Kinetics of Fluid Demixing in Complex Plasmas: Domain Growth Analysis using Minkowski Tensors
Böbel, Alexander
2016-01-01
A molecular dynamics simulation of the demixing process of a binary complex plasma is analysed and the role of distinct interaction potentials is discussed by using morphological Minkowski tensor analysis of the minority phase domain growth in a demixing simulated binary complex plasma. These Minkowski tensor methods are compared with previous results that utilized a power spectrum method based on the time-dependent average structure factor. It is shown that the Minkowski tensor methods are superior to the previously used power spectrum method in the sense of higher sensitivity to changes in domain size. By analysis of the slope of the temporal evolution of Minkowski tensor measures qualitative differences between the case of particle interaction with a single length scale compared to particle interactions with two different length scales (dominating long range interaction) are revealed. After proper scaling the graphs for the two length scale scenario coincide, pointing towards universal behaviour. The quali...
Undercooling and demixing in rapidly solidified Cu-Co alloys
Battezzati, L.; Curiotto, S.; Johnson, Erik;
2007-01-01
The Cu–Co system displays a metastable miscibility gap in the liquid state. A considerable amount of work has been performed to study phase separation and related microstructures showing that demixing of the liquid is followed by coagulation before dendritic solidification. Due to kinetic...
Demixing and gelation behavior of ternary cellulose acetate solutions
Reuvers, A.J.; Altena, F.W.; Smolders, C.A.
1986-01-01
The demixing behavior on cooling of ternary systems of cellulose acetate/solvent/water has been examined for CA concentrations up to 40 wt% CA in several solvents. Cloud points have been measured as a function of cooling rate. The rapid process of liquid - liquid demixing can be discriminated from t
Stress-Driven Selection of Novel Phenotypes
Fox, George E.; Stepaov, Victor G.; Liu, Yamei
2011-01-01
A process has been developed that can confer novel properties, such as metal resistance, to a host bacterium. This same process can also be used to produce RNAs and peptides that have novel properties, such as the ability to bind particular compounds. It is inherent in the method that the peptide or RNA will behave as expected in the target organism. Plasmid-born mini-gene libraries coding for either a population of combinatorial peptides or stable, artificial RNAs carrying random inserts are produced. These libraries, which have no bias towards any biological function, are used to transform the organism of interest and to serve as an initial source of genetic variation for stress-driven evolution. The transformed bacteria are propagated under selective pressure in order to obtain variants with the desired properties. The process is highly distinct from in vitro methods because the variants are selected in the context of the cell while it is experiencing stress. Hence, the selected peptide or RNA will, by definition, work as expected in the target cell as the cell adapts to its presence during the selection process. Once the novel gene, which produces the sought phenotype, is obtained, it can be transferred to the main genome to increase the genetic stability in the organism. Alternatively, the cell line can be used to produce novel RNAs or peptides with selectable properties in large quantity for separate purposes. The system allows for easy, large-scale purification of the RNAs or peptide products. The process has been reduced to practice by imposing sub-inhibitory concentrations of NiCl2 on cells of the bacterium Escherichia coli that were transformed separately with the peptide library and RNA library. The evolved resistant clones were isolated, and sequences of the selected mini-gene variants were established. Clones resistant to NiCl2 were found to carry identical plasmid variants with a functional mini-gene that specifically conferred significant nickel
Composition demixing effect on cathodic arc ion plating
无
2006-01-01
The composition demixing effect has been found often in alloy coatings deposited by cathodic arc ion plating using various alloy cathode targets.The characteristics of composition demixing phenomena were summarized.Beginning with the ionization zone near the surface of the cathode target, a physical model in terms of the ions generated in the ionization zone and their movement in the plating room modified by bias electric field was proposed.Based on the concept of electric charge state, the simulation calculation of the composition demixing effect was carried out.The percentage of atoms of an element in coating and from the alloy target was demonstrated by direct comparison.The influences of the composition change of the alloy target and the bias electric field on the composition demixing effect were discussed in detail.It is also proposed that the average charge states of the elements may be used to calculate the composition demixing effect and to design the composition of the alloy target.
Mechanically induced martensitic transformation as a stress driven process
Geijselaers, Hubertus J.M.; Perdahcioglu, Emin Semih
2009-01-01
Combined shear-tension tests at room temperature performed on a 12Cr9Ni4Mo low carbon austenitic stainless steel have been reviewed and evaluated under the assumption that the martensitic transformation is exclusively stress driven. It is shown that the start of the transformation is very well
Origin of suppressed demixing in casein/xanthan mixtures
van Gruijthuijsen, K.; Herle, V.; Tuinier, R.; Schurtenberger, P.; Stradner, A.
2012-01-01
We explore the properties of casein/xanthan mixtures for xanthan concentrations beyond those inducing phase separation. Previous work has successfully described the onset of demixing by depletion theory in the protein limit, where the xanthan polysaccharides, the polymers, are larger than the casein
He, Mo-Rigen; Samudrala, Saritha K; Kim, Gyuseok; Felfer, Peter J; Breen, Andrew J; Cairney, Julie M; Gianola, Daniel S
2016-04-13
The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone.
A numerical model of stress driven grain boundary diffusion
Sethian, J. A.; Wilkening, Jon
2004-01-01
The stress driven grain boundary diffusion problem is a continuum model of mass transport phenomena in microelectronic circuits due to high current densities (electromigration) and gradients in normal stress along grain boundaries. The model involves coupling many different equations and phenomena, and difficulties such as non-locality, stiffness, complex geometry, and singularities in the stress tensor near corners and junctions make the problem difficult to analyze rigorously and simulate numerically. We present a new numerical approach to this problem using techniques from semigroup theory to represent the solution. The generator of this semigroup is the composition of a type of Dirichlet to Neumann map on the grain boundary network with the Laplace operator on the network. To compute the former, we solve the equations of linear elasticity several times, once for each basis function on the grain boundary. We resolve singularities in the stress field near corners and junctions by adjoining special singular basis functions to both finite element spaces (2d for elasticity, 1d for grain boundary functions). We develop data structures to handle jump discontinuities in displacement across grain boundaries, singularities in the stress field, complicated boundary conditions at junctions and interfaces, and the lack of a natural ordering for the nodes on a branching grain boundary network. The method is used to study grain boundary diffusion for several geometries.
Simultaneous Denoising, Deconvolution, and Demixing of Calcium Imaging Data.
Pnevmatikakis, Eftychios A; Soudry, Daniel; Gao, Yuanjun; Machado, Timothy A; Merel, Josh; Pfau, David; Reardon, Thomas; Mu, Yu; Lacefield, Clay; Yang, Weijian; Ahrens, Misha; Bruno, Randy; Jessell, Thomas M; Peterka, Darcy S; Yuste, Rafael; Paninski, Liam
2016-01-20
We present a modular approach for analyzing calcium imaging recordings of large neuronal ensembles. Our goal is to simultaneously identify the locations of the neurons, demix spatially overlapping components, and denoise and deconvolve the spiking activity from the slow dynamics of the calcium indicator. Our approach relies on a constrained nonnegative matrix factorization that expresses the spatiotemporal fluorescence activity as the product of a spatial matrix that encodes the spatial footprint of each neuron in the optical field and a temporal matrix that characterizes the calcium concentration of each neuron over time. This framework is combined with a novel constrained deconvolution approach that extracts estimates of neural activity from fluorescence traces, to create a spatiotemporal processing algorithm that requires minimal parameter tuning. We demonstrate the general applicability of our method by applying it to in vitro and in vivo multi-neuronal imaging data, whole-brain light-sheet imaging data, and dendritic imaging data.
Demixing in binary mixtures of apolar and dipolar hard spheres.
Almarza, N G; Lomba, E; Martín, C; Gallardo, A
2008-12-21
We study the demixing transition of mixtures of equal size hard spheres and dipolar hard spheres using computer simulation and integral equation theories. Calculations are carried out at constant pressure, and it is found that there is a strong correlation between the total density and the composition. The critical temperature and the critical total density are found to increase with pressure. The critical mole fraction of the dipolar component on the contrary decreases as pressure is augmented. These qualitative trends are reproduced by the theoretical approaches that on the other hand overestimate by far the value of the critical temperature. Interestingly, the critical parameters for the liquid-vapor equilibrium extrapolated from the mixture results in the limit of vanishing neutral hard sphere concentration agree rather well with recent estimates based on the extrapolation of charged hard dumbbell phase equilibria when dumbbell elongation shrinks to zero [G. Ganzenmuller and P. J. Camp, J. Chem. Phys. 126, 191104 (2007)].
Demixing can occur in binary hard-sphere mixtures with negative nonadditivity.
Santos, A; López de Haro, M
2005-07-01
A binary fluid mixture of nonadditive hard spheres characterized by a size ratio gamma = sigma(2)/sigma(1) infinity) a demixing transition with a critical consolute point at a packing fraction scaling as eta approximately d2(-d) is found, even for slightly negative nonadditivity, if Delta >-1/8 (ln gamma)(2). Arguments concerning the stability of the demixing with respect to freezing are provided.
Li, Ning; Perea, José Darío; Kassar, Thaer; Richter, Moses; Heumueller, Thomas; Matt, Gebhard J.; Hou, Yi; Güldal, Nusret S.; Chen, Haiwei; Chen, Shi; Langner, Stefan; Berlinghof, Marvin; Unruh, Tobias; Brabec, Christoph J.
2017-02-01
The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells.
Li, Ning; Perea, José Darío; Kassar, Thaer; Richter, Moses; Heumueller, Thomas; Matt, Gebhard J.; Hou, Yi; Güldal, Nusret S.; Chen, Haiwei; Chen, Shi; Langner, Stefan; Berlinghof, Marvin; Unruh, Tobias; Brabec, Christoph J.
2017-01-01
The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells. PMID:28224984
Demixed principal component analysis of neural population data
Kobak, Dmitry; Brendel, Wieland; Constantinidis, Christos; Feierstein, Claudia E; Kepecs, Adam; Mainen, Zachary F; Qi, Xue-Lian; Romo, Ranulfo; Uchida, Naoshige; Machens, Christian K
2016-01-01
Neurons in higher cortical areas, such as the prefrontal cortex, are often tuned to a variety of sensory and motor variables, and are therefore said to display mixed selectivity. This complexity of single neuron responses can obscure what information these areas represent and how it is represented. Here we demonstrate the advantages of a new dimensionality reduction technique, demixed principal component analysis (dPCA), that decomposes population activity into a few components. In addition to systematically capturing the majority of the variance of the data, dPCA also exposes the dependence of the neural representation on task parameters such as stimuli, decisions, or rewards. To illustrate our method we reanalyze population data from four datasets comprising different species, different cortical areas and different experimental tasks. In each case, dPCA provides a concise way of visualizing the data that summarizes the task-dependent features of the population response in a single figure. DOI: http://dx.doi.org/10.7554/eLife.10989.001 PMID:27067378
Elusiveness of Fluid-Fluid Demixing in Additive Hard-Core Mixtures
Lafuente, Luis; Cuesta, José A.
2002-09-01
The conjecture that when an additive hard-core mixture phase separates when one of the phases is spatially ordered, well supported by considerable evidence, is in contradiction with some simulations of a binary mixture of hard cubes on cubic lattices. By extending Rosenfeld's fundamental measure theory to lattice models we show that the phase behavior of this mixture is far more complex than simulations show, exhibiting regions of stability of several smectic, columnar, and solid phases, but no fluid-fluid demixing. A comparison with the simulations show that they are, in fact, compatible with a fluid-columnar demixing transition, thus bringing this model into the same demixing scheme as the rest of additive hard-core mixtures.
Fluid-fluid versus fluid-solid demixing in mixtures of parallel hard hypercubes
Lafuente, Luis; Martínez-Ratón, Yuri
2011-02-01
It is well known that increase of the spatial dimensionality enhances the fluid-fluid demixing of a binary mixture of hard hyperspheres, i.e. the demixing occurs for lower mixture size asymmetry as compared to the three-dimensional case. However, according to simulations, in the latter dimension the fluid-fluid demixing is metastable with respect to the fluid-solid transition. According to the results obtained from approximations to the equation of state of hard hyperspheres in higher dimensions, the fluid-fluid demixing might become stable for high enough dimension. However, this conclusion is rather speculative since none of these works have taken into account the stability of the crystalline phase (by a minimization of a given density functional, by spinodal calculations or by MC simulations). Of course, the lack of results is justified by the difficulty of performing density functional calculations or simulations in high dimensions and, in particular, for highly asymmetric binary mixtures. In the present work, we will take advantage of a well tested theoretical tool, namely the fundamental measure density functional theory for parallel hard hypercubes (in the continuum and in the hypercubic lattice). With this, we have calculated the fluid-fluid and fluid-solid spinodals for different spatial dimensions. We have obtained, no matter what the dimensionality, the mixture size asymmetry or the polydispersity (included as a bimodal distribution function centered around the asymmetric edge lengths), that the fluid-fluid critical point is always located above the fluid-solid spinodal. In conclusion, these results point to the existence of demixing between at least one solid phase rich in large particles and one fluid phase rich in small ones, preempting a fluid-fluid demixing, independently of the spatial dimension or the polydispersity.
Density functional theory and demixing of binary hard-rod-polymer mixtures.
Bryk, P
2003-12-01
A density functional theory for a mixture of hard rods and polymers modeled as chains built of hard tangent spheres is proposed by combining the functional due to Yu and Wu for the polymer mixtures [J. Chem. Phys. 117, 2368 (2002)] with Schmidt's functional [Phys. Rev. E 63, 50 201 (2001)] for rod-sphere mixtures. As a simple application of the functional, the demixing transition into polymer-rich and rod-rich phases is examined. When the chain length increases, the phase boundary broadens and the critical packing fraction decreases. The shift of the critical point of a demixing transition is most noticeable for short chains.
Liquid demixing of intrinsically disordered proteins is seeded by poly(ADP-ribose)
Altmeyer, Matthias; Neelsen, Kai J; Teloni, Federico;
2015-01-01
disordered proteins at DNA break sites. Demixing, which relies on electrostatic interactions between positively charged RGG repeats and negatively charged PAR, is amplified by aggregation-prone prion-like domains, and orchestrates the earliest cellular responses to DNA breakage. We propose that PAR...
Michels, J.J.; Breemen, A.J.J.M. van; Usman, K.; Gelinck, G.H.
2011-01-01
This article describes a combined experimental and theoretical study on nanophase structure development as a result of liquid phase demixing in solution-cast blends of the organic semiconductor poly(9,9'-dioctyl fluorene) (PFO) and the ferroelectric polymer poly(vinylidene fluoride-co-trifluoroethyl
Demixing and confinement of non-additive hard-sphere mixtures in slit pores.
Almarza, N G; Martín, C; Lomba, E; Bores, C
2015-01-07
Using Monte Carlo simulation, we study the influence of geometric confinement on demixing for a series of symmetric non-additive hard spheres mixtures confined in slit pores. We consider both a wide range of positive non-additivities and a series of pore widths, ranging from the pure two dimensional limit to a large pore width where results are close to the bulk three dimensional case. Critical parameters are extracted by means of finite size analysis. As a general trend, we find that for this particular case in which demixing is induced by volume effects, the critical demixing densities (and pressures) increase due to confinement between neutral walls, following the expected behavior for phase equilibria of systems confined by pure repulsive walls: i.e., confinement generally enhances miscibility. However, a non-monotonous dependence of the critical pressure and density with pore size is found for small non-additivities. In this latter case, it turns out that an otherwise stable bulk mixture can be unexpectedly forced to demix by simple geometric confinement when the pore width decreases down to approximately one and a half molecular diameters.
Composition dependence of the glass forming ability in binary mixtures: The role of demixing entropy
Nandi, Ujjwal Kumar; Banerjee, Atreyee; Chakrabarty, Suman; Bhattacharyya, Sarika Maitra
2016-07-01
We present a comparative study of the glass forming ability of binary systems with varying composition, where the systems have similar global crystalline structure (CsCl+fcc). Biased Monte Carlo simulations using umbrella sampling technique show that the free energy cost to create a CsCl nucleus increases as the composition of the smaller particles is decreased. We find that systems with comparatively lower free energy cost to form CsCl nucleus exhibit more pronounced pre-crystalline demixing near the liquid/crystal interface. The structural frustration between the CsCl and fcc crystal demands this demixing. We show that closer to the equimolar mixture, the entropic penalty for demixing is lower and a glass forming system may crystallize when seeded with a nucleus. This entropic penalty as a function of composition shows a non-monotonic behaviour with a maximum at a composition similar to the well known Kob-Anderson (KA) model. Although the KA model shows the maximum entropic penalty and thus maximum frustration against CsCl formation, it also shows a strong tendency towards crystallization into fcc lattice of the larger "A" particles which can be explained from the study of the energetics. Thus for systems closer to the equimolar mixture although it is the requirement of demixing which provides their stability against crystallization, for KA model it is not demixing but slow dynamics and the presence of the "B" particles make it a good glass former. The locally favoured structure around "B" particles is quite similar to the CsCl structure and the incompatibility of CsCl and fcc hinders the fcc structure growth in the KA model. Although the glass forming binary systems studied here are quite similar, differing only in composition, we find that their glass forming ability cannot be attributed to a single phenomenon.
Nandi, Ujjwal Kumar; Banerjee, Atreyee; Chakrabarty, Suman; Bhattacharyya, Sarika Maitra
2016-07-21
We present a comparative study of the glass forming ability of binary systems with varying composition, where the systems have similar global crystalline structure (CsCl+fcc). Biased Monte Carlo simulations using umbrella sampling technique show that the free energy cost to create a CsCl nucleus increases as the composition of the smaller particles is decreased. We find that systems with comparatively lower free energy cost to form CsCl nucleus exhibit more pronounced pre-crystalline demixing near the liquid/crystal interface. The structural frustration between the CsCl and fcc crystal demands this demixing. We show that closer to the equimolar mixture, the entropic penalty for demixing is lower and a glass forming system may crystallize when seeded with a nucleus. This entropic penalty as a function of composition shows a non-monotonic behaviour with a maximum at a composition similar to the well known Kob-Anderson (KA) model. Although the KA model shows the maximum entropic penalty and thus maximum frustration against CsCl formation, it also shows a strong tendency towards crystallization into fcc lattice of the larger "A" particles which can be explained from the study of the energetics. Thus for systems closer to the equimolar mixture although it is the requirement of demixing which provides their stability against crystallization, for KA model it is not demixing but slow dynamics and the presence of the "B" particles make it a good glass former. The locally favoured structure around "B" particles is quite similar to the CsCl structure and the incompatibility of CsCl and fcc hinders the fcc structure growth in the KA model. Although the glass forming binary systems studied here are quite similar, differing only in composition, we find that their glass forming ability cannot be attributed to a single phenomenon.
Lampe, André; Tadeus, Georgi; Schmoranzer, Jan
2015-09-01
Multicolor single molecule localization-based super-resolution microscopy (SMLM) approaches are challenged by channel crosstalk and errors in multi-channel registration. We recently introduced a spectral demixing-based variant of direct stochastic optical reconstruction microscopy (SD-dSTORM) to perform multicolor SMLM with minimal color crosstalk. Here, we demonstrate that the spectral demixing procedure is inherently free of errors in multicolor registration and therefore does not require multicolor channel alignment. Furthermore, spectral demixing significantly reduces single molecule noise and is applicable to astigmatism-based 3D multicolor imaging achieving 25 nm lateral and 66 nm axial resolution on cellular nanostructures.
