases. Se estudia la influencia del flujo de gas, la temperatura y la presión parcial de Cl_{2} y CO a temperaturas por debajo de 650°C sobre la velocidad de reacción. La energía de activación es aproximadamente 75 y 110 kJ/mol para el Nb_{2}O_{5} y el Ta_{2}O_{5}, respectivamente. A temperaturas por encima de 650°C, el diagrama de Arrhenius presenta una anomalía que puede ser atribuida a la
Arima, T.; Masuzumi, T.; Furuya, H.; Idemitsu, K.; Inagaki, Y.
2001-01-01
Oxidation kinetics of Zircaloy-4 have been measured using a micro-balance technique in CO-CO 2 gas mixtures between 450 deg. C and 600 deg. C. Oxidation kinetics of Zircaloy-4 obeyed a cubic rate law with time at 450-600 deg. C up to 24 h. At 600 deg. C, the kinetic transition occurred after about 36 h. After the transition, oxidation kinetics obeyed a linear rate law. X-ray diffraction patterns for the samples oxidized at 600 deg. C showed that the volume fraction of tetragonal phase of zirconia decreased with time until the kinetic transition occurred and was almost constant after that. In addition, stresses in the oxide films were found to be larger for the pre-transition samples than for the post-transition ones. (authors)
Krivtcova Nadezhda
2016-01-01
Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.
Krivtsova, Nadezhda Igorevna; Tataurshikov, A.; Kotkova, Elena
2016-01-01
Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.
In vivo cell kinetics in breast carcinogenesis
Bai, Maria; Agnantis, Niki J; Kamina, Sevasti; Demou, Asimina; Zagorianakou, Panayiota; Katsaraki, Aphroditi; Kanavaros, Panayiotis
2001-01-01
Disruption of the balance between apoptosis and proliferation is considered to be an important factor in the development and progression of tumours. In the present study we determined the in vivo cell kinetics along the spectrum of apparently normal epithelium, hyperplasia, preinvasive lesions and invasive carcinoma, in breast tissues affected by fibrocystic changes in which preinvasive and/or invasive lesions developed, as a model of breast carcinogenesis. A total of 32 areas of apparently normal epithelium and 135 ductal proliferative and neoplastic lesions were studied. More than one epithelial lesion per case were analyzed. The apoptotic index (AI) and the proliferative index (PI) were expressed as the percentage of TdT-mediated dUTP-nick end-labelling (TUNEL) and Ki-67-positive cells, respectively. The PI/AI (P/A index) was calculated for each case. The AIs and PIs were significantly higher in hyperplasia than in apparently normal epithelium (P = 0.04 and P = 0.0005, respectively), in atypical hyperplasia than in hyperplasia (P = 0.01 and P = 0.04, respectively) and in invasive carcinoma than in in situ carcinoma (P < 0.001 and P < 0.001, respectively). The two indices were similar in atypical hyperplasia and in in situ carcinoma. The P/A index increased significantly from normal epithelium to hyperplasia (P = 0.01) and from preinvasive lesions to invasive carcinoma (P = 0.04) whereas it was decreased (non-significantly) from hyperplasia to preinvasive lesions. A strong positive correlation between the AIs and the PIs was found (r = 0.83, P < 0.001). These findings suggest accelerating cell turnover along the continuum of breast carcinogenesis. Atypical hyperplasias and in situ carcinomas might be kinetically similar lesions. In the transition from normal epithelium to hyperplasia and from preinvasive lesions to invasive carcinoma the net growth of epithelial cells results from a growth imbalance in favour of proliferation. In the transition from hyperplasia
HIGH PRESSURE COAL COMBUSTON KINETICS PROJECT
Stefano Orsino
2005-03-30
As part of the U.S. Department of Energy (DoE) initiative to improve the efficiency of coal-fired power plants and reduce the pollution generated by these facilities, DOE has funded the High-Pressure Coal Combustion Kinetics (HPCCK) Projects. A series of laboratory experiments were conducted on selected pulverized coals at elevated pressures with the specific goals to provide new data for pressurized coal combustion that will help extend to high pressure and validate models for burnout, pollutant formation, and generate samples of solid combustion products for analyses to fill crucial gaps in knowledge of char morphology and fly ash formation. Two series of high-pressure coal combustion experiments were performed using SRI's pressurized radiant coal flow reactor. The first series of tests characterized the near burner flame zone (NBFZ). Three coals were tested, two high volatile bituminous (Pittsburgh No.8 and Illinois No.6), and one sub-bituminous (Powder River Basin), at pressures of 1, 2, and 3 MPa (10, 20, and 30 atm). The second series of experiments, which covered high-pressure burnout (HPBO) conditions, utilized a range of substantially longer combustion residence times to produce char burnout levels from 50% to 100%. The same three coals were tested at 1, 2, and 3 MPa, as well as at 0.2 MPa. Tests were also conducted on Pittsburgh No.8 coal in CO2 entrainment gas at 0.2, 1, and 2 MPa to begin establishing a database of experiments relevant to carbon sequestration techniques. The HPBO test series included use of an impactor-type particle sampler to measure the particle size distribution of fly ash produced under complete burnout conditions. The collected data have been interpreted with the help of CFD and detailed kinetics simulation to extend and validate devolatilization, char combustion and pollutant model at elevated pressure. A global NOX production sub-model has been proposed. The submodel reproduces the performance of the detailed chemical
Radically Different Kinetics at Low Temperatures
Sims, Ian
2014-06-01
The use of the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, or Reaction Kinetics in Uniform Supersonic Flow) technique coupled with pulsed laser photochemical kinetics methods has shown that reactions involving radicals can be very rapid at temperatures down to 10 K or below. The results have had a major impact in astrochemistry and planetology, as well as proving an exacting test for theory. The technique has also been applied to the formation of transient complexes of interest both in atmospheric chemistry and combustion. Until now, all of the chemical reactions studied in this way have taken place on attractive potential energy surfaces with no overall barrier to reaction. The F + H2 {→} HF + H reaction does possess a substantial energetic barrier ({\\cong} 800 K), and might therefore be expected to slow to a negligible rate at very low temperatures. In fact, this H-atom abstraction reaction does take place efficiently at low temperatures due entirely to tunneling. I will report direct experimental measurements of the rate of this reaction down to a temperature of 11 K, in remarkable agreement with state-of-the-art quantum reactive scattering calculations by François Lique (Université du Havre) and Millard Alexander (University of Maryland). It is thought that long chain cyanopolyyne molecules H(C2)nCN may play an important role in the formation of the orange haze layer in Titan's atmosphere. The longest carbon chain molecule observed in interstellar space, HC11N, is also a member of this series. I will present new results, obtained in collaboration with Jean-Claude Guillemin (Ecole de Chimie de Rennes) and Stephen Klippenstein (Argonne National Labs), on reactions of C2H, CN and C3N radicals (using a new LIF scheme by Hoshina and Endo which contribute to the low temperature formation of (cyano)polyynes. H. Sabbah, L. Biennier, I. R. Sims, Y. Georgievskii, S. J. Klippenstein, I. W. M. Smith, Science 317, 102 (2007). S. D. Le Picard, M
KINETICS AND MECHANISMS OF NOx - CHAR REDUCTION
Suuberg, E.M.
1998-06-19
This study was undertaken in order to improve understanding of several aspects of the NO-carbon reaction. This reaction is of practical importance in combustion systems, but its close examination also provides some fundamental insight into oxidizing gas-carbon reactions. As part of this study, a comprehensive literature review of earlier work on this reaction has been published (Aarna and Suuberg, Fuel, 1997, 76, 475-491). It has been thought for some time that the kinetics of the NO-carbon reaction are unusual, in that they often show a two-regime Arrhenius behavior. It has, however, turned out during this work that NO is not alone in this regard. In this laboratory, we also uncovered evidence of two kinetic regime behavior in CO{sub 2} gasification. In another laboratory, a former colleague has identified the same behavior in N{sub 2}O. The low temperature reaction regime always shows an activation energy which is lower than that in the high temperature regime, leaving little doubt that a shift in mechanism, as opposed to transport limitations, dictates the behavior. The activation energy of the low temperature regime of these reactions is typically less than 100 kJ/mol, and the activation energy of the high temperature regime is generally considerably in excess of this value. In this study, we have resolved some apparent inconsistencies in the explanation of the low temperature regime, whose rate has generally been ascribed to desorption-controlled processes. Part of the problem in characterization of the different temperature regimes is that they overlap to a high degree. It is difficult to probe the low temperature regime experimentally, because of slow relaxation of the surface oxides in that regime. Using careful experimental techniques, we were able to demonstrate that the low temperature regime is indeed characterized by zero order in NO, as it must be. A separate study is being carried out to model the behavior in this regime in NO and in other gases, and
Combustion Kinetic Studies of Gasolines and Surrogates
Javed, Tamour
2016-11-01
Future thrusts for gasoline engine development can be broadly summarized into two categories: (i) efficiency improvements in conventional spark ignition engines, and (ii) development of advance compression ignition (ACI) concepts. Efficiency improvements in conventional spark ignition engines requires downsizing (and turbocharging) which may be achieved by using high octane gasolines, whereas, low octane gasolines fuels are anticipated for ACI concepts. The current work provides the essential combustion kinetic data, targeting both thrusts, that is needed to develop high fidelity gasoline surrogate mechanisms and surrogate complexity guidelines. Ignition delay times of a wide range of certified gasolines and surrogates are reported here. These measurements were performed in shock tubes and rapid compression machines over a wide range of experimental conditions (650 – 1250 K, 10 – 40 bar) relevant to internal combustion engines. Using the measured the data and chemical kinetic analyses, the surrogate complexity requirements for these gasolines in homogeneous environments are specified. For the discussions presented here, gasolines are classified into three categories: (i)\\tLow octane gasolines including Saudi Aramco’s light naphtha fuel (anti-knock index, AKI = (RON + MON)/2 = 64; Sensitivity (S) = RON – MON = 1), certified FACE (Fuels for Advanced Combustion Engines) gasoline I and J (AKI ~ 70, S = 0.7 and 3 respectively), and their Primary Reference Fuels (PRF, mixtures of n-heptane and iso-octane) and multi-component surrogates. (ii)\\t Mid octane gasolines including FACE A and C (AKI ~ 84, S ~ 0 and 1 respectively) and their PRF surrogates. Laser absorption measurements of intermediate and product species formed during gasoline/surrogate oxidation are also reported. (iii)\\t A wide range of n-heptane/iso-octane/toluene (TPRF) blends to adequately represent the octane and sensitivity requirements of high octane gasolines including FACE gasoline F and G
Thermodynamic and kinetic analysis of heterogeneous photocatalysis for semiconductor systems.