Guzman, Gustavo; Nugay, Turgut; Kennedy, Joseph P; Cakmak, Mukerrem
2016-04-12
Amphiphilic polymer co-networks provide a unique route to integrating contrasting attributes of otherwise immiscible components within a bicontinuous percolating morphology and are anticipated to be valuable for applications such as biocatalysis, sensing of metabolites, and dual dialysis membranes. These co-networks are in essence chemically forced blends and have been shown to selectively phase-separate at surfaces during film formation. Here, we demonstrate that surface demixing at the air-film interface in solidifying polymer co-networks is not a unidirectional process; instead, a combination of kinetic and thermodynamic interactions leads to dynamic molecular rearrangement during solidification. Time-resolved gravimetry, low contact angles, and negative out-of-plane birefringence provided strong experimental evidence of the transitory trapping of thermodynamically unfavorable hydrophilic moieties at the air-film interface due to fast asymmetric solvent depletion. We also find that slow-drying hydrophobic elements progressively substitute hydrophilic domains at the surface as the surface energy is minimized. These findings are broadly applicable to common-solvent bicontinuous systems and open the door for process-controlled performance improvements in diverse applications. Similar observations could potentially be coupled with controlled polymerization rates to maximize the intermingling of bicontinuous phases at surfaces, thus generating true three-dimensional, bicontinuous, and undisturbed percolation pathways throughout the material.
Polymer Conformation near the Critical Demixing Point of a Binary Solution
He, Lilin; Cheng, Gang; Melnichenko, Yuri
2012-02-01
We have used Contrast Matching Small Angle Neutron Scattering (CMSANS) to probe directly the conformation change of polyethylene glycerol (PEO) chains in the critical demixing region of Acetonitrile-d3 in (D2O + H2O) at concentration of the components corresponding to zero-average contrast condition. The d-PEO and h-PEO were mixed to match the scattering length density (SLD) of the critical liquid solution, which allowed us to extract single-chain dimension of polymer molecules in the aggregates near the critical point of the solvent. A non-monotonic variation of Rg was detected as temperature approached the critical temperature of phase demixing of acetonitrile- water solution, which was attributed to the interaction asymmetry of the solvent molecules with polymers predicted by Brochard and de Gennes two decades ago. To our best knowledge, this is the first direct experimental evidence supporting this prediction.
López de Haro, Mariano; Tejero, Carlos F; Santos, Andrés
2013-04-28
The problem of demixing in a binary fluid mixture of highly asymmetric additive hard spheres is revisited. A comparison is presented between the results derived previously using truncated virial expansions for three finite size ratios with those that one obtains with the same approach in the extreme case in which one of the components consists of point particles. Since this latter system is known not to exhibit fluid-fluid segregation, the similarity observed for the behavior of the critical constants arising in the truncated series in all instances, while not being conclusive, may cast serious doubts as to the actual existence of a demixing fluid-fluid transition in disparate-sized binary additive hard-sphere mixtures.
Demixing and effective volatility of molten alkali carbonate melts in MCFCs
Brenscheidt, T.; Wendt, H. [Institut fuer Chemische Technologie, Darmstadt (Germany)
1996-12-31
Since the early investigation of A. Klemm, the demixing of the cations of molten binary salt mixtures with a common anion due to the different mobilities of two different cations had been investigated in numerous experiments and the respective results interpreted in terms of structural features of the melts. 1-1 electrolytes had been preferentially investigated. Okada also reported investigations on lithium carbonate/potassium carbonate mixtures in the temperature range from 980 to 1070 K. From this investigation it is known that the heavier potassium cation is faster than lithium in mixtures which are more concentrated in potassium than x{sub K2CO3} = 0,32 (Chemla effect) whereas below this isotachic concentration lithium is faster. This paper investigates demixing in molten carbonate fuel cells.
On the demixing of hyaluronan and alginate in the gel state.
Scognamiglio, Francesca; Travan, Andrea; Cok, Michela; Borgogna, Massimiliano; Marsich, Eleonora; Paoletti, Sergio; Donati, Ivan
2017-02-01
The manuscript focuses on the demixing of hyaluronan and alginate in the hydrogel state. Binary solutions of the two polysaccharides have been treated with Ca(2+) as the alginate cross-linking ion and the radial distribution of the two components in the hydrogels was measured by means of (1)H NMR. These results revealed the presence of alginate-enriched and hyaluronan-enriched domains stemming from a polysaccharide demixing. The hydrogels were characterized by means of uniaxial compression and creep-compliance measurements which showed that the demixing increased the overall resistance of the hydrogel to stress. In addition, due to the viscoelastic properties of hyaluronan, a marked increase of the Newtonian viscosity of the constructs was noticed. The peculiarity of the effect of hyaluronan was demonstrated by the use of an alginate unable to form gel by binding non-calcium binding alginate, i.e. mannuronan, ruling out the effect of viscosity over the time-dependent behavior of the mixed hyaluronan-alginate hydrogels. Copyright © 2016 Elsevier B.V. All rights reserved.
Oonk, H.A.J.; Wijk, H.J. van; Doornhof, D.
1984-01-01
The region of demixing of solid lithium bromide + sodium bromide mixtures has been measured by X-ray diffraction. The critical temperature of mixing corresponding to a thermodynamic fit of the experimental data is 513 K. Estimates are given of the regions of demixing in solid lithium chloride + sodi
Transition from stress-driven to thermally activated stress relaxation in metallic glasses
Qiao, J. C.; Wang, Yun-Jiang; Zhao, L. Z.; Dai, L. H.; Crespo, D.; Pelletier, J. M.; Keer, L. M.; Yao, Y.
2016-09-01
The short-range ordered but long-range disordered structure of metallic glasses yields strong structural and dynamic heterogeneities. Stress relaxation is a technique to trace the evolution of stress in response to a fixed strain, which reflects the dynamic features phenomenologically described by the Kohlrausch-Williams-Watts (KWW) equation. The KWW equation describes a broad distribution of relaxation times with a small number of empirical parameters, but it does not arise from a particular physically motivated mechanistic picture. Here we report an anomalous two-stage stress relaxation behavior in a Cu46Zr46Al8 metallic glass over a wide temperature range and generalize the findings in other compositions. Thermodynamic analysis identifies two categories of processes: a fast stress-driven event with large activation volume and a slow thermally activated event with small activation volume, which synthetically dominates the stress relaxation dynamics. Discrete analyses rationalize the transition mechanism induced by stress and explain the anomalous variation of the KWW characteristic time with temperature. Atomistic simulations reveal that the stress-driven event involves virtually instantaneous short-range atomic rearrangement, while the thermally activated event is the percolation of the fast event accommodated by the long-range atomic diffusion. The insights may clarify the underlying physical mechanisms behind the phenomenological description and shed light on correlating the hierarchical dynamics and structural heterogeneity of amorphous solids.
Fluid-fluid demixing curves for colloid-polymer mixtures in a random colloidal matrix
Annunziata, Mario Alberto; Pelissetto, Andrea
2011-12-01
We study fluid-fluid phase separation in a colloid-polymer mixture adsorbed in a colloidal porous matrix close to the θ point. For this purpose we consider the Asakura-Oosawa model in the presence of a quenched matrix of colloidal hard spheres. We study the dependence of the demixing curve on the parameters that characterize the quenched matrix, fixing the polymer-to-colloid size ratio to 0.8. We find that, to a large extent, demixing curves depend only on a single parameter f, which represents the volume fraction which is unavailable to the colloids. We perform Monte Carlo simulations for volume fractions f equal to 40% and 70%, finding that the binodal curves in the polymer and colloid packing-fraction plane have a small dependence on disorder. The critical point instead changes significantly: for instance, the colloid packing fraction at criticality increases with increasing f. Finally, we observe for some values of the parameters capillary condensation of the colloids: a bulk colloid-poor phase is in chemical equilibrium with a colloid-rich phase in the matrix.
Constitutive modeling of stress-driven grain growth in nanocrystalline metals
Gürses, Ercan
2013-02-08
In this work, we present a variational multiscale model for grain growth in face-centered cubic nanocrystalline (nc) metals. In particular, grain-growth-induced stress softening and the resulting relaxation phenomena are addressed. The behavior of the polycrystal is described by a conventional Taylor-type averaging scheme in which the grains are treated as two-phase composites consisting of a grain interior phase and a grain boundary-affected zone. Furthermore, a grain-growth law that captures the experimentally observed characteristics of the grain coarsening phenomena is proposed. To this end, the grain size is not taken as constant and varies according to the proposed stress-driven growth law. Several parametric studies are conducted to emphasize the influence of the grain-growth rule on the overall macroscopic response. Finally, the model is shown to provide a good description of the experimentally observed grain-growth-induced relaxation in nc-copper. © 2013 IOP Publishing Ltd.
Crowding of polymer coils and demixing in nanoparticle-polymer mixtures.
Lu, Ben; Denton, Alan R
2011-07-20
The Asakura-Oosawa-Vrij (AOV) model of colloid-polymer mixtures idealises nonadsorbing polymers as effective spheres that are fixed in size and impenetrable to hard particles. Real polymer coils, however, are intrinsically polydisperse in size (radius of gyration) and may be penetrated by smaller particles. Crowding by nanoparticles can affect the size distribution of polymer coils, thereby modifying effective depletion interactions and thermodynamic stability. To analyse the influence of crowding on polymer conformations and demixing phase behaviour, we adapt the AOV model to mixtures of nanoparticles and ideal, penetrable polymer coils that can vary in size. We perform Gibbs ensemble Monte Carlo simulations, including trial nanoparticle-polymer overlaps and variations in the radius of gyration. Results are compared with predictions of free-volume theory. Simulation and theory consistently predict that ideal polymers are compressed by nanoparticles, and that compressibility and penetrability stabilise nanoparticle-polymer mixtures.
Structure and dynamics of binary liquid mixtures near their continuous demixing transitions
Roy, Sutapa; Dietrich, S.; Höfling, Felix
2016-10-01
The dynamic and static critical behavior of a family of binary Lennard-Jones liquid mixtures, close to their continuous demixing points (belonging to the so-called model H' dynamic universality class), are studied computationally by combining semi-grand canonical Monte Carlo simulations and large-scale molecular dynamics (MD) simulations, accelerated by graphic processing units (GPU). The symmetric binary liquid mixtures considered cover a variety of densities, a wide range of compressibilities, and various interactions between the unlike particles. The static quantities studied here encompass the bulk phase diagram (including both the binodal and the λ-line), the correlation length, and the concentration susceptibility, of the finite-sized systems above the bulk critical temperature Tc, the compressibility and the pressure at Tc. Concerning the collective transport properties, we focus on the Onsager coefficient and the shear viscosity. The critical power-law singularities of these quantities are analyzed in the mixed phase (above Tc) and non-universal critical amplitudes are extracted. Two universal amplitude ratios are calculated. The first one involves static amplitudes only and agrees well with the expectations for the three-dimensional Ising universality class. The second ratio includes also dynamic critical amplitudes and is related to the Einstein-Kawasaki relation for the interdiffusion constant. Precise estimates of this amplitude ratio are difficult to obtain from MD simulations, but within the error bars our results are compatible with theoretical predictions and experimental values for model H'. Evidence is reported for an inverse proportionality of the pressure and the isothermal compressibility at the demixing transition, upon varying either the number density or the repulsion strength between unlike particles.
Optimal bounds with semidefinite programming: An application to stress-driven shear flows.
Fantuzzi, G; Wynn, A
2016-04-01
We introduce an innovative numerical technique based on convex optimization to solve a range of infinite-dimensional variational problems arising from the application of the background method to fluid flows. In contrast to most existing schemes, we do not consider the Euler-Lagrange equations for the minimizer. Instead, we use series expansions to formulate a finite-dimensional semidefinite program (SDP) whose solution converges to that of the original variational problem. Our formulation accounts for the influence of all modes in the expansion, and the feasible set of the SDP corresponds to a subset of the feasible set of the original problem. Moreover, SDPs can be easily formulated when the fluid is subject to imposed boundary fluxes, which pose a challenge for the traditional methods. We apply this technique to compute rigorous and near-optimal upper bounds on the dissipation coefficient for flows driven by a surface stress. We improve previous analytical bounds by more than 10 times and show that the bounds become independent of the domain aspect ratio in the limit of vanishing viscosity. We also confirm that the dissipation properties of stress-driven flows are similar to those of flows subject to a body force localized in a narrow layer near the surface. Finally, we show that SDP relaxations are an efficient method to investigate the energy stability of laminar flows driven by a surface stress.
Stress-driven buckling patterns in spheroidal core/shell structures.
Yin, Jie; Cao, Zexian; Li, Chaorong; Sheinman, Izhak; Chen, Xi
2008-12-09
Many natural fruits and vegetables adopt an approximately spheroidal shape and are characterized by their distinct undulating topologies. We demonstrate that various global pattern features can be reproduced by anisotropic stress-driven buckles on spheroidal core/shell systems, which implies that the relevant mechanical forces might provide a template underpinning the topological conformation in some fruits and plants. Three dimensionless parameters, the ratio of effective size/thickness, the ratio of equatorial/polar radii, and the ratio of core/shell moduli, primarily govern the initiation and formation of the patterns. A distinct morphological feature occurs only when these parameters fall within certain ranges: In a prolate spheroid, reticular buckles take over longitudinal ridged patterns when one or more parameters become large. Our results demonstrate that some universal features of fruit/vegetable patterns (e.g., those observed in Korean melons, silk gourds, ribbed pumpkins, striped cavern tomatoes, and cantaloupes, etc.) may be related to the spontaneous buckling from mechanical perspectives, although the more complex biological or biochemical processes are involved at deep levels.
Brunet, Charles; Amokrane, Said
2011-01-01
We study by Monte Carlo simulation a binary mixture of neutral and dipolar hard-spheres with non-additive diameters. With a view to understanding the interplay between population inversion for an open pore and the demixing phase transitions, the mixture is considered in the bulk and confined between two parallel hard-walls modeling a slit pore. A uniform field is applied in the pore in order to control its composition as shown previously. The demixing lines in the bulk and in the pore are studied by the Gibbs Ensemble Monte Carlo method. The open pore-bulk mixture equilibrium is studied by a combination of canonical/grand canonical simulations. A moderate electrostatic coupling is considered for remaining close to the conditions in which a jump in the adsorption of the minority species has been observed at zero field. Demixing lines are given in the bulk and for two different pore widths in parallel and normal fields, together with population inversion paths. Similarly to the effect of geometrical confinement...
Rescaled density expansions and demixing in hard-sphere binary mixtures.
López de Haro, M; Tejero, C F
2004-10-08
The demixing transition of a binary fluid mixture of additive hard spheres is analyzed for different size asymmetries by starting from the exact low-density expansion of the pressure. Already within the second virial approximation the fluid separates into two phases of different composition with a lower consolute critical point. By successively incorporating the third, fourth, and fifth virial coefficients, the critical consolute point moves to higher values of the pressure and to lower values of the partial number fraction of the large spheres. When the exact low-density expansion of the pressure is rescaled to higher densities as in the Percus-Yevick theory, by adding more exact virial coefficients a different qualitative movement of the critical consolute point in the phase diagram is found. It is argued that the Percus-Yevick factor appearing in many empirical equations of state for the mixture has a deep influence on the location of the critical consolute point, so that the resulting phase diagram for a prescribed equation has to be taken with caution.
Evolution of self-organized two-dimensional patterns of nanoclusters through demixing
Choudhuri, Madhumita; Iyengar, A. N. Sekar; Datta, Alokmay; Janaki, M. S.
2015-09-01
A mixture of dodecanethiol-capped Au nanoparticles (AuNPs) and the amphiphilic fatty acid, stearic acid, spread as a monomolecular layer on water surface, is observed with Brewster angle microscopy (BAM) to form a two-dimensional network of AuNP clusters through demixing, at concentration of AuNPs by weight (ρ ¯)>10 % and the surface pressure (π )≥10 mN m-1 . For π =15 mN m-1 , the number of nodes (n ) remains unchanged till ˜2 hours and then changes over to a lower n state, where the pattern consists of almost perfect circles with greater in-plane thickness of the AuNP lamellae. For the higher n state the mean-square fluctuation of BAM intensity remains flat and then decays as f (ξ ) =ξ2 α with α ˜0.6 (correlated fluctuations) over the length scales of 400 μ m -6 μ m and below 6 μ m , respectively. For the lower n state the fluctuation decays almost over the entire length scale with α =0.3 , indicating emergence of aperiodicity from quasiperiodicity and a changeover to anticorrelated fluctuations. These patterns can be looked at as two distinct chaotic trajectories in the I -I' phase space of the system (I being the scattered light intensity at any position of the pattern and I' its gradient) with characteristic Lyapunov exponents.
On the origin of multi-component bulk metallic glasses: Atomic size mismatches and de-mixing
Zhang, Kai; Dice, Bradley; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D.; O'Hern, Corey S.
2015-08-01
The likelihood that an undercooled liquid vitrifies or crystallizes depends on the cooling rate R . The critical cooling rate R c , below which the liquid crystallizes upon cooling, characterizes the glass-forming ability (GFA) of the system. While pure metals are typically poor glass formers with R c > 1 0 12 K/s , specific multi-component alloys can form bulk metallic glasses (BMGs) even at cooling rates below R ˜ 1 K / s . Conventional wisdom asserts that metal alloys with three or more components are better glass formers (with smaller R c ) than binary alloys. However, there is currently no theoretical framework that provides quantitative predictions for R c for multi-component alloys. In this manuscript, we perform simulations of ternary hard-sphere systems, which have been shown to be accurate models for the glass-forming ability of BMGs, to understand the roles of geometric frustration and demixing in determining R c . Specifically, we compress ternary hard sphere mixtures into jammed packings and measure the critical compression rate, below which the system crystallizes, as a function of the diameter ratios σB/σA and σC/σA and number fractions xA, xB, and xC. We find two distinct regimes for the GFA in parameter space for ternary hard spheres. When the diameter ratios are close to 1, such that the largest (A) and smallest (C) species are well-mixed, the GFA of ternary systems is no better than that of the optimal binary glass former. However, when σC/σA ≲ 0.8 is below the demixing threshold for binary systems, adding a third component B with σC < σB < σA increases the GFA of the system by preventing demixing of A and C. Analysis of the available data from experimental studies indicates that most ternary BMGs are below the binary demixing threshold with σC/σA < 0.8.
Hong, Min-Eui; Hwang, Sung Kwan; Chang, Won Seok; Kim, Byung Woo; Lee, Jeewon; Sim, Sang Jun
2015-06-01
High temperatures (30-36 °C) inhibited astaxanthin accumulation in Haematococcus pluvialis under photoautotrophic conditions. The depression of carotenogenesis was primarily attributed to excess intracellular less reactive oxygen species (LROS; O2 (-) and H2O2) levels generated under high temperature conditions. Here, we show that the heat stress-driven inefficient astaxanthin production was improved by accelerating the iron-catalyzed Haber-Weiss reaction to convert LROS into more reactive oxygen species (MROS; O2 and OH·), thereby facilitating lipid peroxidation. As a result, during 18 days of photoautotrophic induction, the astaxanthin concentration of cells cultured in high temperatures in the presence of iron (450 μM) was dramatically increased by 75 % (30 °C) and 133 % (36 °C) compared to that of cells exposed to heat stress alone. The heat stress-driven Haber-Weiss reaction will be useful for economically producing astaxanthin by reducing energy cost and enhancing photoautotrophic astaxanthin production, particularly outdoors utilizing natural solar radiation including heat and light for photo-induction of H. pluvialis.