Liu, Baoshun; Zhao, Xiujian; Terashima, Chiaki; Fujishima, Akira; Nakata, Kazuya
2014-05-21
Since the report of the Honda-Fujishima effect, heterogeneous photocatalysis has attracted much attention around the world because of its potential energy and environmental applications. Although great progresses have been made in recent years, most were focused on preparing highly-active photocatalysts and investigating visible light utilization. In fact, we are still unclear on the thermodynamic and kinetic nature of photocatalysis to date, which sometimes leads to misunderstandings for experimental results. It is timely to give a review and discussion on the thermodynamics and kinetics of photocatalysis, so as to direct future researches. However, there is an absence of a detailed review on this topic until now. In this article, we tried to review and discuss the thermodynamics and kinetics of photocatalysis. We explained the thermodynamic driving force of photocatalysis, and distinguished the functions of light and heat in photocatalysis. The Langmuir-Hinshelwood kinetic model, the ˙OH oxidation mechanism, and the direct-indirect (D-I) kinetic model were reviewed and compared. Some applications of the D-I model to study photocatalytic kinetics were also discussed. The electron transport mode and its importance in photocatalysis were investigated. Finally, the intrinsic relation between the kinetics and the thermodynamics of photocatalytic reactions was discussed.
Calculation of Kinetic Parameters of TRIGA Reactor
Snoj, Luka; Kavcic, Andrej; Zerovnik, Gasper; Ravnik, Matjaz
2008-01-01
Modern Monte Carlo transport codes in combination of fast computer clusters enable very accurate calculations of the most important reactor kinetic parameters. Such are the effective delayed neutron fraction, β eff , and mean neutron generation time, Λ. We calculated the β eff and Λ for various realistic and hypothetical annular TRIGA Mark II cores with different types and amount of fuel. It can be observed that the effective delayed neutron fraction strongly depends on the number of fuel elements in the core or on the core size. E.g., for 12 wt. % uranium standard fuel with 20 % enrichment, β eff varies from 0.0080 for a small core (43 fuel rods) to 0.0075 for a full core (90 fuel rods). It is interesting to note that calculated value of β eff strongly depends also on the delayed neutron nuclear data set used in calculations. The prompt neutron life-time mainly depends on the amount (due to either content or enrichment) of 235 U in the fuel as it is approximately inversely proportional to the average absorption cross-section of the fuel. E.g., it varies from 28 μs for 30 wt. % uranium content fuelled core to 48 μs for 8.5 wt. % uranium content LEU fuelled core. The results are especially important for pulse mode operation and analysis of the pulses. (authors)
Reduced chemical kinetic mechanisms for hydrocarbon fuels
Montgomery, C.J.; Cremer, M.A.; Heap, M.P.; Chen, J-Y.; Westbrook, C.K.; Maurice, L.Q.
1999-01-01
Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, a variety of different reduced chemical kinetic mechanisms for ethylene and n-heptane have been generated. The reduced mechanisms have been compared to detailed chemistry calculations in simple homogeneous reactors and experiments. Reduced mechanisms for combustion of ethylene having as few as 10 species were found to give reasonable agreement with detailed chemistry over a range of stoichiometries and showed significant improvement over currently used global mechanisms. The performance of reduced mechanisms derived from a large detailed mechanism for n-heptane was compared to results from a reduced mechanism derived from a smaller semi-empirical mechanism. The semi-empirical mechanism was advantageous as a starting point for reduction for ignition delay, but not for PSR calculations. Reduced mechanisms with as few as 12 species gave excellent results for n-heptane/air PSR calculations but 16-25 or more species are needed to simulate n-heptane ignition delay
Kinetic energy recovery systems in motor vehicles
Śliwiński, C.
2016-09-01
The article draws attention to the increasing environmental pollution caused by the development of vehicle transport and motorization. Different types of design solutions used in vehicles for the reduction of fuel consumption, and thereby emission of toxic gasses into the atmosphere, were specified. Historical design solutions concerning energy recovery devices in mechanical vehicles which used flywheels to accumulate kinetic energy were shown. Developmental tendencies in the area of vehicle manufacturing in the form of hybrid electric and electric devices were discussed. Furthermore, designs of energy recovery devices with electrical energy storage from the vehicle braking and shock absorbing systems were presented. A mechanical energy storing device using a flywheel operating under vacuum was presented, as were advantages and disadvantages of both systems, the limitations they impose on individual constructions and safety issues. The paper also discusses a design concept of an energy recovery device in mechanical vehicles which uses torsion springs as the main components of energy accumulation during braking. The desirability of a cooperation of both the mechanical- and electrical energy recovery devices was indicated.
Probabilistic approach to lysozyme crystal nucleation kinetics.
Dimitrov, Ivaylo L; Hodzhaoglu, Feyzim V; Koleva, Dobryana P
2015-09-01
Nucleation of lysozyme crystals in quiescent solutions at a regime of progressive nucleation is investigated under an optical microscope at conditions of constant supersaturation. A method based on the stochastic nature of crystal nucleation and using discrete time sampling of small solution volumes for the presence or absence of detectable crystals is developed. It allows probabilities for crystal detection to be experimentally estimated. One hundred single samplings were used for each probability determination for 18 time intervals and six lysozyme concentrations. Fitting of a particular probability function to experimentally obtained data made possible the direct evaluation of stationary rates for lysozyme crystal nucleation, the time for growth of supernuclei to a detectable size and probability distribution of nucleation times. Obtained stationary nucleation rates were then used for the calculation of other nucleation parameters, such as the kinetic nucleation factor, nucleus size, work for nucleus formation and effective specific surface energy of the nucleus. The experimental method itself is simple and adaptable and can be used for crystal nucleation studies of arbitrary soluble substances with known solubility at particular solution conditions.
Kinetic Consideration of AFP irma assay
Aly, M. A.; Moustafa, K.A.
2003-01-01
Alpha-fetoprotein (AFP) is a glycoprotein produced by the yolk sac and later by the fetal liver during pregnancy. When the neural tube is not properly formed, by the fetal liver during pregnancy. When the neural tube is not properly formed, large amounts of AFP pass into the amniotic fluid and reach the mother's blood. During pregnancy, the major interest in AFP determination in maternal serum and amniotic fluid is on the early diagnosis of fetal abnormalities. AFP also used as a tumor marker for hepatocellular carcinoma. There are many different techniques for measuring AFP in blood, but the more accurate one is the immunoassay technique. The kinetics of the interaction between AFP antigen and two matched antibodies, one labeled with radioactive isotope 1 25I (tracer) and the other is unlabelled and attached to a solid support (tube), are studied using the more recently, two sites (sandwich) immunoradiometric assay (IRMA) technique. We present here a method for determining the rate constants, using an advanced computer program (RKY), which based on the nelder-mead optimization principle. The rate constant, at three variable temperatures and three different antigen concentrations, as well as the half time of exchange (t 1/2 ) were calculated
Thermoluminescence of zircon: a kinetic model
Turkin, A A; Vainshtein, D I; Hartog, H W D
2003-01-01
The mineral zircon, ZrSiO sub 4 , belongs to a class of promising materials for geochronometry by means of thermoluminescence (TL) dating. The development of a reliable and reproducible method for TL dating with zircon requires detailed knowledge of the processes taking place during exposure to ionizing radiation, long-term storage, annealing at moderate temperatures and heating at a constant rate (TL measurements). To understand these processes one needs a kinetic model of TL. This paper is devoted to the construction of such a model. The goal is to study the qualitative behaviour of the system and to determine the parameters and processes controlling TL phenomena of zircon. The model considers the following processes: (i) Filling of electron and hole traps at the excitation stage as a function of the dose rate and the dose for both (low dose rate) natural and (high dose rate) laboratory irradiation. (ii) Time dependence of TL fading in samples irradiated under laboratory conditions. (iii) Short time anneali...
Kinetic stability of field-reversed configurations
Staudenmeier, J.L.; Hsiao, M.-Y.