Ruwanti Dewi Cahya Ningrum
2016-10-01
Full Text Available Polysulfone (PSf-Polyvinylidene fluoride (PVDF membranes were fabricated via phase inversion method and immersion precipitation technique. In particular, the effect of varied amount of NMP addition into coagulation bath on permeability, mechanical properties, chemical resistance and thermal stability of membranes were investigated. The presence of solvent in coagulation bath caused delayed liquid-liquid demixing that caused increasing chance of disoriented interactions in PSf/PVDF blend membrane thus larger pore and dominated macrovoids membranes resulted. It was found that the increase of solvent addition lead to increasing of flux and decreasing of mechanical strength whereas a remarkably and enhanced chemical resistance has been achieved which showed excellent resistance in H2SO4 but degraded upon exposure to a concentration of 15% NaOH solution. Furthermore, TGA analysis revealed that the membrane exhibit improved thermal stability while the morphology of membrane showed the formation of asymmetry structure.
Rac1 and Cdc42 GTPases regulate shear stress-driven β-catenin signaling in osteoblasts
Wan, Qiaoqiao; Cho, Eunhye [Department of Biomedical Engineering, Indiana University-Purdue University Indianapolis, Indianapolis, IN 46202 (United States); Yokota, Hiroki [Department of Biomedical Engineering, Indiana University-Purdue University Indianapolis, Indianapolis, IN 46202 (United States); Department of Anatomy and Cell Biology, Indiana University School of Medicine, Indianapolis, IN 46202 (United States); Na, Sungsoo, E-mail: sungna@iupui.edu [Department of Biomedical Engineering, Indiana University-Purdue University Indianapolis, Indianapolis, IN 46202 (United States)
2013-04-19
Highlights: •Shear stress increased TCF/LEF activity and stimulated β-catenin nuclear localization. •Rac1, Cdc42, and RhoA displayed distinct dynamic activity patterns under flow. •Rac1 and Cdc42, but not RhoA, regulate shear stress-driven TCF/LEF activation. •Cytoskeleton did not significantly affect shear stress-induced TCF/LEF activation. -- Abstract: Beta-catenin-dependent TCF/LEF (T-cell factor/lymphocyte enhancing factor) is known to be mechanosensitive and an important regulator for promoting bone formation. However, the functional connection between TCF/LEF activity and Rho family GTPases is not well understood in osteoblasts. Herein we investigated the molecular mechanisms underlying oscillatory shear stress-induced TCF/LEF activity in MC3T3-E1 osteoblast cells using live cell imaging. We employed fluorescence resonance energy transfer (FRET)-based and green fluorescent protein (GFP)-based biosensors, which allowed us to monitor signal transduction in living cells in real time. Oscillatory (1 Hz) shear stress (10 dynes/cm{sup 2}) increased TCF/LEF activity and stimulated translocation of β-catenin to the nucleus with the distinct activity patterns of Rac1 and Cdc42. The shear stress-induced TCF/LEF activity was blocked by the inhibition of Rac1 and Cdc42 with their dominant negative mutants or selective drugs, but not by a dominant negative mutant of RhoA. In contrast, constitutively active Rac1 and Cdc42 mutants caused a significant enhancement of TCF/LEF activity. Moreover, activation of Rac1 and Cdc42 increased the basal level of TCF/LEF activity, while their inhibition decreased the basal level. Interestingly, disruption of cytoskeletal structures or inhibition of myosin activity did not significantly affect shear stress-induced TCF/LEF activity. Although Rac1 is reported to be involved in β-catenin in cancer cells, the involvement of Cdc42 in β-catenin signaling in osteoblasts has not been identified. Our findings in this study demonstrate
López-Sánchez, Erik; Estrada-Álvarez, César D; Pérez-Ángel, Gabriel; Méndez-Alcaraz, José Miguel; González-Mozuelos, Pedro; Castañeda-Priego, Ramón
2013-09-14
Asymmetric binary mixtures of hard-spheres exhibit several interesting thermodynamic phenomena, such as multiple kinds of glassy states. When the degrees of freedom of the small spheres are integrated out from the description, their effects are incorporated into an effective pair interaction between large spheres known as the depletion potential. The latter has been widely used to study both the phase behavior and dynamic arrest of the big particles. Depletion forces can be accounted for by a contraction of the description in the multicomponent Ornstein-Zernike equation [R. Castañeda-Priego, A. Rodríguez-López, and J. M. Méndez-Alcaraz, Phys. Rev. E 73, 051404 (2006)]. Within this theoretical scheme, an approximation for the difference between the effective and bare bridge functions is needed. In the limit of infinite dilution, this difference is irrelevant and the typical Asakura-Osawa depletion potential is recovered. At higher particle concentrations, however, this difference becomes important, especially where the shell of first neighbors is formed, and, as shown here, cannot be simply neglected. In this work, we use a variant of the Verlet expression for the bridge functions to highlight their importance in the calculation of the depletion potential at high densities and close to the spinodal decomposition. We demonstrate that the modified Verlet closure predicts demixing in binary mixtures of hard spheres for different size ratios and compare its predictions with both liquid state and density functional theories, computer simulations, and experiments. We also show that it provides accurate correlation functions even near the thermodynamic instability; this is explicitly corroborated with results of molecular dynamics simulations of the whole mixture. Particularly, our findings point toward a possible universal behavior of the depletion potential around the spinodal line.
Guilhem Bourrie
2014-12-01
Full Text Available Sodium adsorption ratio SAR defined as SAR = (Na / V w(Ca+Mg/2 here concentrations of cations in solution are expressed in meq/L has long been considered as correlated to exchangeable sodium percentage (ESP on clay minerals or soil exchange complex, and as the key concept to explain swelling of clay minerals and the difficulties of reclaiming salt-affected soils. Though its basis is empirical, it was alleged to be theoretically justified on the basis of ion exchange, derived from the Gapon convention. However, it has long been challenged on the basis of both field observations and experimental evidence : it fails to account for the fact that calcium and magnesium do not play the same role, while potassium is absent from the formula ; calcium concentration must be “corrected “when calcite is present etc. There exist specific ion effects. Experimental measurements of the decrease of permeability when solutions are diluted led Quirk and Schofield (1955 to define the concept of critical threshold, and to show that potassium and magnesium play an intermediate role between sodium and calcium. This threshold is simply determined by the concentration of calcium, irrespective of the value of SAR or ESP. Indeed, demixing of Ca-Na clay minerals during ion exchange, a phenomenon well known since Glaeser and Mering (1954, implies that there exists an interaction between adjacent sites. This undermines the theoretical basis of SAR : the derivation of SAR from ion exchange equilibria implies to use an equilibrium constant. This parameter is no more constant if demixing occurs. The results obtained are positive : demixing leads to expulsion of sodium from inner exchange surfaces and its replacement by calcium, according to the “three crystals pore”proposed by Quirk (2003b. Sodium can then be more easily leached, as permeability is maintained by clusters of Ca-sites. Calcium concentration in solution appears thus as the simpler parameter to guide
Cuetos, Alejandro; Martínez-Haya, Bruno; Lago, Santiago; Rull, Luis F
2007-06-01
Parsons-Lee and Onsager theories are formulated for the isotropic-nematic transition in a binary mixture of hard rods and hard spheres. Results for the phase coexistence and for the equation of state in both phases for mixtures with different relative sizes and composition are presented. The two theories explain correctly the general behavior observed in experiments and computer simulations for these fluids. In particular, the theory accounts for the destabilization of the nematic phase when spherical or globular macromolecules are added to a system of rodlike colloids, and the entrance of the system into a demixed regime at high volume fractions of the spherical particles. Upon demixing a nematic state rich in rods coexists in equilibrium with an isotropic state much more diluted in the rodlike component. Onsager theory fails on quantitative grounds for aspect ratios of the rodlike molecules smaller than 100, and in the cases where the molar fractions of spheres becomes close to unity. On the contrary, the Parsons-Lee approximation remains accurate down to aspect ratios as small as 5. The spinodal analysis indicates that the isotropic-isotropic and nematic-nematic coexistences become feasible for sufficiently large spheres and long rods, respectively. The latter type of coexistence interferes partially with the isotropic-nematic coexistence regime of interest to the present work. Overall, the study serves to rationalize and control key aspects of the behavior of these binary nematogenic colloidal systems, which can be tuned with an appropriate choice of the relative size and molar fractions of the particles.
Nabarro, FRN
1998-11-13
Full Text Available This article shows the differences of two-dimensional polycrystal of a material with a rectangular unit cell with lattice spacing b and b (1 + epsilon), subjected to a uniform external stress sigma. Consider a grain in which the lattice vector...
Wilson, David B.
1981-01-01
Surveys the research of scientists like Joule, Kelvin, Maxwell, Clausius, and Boltzmann as it comments on the basic conceptual issues involved in the development of a more precise kinetic theory and the idea of a kinetic atom. (Author/SK)
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....
Lettinga, M Paul [IFF, Institut Weiche Materie, Forschungszentrum Juelich, D-52425 Juelich (Germany); Kang, Kyongok [IFF, Institut Weiche Materie, Forschungszentrum Juelich, D-52425 Juelich (Germany); Imhof, Arnout [Soft Condensed Matter, Debye Institute, Utrecht University, Princetonplein 5, 3584 CC Utrecht (Netherlands); Derks, Didi [Soft Condensed Matter, Debye Institute, Utrecht University, Princetonplein 5, 3584 CC Utrecht (Netherlands); Dhont, Jan K G [IFF, Institut Weiche Materie, Forschungszentrum Juelich, D-52425 Juelich (Germany)
2005-11-16
We investigate the kinetics of phase separation for a mixture of rod-like viruses (fd) and polymer (dextran), which effectively constitutes a system of attractive rods. This dispersion is quenched from a flow-induced fully nematic state into the region where the nematic and the isotropic phase coexist. We show experimental evidence that the kinetic pathway depends on the overall concentration. When the quench is made at high concentrations, the system is meta-stable and we observe typical nucleation-and-growth. For quenches at low concentration the system is unstable and the system undergoes a spinodal decomposition. At intermediate concentrations we see the transition between both demixing processes, where we locate the spinodal point.
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....
Weakening gravity on redshift-survey scales with kinetic matter mixing
D'Amico, Guido; Huang, Zhiqi; Mancarella, Michele; Vernizzi, Filippo
2017-02-01
We explore general scalar-tensor models in the presence of a kinetic mixing between matter and the scalar field, which we call Kinetic Matter Mixing. In the frame where gravity is de-mixed from the scalar this is due to disformal couplings of matter species to the gravitational sector, with disformal coefficients that depend on the gradient of the scalar field. In the frame where matter is minimally coupled, it originates from the so-called beyond Horndeski quadratic Lagrangian. We extend the Effective Theory of Interacting Dark Energy by allowing disformal coupling coefficients to depend on the gradient of the scalar field as well. In this very general approach, we derive the conditions to avoid ghost and gradient instabilities and we define Kinetic Matter Mixing independently of the frame metric used to described the action. We study its phenomenological consequences for a ΛCDM background evolution, first analytically on small scales. Then, we compute the matter power spectrum and the angular spectra of the CMB anisotropies and the CMB lensing potential, on all scales. We employ the public version of COOP, a numerical Einstein-Boltzmann solver that implements very general scalar-tensor modifications of gravity. Rather uniquely, Kinetic Matter Mixing weakens gravity on short scales, predicting a lower σ8 with respect to the ΛCDM case. We propose this as a possible solution to the tension between the CMB best-fit model and low-redshift observables.
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.
Weakening Gravity on Redshift-Survey Scales with Kinetic Matter Mixing
D'Amico, Guido; Mancarella, Michele; Vernizzi, Filippo
2017-01-01
We explore general scalar-tensor models in the presence of a kinetic mixing between matter and the scalar field, which we call Kinetic Matter Mixing. In the frame where gravity is de-mixed from the scalar this is due to disformal couplings of matter species to the gravitational sector, with disformal coefficients that depend on the gradient of the scalar field. In the frame where matter is minimally coupled, it originates from the so-called beyond Horndeski quadratic Lagrangian. We extend the Effective Theory of Interacting Dark Energy by allowing disformal coupling coefficients to depend on the gradient of the scalar field as well. In this very general approach, we derive the conditions to avoid ghost and gradient instabilities and we define Kinetic Matter Mixing independently of the frame metric used to described the action. We study its phenomenological consequences for a $\\Lambda$CDM background evolution, first analytically on small scales. Then, we compute the matter power spectrum and the angular spectr...
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...
Lorentz JÄNTSCHI
2003-03-01
Full Text Available Mathematics and computer programming have a major contribution to chemistry. Two directions can be identified: one that searches and tries (rich to explain the structural binding and shape of the chemical compounds [1] with major applications in QSPR/QSAR studies [2], and applied sciences such as engineering of materials or agriculture [3]; the second direction is to models the kinetic processes that are involved in chemical reactions [4]. Many such models are available here. The present paper describes three variants of well the known kinetic models and presents the mathematical equations associated with them. The differential equations are numerically solved and fitted with MathCad program. [1] Diudea M., Gutman I., Jäntschi L., Molecular Topology, Nova Science, Huntington, New York, 332 p., 2001, 2002. [2] Diudea M. V., Ed., QSPR / QSAR Studies by Molecular Descriptors, Nova Science, Huntington, New York, 438 p., 2001. [3] Jäntschi L., Microbiology and Toxicology. Phytochemistry Studies (in Romanian, Amici, Cluj-Napoca, 184 p., 2003. [4] Jäntschi L., Unguresan M., Physical Chemistry. Molecular Kinetic and Dynamic (in Romanian, Mediamira, Cluj-Napoca, 159 p., 2001.
Bullingham, R E; McQuay, H J; Moore, A; Bennett, M R
1980-11-01
Buprenorphine kinetics was determined in surgical patients using radioimmunoassay. Buprenorphine was measured in the plasma of 24 patients who had received 0.3 mg buprenorphine intraoperatively. After 3 hr 10 of these patients then received a further 0.3 mg buprenorphine intravenously for postoperative pain relief, and 11 patients were given 0.3 mg intramuscularly; again, plasma levels were measured for 3 hr. The data fitted closely to a triexponential decay curve. There was a very fast initial phase, with a half-life (t1/2) of 2 min. The terminal t1/2 was slow, approximately 3 hr. Comparison of the kinetics of the same patient, awake and anesthetized, showed that the clearance was significantly lower in the anesthetized state. A notable feature of the drug given intramuscularly is rapid systemic availability, so that peaks are obtained in 2 to 5 min, and in 10 min the resulting levels are the same as for the intravenous and intramuscular routes.
Clustering and heterogeneous dynamics in a kinetic Monte Carlo model of self-propelled hard disks.
Levis, Demian; Berthier, Ludovic
2014-06-01
We introduce a kinetic Monte Carlo model for self-propelled hard disks to capture with minimal ingredients the interplay between thermal fluctuations, excluded volume, and self-propulsion in large assemblies of active particles. We analyze in detail the resulting (density, self-propulsion) nonequilibrium phase diagram over a broad range of parameters. We find that purely repulsive hard disks spontaneously aggregate into fractal clusters as self-propulsion is increased and rationalize the evolution of the average cluster size by developing a kinetic model of reversible aggregation. As density is increased, the nonequilibrium clusters percolate to form a ramified structure reminiscent of a physical gel. We show that the addition of a finite amount of noise is needed to trigger a nonequilibrium phase separation, showing that demixing in active Brownian particles results from a delicate balance between noise, interparticle interactions, and self-propulsion. We show that self-propulsion has a profound influence on the dynamics of the active fluid. We find that the diffusion constant has a nonmonotonic behavior as self-propulsion is increased at finite density and that activity produces strong deviations from Fickian diffusion that persist over large time scales and length scales, suggesting that systems of active particles generically behave as dynamically heterogeneous systems.
Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio
2015-01-12
This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Brown, M. E.; Phillpotts, C. A. R.
1978-01-01
Discusses the principle of nonisothermal kinetics and some of the factors involved in such reactions, especially when considering the reliability of the kinetic parameters, compared to those of isothermal conditions. (GA)
Gorban, A. N.; Karlin, I.V.
2003-01-01
Nonlinear kinetic equations are reviewed for a wide audience of specialists and postgraduate students in physics, mathematical physics, material science, chemical engineering and interdisciplinary research. Contents: The Boltzmann equation, Phenomenology and Quasi-chemical representation of the Boltzmann equation, Kinetic models, Discrete velocity models, Direct simulation, Lattice Gas and Lattice Boltzmann models, Minimal Boltzmann models for flows at low Knudsen number, Other kinetic equati...
Kinetics of methane fermentation
Chen, Y. R.; Hashimoto, A. G.
1978-01-01
The kinetics on methane fermentation are described using published data for livestock residue, sewage sludge, and municipal refuse. Methods are presented to determine the kinetic constants and the finally attainable methane production using steady-state methane production data. The effects of temperature, loading rate, and influent substrate concentration on methane fermentation kinetics are discussed. These relationships were used to predict the rate of methane production of a pilot-scale fermentor with excellent results.
Modulated structure formation in demixing paraffin blends
Gilbert, E P
2002-01-01
Small angle scattering (SANS and SAXS) and differential scanning calorimetry have been measured from C sub 2 sub 8 :C sub 3 sub 6 normal paraffin mixtures of varying composition quenched from the melt. Satellite peaks are observed in the SAXS whose offset in Q, relative to Bragg diffraction peaks associated with the average structure, are composition dependent. The offset is close to the position of the most intense peak observed in SANS. Scattering from the quenched structures is consistent with a correlated displacement and substitutional disorder model yielding modulations that are incommensurate with the average lattice. DSC shows an additional endotherm in the mixtures that is not present in the pure components and is associated with this superstructure formation. (orig.)
Demixing light paths inside disordered metamaterials
Vellekoop, Ivo Micha; van Putten, E.G.; Putten, E.G.; Lagendijk, Aart; Mosk, Allard
2008-01-01
We experimentally demonstrate the first method to focus light inside disordered photonic metamaterials. In such materials, scattering prevents light from forming a geometric focus. Instead of geometric optics, we used multi-path interference to make the scattering process itself concentrate light on
Demixing light paths inside disordered metamaterials
Vellekoop, I.M.; Putten, E.G.; Lagendijk, A.; Mosk, A.P.
2008-01-01
We experimentally demonstrate the first method to focus light inside disordered photonic metamaterials. In such materials, scattering prevents light from forming a geometric focus. Instead of geometric optics, we used multi-path interference to make the scattering process itself concentrate light on
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
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
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
Kinetic equations: computation
Pareschi, Lorenzo
2013-01-01
Kinetic equations bridge the gap between a microscopic description and a macroscopic description of the physical reality. Due to the high dimensionality the construction of numerical methods represents a challenge and requires a careful balance between accuracy and computational complexity.
Thermal kinetic inductance detector
Cecil, Thomas; Gades, Lisa; Miceli, Antonio; Quaranta, Orlando
2016-12-20
A microcalorimeter for radiation detection that uses superconducting kinetic inductance resonators as the thermometers. The detector is frequency-multiplexed which enables detector systems with a large number of pixels.
SRD 17 NIST Chemical Kinetics Database (Web, free access) The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.
Electrochemical kinetics theoretical aspects
Vetter, Klaus J
1967-01-01
Electrochemical Kinetics: Theoretical Aspects focuses on the processes, methodologies, reactions, and transformations in electrochemical kinetics. The book first offers information on electrochemical thermodynamics and the theory of overvoltage. Topics include equilibrium potentials, concepts and definitions, electrical double layer and electrocapillarity, and charge-transfer, diffusion, and reaction overvoltage. Crystallization overvoltage, total overvoltage, and resistance polarization are also discussed. The text then examines the methods of determining electrochemical reaction mechanisms
Multiple alternative substrate kinetics.