1991-01-01
The internal tilt mode is considered to be the biggest threat to Field-Reversed Configuration (FRC) global stability. The tilt stability of the FRC is studied using the MHD, Hall MHD, and the Vlasov-fluid (Vlasov ions, cold massless fluid electrons) models. Nonlinear Hall MHD calculations showed that the FRC was stable to the tilt mode when the s value of the FRC was below a critical value that was dependent on plasma length. The critical s value is larger for longer plasma equilibria. The stability of FRC's with toroidal field was studied with a linear initial value MHD code. The calculations showed an axial perturbation wavelength of the most unstable eigenfunction that was consistent with internal probe measurements made on translated FRC's. Linear Vlasov-fluid eigenvalue calculations showed that kinetic ion effects can change both the growth rate and the structure of the eigenfunctions when compared to the corresponding MHD modes. Calculations on short FRC equilibria indicate that MHD is not the appropriate small gyroradius limit of the Vlasov-fluid model because the axial transit time of a thermal ion is approximately equal to an MHD growth time for the tilt mode. Calculations were done using a small number of unstable MHD eigenfunctions as basis functions in order to reduce the dimensionality of the stability problem. The results indicated that this basis set can produce inaccurate growth rates at large value for s for some equilibria
Nonlocal nonlinear coupling of kinetic sound waves
O. Lyubchyk
2014-11-01
Full Text Available We study three-wave resonant interactions among kinetic-scale oblique sound waves in the low-frequency range below the ion cyclotron frequency. The nonlinear eigenmode equation is derived in the framework of a two-fluid plasma model. Because of dispersive modifications at small wavelengths perpendicular to the background magnetic field, these waves become a decay-type mode. We found two decay channels, one into co-propagating product waves (forward decay, and another into counter-propagating product waves (reverse decay. All wavenumbers in the forward decay are similar and hence this decay is local in wavenumber space. On the contrary, the reverse decay generates waves with wavenumbers that are much larger than in the original pump waves and is therefore intrinsically nonlocal. In general, the reverse decay is significantly faster than the forward one, suggesting a nonlocal spectral transport induced by oblique sound waves. Even with low-amplitude sound waves the nonlinear interaction rate is larger than the collisionless dissipation rate. Possible applications regarding acoustic waves observed in the solar corona, solar wind, and topside ionosphere are briefly discussed.
Fully implicit kinetic modelling of collisional plasmas
Mousseau, V.A.
1996-05-01
This dissertation describes a numerical technique, Matrix-Free Newton Krylov, for solving a simplified Vlasov-Fokker-Planck equation. This method is both deterministic and fully implicit, and may not have been a viable option before current developments in numerical methods. Results are presented that indicate the efficiency of the Matrix-Free Newton Krylov method for these fully-coupled, nonlinear integro-differential equations. The use and requirement for advanced differencing is also shown. To this end, implementations of Chang-Cooper differencing and flux limited Quadratic Upstream Interpolation for Convective Kinematics (QUICK) are presented. Results are given for a fully kinetic ion-electron problem with a self consistent electric field calculated from the ion and electron distribution functions. This numerical method, including advanced differencing, provides accurate solutions, which quickly converge on workstation class machines. It is demonstrated that efficient steady-state solutions can be achieved to the non-linear integro-differential equation, obtaining quadratic convergence, without incurring the large memory requirements of an integral operator. Model problems are presented which simulate plasma impinging on a plate with both high and low neutral particle recycling typical of a divertor in a Tokamak device. These model problems demonstrate the performance of the new solution method
Kinetics of strength gain of biocidal cements
Rodin Aleksandr Ivanovich
Full Text Available Biocorrosion becomes the determinative durability factor of buildings and constructions. Damages of construction materials caused by bacteria, filamentous fungi, actinomycetes constitute a serious danger to the constructions of a building or a structure and to the health of people. Biodeteriorations are typical both in old and new constructions. A great quantity of destruction factors of industrial and residential buildings under the influence of microorganisms was established in practice. Providing products and constructions based on concretes fungicidal and bactericidal properties is an important direction of modern construction material science. The most efficient way to solve this task is creation of biocidal cements. The article presents the results of experimental studies of kinetic dependences of strength gain by biocidal cements by physico-mechanical and physico-chemical analysis methods. The identical velocity character of initial hydration of the developed compositions of biocidal cements is set, as well as a more calm behavior of hardening processes at later terms. It has been established that the compositions of biocidal cements modified by sodium sulfate and sodium fluoride possess the greatest strength.
Chemical Kinetics of Progesterone Radioimmunoassay System
Abdel-Fattah, A.A.; Moustsfs, K.A.; El-Kolally, M.T.