Anderson, Vernon E
2015-11-01
The specificity of enzymes for their respective substrates has been a focal point of enzyme kinetics since the initial characterization of metabolic chemistry. Various processes to quantify an enzyme's specificity using kinetics have been utilized over the decades. Fersht's definition of the ratio kcat/Km for two different substrates as the "specificity constant" (ref [7]), based on the premise that the important specificity existed when the substrates were competing in the same reaction, has become a consensus standard for enzymes obeying Michaelis-Menten kinetics. The expansion of the theory for the determination of the relative specificity constants for a very large number of competing substrates, e.g. those present in a combinatorial library, in a single reaction mixture has been developed in this contribution. The ratio of kcat/Km for isotopologs has also become a standard in mechanistic enzymology where kinetic isotope effects have been measured by the development of internal competition experiments with extreme precision. This contribution extends the theory of kinetic isotope effects to internal competition between three isotopologs present at non-tracer concentrations in the same reaction mix. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment.
Onsager reciprocity principle for kinetic models and kinetic schemes
Mahendra, Ajit Kumar
2013-01-01
Boltzmann equation requires some alternative simpler kinetic model like BGK to replace the collision term. Such a kinetic model which replaces the Boltzmann collision integral should preserve the basic properties and characteristics of the Boltzmann equation and comply with the requirements of non equilibrium thermodynamics. Most of the research in development of kinetic theory based methods have focused more on entropy conditions, stability and ignored the crucial aspect of non equilibrium thermodynamics. The paper presents a new kinetic model formulated based on the principles of non equilibrium thermodynamics. The new kinetic model yields correct transport coefficients and satisfies Onsager's reciprocity relationship. The present work also describes a novel kinetic particle method and gas kinetic scheme based on this linkage of non-equilibrium thermodynamics and kinetic theory. The work also presents derivation of kinetic theory based wall boundary condition which complies with the principles of non-equili...
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.
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.
Kinetics and Catalysis Demonstrations.
Falconer, John L.; Britten, Jerald A.
1984-01-01
Eleven videotaped kinetics and catalysis demonstrations are described. Demonstrations include the clock reaction, oscillating reaction, hydrogen oxidation in air, hydrogen-oxygen explosion, acid-base properties of solids, high- and low-temperature zeolite reactivity, copper catalysis of ammonia oxidation and sodium peroxide decomposition, ammonia…
Van Kooy, L.; Mooij, M.; Rem, P.
2004-01-01
Separations by density, such as the separation of non-ferrous scrap into light and heavy alloys, are often realized by means of heavy media. In principle, kinetic gravity separations in water can be faster and cheaper, because they do not rely on suspensions or salt solutions of which the density
Kinetic Damage from Meteorites
Cooke, W.; Brown, P.; Matney, M.
2017-01-01
Comparing the natural meteorite flux at the Earth's surface to that of space debris, re-entering debris is 2 orders of magnitude less of a kinetic hazard at all but the very largest (and therefore rarest) sizes compared to natural impactors. Debris re-entries over several metric tonnes are roughly as frequent as natural impactors, but the survival fraction is expected to be much higher. Kinetic hazards from meteorites are very small, with only one recorded (indirect) injury reported. We expect fatalities to be even more rare, on the order of one person killed per several millennia. That several reports exist of small fragments/sand hitting people during meteorite falls is consistent with our prediction that this should occur every decade or so.
Kinetic Actviation Relaxation Technique
Béland, Laurent Karim; El-Mellouhi, Fedwa; Joly, Jean-François; Mousseau, Normand
2011-01-01
We present a detailed description of the kinetic Activation-Relaxation Technique (k-ART), an off-lattice, self-learning kinetic Monte Carlo algorithm with on-the-fly event search. Combining a topological classification for local environments and event generation with ART nouveau, an efficient unbiased sampling method for finding transition states, k-ART can be applied to complex materials with atoms in off-lattice positions or with elastic deformations that cannot be handled with standard KMC approaches. In addition to presenting the various elements of the algorithm, we demonstrate the general character of k-ART by applying the algorithm to three challenging systems: self-defect annihilation in c-Si, self-interstitial diffusion in Fe and structural relaxation in amorphous silicon.
V.G. Morozov
2009-01-01
Full Text Available We present a kinetic theory of radiative processes in many-component plasmas with relativistic electrons and nonrelativistic heavy particles. Using the non-equilibrium Green's function technique in many-particle QED, we show that the transverse field correlation functions can be naturally decomposed into sharply peaked (non-Lorentzian parts that describe resonant (propagating photons and off-shell parts corresponding to virtual photons in the medium. Analogous decompositions are obtained for the longitudinal field correlation functions and the correlation functions of relativistic electrons. We derive a kinetic equation for the resonant photons with a finite spectral width and show that the off-shell parts of the particle and field correlation functions are essential to calculate the local radiating power in plasmas and recover the results of vacuum QED. The plasma effects on radiative processes are discussed.
Kinetic Tetrazolium Microtiter Assay
Pierson, Duane L.; Stowe, Raymond; Koenig, David
1993-01-01
Kinetic tetrazolium microtiter assay (KTMA) involves use of tetrazolium salts and Triton X-100 (or equivalent), nontoxic, in vitro color developer solubilizing colored metabolite formazan without injuring or killing metabolizing cells. Provides for continuous measurement of metabolism and makes possible to determine rate of action of antimicrobial agent in real time as well as determines effective inhibitory concentrations. Used to monitor growth after addition of stimulatory compounds. Provides for kinetic determination of efficacy of biocide, greatly increasing reliability and precision of results. Also used to determine relative effectiveness of antimicrobial agent as function of time. Capability of generating results on day of test extremely important in treatment of water and waste, disinfection of hospital rooms, and in pharmaceutical, agricultural, and food-processing industries. Assay also used in many aspects of cell biology.
Flocculation Kinetics of Chitosan
陈亮; 林志艳; 陈东辉
2003-01-01
Under the various conditions, the experiments of flocculation of bentonite solution with chitosan were carried out. And the flocculation kinetics was studied by the changes of floc size along with time. The results show that hydraulic gradient G (s-1) plays a key role in growing up of floc size and both of molecular weight and initial turbidity of bentonite solution influence the floc size in steady state and the time needed for steady floc size.
Kinetic distance and kinetic maps from molecular dynamics simulation
Noe, Frank
2015-01-01
Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly-interconverting states. Here we build upon diffusion map theory and define a kinetic distance for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine...
Kinetics of tetrataenite disordering
Dos Santos, E., E-mail: edisanfi@cbpf.br [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil); Gattacceca, J.; Rochette, P. [Centre Européen de Recherche et d’Enseignement des Géosciences de l’Environnement, UM34, CNRS/Aix-Marseille University, Aix-en-Provence (France); Fillion, G. [Laboratoire National des Champs Magnétiques Intenses (LNCMI), CNRS, UJF, 38042 Grenoble (France); Scorzelli, R.B. [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil)
2015-02-01
Tetrataenite is a chemically ordered L1{sub 0}-type Fe{sub 50}Ni{sub 50} alloy detected for the first time in 1977 by {sup 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{sub 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.
Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)
1993-12-01
This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.
Stochastic Electrochemical Kinetics
Beruski, O
2016-01-01
A model enabling the extension of the Stochastic Simulation Algorithm to electrochemical systems is proposed. The physical justifications and constraints for the derivation of a chemical master equation are provided and discussed. The electrochemical driving forces are included in the mathematical framework, and equations are provided for the associated electric responses. The implementation for potentiostatic and galvanostatic systems is presented, with results pointing out the stochastic nature of the algorithm. The electric responses presented are in line with the expected results from the theory, providing a new tool for the modeling of electrochemical kinetics.
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.
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
Hoornaert P.
2006-11-01
Full Text Available Une solution technique et économique a été mise au point pour traiter les pieds de bacsprovenant de la démixtion de mélanges méthanol - supercarburant au contact de traces d'eau. Le procédé consiste à provoquer une deuxième démixtion par addition d'eau à la phase à traiter. Les hydrocarbures ainsi relargués sont séparés parfaitement en utilisant un coalesceur à résines oléophiles. Il est ainsi possible de récupérer et de recycler la quasi-totalité des hydrocarbures contenus dans lespieds de bacs . L'effluent aqueux résiduel chargé en alcool peut, soit être recyclé, soit traité par la station de traitement d'eaux de la raffinerie. A technical and economic solution has been developed for processing bottoms of storage tankscoming from the demixing of methanol/premium-gasoline blends in contact with traces of water. The process consists in producing a second demixing by the addition of water to the phase to be processed. The hydrocarbons thus salted out are effectively separated by an oleophilic-resin coalescer. In this way almost all of the hydrocarbons contained in the bottoms of storage tankscan be recovered and recycled. The residual aqueous effluent containing alcohol can either be recycled or processed by the waste-water treatment station of the refinery.
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
Stochastic Kinetics of Nascent RNA
Xu, Heng; Skinner, Samuel O.; Sokac, Anna Marie; Golding, Ido
2016-09-01
The stochastic kinetics of transcription is typically inferred from the distribution of RNA numbers in individual cells. However, cellular RNA reflects additional processes downstream of transcription, hampering this analysis. In contrast, nascent (actively transcribed) RNA closely reflects the kinetics of transcription. We present a theoretical model for the stochastic kinetics of nascent RNA, which we solve to obtain the probability distribution of nascent RNA per gene. The model allows us to evaluate the kinetic parameters of transcription from single-cell measurements of nascent RNA. The model also predicts surprising discontinuities in the distribution of nascent RNA, a feature which we verify experimentally.
Marklof, Jens
2009-01-01
One of the central challenges in kinetic theory is the derivation of macroscopic evolution equations--describing, for example, the dynamics of an electron gas--from the underlying fundamental microscopic laws of classical or quantum mechanics. An iconic mathematical model in this research area is the Lorentz gas, which describes an ensemble of non-interacting point particles in an infinite array of spherical scatterers. In the case of a disordered scatterer configuration, the classical results by Gallavotti, Spohn and Boldrighini-Bunimovich-Sinai show that the time evolution of a macroscopic particle cloud is governed, in the limit of small scatterer density (Boltzmann-Grad limit), by the linear Boltzmann equation. In this lecture I will discuss the recent discovery that for a periodic configuration of scatterers the linear Boltzmann equation fails, and the random flight process that emerges in the Boltzmann-Grad limit is substantially more complicated. The key ingredient in the description of the limiting st...
Kinetic inductance magnetometer.
Luomahaara, Juho; Vesterinen, Visa; Grönberg, Leif; Hassel, Juha
2014-09-10
Sensing ultra-low magnetic fields has various applications in the fields of science, medicine and industry. There is a growing need for a sensor that can be operated in ambient environments where magnetic shielding is limited or magnetic field manipulation is involved. To this end, here we demonstrate a new magnetometer with high sensitivity and wide dynamic range. The device is based on the current nonlinearity of superconducting material stemming from kinetic inductance. A further benefit of our approach is of extreme simplicity: the device is fabricated from a single layer of niobium nitride. Moreover, radio frequency multiplexing techniques can be applied, enabling the simultaneous readout of multiple sensors, for example, in biomagnetic measurements requiring data from large sensor arrays.
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.
Ruan, Zhongyuan; Karsai, Marton; Kertesz, Janos
2015-01-01
Diffusion of information, behavioural 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, non-zero rate of dynamically-introduced innovators leads to global spreading, the kinetics by which the asymptotic state is approached show rich behaviour. In particular we find that, as a function of the density of immune nodes, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of fragmentation of the network, and has its origin in the competition between cascading behaviour induced by innovators and blocking of adoption due ...
Dimensional enhancement of kinetic energies
Schleich, W.P.; Dahl, Jens Peder
2002-01-01
Simple thermodynamics considers kinetic energy to be an extensive variable which is proportional to the number N of particles. We present a quantum state of N noninteracting particles for which the kinetic energy increases quadratically with N. This enhancement effect is tied to the quantum centr...
Kinetic competition during glass formation
Perepezko, J.H., E-mail: perepezk@engr.wisc.edu [University of Wisconsin-Madison, Department of Materials Science and Engineering, 1509 University Ave., Madison, WI 53706 (United States); Santhaweesuk, C.; Wang, J.Q. [University of Wisconsin-Madison, Department of Materials Science and Engineering, 1509 University Ave., Madison, WI 53706 (United States); Imhoff, S.D. [Los Alamos National Laboratory, Materials Science and Technology Div., Los Alamos, NM 87545 (United States)
2014-12-05
Highlights: • The kinetics of glass formation has been elucidated in an Fe and Au-base alloy. • A critical cooling rate range should be considered for glass formation. • Wedge casting, calorimetry and upquenching data are used to model TTT curves. - Abstract: For vitrification of an alloy melt during cooling there is a kinetic competition with the nucleation and growth of metastable and stable crystalline phases. Many of the measures of glass forming ability (GFA) attempt to capture some of the features of the kinetic competition, but the GFA metrics are static measures and the kinetic processes are dynamic in nature. In fact, the critical cooling rate for glass formation should be viewed in terms of a critical cooling rate range to acknowledge the stochastic nature of crystal nucleation behavior. Direct measurements of the critical cooling rate range confirm this behavior and also provide useful input for kinetics analysis. Usually kinetics analyses are based upon crystallization behavior that is measured either isothermally or upon heating to temperatures near the crystallization onset, T{sub x} and the results are extrapolated to much higher temperatures. This practice is based upon a number of assumptions about transport behavior in the undercooled liquid. With rapid up-quenching of amorphous samples, the high temperature crystallization behavior can be measured and used to refine the kinetics analysis and provide useful insight on the kinetic competition and glass forming ability.
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 models can be used in mass balances for design of processes under process conditions not yet studied experimentally. The value of the predictive kinetic model depends on the quality of the experimental data on which the model is based, and well-founded kinetic models for enzyme reactions have...... a considerable predictive power. This is also true for cell reaction models, when the model is used in its proper context. The chapter first discusses the kinetics for enzymatically catalyzed reactions (“enzyme reactions”). The kinetics can be derived from a mechanistic model. Then, the chapter derives empirical...
Kinetic distance and kinetic maps from molecular dynamics simulation.
Noé, Frank; Clementi, Cecilia
2015-10-13
Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly interconverting states. Here, we build upon diffusion map theory and define a kinetic distance metric for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here, we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine pancreatic trypsin inhibitor and protein-inhibitor association in trypsin and benzamidine. We find that the total kinetic variance (TKV) is an excellent indicator of model quality and can be used to rank different input feature sets.
The Kinetics of Enzyme Mixtures
Simon Brown
2014-03-01
Full Text Available Even purified enzyme preparations are often heterogeneous. For example, preparations of aspartate aminotransferase or cytochrome oxidase can consist of several different forms of the enzyme. For this reason we consider how different the kinetics of the reactions catalysed by a mixture of forms of an enzyme must be to provide some indication of the characteristics of the species present. Based on the standard Michaelis-Menten model, we show that if the Michaelis constants (Km of two isoforms differ by a factor of at least 20 the steady-state kinetics can be used to characterise the mixture. However, even if heterogeneity is reflected in the kinetic data, the proportions of the different forms of the enzyme cannot be estimated from the kinetic data alone. Consequently, the heterogeneity of enzyme preparations is rarely reflected in measurements of their steady-state kinetics unless the species present have significantly different kinetic properties. This has two implications: (1 it is difficult, but not impossible, to detect molecular heterogeneity using kinetic data and (2 even when it is possible, a considerable quantity of high quality data is required.
Kinetic properties of cyanase.
Anderson, P M; Little, R M
1986-04-01
Cyanase is an inducible enzyme in Escherichia coli that catalyzes the hydrolysis of cyanate. Bicarbonate is required for activity, perhaps as a substrate, and the initial product of the reaction is carbamate, which spontaneously breaks down to ammonia and bicarbonate [Anderson, P. M. (1980) Biochemistry 19, 2882]. The purpose of this study was to characterize the kinetic properties of cyanase. Initial velocity studies showed that both cyanate and bicarbonate act as competitive substrate inhibitors. A number of monovalent anions act as inhibitors. Azide and acetate appear to act as competitive inhibitors with respect to cyanate and bicarbonate, respectively. Chloride, bromide, nitrate, nitrite, and formate also inhibit, apparently as the result of binding at either substrate site. Malonate and several other dicarboxylic dianions at very low concentrations display "slow-binding", reversible inhibition which can be prevented by saturating concentrations of either substrate. The results are consistent with a rapid equilibrium random mechanism in which bicarbonate acts as a substrate, bicarbonate and cyanate bind at adjacent anion-binding sites, and both substrates can bind at the other substrate anion binding site to give a dead-end complex.
Measuring Kinetic Plasma Eigenmodes
Mattingly, Sean; Berumen, Jorge; Chu, Feng; Hood, Ryan; Skiff, Fred
2015-11-01
We present a method for measuring kinetic plasma eigenmodes of a cylindrical axially magnetized (1 kG) laboratory plasma (n ~109cm-3 , Te ~ 5eV , Ti ~ 0 . 06eV) by measuring velocity space correlation functions. This method simultaneously observes two separate laser induced fluorescence schemes. Each scheme has its own indepedently tunable laser and its own set of collection optics. With this setup, we are able to measure the time - averaged correlation function as a function of position on the cylindrical axis parallel to the magnetic field (z) and velocity on the deconvolved ion velocity distribution function (v) : C (z , v ,z' ,v' , τ) = t. The freedom of two lasers allows us to measure a two dimensional velocity correlation matrix. This matrix is investigated with the Vlasov equation in the collisionless and weakly collisional regime. The former case, which is continuous, is diagonalized with an integral transform defined by P. J. Morrison while the latter case, which is discrete, is diagonalized through the use of Hermite polynomials.
Marklof, Jens
2010-03-01
One of the central challenges in kinetic theory is the derivation of macroscopic evolution equations--describing, for example, the dynamics of an electron gas--from the underlying fundamental microscopic laws of classical or quantum mechanics. An iconic mathematical model in this research area is the Lorentz gas, which describes an ensemble of non-interacting point particles in an infinite array of spherical scatterers. In the case of a disordered scatterer configuration, the classical results by Gallavotti, Spohn and Boldrighini-Bunimovich-Sinai show that the time evolution of a macroscopic particle cloud is governed, in the limit of small scatterer density (Boltzmann-Grad limit), by the linear Boltzmann equation. In this lecture I will discuss the recent discovery that for a periodic configuration of scatterers the linear Boltzmann equation fails, and the random flight process that emerges in the Boltzmann-Grad limit is substantially more complicated. The key ingredient in the description of the limiting stochastic process is the renormalization dynamics on the space of lattices, a powerful technique that has recently been successfully applied also to other open problems in mathematical physics, including KAM theory and quantum chaos. This lecture is based on joint work with Andreas Strömbergsson, Uppsala.
Modelling heart rate kinetics.
Zakynthinaki, Maria S
2015-01-01
The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women).
Modelling heart rate kinetics.
Maria S Zakynthinaki
Full Text Available The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise. Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women.
Zakynthinaki, Maria S.