2004-01-01
Progesterone is one of the steroids secreted by the corpus Iuteum in females during the menstrual cycle, and in a much higher amount by the placenta during pregnancy. It is also secreted in a minor quantities by the adrenal cortex in both males and females. Measurement of serum progesterone represents one of diagnostic values in menstrual disorders and infertility. The progesterone radioimmunoassay is based on the competition between unlabelled progesterone and a fixed quantity of 125 I-labeled progesterone for a limited number of binding sites on progesterone specific antibody. Allowing for a fixed amount of magnetizable immunosorbent to react, the antigen-antibody complex is bound on solid particles which are then separated by magnetic rack, and the radioactivity of the solid phase was counted using gamma counter. In this work, the chemical kinetics of the assay was followed, where the specific rate constant (K) was calculated at 4 degree and 37 degree and the activation energy (E act ) were calculated and the reaction rate was deduced
Methane production from cellulosic wastes: kinetic studies
Goma, G; De La Torre, I; Maugheri, F; Yameogo, T
1979-09-01
The anaerobic fermentation is studied on lignocellulosic materials and sucrose as substrate. With the lignocellulosic material cellulolysis is rate limiting. The reducing sugar concentration in the fermentation broth is less than 15 mgl/sup -1/. With rumen bacteria, 50% of the initial polyoside are used and 12% of the lignin is solubilized. With sucrose studies on the kinetic behaviour of the mixed population responsible of the acidogenesis step permite to find the optimal temperature (40/sup 0/C) feed substrate concentration (50 gl/sup -1/) residence time (60 hours) and pH (5,5 - 6). The better technology is a plug flow fermentor with cell recycling. Modeling of the behaviour of this reactor was performed. The use of this reactor for the selection of acido resistant bacteria is discussed. For methanogenesis, in continuous culture, the ideal technology seems to be an association of two reactors. In the first step, a plug flow reactor must be used for acidogenesis, and in the second step a well mixed reactor permit the conversion of organic acids in methane.
Controlling vortex motion and vortex kinetic friction
Nori, Franco; Savel'ev, Sergey
2006-01-01
We summarize some recent results of vortex motion control and vortex kinetic friction. (1) We describe a device [J.E. Villegas, S. Savel'ev, F. Nori, E.M. Gonzalez, J.V. Anguita, R. Garcia, J.L. Vicent, Science 302 (2003) 1188] that can easily control the motion of flux quanta in a Niobium superconducting film on an array of nanoscale triangular magnets. Even though the input ac current has zero average, the resulting net motion of the vortices can be directed along either one direction, the opposite direction, or producing zero net motion. We also consider layered strongly anisotropic superconductors, with no fixed spatial asymmetry, and show [S. Savel'ev, F. Nori, Nature Materials 1 (2002) 179] how, with asymmetric drives, the ac motion of Josephson and/or pancake vortices can provide a net dc vortex current. (2) In analogy with the standard macroscopic friction, we present [A. Maeda, Y. Inoue, H. Kitano, S. Savel'ev, S. Okayasu, I. Tsukada, F. Nori , Phys. Rev. Lett. 94 (2005) 077001] a comparative study of the friction force felt by vortices in superconductors and charge density waves
Controlling vortex motion and vortex kinetic friction
Nori, Franco; Savel'ev, Sergey
2006-05-01
We summarize some recent results of vortex motion control and vortex kinetic friction. (1) We describe a device [J.E. Villegas, S. Savel'ev, F. Nori, E.M. Gonzalez, J.V. Anguita, R. Garcìa, J.L. Vicent, Science 302 (2003) 1188] that can easily control the motion of flux quanta in a Niobium superconducting film on an array of nanoscale triangular magnets. Even though the input ac current has zero average, the resulting net motion of the vortices can be directed along either one direction, the opposite direction, or producing zero net motion. We also consider layered strongly anisotropic superconductors, with no fixed spatial asymmetry, and show [S. Savel'ev, F. Nori, Nature Materials 1 (2002) 179] how, with asymmetric drives, the ac motion of Josephson and/or pancake vortices can provide a net dc vortex current. (2) In analogy with the standard macroscopic friction, we present [A. Maeda, Y. Inoue, H. Kitano, S. Savel'ev, S. Okayasu, I. Tsukada, F. Nori , Phys. Rev. Lett. 94 (2005) 077001] a comparative study of the friction force felt by vortices in superconductors and charge density waves.
Kinetics of Crystallization in Polydisperse Emulsions.
Kashchiev; Kaneko; Sato
1998-12-01
The kinetics of isothermal crystallization of the droplets in polydisperse emulsions are analyzed under the condition that each emulsion droplet gives birth to one nucleus only. Expressions are derived for the time dependences of the number of crystallized droplets and the fraction of crystallized droplet volume in the cases of either volume or surface nucleation of the crystals in the droplets. The time for half-crystallization is determined as a function of the emulsion polydispersity, and it is found that the more polydisperse the emulsion, the shorter this time in comparison with that for the corresponding monodisperse emulsion. Formulae are also obtained for the change of the velocity Kv of propagation of ultrasound through polydisperse emulsions during the time t of isothermal crystallization of the droplets in them. Good agreement is found between theory and experiment in an analysis of available Kv(t) data for crystallization in polydisperse palm oil-in-water and n-hexadecane-in-water emulsions. The results obtained are directly applicable to devitrification and polymorphic transformation of disperse solid phases. Copyright 1998 Academic Press.