2015-01-01
The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164
Kinetic Magnetorotational Turbulence and Dynamo
Kunz, Matthew; Stone, James; Quataert, Eliot
2016-10-01
Low-luminosity black-hole accretion flows, such as that at the Galactic center, are collisionless. A kinetic approach is thus necessary to understand the transport of heat and angular momentum, the acceleration of particles, and the growth and structure of the magnetic field in these systems. We present results from the first 6D kinetic numerical simulation of magnetorotational turbulence and dynamo, using the local shearing-box model. Special attention will be paid to the enhanced transport of angular momentum by field-aligned pressure anisotropies, as well as to the ion-Larmor-scale kinetic instabilities (firehose, mirror, ion-cyclotron) which regulate those anisotropies. Energy spectra and phase-space evolution will be discussed. Time permitting, dedicated nonlinear studies of firehose and mirror instabilities in a shearing plasma will also be presented as a complement to the study of the magnetorotational instability. The profits, perils, and price of using a kinetic approach will be briefly mentioned.
Kinetic properties of fractal media
Chumak, Oleg V
2016-01-01
Kinetic processes in fractal stellar media are analyzed in terms of the approach developed in our earlier paper (Chumak, Rastorguev, 2016) involving a generalization of the nearest neighbor and random force distributions to fractal media. Diffusion is investigated in the approximation of scale-dependent conditional density based on an analysis of the solutions of the corresponding Langevin equations. It is shown that kinetic parameters (time scales, coefficients of dynamic friction, diffusion, etc.) for fractal stellar media can differ significantly both qualitatively and quantitatively from the corresponding parameters for a quasi-uniform random media with limited fluctuations. The most important difference is that in the fractal case kinetic parameters depend on spatial scale length and fractal dimension of the medium studied. A generalized kinetic equation for stellar media (fundamental equation of stellar dynamics) is derived in the Fokker-Planck approximation with the allowance for the fractal properties...
Kinetics Modeling of Cancer Immunology.
1986-05-09
CANCER IMMUNOLOGY -1 DTICS ELECTED SEP 9 8 UNITED STATES NAVAL ACADEMY ANNAPOLIS, MARYLAND V ,1986 %,e docment ha le approved for public A." I and sale...1986 4. TITLE (and Subtitle) S. TYPE OF REPORT & PERIOD COVERED KINETICS MODELING OF CANCER IMMUNOLOGY Final: 1985/1986 6. PERFORMING ORG. REPORT...137 (1986) "Kinetics Modeling of Cancer Immunology " A Trident Scholar Project Report by Midn I/C Scott Helmers, Class of 1986 United States Naval
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...
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....
Non-isothermal decomposition kinetics of magnesite
Maitra, S; Mukherjee, S.; Saha, N; Pramanik, J
2007-01-01
Kinetics of thermal decomposition of Indian magnesite was studied by thermo-gravimetric analysis under non-isothermal condition. Coats and Redfern Integral approximation method was used to determine the kinetic parameters. Using the kinetic parameters different kinetic functions were analyzed with the experimental data to ascertain the decomposition mechanism of magnesium carbonate and it was observed that the decomposition reaction followed a contracting sphere kinetic mechanism.
Parallelization of Kinetic Theory Simulations
Howell, Jim; Colbry, Dirk; Pickett, Rodney; Staber, Alec; Sagert, Irina; Strother, Terrance
2013-01-01
Numerical studies of shock waves in large scale systems via kinetic simulations with millions of particles are too computationally demanding to be processed in serial. In this work we focus on optimizing the parallel performance of a kinetic Monte Carlo code for astrophysical simulations such as core-collapse supernovae. Our goal is to attain a flexible program that scales well with the architecture of modern supercomputers. This approach requires a hybrid model of programming that combines a message passing interface (MPI) with a multithreading model (OpenMP) in C++. We report on our approach to implement the hybrid design into the kinetic code and show first results which demonstrate a significant gain in performance when many processors are applied.
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...
Kinetic Measurements for Enzyme Immobilization.
Cooney, Michael J
2017-01-01
Enzyme kinetics is the study of the chemical reactions that are catalyzed by enzymes, with a focus on their reaction rates. The study of an enzyme's kinetics considers the various stages of activity, reveals the catalytic mechanism of this enzyme, correlates its value to assay conditions, and describes how a drug or a poison might inhibit the enzyme. Victor Henri initially reported that enzyme reactions were initiated by a bond between the enzyme and the substrate. By 1910, Michaelis and Menten were advancing their work by studying the kinetics of an enzyme saccharase which catalyzes the hydrolysis of sucrose into glucose and fructose. They published their analysis and ever since the Michaelis-Menten equation has been used as the standard to describe the kinetics of many enzymes. Unfortunately, soluble enzymes must generally be immobilized to be reused for long times in industrial reactors. In addition, other critical enzyme properties have to be improved like stability, activity, inhibition by reaction products, and selectivity towards nonnatural substrates. Immobilization is by far the chosen process to achieve these goals.Although the Michaelis-Menten approach has been regularly adapted to the analysis of immobilized enzyme activity, its applicability to the immobilized state is limited by the barriers the immobilization matrix places upon the measurement of compounds that are used to model enzyme kinetics. That being said, the estimated value of the Michaelis-Menten coefficients (e.g., V max, K M) can be used to evaluate effects of immobilization on enzyme activity in the immobilized state when applied in a controlled manner. In this review enzyme activity and kinetics are discussed in the context of the immobilized state, and a few novel protocols are presented that address some of the unique constraints imposed by the immobilization barrier.
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.
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
Robustness Analysis of Kinetic Structures
Kirkegaard, Poul Henning; Sørensen, John Dalsgaard
2009-01-01
The present paper considers robustness of kinetic structures. Robustness of structures has obtained a renewed interest due to a much more frequent use of advanced types of structures with limited redundancy and serious consequences in case of failure. Especially for these types of structural syst...... systems, it is of interest to investigate how robust the structures are, or what happens if a structural element is added to or removed from the original structure. The present paper discusses this issue for kinetic structures in architecture....
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
Non-kinetic capabilities: complementing the kinetic prevalence to targeting
Ducheine, P.A.L.; Ducheine, P.A.L.; Schmitt, M.N.; Osinga, F.P.B.
2016-01-01
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, thereby complementing our
Non-kinetic capabilities: complementing the kinetic prevalence to targeting
Ducheine, P.A.L.; Ducheine, P.A.L.; Schmitt, M.N.; Osinga, F.P.B.
2016-01-01
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, thereby complementing our
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
Kinetic theory of hard spheres
Beijeren, H. van; Ernst, M.H.
1979-01-01
Kinetic equations for the hard-sphere system are derived by diagrammatic techniques. A linear equation is obtained for the one-particle-one particle equilibrium time correlation function and a nonlinear equation for the one-particle distribution function in nonequilibrium. Both equations are nonloca
Superconductivity by kinetic energy saving?
Van der Marel, D; Molegraaf, HJA; Presura, C; Santoso, [No Value; Hewson, AC; Zlatic,
2003-01-01
A brief introduction is given in the generic microscopic framework of superconductivity. The consequences for the temperature dependence of the kinetic energy, and the correlation energy are discussed for two cases: The BCS scenario and the non-Fermi liquid scenario. A quantitative comparison is mad
Biodegradation kinetics at low concentrations (
Toräng, Lars; Albrechtsen, Hans-Jørgen; Nyholm, Niels
2000-01-01
Aerobic biodegradation of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in groundwater added sediment fines. At concentrations at or below 1 mu g/L of 2,4-D degradation kinetic was of true first order without significant growth of specific degraders and with half-life for mineralization...
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...
Disco Dancing and Kinetic Theory
Karakas, Mehmet
2010-01-01
This paper provides an example of an innovative science activity used in a science methods course for future elementary teachers at a small university in northeastern Turkey. The activity aims to help prospective elementary teachers understand kinetic-molecular theory in a simple way and to expose these preservice teachers to an innovative…
Mass Conservation and Chemical Kinetics.
Barbara, Thomas M.; Corio, P. L.
1980-01-01
Presents a method for obtaining all mass conservation conditions implied by a given mechanism in which the conditions are used to simplify integration of the rate equations and to derive stoichiometric relations. Discusses possibilities of faulty inference of kinetic information from a given stoichiometry. (CS)
Superconductivity by kinetic energy saving?
Van der Marel, D; Molegraaf, HJA; Presura, C; Santoso, [No Value; Hewson, AC; Zlatic,
2003-01-01
A brief introduction is given in the generic microscopic framework of superconductivity. The consequences for the temperature dependence of the kinetic energy, and the correlation energy are discussed for two cases: The BCS scenario and the non-Fermi liquid scenario. A quantitative comparison is
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...
Superconductivity by kinetic energy saving?
Van der Marel, D; Molegraaf, HJA; Presura, C; Santoso, [No Value; Hewson, AC; Zlatic,
2003-01-01
A brief introduction is given in the generic microscopic framework of superconductivity. The consequences for the temperature dependence of the kinetic energy, and the correlation energy are discussed for two cases: The BCS scenario and the non-Fermi liquid scenario. A quantitative comparison is mad
Surfactant adsorption kinetics in microfluidics
Riechers, Birte; Maes, Florine; Akoury, Elias; Semin, Benoît; Gruner, Philipp; Baret, Jean-Christophe
2016-10-01
Emulsions are metastable dispersions. Their lifetimes are directly related to the dynamics of surfactants. We design a microfluidic method to measure the kinetics of adsorption of surfactants to the droplet interface, a key process involved in foaming, emulsification, and droplet coarsening. The method is based on the pH decay in the droplet as a direct measurement of the adsorption of a carboxylic acid surfactant to the interface. From the kinetic measurement of the bulk equilibration of the pH, we fully determine the adsorption process of the surfactant. The small droplet size and the convection during the droplet flow ensure that the transport of surfactant through the bulk is not limiting the kinetics of adsorption. To validate our measurements, we show that the adsorption process determines the timescale required to stabilize droplets against coalescence, and we show that the interface should be covered at more than 90% to prevent coalescence. We therefore quantitatively link the process of adsorption/desorption, the stabilization of emulsions, and the kinetics of solute partitioning—here through ion exchange—unraveling the timescales governing these processes. Our method can be further generalized to other surfactants, including nonionic surfactants, by making use of fluorophore-surfactant interactions.
Chemical kinetics on extrasolar planets.
Moses, Julianne I
2014-04-28
Chemical kinetics plays an important role in controlling the atmospheric composition of all planetary atmospheres, including those of extrasolar planets. For the hottest exoplanets, the composition can closely follow thermochemical-equilibrium predictions, at least in the visible and infrared photosphere at dayside (eclipse) conditions. However, for atmospheric temperatures approximately planets.
Kinetic Modeling of Biological Systems
Resat, Haluk; Petzold, Linda; Pettigrew, Michel F.
2009-04-21
The dynamics of how its constituent components interact define the spatio-temporal response of a natural system to stimuli. Modeling the kinetics of the processes that represent a biophysical system has long been pursued with the aim of improving our understanding of the studied system. Due to the unique properties of biological systems, in addition to the usual difficulties faced in modeling the dynamics of physical or chemical systems, biological simulations encounter difficulties that result from intrinsic multiscale and stochastic nature of the biological processes. This chapter discusses the implications for simulation of models involving interacting species with very low copy numbers, which often occur in biological systems and give rise to significant relative fluctuations. The conditions necessitating the use of stochastic kinetic simulation methods and the mathematical foundations of the stochastic simulation algorithms are presented. How the well-organized structural hierarchies often seen in biological systems can lead to multiscale problems, and possible ways to address the encountered computational difficulties are discussed. We present the details of the existing kinetic simulation methods, and discuss their strengths and shortcomings. A list of the publicly available kinetic simulation tools and our reflections for future prospects are also provided.
An equilibrium and kinetic modeling
SERVER
2007-06-18
Jun 18, 2007 ... Potato dextrose agar medium was prepared by taking 200 g of peeled and sliced potato with .... of glucose as carbon source and ammonium chloride as nitrogen source each. .... Pore and solid diffusion kinetics in fixed bed ...
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…
Kinetic energy equations for the average-passage equation system
Johnson, Richard W.; Adamczyk, John J.
1989-01-01
Important kinetic energy equations derived from the average-passage equation sets are documented, with a view to their interrelationships. These kinetic equations may be used for closing the average-passage equations. The turbulent kinetic energy transport equation used is formed by subtracting the mean kinetic energy equation from the averaged total instantaneous kinetic energy equation. The aperiodic kinetic energy equation, averaged steady kinetic energy equation, averaged unsteady kinetic energy equation, and periodic kinetic energy equation, are also treated.
Kinetic energy equations for the average-passage equation system
Johnson, Richard W.; Adamczyk, John J.
1989-01-01
Important kinetic energy equations derived from the average-passage equation sets are documented, with a view to their interrelationships. These kinetic equations may be used for closing the average-passage equations. The turbulent kinetic energy transport equation used is formed by subtracting the mean kinetic energy equation from the averaged total instantaneous kinetic energy equation. The aperiodic kinetic energy equation, averaged steady kinetic energy equation, averaged unsteady kinetic energy equation, and periodic kinetic energy equation, are also treated.
Undercooling and demixing of copper-based alloys
Kolbe, M.; Brillo, J.; Egry, I.
2006-01-01
Since the beginning of materials science research under microgravity conditions immiscible alloys have been an interesting subject. New possibilities to investigate such systems are offered by containerless processing techniques. Of particular interest is the ternary system Cu-Fe-Co, and its limi...
Depletion induced demixing in polydisperse mixtures of hard spheres
Sear, RP
1998-01-01
Polydisperse mixtures are those in which components with a whole range of sizes are present. It is shown that the fluid phase of polydisperse hard spheres is thermodynamically unstable unless the density of large spheres decreases at least exponentially as their size increases. The instability is with respect to the large spheres crystallising out into multiple solid phases.
Kinetic investigation of wood pyrolysis
Thurner, F.; Mann, U.; Beck, S. R.
1980-06-01
The objective of this investigation was to determine the kinetics of the primary reactions of wood pyrolysis. A new experimental method was developed which enabled us to measure the rate of gas, tar, and char production while taking into account the temperature variations during the wood heating up. The experimental method developed did not require any sophisticated instruments. It facilitated the collection of gas, tar and residue (unreacted wood and char) as well as accurate measurement of the temperature inside the wood sample. Expressions relating the kinetic parameters to the measured variables were derived. The pyrolysis kinetics was investigated in the range of 300 to 400/sup 0/C at atmospheric pressure and under nitrogen atmosphere. Reaction temperature and mass fractions of gas, tar, and residue were measured as a function of time. Assuming first-order reactions, the kinetic parameters were determined using differential method. The measured activation energies of wood pyrolysis to gas, tar, and char were 88.6, 112.7, and 106.5 kJ/mole, respectively. These kinetic data were then used to predict the yield of the various pyrolysis products. It was found that the best prediction was obtained when an integral-mean temperature obtained from the temperature-time curve was used as reaction temperature. The pyrolysis products were analyzed to investigate the influence of the pyrolysis conditions on the composition. The gas consisted mainly of carbon dioxide, carbon monoxide, oxygen, and C/sub 3//sup +/-compounds. The gas composition depended on reaction time as well as reactor temperature. The tar analysis indicated that the tar consisted of about seven compounds. Its major compound was believed to be levoglucosan. Elemental analysis for the char showed that the carbon content increased with increasing temperature.
Tang, J. Y
2015-01-01
The Michaelis-Menten kinetics and the reverse Michaelis-Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would...
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)
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.
Kinetics of yttrium oxide carbochlorination
Gaviria, J.P., E-mail: gaviriaj@cab.cnea.gov.ar [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Fouga, G.G. [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Bohe, A.E. [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Centro Regional Universitario Bariloche - Universidad Nacional del Comahue (Argentina)
2011-04-20
Research highlights: {yields} Chlorination kinetics of Y{sub 2}O{sub 3}-C system was studied by thermogravimetry. {yields} The influence of carbon content, flow rate, sample mass and pCl{sub 2} were evaluated. {yields} Reaction proceeds through three successive stages until the formation of YCl{sub 3}(l). {yields}STAGE I is the formation of YOCl(s) and is under chemical control for T < 700 {sup o}C. {yields}STAGE I follows a nucleation and growth model. Kinetics parameters were obtained. - Abstract: The chlorination kinetics of the Y{sub 2}O{sub 3}-sucrose carbon system was studied by thermogravimetry. This work is a continuation of a previous one in which the reaction stages and the stoichiometry of each reaction have been determined. The influence of carbon content, total flow rate, sample initial mass and chlorine partial pressure was evaluated. The effect of carbon content on the reactive mixture was studied between 6.7 and 70% (carbon mass/total mass). The results showed that the reaction rate of each stage is strongly increased as the carbon content increases and the range of occurrence of the stages depends on the amount of carbon in the solid reactive mixture. The formation reaction of YOCl (STAGE I) is chemically controlled for temperatures lower than 700 {sup o}C with average effective activation energies of 165 {+-} 6 and 152 {+-} 7 kJ/mol for 8.7 and 16.7%C, respectively. The formation of the YOCl follows a nucleation and growth mechanism, with a combination of continuous nucleation and site saturation, and anisotropic growth controlled by diffusion. The kinetics of STAGE I can be expressed by the following global rate equation that includes the variables analyzed: (d{alpha})/(dt) =k{sub 0}Bexp(-(Ea)/(R{sub g}T) )pCl{sub 2}{l_brace}n(1-{alpha})[-ln(1-{alpha})]{r_brace}{sup (n-1)/n} where k{sub 0}B = 1.9 x 10{sup 4}, n = 1.20 for 8.7%C, and k{sub 0}B = 8.4 x 10{sup 3}, n = 1.14 for 16.7%C. STAGES II and III correspond to the YOCl carbochlorination to
Kinetic modelling of enzymatic starch hydrolysis
Bednarska, K.A.
2015-01-01
Kinetic modelling of enzymatic starch hydrolysis – a summary K.A. Bednarska The dissertation entitled ‘Kinetic modelling of enzymatic starch hydrolysis’ describes the enzymatic hydrolysis and kinetic modelling of liquefaction and saccharification of wheat starch. A
Kinetic models of conjugated metabolic cycles
Ershov, Yu. A.
2016-01-01
A general method is developed for the quantitative kinetic analysis of conjugated metabolic cycles in the human organism. This method is used as a basis for constructing a kinetic graph and model of the conjugated citric acid and ureapoiesis cycles. The results from a kinetic analysis of the model for these cycles are given.
Variational Approach to Molecular Kinetics.
Nüske, Feliks; Keller, Bettina G; Pérez-Hernández, Guillermo; Mey, Antonia S J S; Noé, Frank
2014-04-08
The eigenvalues and eigenvectors of the molecular dynamics propagator (or transfer operator) contain the essential information about the molecular thermodynamics and kinetics. This includes the stationary distribution, the metastable states, and state-to-state transition rates. Here, we present a variational approach for computing these dominant eigenvalues and eigenvectors. This approach is analogous to the variational approach used for computing stationary states in quantum mechanics. A corresponding method of linear variation is formulated. It is shown that the matrices needed for the linear variation method are correlation matrices that can be estimated from simple MD simulations for a given basis set. The method proposed here is thus to first define a basis set able to capture the relevant conformational transitions, then compute the respective correlation matrices, and then to compute their dominant eigenvalues and eigenvectors, thus obtaining the key ingredients of the slow kinetics.
Biochemical kinetics in changing volumes.