Hydrogen peroxide kinetics in water radiolysis
Iwamatsu, Kazuhiro; Sundin, Sara; LaVerne, Jay A.
2018-04-01
The kinetics of the formation and reaction of hydrogen peroxide in the long time γ- radiolysis of water is examined using a combination of experiment with model calculations. Escape yields of hydrogen peroxide on the microsecond time scale are easily measured with added radical scavengers even with substantial amounts of initial added hydrogen peroxide. The γ-radiolysis of aqueous hydrogen peroxide solutions without added radical scavengers reach a steady state limiting concentration of hydrogen peroxide with increasing dose, and that limit is directly proportional to the initial concentration of added hydrogen peroxide. The dose necessary to reach that limiting hydrogen peroxide concentration is also proportional to the initial concentration, but dose rate has a very small effect. The addition of molecular hydrogen to aqueous solutions of hydrogen peroxide leads to a decrease in the high dose limiting hydrogen peroxide concentration that is linear with the initial hydrogen concentration, but the amount of decrease is not stoichiometric. Proton irradiations of solutions with added hydrogen peroxide and hydrogen are more difficult to predict because of the decreased yields of radicals; however, with a substantial increase in dose rate there is a sufficient decrease in radical yields that hydrogen addition has little effect on hydrogen peroxide decay.
The kinetic fragility of natural silicate melts
Giordano, Daniele; Dingwell, Donald B
2003-01-01
Newtonian viscosities of 19 multicomponent natural and synthetic silicate liquids, with variable contents of SiO 2 (41-79 wt%), Al 2 O 3 (10-19 wt%), TiO 2 (0-3 wt%), FeO tot (0-11 wt%); alkali oxides (5-17 wt%), alkaline-earth oxides (0-35 wt%), and minor oxides, obtained at ambient pressure using the high-temperature concentric cylinder, the low-temperature micropenetration, and the parallel plates techniques, have been analysed. For each silicate liquid, regression of the experimentally determined viscosities using the well known Vogel-Fulcher-Tammann (VFT) equation allowed the viscosity of all these silicates to be accurately described. The results of these fits, which provide the basis for the subsequent analysis here, permit qualitative and quantitative correlations to be made between the VFT adjustable parameters (A VFT , B VFT , and T 0 ). The values of B VFT and T 0 , calibrated via the VFT equation, are highly correlated. Kinetic fragility appears to be correlated with the number of non-bridging oxygens per tetrahedrally coordinated cation (NBO/T). This is taken to infer that melt polymerization controls melt fragility in liquid silicates. Thus NBO/T might form an useful ingredient of a structure-based model of non-Arrhenian viscosity in multicomponent silicate melts
Decohesion Kinetics in Polymer Organic Solar Cells
Bruner, Christopher; Novoa, Fernando; Dupont, Stephanie; Dauskardt, Reinhold
2014-01-01
© 2014 American Chemical Society. We investigate the role of molecular weight (MW) of the photoactive polymer poly(3-hexylthiophene) (P3HT) on the temperature-dependent decohesion kinetics of bulk heterojunction (BHJ) organic solar cells (OSCs). The MW of P3HT has been directly correlated to its carrier field effect mobilities and the ambient temperature also affects OSC in-service performance and P3HT arrangement within the BHJ layer. Under inert conditions, time-dependent decohesion readily occurs within the BHJ layer at loads well below its fracture resistance. We observe that by increasing the MW of P3HT, greater resistance to decohesion is achieved. However, failure consistently occurs within the BHJ layer representing the weakest layer within the device stack. Additionally, it was found that at temperatures below the glass transition temperature (∼41-45 °C), decohesion was characterized by brittle failure via molecular bond rupture. Above the glass transition temperature, decohesion growth occurred by a viscoelastic process in the BHJ layer, leading to a significant degree of viscoelastic deformation. We develop a viscoelastic model based on molecular relaxation to describe the resulting behavior. The study has implications for OSC long-term reliability and device performance, which are important for OSC production and implementation.