Pawłowski, Piotr H; Zielenkiewicz, Piotr
2004-01-01
The need of taking into account the change of compartment volume when developing chemical kinetics analysis inside the living cell is discussed. Literature models of a single enzymatic Michaelis-Menten process, glycolytic oscillations, and mitotic cyclin oscillations were tested with appropriate theoretical extension in the direction of volume modification allowance. Linear and exponential type of volume increase regimes were compared. Due to the above, in a growing cell damping of the amplitude, phase shift, and time pattern deformation of the metabolic rhythms considered were detected, depending on the volume change character. The performed computer simulations allow us to conclude that evolution of the cell volume can be an essential factor of the chemical kinetics in a growing cell. The phenomenon of additional metabolite oscillations caused by the periodic cell growth and division was theoretically predicted and mathematically described. Also, the hypothesis of the periodized state in the growing cell as the generalization of the steady-state was formulated.
Kinetic activation-relaxation technique
Béland, Laurent Karim; Brommer, Peter; El-Mellouhi, Fedwa; Joly, Jean-François; Mousseau, Normand
2011-10-01
We present a detailed description of the kinetic activation-relaxation technique (k-ART), an off-lattice, self-learning kinetic Monte Carlo (KMC) algorithm with on-the-fly event search. Combining a topological classification for local environments and event generation with ART nouveau, an efficient unbiased sampling method for finding transition states, k-ART can be applied to complex materials with atoms in off-lattice positions or with elastic deformations that cannot be handled with standard KMC approaches. In addition to presenting the various elements of the algorithm, we demonstrate the general character of k-ART by applying the algorithm to three challenging systems: self-defect annihilation in c-Si (crystalline silicon), self-interstitial diffusion in Fe, and structural relaxation in a-Si (amorphous silicon).
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.
Kinetic mixing at strong coupling
Del Zotto, Michele; Heckman, Jonathan J.; Kumar, Piyush; Malekian, Arada; Wecht, Brian
2017-01-01
A common feature of many string-motivated particle physics models is additional strongly coupled U (1 )'s. In such sectors, electric and magnetic states have comparable mass, and integrating out modes also charged under U (1 ) hypercharge generically yields C P preserving electric kinetic mixing and C P violating magnetic kinetic mixing terms. Even though these extra sectors are strongly coupled, we show that in the limit where the extra sector has approximate N =2 supersymmetry, we can use formal methods from Seiberg-Witten theory to compute these couplings. We also calculate various quantities of phenomenological interest such as the cross section for scattering between visible sector states and heavy extra sector states as well as the effects of supersymmetry breaking induced from coupling to the minimal supersymmetric Standard Model.
Kinetic Quantum Theory of Gravity
DeAquino, F
2002-01-01
Starting from the action function we have derived a theoretical background that leads to quantization of gravity and the deduction of a correlation between the gravitational and inertial masses, which depends on the kinetic momentum of the particle. We show that there is a reaffirmation of the strong equivalence principle and consequently the Einstein's equations are preserved. In fact such equations are deduced here directly from this kinetic approach to Gravity. Moreover, we have obtained a generalized equation for inertial forces, which incorporates the Mach's principle into Gravitation. Also, we have deduced the equation of Entropy; the Hamiltonian for a particle in an electromagnetic field and the reciprocal fine structure constant. It is possible to deduce the expression of the Casimir force and also to explain the Inflation Period and the Missing Matter without assuming the existence of vacuum fluctuations. This new approach for Gravity will allow us to understand some crucial matters in Cosmology.
Kinetic Quantum Theory of Gravity
DeAquino, F
2002-01-01
Gravity is here quantized starting from the generalization of the action function. This leads to an equation of correlation between gravitational and inertial masses, which depends on the particle's kinetic energy. We show that there is a reaffirmation of the strong equivalence principle and consequently the Einstein's equations are preserved. In fact such equations are deduced here directly from this kinetic approach to Gravity. Moreover, we have obtained a generalized equation for inertial forces, which incorporates the Mach's principle into Gravitation. Also, we have deduced the equation of Entropy; the Hamiltonian for a particle in an electromagnetic field and the reciprocal fine structure constant. It is possible to deduce the expression of the Casimir force and also to explain the Inflation Period and the Missing Matter without assuming the existence of vacuum fluctuations. This new approach for Gravity will allow us to understand some crucial matters in Cosmology.
Kinetic activation-relaxation technique.
Béland, Laurent Karim; Brommer, Peter; El-Mellouhi, Fedwa; Joly, Jean-François; Mousseau, Normand
2011-10-01
We present a detailed description of the kinetic activation-relaxation technique (k-ART), an off-lattice, self-learning kinetic Monte Carlo (KMC) algorithm with on-the-fly event search. Combining a topological classification for local environments and event generation with ART nouveau, an efficient unbiased sampling method for finding transition states, k-ART can be applied to complex materials with atoms in off-lattice positions or with elastic deformations that cannot be handled with standard KMC approaches. In addition to presenting the various elements of the algorithm, we demonstrate the general character of k-ART by applying the algorithm to three challenging systems: self-defect annihilation in c-Si (crystalline silicon), self-interstitial diffusion in Fe, and structural relaxation in a-Si (amorphous silicon).
Kinetic ELISA in Microfluidic Channels
Debashis Dutta
2011-06-01
Full Text Available In this article, we describe the kinetic ELISA of Blue Tongue and Epizootic Hemorrhagic Disease viral antibodies in microfluidic channels by monitoring the rate of generation of the enzyme reaction product under static conditions. It has been shown that this format of the immunoassay allows very reliable quantitation of the target species using inexpensive glass microchips and a standard epifluorescence microscope system coupled to a CCD camera. For the viral antibodies assayed here, the limit of detection (LOD for the analyte concentration in our microchips was established to be 3–5 times lower than that obtained on commercial microwell plates using a fiftieth of the sample volume and less than a third of the incubation time. Our analyses further show that when compared to the end-point ELISA format, the kinetic mode of this assay yields an improvement in the LOD by over an order of magnitude in microfluidic devices. This benefit is primarily realized as the observed variation in the background fluorescence (signal at the start of the enzyme reaction period was significantly larger than that in the rate of signal generation upon repeating these assays in different microchannels/microchips. Because the kinetic ELISA results depend only on the latter quantity, the noise level in them was substantially lower compared to that in its end-point counterpart in which the absolute fluorescence measurements are of greater significance. While a similar benefit was also recorded through implementation of kinetic ELISAs on the microwell platform, the improvement in LOD registered in that system was not as significant as was observed in the case of microfluidic assays.
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)
Hydration kinetics of transgenic soybeans
Aline Francielle Fracasso
2015-01-01
Full Text Available The kinetic and experimental analyses of the hydration process of transgenic soybeans (BRS 225 RR are provided. The importance of the hydration process consists of the grain texture modifications which favor grinding and extraction of soybeans. The soaking isotherms were obtained for four different temperatures. Results showed that temperature affected transgenic soybeans´ hydration rate and time. Moisture content d.b. of the soybeans increased from 0.12 ± 0.01 kg kg-1 to 1.45 ± 0.19 kg kg-1 during 270 min. of process. Two models were used to fit the kinetic curves: an empirical model developed by Peleg (1988 and a phenomenological one, proposed by Omoto et al. (2009. The two models adequately represented the hydration kinetics. Peleg model was applied to the experimental data and the corresponding parameters were obtained and correlated to temperature. The model by Omoto et al. (2009 showed a better statistical fitting. Although Ks was affected by temperature (Ks = 0.38079 exp (-2289.3 T-1, the equilibrium concentration remained practically unchanged.
Fribrinolysis Kinetics and Its Application
WEI Wenning; YANG Rui; GUO Tao; YANG Yan; HU Yu
2007-01-01
A new, convenient, and rapid method for kinetic measurement of human fibrinolysis was established. The alteration of absorbance (A) in the process of blood coagulation and lyses was automatically scanned and recorded using a UV2000 spectrophotometer connected to a computer. The parameters of human fibrinolysis kinetics were established. Urokinase at 20 U/mL was the optimal concentration used. There was significant difference in fibrinolysis kinetics and plasma plasminogen concentration between 22 normal subjects and 27 patients with acute myeloblastic leukemia (P＜0.05 and ＜0.01 respectively). The coefficience of variation was (5.24±1.51)%. This method could also be used to measure the plasma fibrinogen concentration at the same time. It was concluded that this method was stable and was capable of providing dynamic, direct experimental data and multiparemeters for clinicians. It was also valuable in evaluating the anti- and pro-fibrinolytic capcity of patients' plasmas, allowing for monitoring of therapy, choice of drugs and adjustment of drug concentrations.
Classical kinetic energy, quantum fluctuation terms and kinetic-energy functionals
Hamilton, I. P.; Mosna, Ricardo A.; Site, L. Delle
2006-01-01
We employ a recently formulated dequantization procedure to obtain an exact expression for the kinetic energy which is applicable to all kinetic-energy functionals. We express the kinetic energy of an N-electron system as the sum of an N-electron classical kinetic energy and an N-electron purely quantum kinetic energy arising from the quantum fluctuations that turn the classical momentum into the quantum momentum. This leads to an interesting analogy with Nelson's stochastic approach to quant...
Reaction networks and kinetics of biochemical systems.
Arceo, Carlene Perpetua P; Jose, Editha C; Lao, Angelyn R; Mendoza, Eduardo R
2017-01-01
This paper further develops the connection between Chemical Reaction Network Theory (CRNT) and Biochemical Systems Theory (BST) that we recently introduced [1]. We first use algebraic properties of kinetic sets to study the set of complex factorizable kinetics CFK(N) on a CRN, which shares many characteristics with its subset of mass action kinetics. In particular, we extend the Theorem of Feinberg-Horn [9] on the coincidence of the kinetic and stoichiometric subsets of a mass action system to CF kinetics, using the concept of span surjectivity. We also introduce the branching type of a network, which determines the availability of kinetics on it and allows us to characterize the networks for which all kinetics are complex factorizable: A "Kinetics Landscape" provides an overview of kinetics sets, their algebraic properties and containment relationships. We then apply our results and those (of other CRNT researchers) reviewed in [1] to fifteen BST models of complex biological systems and discover novel network and kinetic properties that so far have not been widely studied in CRNT. In our view, these findings show an important benefit of connecting CRNT and BST modeling efforts. Copyright © 2016 Elsevier Inc. All rights reserved.
Oxidation kinetics of aluminum diboride
Whittaker, Michael L., E-mail: michaelwhittaker2016@u.northwestern.edu [Department of Materials Science and Engineering, University of Utah, 122S. Central Campus Drive, Salt Lake City, UT 84112 (United States); Sohn, H.Y. [Department of Metallurgical Engineering, University of Utah, 135S 1460 E, Rm 00412, Salt Lake City, UT 84112 (United States); Cutler, Raymond A. [Ceramatec, Inc., 2425S. 900W., Salt Lake City, UT 84119 (United States)
2013-11-15
The oxidation characteristics of aluminum diboride (AlB{sub 2}) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB{sub 2} in the onset of oxidation and final conversion fraction, with AlB{sub 2} beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB{sub 2} and Al+2B in both air and oxygen. AlB{sub 2} exhibited O{sub 2}-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O{sub 2} than in air. Differences in the composition and morphology between oxidized Al+2B and AlB{sub 2} suggested that Al{sub 2}O{sub 3}–B{sub 2}O{sub 3} interactions slowed Al+2B oxidation by converting Al{sub 2}O{sub 3} on aluminum particles into a Al{sub 4}B{sub 2}O{sub 9} shell, while the same Al{sub 4}B{sub 2}O{sub 9} developed a needle-like morphology in AlB{sub 2} that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB{sub 2}, but both appear to be resistant to oxidation in cool, dry environments. - Graphical abstract: Isothermal kinetic data for AlB{sub 2} in air, showing a constantly decreasing activation energy with increasing conversion. Model-free analysis allowed for the calculation of global kinetic parameters despite many simultaneous mechanisms occurring concurrently. (a) Time
Watching nanoparticle kinetics in liquid
Yugang Sun
2012-04-01
Full Text Available Real-time monitoring of reaction kinetics involved in nanoparticle growth and transformation in liquid environments is crucial for understanding the complex chemical and physical events associated with nanophase evolution. Accordingly, in situ techniques that can “see through” liquids to probe nanomaterial variation are in high demand, as they will help us understand reaction mechanisms and design better synthetic strategies for building nanoparticles with precisely tailored properties. In this review, in situ transmission x-ray microscopy and time-resolved high-energy x-ray scattering techniques are discussed, highlight their capabilities in studying the dynamic processes of nanoparticles.
Collisions in Chiral Kinetic Theory
Chen, Jing-Yuan; Stephanov, Mikhail A
2015-01-01
Using a covariant formalism, we construct a chiral kinetic theory Lorentz invariant to order $\\mathcal O(\\hbar)$ which includes collisions. We find a new contribution to the particle number current due to the side jumps required by the conservation of angular momentum during collisions. We also find a conserved symmetric stress-energy tensor as well as the $H$-function obeying Boltzmann's $H$-theorem. We demonstrate their use by finding a general equilibrium solution and the values of the anomalous transport coefficients characterizing chiral vortical effect.
Freezing Kinetics in Overcompressed Water
Bastea, M; Bastea, S; Reaugh, J; Reisman, D
2006-09-27
We report high pressure dynamic compression experiments of liquid water along a quasi-adiabatic path leading to the formation of ice VII. We observe dynamic features resembling Van der Waals loops and find that liquid water is compacted to a metastable state close to the ice density before the onset of crystallization. By analyzing the characteristic kinetic time scale involved we estimate the nucleation barrier and conclude that liquid water has been compressed to a high pressure state close to its thermodynamic stability limit.
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
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...
Kinetic Chain Rehabilitation: A Theoretical Framework
Aaron Sciascia
2012-01-01
Full Text Available Sequenced physiologic muscle activations in the upper and lower extremity result in an integrated biomechanical task. This sequencing is known as the kinetic chain, and, in upper extremity dominant tasks, the energy development and output follows a proximal to distal sequencing. Impairment of one or more kinetic chain links can create dysfunctional biomechanical output leading to pain and/or injury. When deficits exist in the preceding links, they can negatively affect the shoulder. Rehabilitation of shoulder injuries should involve evaluation for and restoration of all kinetic chain deficits that may hinder kinetic chain function. Rehabilitation programs focused on eliminating kinetic chain deficits, and soreness should follow a proximal to distal rationale where lower extremity impairments are addressed in addition to the upper extremity impairments. A logical progression focusing on flexibility, strength, proprioception, and endurance with kinetic chain influence is recommended.
Kinetic chain rehabilitation: a theoretical framework.
Sciascia, Aaron; Cromwell, Robin
2012-01-01
Sequenced physiologic muscle activations in the upper and lower extremity result in an integrated biomechanical task. This sequencing is known as the kinetic chain, and, in upper extremity dominant tasks, the energy development and output follows a proximal to distal sequencing. Impairment of one or more kinetic chain links can create dysfunctional biomechanical output leading to pain and/or injury. When deficits exist in the preceding links, they can negatively affect the shoulder. Rehabilitation of shoulder injuries should involve evaluation for and restoration of all kinetic chain deficits that may hinder kinetic chain function. Rehabilitation programs focused on eliminating kinetic chain deficits, and soreness should follow a proximal to distal rationale where lower extremity impairments are addressed in addition to the upper extremity impairments. A logical progression focusing on flexibility, strength, proprioception, and endurance with kinetic chain influence is recommended.
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.
KINETICS STUDY ON NITRATION OF METHYL RICINOLEATE
Abdullah, Abdullah; Triyono, Triyono; Trisunaryanti, Wega; Haryadi, Winarto
2012-01-01
Kinetics parameter values of methyl ricinoleate nitration (rate constant, reaction order and the rate of reaction) have been determined. Nitration was carried out with both concentrations of HNO3 and acetic anhydride in excess to the concentration of methyl ricinoleate. Thus, the kinetics parameter value was only affected by the concentration of methyl ricinoleate. Based on kinetic study conducted, it could be concluded that the nitration follows pseudo first-order, and the reaction rate for ...
Generalized Bloch-Wangsness-Redfield Kinetic Equations
Fatkullin, Nail
2011-01-01
We present a compact and general derivation of the generalized Bloch-Wangsness-Redfield kinetic equations for systems with the static spin Hamiltonian utilizing the concept of the Liouville space. We show that the assumptions of short correlation times and large heat capacity of the lattice are sufficient to derive the kinetic equations without the use of perturbation theory for the spin-lattice interaction operator. The perturbation theory is only applied for calculation of the kinetic coeff...
Drug-Target Kinetics in Drug Discovery.
Tonge, Peter J
2017-07-14
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.
Dissolution Kinetics of Alumina Calcine
Batcheller, Thomas Aquinas
2001-09-01
Dissolution kinetics of alumina type non-radioactive calcine was investigated as part of ongoing research that addresses permanent disposal of Idaho High Level Waste (HLW). Calcine waste was produced from the processing of nuclear fuel at the Idaho Nuclear Technology and Engineering Center (INTEC). Acidic radioactive raffinates were solidified at ~500°C in a fluidized bed reactor to form the dry granular calcine material. Several Waste Management alternatives for the calcine are presented in the Idaho High Level Waste Draft EIS. The Separations Alternative addresses the processing of the calcine so that the HLW is ready for removal to a national geological repository by the year 2035. Calcine dissolution is the key front-end unit operation for the separations alternative.
Thompson, A.S.; Thompson, B.R.
1988-09-01
The analytical model of nuclear reactor transients, incorporating both mechanical and nuclear effects, simulates reactor kinetics. Linear analysis shows the stability borderline for small power perturbations. In a stable system, initial power disturbances die out with time. With an unstable combination of nuclear and mechanical characteristics, initial disturbances persist and may increase with time. With large instability, oscillations of great magnitude occur. Stability requirements set limits on the power density at which particular reactors can operate. The limiting power density depends largely on the product of two terms: the fraction of delayed neutrons and the frictional damping of vibratory motion in reactor core components. As the fraction of delayed neutrons is essentially fixed, mechanical damping largely determines the maximum power density. A computer program, based on the analytical model, calculates and plots reactor power as a nonlinear function of time in response to assigned values of mechanical and nuclear characteristics.
Kinetic features of breunnerite decarbonization
Vusikhis, A. S.; Gulyaeva, R. I.; Leont'ev, L. I.; Ovchinnikova, L. A.; Selivanov, E. N.
2016-09-01
The decarbonization of breunnerite from talc waste is analyzed by thermogravimetry. The temperatures of thermal effects are determined, and kinetic models for the process are proposed to describe the mechanism of breunnerite decomposition. The unit cell parameters of breunnerite (Mg x Fe1- x )CO3 and the product of its decomposition, iron-magnesium oxide (Mg,Fe)O, are calculated. The apparent activation energies E a of the decomposition are calculated using the Ozawa-Flynn-Wall and Kissenger model-free methods and the Avrami-Erofeev one-step model. Depending on the chosen model, the values of E a range within 180-185 kJ/mol. The conditions of breunnerite roasting for the subsequent use of the obtained material in metallurgical processes are substantiated.
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.
Relativistic Kinetic Theory: An Introduction
Sarbach, Olivier
2013-01-01
We present a brief introduction to the relativistic kinetic theory of gases with emphasis on the underlying geometric and Hamiltonian structure of the theory. Our formalism starts with a discussion on the tangent bundle of a Lorentzian manifold of arbitrary dimension. Next, we introduce the Poincare one-form on this bundle, from which the symplectic form and a volume form are constructed. Then, we define an appropriate Hamiltonian on the bundle which, together with the symplectic form yields the Liouville vector field. The corresponding flow, when projected onto the base manifold, generates geodesic motion. Whenever the flow is restricted to energy surfaces corresponding to a negative value of the Hamiltonian, its projection describes a family of future-directed timelike geodesics. A collisionless gas is described by a distribution function on such an energy surface, satisfying the Liouville equation. Fibre integrals of the distribution function determine the particle current density and the stress-energy ten...
Efficient kinetic Monte Carlo simulation
Schulze, Tim P.
2008-02-01
This paper concerns kinetic Monte Carlo (KMC) algorithms that have a single-event execution time independent of the system size. Two methods are presented—one that combines the use of inverted-list data structures with rejection Monte Carlo and a second that combines inverted lists with the Marsaglia-Norman-Cannon algorithm. The resulting algorithms apply to models with rates that are determined by the local environment but are otherwise arbitrary, time-dependent and spatially heterogeneous. While especially useful for crystal growth simulation, the algorithms are presented from the point of view that KMC is the numerical task of simulating a single realization of a Markov process, allowing application to a broad range of areas where heterogeneous random walks are the dominate simulation cost.
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)
Kinetics of borided gear steels
Ibrahim Gunes
2013-06-01
In this study, the case properties and diffusion kinetics of GS18NiMoCr36 (GS18), GS22NiMoCr56 (GS22) and GS32NiCrMo6.4 (GS32) gear steels borided in Ekabor-II powder were investigated by conducting a series of experiments at temperatures of 1123, 1173 and 1223 K for 2, 4 and 6 h. The boride layer was characterized by optical microscopy, X-ray diffraction technique and microVickers hardness tester. X-ray diffraction analysis of boride layers on the surface of the steels revealed the existence of FeB, Fe2B, CrB and Cr2B compounds. The thickness of the boride layer increases by increasing boriding time and temperature for all steels. The hardness of the boride compounds formed on the surface of the steels GS18, GS22 and GS32 ranged from 1624 to 1905 HV0,05, 1702 to 1948 HV0,05, and 1745 to 2034 HV0,05 respectively, whereas Vickers hardness values of the untreated steels GS18, GS22 and GS32 were 335 HV0,05, 358 HV0,05 and 411 HV0,05, respectively. The activation energies (Q) of borided steels were 228.644 kJ/mol for GS18, 280.609 kJ/mol for GS22 and 294.359 kJ/mol for GS32. The growth kinetics of the boride layers forming on the GS18, GS22 and GS32 steels and the thickness of boride layers were also investigated.
The kinetics of denitrification in permeable sediments
Evrard, Victor; Glud, Ronnie N.; Cook, Perran L. M.
2013-01-01
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...
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…
Enhancing Thai Students' Learning of Chemical Kinetics
Chairam, Sanoe; Somsook, Ekasith; Coll, Richard K.
2009-01-01
Chemical kinetics is an extremely important concept for introductory chemistry courses. The literature suggests that instruction in chemical kinetics is often teacher-dominated at both the secondary school and tertiary levels, and this is the case in Thailand--the educational context for this inquiry. The work reported here seeks to shift students…
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.
Kinetic inductance measured in a superconducting wire
Meservey, R. H.; Tedrow, P. M.
1970-01-01
Ultrasensitive technique to measure kinetic inductance has test specimen included as part of the inductance of a tank circuit of a tunnel diode oscillator. Frequency counter measures shift in frequency of oscillator, caused by changes in inductance. Frequency shift in tank circuit is proportional to change in kinetic inductance
Towards Free-Form Kinetic Structures
Parigi, Dario; Kirkegaard, Poul Henning
2012-01-01
Kinetic Reciprocal System (KRS) are a new kinetic system based on the principle of reciprocity [1] with internal pin-slot constraints. A morphogenetic procedure that can handle a set of many rigid bodies interconnected reciprocally with multiple pin-slot constraint was developed for the generatio...
KINETICS OF NON-ISOTHERMAL CRYSTALLIZATION
ZHANG Zhiying; CAO Zhenlin
1990-01-01
A kinetic equation of non-isothermal crystamzation was derived by extending Avrami's equation to the non-isothermal situation. More crystallization information can be obtained from this kinetic equation. The curves of non-isothermal and isothermal crystallizations were analysed and compared for poly (ethylene terephthalate ) (PET), and the results were discussed.
Kinetic energy driven pairing in cuprate superconductors
Maier, TA; Jarrell, M; Macridin, A; Slezak, C
2004-01-01
Pairing occurs in conventional superconductors through a reduction of the electronic potential energy accompanied by an increase in kinetic energy. In the underdoped cuprates, optical experiments show that pairing is driven by a reduction of the electronic kinetic energy. Using the dynamical cluster
Kinetics of polymer adsorption, desorption and exchange.
Dijt, J.C.
1993-01-01
The aim of the study in this thesis was to gain more insight in the kinetics of polymer adsorption. To this end some well-characterised polymers have been systematically investigated.In the process of polymer adsorption one may distinguish three kinetic contributions: transport to the surface, attac
Thermodynamics, kinetics and process control of nitriding
Mittemeijer, Eric J.; Somers, Marcel A. J.
1999-01-01
, 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...
Crystallization Kinetics within a Generic Modeling Framework
Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist V.
2014-01-01
to the modeling of various kinetic phenomena like nucleation, growth, agglomeration, and breakage are discussed in terms of model forms, model parameters, their availability and/or estimation, and their selection and application for specific crystallization operational scenarios under study. The advantages......A new and extended version of a generic modeling framework for analysis and design of crystallization operations is presented. The new features of this framework are described, with focus on development, implementation, identification, and analysis of crystallization kinetic models. Issues related...... of employing a well-structured model library for storage, use/reuse, and analysis of the kinetic models are highlighted. Examples illustrating the application of the modeling framework for kinetic model discrimination related to simulation of specific crystallization scenarios and for kinetic model parameter...
Figaro, S; Avril, J P; Brouers, F; Ouensanga, A; Gaspard, S
2009-01-30
Adsorption kinetic of molasses wastewaters after anaerobic digestion (MSWD) and melanoidin respectively on activated carbon was studied at different pH. The kinetic parameters could be determined using classical kinetic equations and a recently published fractal kinetic equation. A linear form of this equation can also be used to fit adsorption data. Even with lower correlation coefficients the fractal kinetic equation gives lower normalized standard deviation values than the pseudo-second order model generally used to fit adsorption kinetic data, indicating that the fractal kinetic model is much more accurate for describing the kinetic adsorption data than the pseudo-second order kinetic model.
NEW DEFINITIONS OF KINETIC VISUAL ACUITY AND KINETIC VISUAL FIELD AND THEIR AGING EFFECTS
Jinglong WU
2009-01-01
However, traditional kinetic visual acuity and kinetic visual field measurements do not factor in the effects of individual differences in simple reaction times. This study identifies problems with the traditional method employed to define kinetic visual acuity and kinetic visual fields, and proposes new definitions of kinetic visual acuity and kinetic visual fields that measure simple reaction times and their aging effects. Simple reaction time tests reveal that simple reaction times of senior citizens are longer than those of younger people. The results of appraisal tests between traditional and new kinetic visual acuity definitions demonstrate the appropriateness of the new kinetic visual acuity definition. The study also takes a quantitative look at the aging effects of kinetic visual fields, measuring kinetic visual field characteristics of senior citizens while assessing space dependence, light dependence and index speed dependence of young people. The results obtained show that kinetic visual field ranges decrease with age, particularly in upward visual fields rather than downward visual fields in all target conditions. Visual field angle reductions in the temple sides of upward visual fields were of particular note.
Karkheck, John; Stell, George
1981-08-01
A kinetic mean-field theory for the evolution of the one-particle distribution function is derived from maximizing the entropy. For a potential with a hard-sphere core plus tail, the resulting theory treats the hard-core part as in the revised Enskog theory. The tail, weighted by the hard-sphere pair distribution function, appears linearly in a mean-field term. The kinetic equation is accompanied by an entropy functional for which an H theorem was proven earlier. The revised Enskog theory is obtained by setting the potential tail to zero, the Vlasov equation is obtained by setting the hard-sphere diameter to zero, and an equation of the Enskog-Vlasov type is obtained by effecting the Kac limit on the potential tail. At equilibrium, the theory yields a radial distribution function that is given by the hard-sphere reference system and thus furnishes through the internal energy a thermodynamic description which is exact to first order in inverse temperature. A second natural route to thermodynamics (from the momentum flux which yields an approximate equation of state) gives somewhat different results; both routes coincide and become exact in the Kac limit. Our theory furnishes a conceptual basis for the association in the heuristically based modified Enskog theory (MET) of the contact value of the radial distribution function with the ''thermal pressure'' since this association follows from our theory (using either route to thermodynamics) and moreover becomes exact in the Kac limit. Our transport theory is readily extended to the general case of a soft repulsive core, e.g., as exhibited by the Lennard-Jones potential, via by-now-standard statistical-mechanical methods involving an effective hard-core potential, thus providing a self-contained statistical-mechanical basis for application to such potentials that is lacking in the standard versions of the MET. We obtain very good agreement with experiment for the thermal conductivity and shear viscosity of several
Thermal Decomposition Kinetics of HMX
Burnham, A K; Weese, R K
2004-11-18
Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of thermal analysis data types, including mass loss for isothermal and constant rate heating in an open pan and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 165 kJ/mol range for open pan experiments and about 150 to 165 kJ/mol for sealed pan experiments. Our activation energies tend to be slightly lower than those derived from data supplied by the University of Utah, which we consider the best previous thermal analysis work. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated in closed pan experiments, and one global reaction appears to fit the data well. Comparison of our rate measurements with additional literature sources for open and closed low temperature pyrolysis from Sandia gives a likely activation energy of 165 kJ/mol at 10% conversion.
Thermal Decomposition Kinetics of HMX
Burnham, A K; Weese, R K
2004-05-05
Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of types of data, including mass loss for isothermal and constant rate heating in an open pan, and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 150 kJ/mol regime for open pan experiments and about 160 kJ/mol for sealed pan experiments. Our activation energies are about 10% lower than those derived from data supplied by the University of Utah, which we consider the best previous work. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated for closed pan experiments, and one global reaction appears to fit the data well.
Thermal Decomposition Kinetics of HMX
Burnham, A K; Weese, R K
2005-03-17
Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of types of data, including mass loss for isothermal and constant rate heating in an open pan, and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 165 kJ/mol regime for open pan experiments and about 150-165 kJ/mol for sealed-pan experiments. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated for closed pan experiments, and one global reaction fits the data fairly well. Our A-E values lie in the middle of the values given in a compensation-law plot by Brill et al. (1994). Comparison with additional open and closed low temperature pyrolysis experiments support an activation energy of 165 kJ/mol at 10% conversion.
Bicarbonate kinetics in Indian males
T Raj; R Kuriyan; A V Kurpad
2006-06-01
Measurement of rates of in vivo substrate oxidation such as that of glucose, fatty acids and amino acids, are based on tracer (14C or 13C) data, and often depend on the isotopic content of expired CO2. The recovery of tracer-labelled CO2 generated from the oxidation of 13C labelled substrates may not be 100% over short term. This can lead to underestimation of oxidation rate of substrates, and consequently a correction for the incomplete recovery of tracer has to be applied by the determination of the recovery of 13CO2 in the breath during tracer bicarbonate infusions. We have studied the recovery of tracer-labelled bicarbonate using a bolus administration model, and further characterized kinetics of bicarbonate using a three-compartment model, to assess which compartmental fluxes changed during the change from a fasted state to fed state. Recovery of bicarbonate was lower at 69% and 67% (fasted and fed state) than the value of 71% and 74% found during earlier longer term of continuous infusions. During feeding, there was a 20-fold increase in the flux of bicarbonate between the central compartment and the compartment that was equivalent to the viscera. This study shows that the difference between the fasted and fed state recovery of tracer bicarbonate similar to that obtained with continuous infusions, and that bicarbonate fluxes show large changes between different compartments in the body depending on metabolic state.
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.
Complex kinetics of fluctuating enzymes: phase diagram characterization of a minimal kinetic scheme.
Min, Wei; Jiang, Liang; Xie, X Sunney
2010-05-03
Enzyme molecules are dynamic entities with stochastic fluctuation in both protein conformation and enzymatic activity. However, such a notion of fluctuating enzymes, best characterized by recent single-molecule experiments, was not considered in the classic Michaelis-Menten (MM) kinetic scheme. Here we incorporate the fluctuation concept into the reversible MM scheme, and solve analytically all the possible kinetics (i.e., substrate concentration dependent enzymatic velocity) for a minimal model of fluctuating enzymes. Such a minimal model is found to display a variety of distinct kinetic behaviors (phases) in addition to the classic MM kinetics; excess substrate inhibition, sigmoidal kinetics, and concave biphasic kinetics. We find that all these kinetic phases are interrelated and unified under the framework of fluctuating enzymes and can be adequately described by a phase diagram that consists of two master parameters. Functionally, substrate inhibition, sigmoidal kinetics, and convex biphasic phases exhibit positive cooperativity, whereas concave biphasic phases display negative cooperativity. Remarkably, all these complex kinetics are produced by fluctuating enzymes with single substrate binding site, but the two conformations are, therefore, fundamentally different from the classic MWC and KNF models that require multiple subunit or binding sites. This model also suggests that, for a given enzyme/substrate pair, the non-MM behaviors could undergo transitions among different kinetic phases induced by varying product concentrations, owing to the fundamental Haldane symmetry in the reversible MM scheme.
Modeling of Reactor Kinetics and Dynamics
Matthew Johnson; Scott Lucas; Pavel Tsvetkov
2010-09-01
In order to model a full fuel cycle in a nuclear reactor, it is necessary to simulate the short time-scale kinetic behavior of the reactor as well as the long time-scale dynamics that occur with fuel burnup. The former is modeled using the point kinetics equations, while the latter is modeled by coupling fuel burnup equations with the kinetics equations. When the equations are solved simultaneously with a nonlinear equation solver, the end result is a code with the unique capability of modeling transients at any time during a fuel cycle.
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.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.
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.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
Kinetic approach to granular gases.
Puglisi, A; Loreto, V; Marini Bettolo Marconi, U; Vulpiani, A
1999-05-01
We address the problem of the so-called "granular gases," i.e., gases of massive particles in rapid movement undergoing inelastic collisions. We introduce a class of models of driven granular gases for which the stationary state is the result of the balance between the dissipation and the random forces which inject energies. These models exhibit a genuine thermodynamic limit, i.e., at fixed density the mean values of kinetic energy and dissipated energy per particle are independent of the number N of particles, for large values of N. One has two regimes: when the typical relaxation time tau of the driving Brownian process is small compared with the mean collision time tau(c) the spatial density is nearly homogeneous and the velocity probability distribution is Gaussian. In the opposite limit tau>tau(c) one has strong spatial clustering, with a fractal distribution of particles, and the velocity probability distribution strongly deviates from the Gaussian one. Simulations performed in one and two dimensions under the Stosszahlansatz Boltzmann approximation confirm the scenario. Furthermore, we analyze the instabilities bringing to the spatial and the velocity clusterization. Firstly, in the framework of a mean-field model, we explain how the existence of the inelasticity can lead to a spatial clusterization; on the other hand, we discuss, in the framework of a Langevin dynamics treating the collisions in a mean-field way, how a non-Gaussian distribution of velocity can arise. The comparison between the numerical and the analytical results exhibits an excellent agreement.
Kinetics of aluminum lithium alloys
Pletcher, Ben A.
2009-12-01
Aluminum lithium alloys are increasingly used in aerospace for their high strength-to-weight ratio. Additions of lithium, up to 4.2 wt% decrease the alloy density while increasing the modulus and yield strength. The metastable, second phase Al3Li or delta' is intriguing, as it remains spherical and coherent with the matrix phase, alpha, well into the overaged condition. Small interfacial strain energy allows these precipitates to remain spherical for volume fractions (VV ) of delta' less than 0.3, making this alloy system ideal for investigation of late-stage coarsening phenomena. Experimental characterization of three binary Al-Li alloys are presented as a critical test of diffusion screening theory and multi-particle diffusion simulations. Quantitative transmission electron microscopy is used to image the precipitates directly using the centered dark-field technique. Images are analyzed autonomously within a novel Matlab function that determines the center and size of each precipitate. Particle size distribution, particle growth kinetics, and maximum particle size are used to track the precipitate growth and correlate with the predictions of screening theory and multi-particle diffusion simulations. This project is the first extensive study of Al-Li alloys, in over 25 years, applying modern transmission electron microscopy and image analysis techniques. Previous studies sampled but a single alloy composition, and measured far fewer precipitates. This study investigates 3 alloys with volume fractions of the delta precipitates, VV =0.1-0.27, aged at 225C for 1 to 10 days. More than 1000 precipitates were sampled per aging time, creating more statistically significant data. Experimental results are used to test the predictions based on diffusion screening theory and multi-particle aging simulations. (Full text of this dissertation may be available via the University of Florida Libraries web site. Please check http://www.uflib.ufl.edu/etd.html)
Kinetic effects in edge plasma: kinetic modeling for edge plasma and detached divertor
Takizuka, T.
2017-03-01
Detached divertor is considered a solution for the heat control in magnetic-confinement fusion reactors. Numerical simulations using the comprehensive divertor codes based on the plasma fluid modeling are indispensable for the design of the detached divertor in future reactors. Since the agreement in the results between detached-divertor experiments and simulations has been rather fair but not satisfactory, further improvement of the modeling is required. The kinetic effect is one of key issues for improving the modeling. Complete kinetic behaviors are able to be simulated by the kinetic modeling. In this paper at first, major kinetic effects in edge plasma and detached divertor are listed. One of the most powerful kinetic models, particle-in-cell (PIC) model, is described in detail. Several results of PIC simulations of edge-plasma kinetic natures are presented. Future works on PIC modeling and simulation for the deeper understanding of edge plasma and detached divertor are discussed.
Amplification of kinetic oscillations in gene expression
Zhdanov, V. P.
2008-10-01
Because of the feedbacks between the DNA transcription and mRNA translation, the gene expression in cells may exhibit bistability and oscillations. The deterministic and stochastic calculations presented illustrate how the bistable kinetics of expression of one gene in a cell can be influenced by the kinetic oscillations in the expression of another gene. Due to stability of the states of the bistable kinetics of gene 1 and the relatively small difference between the maximum and minimum protein amounts during the oscillations of gene 2, the induced oscillations of gene 1 are found to typically be related either to the low-or high-reactive state of this gene. The quality of the induced oscillations may be appreciably better than that of the inducing oscillations. This means that gene 1 can serve as an amplifier of the kinetic oscillations of gene 2.
A Course in Kinetics and Catalysis.
Bartholomew, C. H.
1981-01-01
Describes a one-semester, three-credit hour course integrating the fundamentals of kinetics and the scientific/engineering principles of heterogeneous catalysis. Includes course outline, list of texts, background readings, and topical journal articles. (SK)
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...
ALCHEMIC: Advanced time-dependent chemical kinetics
Semenov, Dmitry A.
2017-08-01
ALCHEMIC solves chemical kinetics problems, including gas-grain interactions, surface reactions, deuterium fractionization, and transport phenomena and can model the time-dependent chemical evolution of molecular clouds, hot cores, corinos, and protoplanetary disks.
The Early Development of Kinetic Theory.
Whitaker, Robert D.
1979-01-01
A review of the work of Bernoulli and other early contributors to kinetic theory. One significant point is that the most outstanding work in this early period was done by a little-known Scotsman, John J. Waterston. (BB)
Nitrogen uptake kinetics of freshly isolated zooxanthellae
Wafar, M.V.M.; Wafar, S.; Rajkumar, R.