Kinetics and mechanism of Prussian blue formation
R.K. Adhikamsetty
2009-04-01
Full Text Available The kinetics of reaction between ferrocyanide and ferric ions under acidic conditions was studied at fixed ionic strength (0.1 M and (25 plus or minus 0.1 oC by using the stopped flow technique, under limiting conditions of [ferrocyanide] and with other reactants in excess. The reaction had first-order dependence on ferrocyanide, Fe(III and H+ ion concentrations and had negative salt effect. On the basis of the experimental findings, a plausible mechanism for the formation of soluble form of Prussian blue (KFe{Fe(CN6}x H2O and rate law are proposed. The activation parameters for the title reaction are estimated. A relatively low energy of activation (23 kJ mol-1 and high negative entropy of activation (-231 J K-1 mol-1 agree well with the proposed mechanism and configuration of complex ion leading to the formation of insoluble Prussian blue, Fe4{Fe(CN6}3 y H2O.
Mechanism and kinetics of hydrated electron diffusion
Tay, Kafui A.; Coudert, Francois-Xavier; Boutin, Anne
2008-01-01
Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be understood within the traditional framework of transfer diffusion processes, where the diffusive step is akin to the exchange of an extramolecular electron between neighboring water molecules. This is a second-order process with a computed rate constant of 5.0 ps -1 at 298 K. In agreement with experiment the electron diffusion exhibits Arrhenius behavior over the temperature range of 298-400 K. We compute an activation energy of 8.9 kJ mol -1 . Through analysis of Arrhenius plots and the application of a simple random walk model it is demonstrated that the computed rate constant for exchange of an excess electron is indeed the phenomenological rate constant associated with the diffusive process
Dehydration kinetics of talc at 1 bar
Ganguly, J.; Bose, K.
1991-01-01
Experimental results on the dehydration kinetics of talc, which is likely to be a major potential resource for water and hydrogen in carbonaceous chondrites, is presented. The rate of dehydration of an essentially pure Mg-end member natural talc, (Mg(.99)Fe(.01))3Si4O10(OH)2, was studied by measuring in situ weight change under isothermal condition at 1 bar as a function of time in the temperature range 775 to 985 C. The grain size of the starting material was 0.7 to 1 micron. It was found that the data up to 50 to 60 percent dehydration can be fitted by an equation of the form alpha = exp(-Kt(exp n)), where alpha is the weight fraction of talc remaining, K is a rate constant and n is a numerical constant for a given temperature. For any set of isothermal data, there is a major change in the value of n for larger dehydration. For up to approximately 50 percent dehydration, all rate constants can be described by an Arrheniun relation with an activation energy of 432 (+/- 30) kJ/mol; n has a nearly constant value of 0.54 between 775 and 875 C, but increases almost linearly according to n = -10.77 + 0.012T C at T greater than or equal to 875 C.
Kinetics of intralymphatically delivered monoclonal antibodies
Wahl, R.L.; Geatti, O.; Liebert, M.; Beers, B.; Jackson, G.; Laino, L.; Kronberg, S.; Wilson, B.S.; Beierwaltes, W.H.
1985-01-01
Radiolabeled monoclonal antibody (MoAb) administration subcutaneously (sq), so that preferential uptake is to the lymphatics, holds significant promise for the detection of lymph node metastases. Only limited information is available about clearance rates of intralymphatically administered MoAbs. I-131 labeled intact IgG (225.28S), F(ab's)2 (225.28S) or IgM (FT162) were administered sq to anesthetized Balb/C mice. Eight mice were studied with each MoAb, 4 with a foot-pad injection, 4 with an anterior abdominal injection. Gamma camera images were collected into a computer, over the first 6 hrs after injection with the animals anesthetized and immobile. Animals were then allowed to move about freely. Additional images were then acquired out to 48 hrs. Regions of interest wre selected over the injection site and the kinetics of antibody egress determined. Clearance rates from local sq injection sites are influenced by motion and somewhat by location. The class and fragment status of the MoAb appear relatively less important in determining clearance rates from sq injections than they are in determining whole-body clearance after iv injections. Additional studies using Fab fragments and additional monoclonals will be useful in extending these observations
Muonium kinetics in sub- and supercritical water
Ghandi, K.; Addison-Jones, B.; Brodovitch, J.C.; Kecman, S.; McKenzie, I.; Percival, P.W
2003-02-01
Muonium is long-lived in pure water and has been studied over a very wide range of temperatures and pressures, from 5 deg. C to over 400 deg. C and from 1 to 400 bar. We have determined rate constants for representative reactions of muonium in aqueous solution; equivalent data on H atom kinetics is sparse and stops well short of the maximum temperature and pressure attained in our experiments. The results show remarkable deviations from the predictions of standard reaction theories. In particular, rate constants pass through a maximum with temperature well below the critical point. This seems to be a general phenomenon, since we have observed it for spin-exchange and chemical reactions that are diffusion limited at low temperatures, as well as for activated reactions. We believe that a key factor in the drop of rate constants at high temperature is the cage effect, in particular the number of collisions between a pair of reactants over the duration of their encounter. Whatever the reason, the implications are profound for both the efficiency of supercritical water oxidation reactors and for the modelling of radiation chemistry in pressurized water nuclear reactors.