Zooxanthellae freshly isolated from the coral host Pocillopora damicornis exhibited substrate-saturable uptake kinetics for ammonium, nitrate and urea. Maximum uptake velocity for ammonium [10.1 nmol. ( mu chl-a)./1h/1] was greater than...
Electron Kinetics in Hypersonic Plasmas Project
National Aeronautics and Space Administration — The goal of this SBIR project is to advance the state-of-the-art in computations of hypersonic plasmas by adding high-fidelity kinetic models for electrons. Electron...
SATL MODEL LESSON IN CHEMICAL KINETICS
Preferred Customer
Department of Chemistry, The Federal Urdu University of Arts, Science and ... are several strategies, through which teaching and learning of scientific subjects in ... the linear relationships among various factors involved in chemical kinetics.
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...
Quantifying hydrate formation and kinetic inhibition
Sloan, E.D.; Subramanian, S.; Matthews, P.N.; Lederhos, J.P.; Khokhar, A.A. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research
1998-08-01
In the Prausnitz tradition, molecular and macroscopic evidence of hydrate formation and kinetic inhibition is presented. On the microscopic level, the first Raman spectra are presented for the formation of both uninhibited and inhibited methane hydrates with time. This method has the potential to provide a microscopic-based kinetics model. Three macroscopic aspects of natural gas hydrate kinetic inhibition are also reported: (1) The effect of hydrate dissociation residual structures was measured, which has application in decreasing the time required for subsequent formation. (2) The performance of a kinetic inhibitor (poly(N-vinylcaprolactam) or PVCap) was measured and correlated as a function of PVCap molecular weight and concentrations of PVCap, methanol, and salt in the aqueous phase. (3) Long-duration test results indicated that the use of PVCap can prevent pipeline blockage for a time exceeding the aqueous phase residence time in some gas pipelines.
Large kinetic power in FRII radio jets
Ito, Hirotaka; Kino, Motoki; Kawakatu, Nozomu; Isobe, Naoki; Yamada, Shoichi
2007-10-01
We investigate the total kinetic powers ( L j) and ages ( t age) of powerful jets of four FR II radio sources (Cygnus A, 3C 223, 3C 284, and 3C 219) by the detail comparison of the dynamical model of expanding cocoons with observed ones. It is found that these sources have quite large kinetic powers with the ratio of L j to the Eddington luminosity ( L Edd) resides in 0.02< L j/ L Edd<10. Reflecting the large kinetic powers, we also find that the total energy stored in the cocoon ( E c) exceed the energy derived from the minimum energy condition ( E min ): 2< E c/ E min <160. This implies that a large amount of kinetic power is carried by invisible components such as thermal leptons (electron and positron) and/or protons.
Large Kinetic Power in FRII Radio Jets
Ito, H; Kawakatu, N; Isobe, N; Yamada, S
2007-01-01
We investigate the total kinetic powers (L_{j}) and ages (t_{age}) of powerful jets of four FR II radio sources (Cygnus A, 3C 223, 3C 284, and 3C 219) by the detail comparison of the dynamical model of expanding cocoons with observed ones. It is found that these sources have quite large kinetic powers with the ratio of L_{j} to the Eddington luminosity (L_{Edd}) resides in $0.02
How ambiguous is the local kinetic energy?
Anderson, James S M; Ayers, Paul W; Hernandez, Juan I Rodriguez
2010-08-26
The local kinetic energy and the closely related local electronic stress tensor are commonly used to elucidate chemical bonding patterns, especially for covalent bonds. We use three different approaches-transformation properties of the stress tensor, quasiprobability distributions, and the virial theorem from density-functional theory-to clarify the inherent ambiguity in these quantities, discussing the implications for analyses based on the local kinetic energy and stress tensor. An expansive-but not universal-family of local kinetic energy forms that includes the most common choices and is suitable for both chemical-bonding and atoms-in-molecule analysis is derived. A family of local electronic stress tensors is also derived. Several local kinetic energy functions that are mathematically justified, but unlikely to be conceptually useful, are derived. The implications of these forms for atoms-in-molecule analysis are discussed.
Progress in antenna coupled kinetic inductance detectors
Baryshev, A.; Baselmans, J.J.A.; Freni, A.; Gerini, G.; Hoevers, H.; 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
Kinetics of microwave drying of apples
G. V. Kalashnikov
2012-01-01
Full Text Available The influence of main technological parameters was studied as a result of research of microwave drying of apples and the analysis of kinetic regularity of the process was performed.
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...
Kinetic exchange models for social opinion formation
Lallouache, Mehdi; Chakrabarti, Bikas K
2010-01-01
We propose a minimal model for the collective dynamics of opinion formation in the society, by modifying kinetic exchange dynamics studied in the context of income, money or wealth distributions in a society.
Extracellular enzyme kinetics scale with resource availability
Microbial community metabolism relies on external digestion, mediated by extracellular enzymes that break down complex organic matter into molecules small enough for cells to assimilate. We analyzed the kinetics of 40 extracellular enzymes that mediate the degradation and assimi...
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.
Finite-dimensional collisionless kinetic theory
Burby, J W
2016-01-01
A collisionless kinetic plasma model may often be cast as an infinite-dimensional noncanonical Hamiltonian system. I show that, when this is the case, the model can be discretized in space and particles while preserving its Hamiltonian structure, thereby producing a finite-dimensional Hamiltonian system that approximates the original kinetic model. I apply the general theory to two example systems: the relativistic Vlasov-Maxwell system with spin, and a gyrokinetic Vlasov-Maxwell system.
Determination of solvation kinetics in supercritical fluids
Bright, F.V.
1993-01-01
Objective was to study solvation processes in pure and entrainer-modified supercritical fluids. Specific topics were: Kinetics for solvation in supercritical media, influence on entrainers on solvation, reversibility of solvation, effects of solvation on intramolecular solute-solute interaction kinetics, and impact of fluid density on these processes. Time-resolved fluorescence spectroscopy was used as the main analytical tool. A summary is given of the 2.5 years' research.
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
The kinetics of the hydrogen chloride oxidation
Gonzalez Martinez Isai
2013-01-01
Full Text Available Hydrogen chloride (HCl oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.
Kinetics and Product Channels in Combustion Chemistry
Hershberger, John F. [North Dakota State Univ., Fargo, ND (United States)
2017-02-28
We report study of the chemical kinetics and/or photochemistry of several chemical reactions of potential interest in understanding the gas phase combustion chemistry of nitrogen-containing molecules. Studies completed during the final grant period include determination of quantum yields of the photolysis of HCNO, fulminic acid, a kinetics and product channel study of the reaction of CN radicals with methyl bromide, and study of the products of the reaction of hydroxymethyl radical with nitric oxide.
Determination of rate distributions from kinetic experiments.
Steinbach, P J; Chu, K.; Frauenfelder, H; Johnson, J B; Lamb, D C; Nienhaus, G. U.; Sauke, T B; Young, R. D.
1992-01-01
Rate processes in proteins are often not adequately described by simple exponential kinetics. Instead of modeling the kinetics in the time domain, it can be advantageous to perform a numerical inversion leading to a rate distribution function f(lambda). The features observed in f(lambda) (number, positions, and shapes of peaks) can then be interpreted. We discuss different numerical techniques for obtaining rate distribution functions, with special emphasis on the maximum entropy method. Exam...
Preventing Corrosion by Controlling Cathodic Reaction Kinetics
2016-03-25
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...dominate the metal’s cathodic behavior. Within an alkaline environment, we expect the following reduction reactions to be catalyzed on the oxide
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.
Kinetic Chain Rehabilitation: A Theoretical Framework
Aaron Sciascia; Robin Cromwell
2012-01-01
Sequenced physiologic muscle activations in the upper and lower extremity result in an integrated biomechanical task. This sequencing is known as the kinetic chain, and, in upper extremity dominant tasks, the energy development and output follows a proximal to distal sequencing. Impairment of one or more kinetic chain links can create dysfunctional biomechanical output leading to pain and/or injury. When deficits exist in the preceding links, they can negatively affect the shoulder. Rehabilit...
Kinetic partitioning mechanism of HDV ribozyme folding
Chen, Jiawen; Gong, Sha; Wang, Yujie; Zhang, Wenbing
2014-01-01
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.
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.
Mechanisms and kinetics of coal hydrogenation
Baldwin, R M; Furlong, M W
1981-05-01
Colorado School of Mines is engaged in an experimental program to develop comprehensive models for the effects of coal composition upon the kinetics and mechanisms of coal hydrogenation, for the effects of mineral matter additives (disposable catalysts) upon kinetics and mechanisms of coal hydrogenation, and for the kinetics and mechanisms of the hydrogenation of coal derived products such as preasphaltenes, and asphaltenes. Experimental work was completed on a suite of bituminous coals, thus completing the initial phase of the coal reactivity study. Eleven of the 14 coals of the suite were successfully run in duplicate. Conversion to THF solubles was correlated well by pseudo-second order kinetics. The resulting kinetic rate constants correlated with H/C ratio, mean-max vitrinite reflectance, and a specially-defined fraction of reactive macerals. The data did not correlate well with O/C ratios of the parent coals. Computer-derived statistical fits of various kinetic models were limited in their effectiveness at fitting the experimental data. Experimental work on the first phase of the disposal catalyst studies was completed. Statistical significance testing of the experimental data showed: fractional conversion and yield of light hydrocarbon products increased with time; and mineral properties of the additives were more significant in increasing overall conversion than the additive surface areas. The relative effects of the additives are given.
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
Resonance Van Hove singularities in wave kinetics
Shi, Yi-Kang; Eyink, Gregory L.
2016-10-01
Wave kinetic theory has been developed to describe the statistical dynamics of weakly nonlinear, dispersive waves. However, we show that systems which are generally dispersive can have resonant sets of wave modes with identical group velocities, leading to a local breakdown of dispersivity. This shows up as a geometric singularity of the resonant manifold and possibly as an infinite phase measure in the collision integral. Such singularities occur widely for classical wave systems, including acoustical waves, Rossby waves, helical waves in rotating fluids, light waves in nonlinear optics and also in quantum transport, e.g. kinetics of electron-hole excitations (matter waves) in graphene. These singularities are the exact analogue of the critical points found by Van Hove in 1953 for phonon dispersion relations in crystals. The importance of these singularities in wave kinetics depends on the dimension of phase space D =(N - 2) d (d physical space dimension, N the number of waves in resonance) and the degree of degeneracy δ of the critical points. Following Van Hove, we show that non-degenerate singularities lead to finite phase measures for D > 2 but produce divergences when D ≤ 2 and possible breakdown of wave kinetics if the collision integral itself becomes too large (or even infinite). Similar divergences and possible breakdown can occur for degenerate singularities, when D - δ ≤ 2, as we find for several physical examples, including electron-hole kinetics in graphene. When the standard kinetic equation breaks down, then one must develop a new singular wave kinetics. We discuss approaches from pioneering 1971 work of Newell & Aucoin on multi-scale perturbation theory for acoustic waves and field-theoretic methods based on exact Schwinger-Dyson integral equations for the wave dynamics.
Simplification of the unified gas kinetic scheme
Chen, Songze; Guo, Zhaoli; Xu, Kun
2016-08-01
The unified gas kinetic scheme (UGKS) is an asymptotic preserving (AP) scheme for kinetic equations. It is superior for transition flow simulation and has been validated in the past years. However, compared to the well-known discrete ordinate method (DOM), which is a classical numerical method solving the kinetic equations, the UGKS needs more computational resources. In this study, we propose a simplification of the unified gas kinetic scheme. It allows almost identical numerical cost as the DOM, but predicts numerical results as accurate as the UGKS. In the simplified scheme, the numerical flux for the velocity distribution function and the numerical flux for the macroscopic conservative quantities are evaluated separately. The equilibrium part of the UGKS flux is calculated by analytical solution instead of the numerical quadrature in velocity space. The simplification is equivalent to a flux hybridization of the gas kinetic scheme for the Navier-Stokes (NS) equations and the conventional discrete ordinate method. Several simplification strategies are tested, through which we can identify the key ingredient of the Navier-Stokes asymptotic preserving property. Numerical tests show that, as long as the collision effect is built into the macroscopic numerical flux, the numerical scheme is Navier-Stokes asymptotic preserving, regardless the accuracy of the microscopic numerical flux for the velocity distribution function.
Chemical Kinetic Modeling of Advanced Transportation Fuels
PItz, W J; Westbrook, C K; Herbinet, O
2009-01-20
Development of detailed chemical kinetic models for advanced petroleum-based and nonpetroleum based fuels is a difficult challenge because of the hundreds to thousands of different components in these fuels and because some of these fuels contain components that have not been considered in the past. It is important to develop detailed chemical kinetic models for these fuels since the models can be put into engine simulation codes used for optimizing engine design for maximum efficiency and minimal pollutant emissions. For example, these chemistry-enabled engine codes can be used to optimize combustion chamber shape and fuel injection timing. They also allow insight into how the composition of advanced petroleum-based and non-petroleum based fuels affect engine performance characteristics. Additionally, chemical kinetic models can be used separately to interpret important in-cylinder experimental data and gain insight into advanced engine combustion processes such as HCCI and lean burn engines. The objectives are: (1) Develop detailed chemical kinetic reaction models for components of advanced petroleum-based and non-petroleum based fuels. These fuels models include components from vegetable-oil-derived biodiesel, oil-sand derived fuel, alcohol fuels and other advanced bio-based and alternative fuels. (2) Develop detailed chemical kinetic reaction models for mixtures of non-petroleum and petroleum-based components to represent real fuels and lead to efficient reduced combustion models needed for engine modeling codes. (3) Characterize the role of fuel composition on efficiency and pollutant emissions from practical automotive engines.
A kinetic model for predicting biodegradation.
Dimitrov, S; Pavlov, T; Nedelcheva, D; Reuschenbach, P; Silvani, M; Bias, R; Comber, M; Low, L; Lee, C; Parkerton, T; Mekenyan, O
2007-01-01
Biodegradation plays a key role in the environmental risk assessment of organic chemicals. The need to assess biodegradability of a chemical for regulatory purposes supports the development of a model for predicting the extent of biodegradation at different time frames, in particular the extent of ultimate biodegradation within a '10 day window' criterion as well as estimating biodegradation half-lives. Conceptually this implies expressing the rate of catabolic transformations as a function of time. An attempt to correlate the kinetics of biodegradation with molecular structure of chemicals is presented. A simplified biodegradation kinetic model was formulated by combining the probabilistic approach of the original formulation of the CATABOL model with the assumption of first order kinetics of catabolic transformations. Nonlinear regression analysis was used to fit the model parameters to OECD 301F biodegradation kinetic data for a set of 208 chemicals. The new model allows the prediction of biodegradation multi-pathways, primary and ultimate half-lives and simulation of related kinetic biodegradation parameters such as biological oxygen demand (BOD), carbon dioxide production, and the nature and amount of metabolites as a function of time. The model may also be used for evaluating the OECD ready biodegradability potential of a chemical within the '10-day window' criterion.
KINETICS OF HYDROLYSIS OF TRIBUTYRIN BY LIPASE
SULAIMAN AL-ZUHAIR
2006-06-01
Full Text Available Kinetics of the enzymatic hydrolysis of tributyrin using lipase has been investigated. The initial rate of reaction was determined experimentally at different substrate concentration by measuring the rate of butyric acid produced. Michaels-Menten kinetic model has been proposed to predict the initial rate of hydrolysis of tributyrin in micro-emulsion system. The kinetic parameters were estimated by fitting the data to the model using three methods, namely, the Lineweaver-Burk, Edie-Hofstee and Hanes methods. The Michaels-Menten model with the constant predicted by Edie-Hofstee and Hanes methods predicted the initial rate of reaction at various substrate concentrations better than the model with the constant predicted Lineweaver-Burk method, especially at high substrate concentrations.
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...
Kinetic regulation of coated vesicle secretion
Foret, Lionel
2008-01-01
The secretion of vesicles for intracellular transport often rely on the aggregation of specialized membrane-bound proteins into a coat able to curve cell membranes. The nucleation and growth of a protein coat is a kinetic process that competes with the energy-consuming turnover of coat components between the membrane and the cytosol. We propose a generic kinetic description of coat assembly and the formation of coated vesicles, and discuss its implication to the dynamics of COP vesicles that traffic within the Golgi and with the Endoplasmic Reticulum. We show that stationary coats of fixed area emerge from the competition between coat growth and the recycling of coat components, in a fashion resembling the treadmilling of cytoskeletal filaments. We further show that the turnover of coat components allows for a highly sensitive switching mechanism between a quiescent and a vesicle producing membrane, upon a slowing down of the exchange kinetics. We claim that the existence of this switching behaviour, also tri...
A simple theory of protein folding kinetics
Pande, Vijay S
2010-01-01
We present a simple model of protein folding dynamics that captures key qualitative elements recently seen in all-atom simulations. The goals of this theory are to serve as a simple formalism for gaining deeper insight into the physical properties seen in detailed simulations as well as to serve as a model to easily compare why these simulations suggest a different kinetic mechanism than previous simple models. Specifically, we find that non-native contacts play a key role in determining the mechanism, which can shift dramatically as the energetic strength of non-native interactions is changed. For protein-like non-native interactions, our model finds that the native state is a kinetic hub, connecting the strength of relevant interactions directly to the nature of folding kinetics.
Nanopore DNA sequencing using kinetic proofreading
Ling, Xinsheng
We propose a method of DNA sequencing by combining the physical method of nanopore electrical measurements and Southern's sequencing-by-hybridization. The new key ingredient, essential to both lowering the costs and increasing the precision, is an asymmetric nanopore sandwich device capable of measuring the DNA hybridization probe twice separated by a designed waiting time. Those incorrect probes appearing only once in nanopore ionic current traces are discriminated from the correct ones that appear twice. This method of discrimination is similar to the principle of kinetic proofreading proposed by Hopfield and Ninio in gene transcription and translation processes. An error analysis is of this nanopore kinetic proofreading (nKP) technique for DNA sequencing is carried out in comparison with the most precise 3' dideoxy termination method developed by Sanger. Nanopore DNA sequencing using kinetic proofreading.
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).
Filamentary and hierarchical pictures - Kinetic energy criterion
Klypin, Anatoly A.; Melott, Adrian L.
1992-01-01
We present a new criterion for formation of second-generation filaments. The criterion called the kinetic energy ratio, KR, is based on comparison of peculiar velocities at different scales. We suggest that the clumpiness of the distribution in some cases might be less important than the 'coldness' or 'hotness' of the flow for formation of coherent structures. The kinetic energy ratio is analogous to the Mach number except for one essential difference. If at some scale KR is greater than 1, as estimated at the linear stage, then when fluctuations of this scale reach nonlinearity, the objects they produce must be anisotropic ('filamentary'). In the case of power-law initial spectra the kinetic ratio criterion suggests that the border line is the power-spectrum with the slope n = -1.
Turbulence kinetic energy equation for dilute suspensions
Abou-Arab, T. W.; Roco, M. C.
1989-01-01
A multiphase turbulence closure model is presented which employs one transport equation, namely the turbulence kinetic energy equation. The proposed form of this equation is different from the earlier formulations in some aspects. The power spectrum of the carrier fluid is divided into two regions, which interact in different ways and at different rates with the suspended particles as a function of the particle-eddy size ratio and density ratio. The length scale is described algebraically. A mass/time averaging procedure for the momentum and kinetic energy equations is adopted. The resulting turbulence correlations are modeled under less retrictive assumptions comparative to previous work. The closures for the momentum and kinetic energy equations are given. Comparisons of the predictions with experimental results on liquid-solid jet and gas-solid pipe flow show satisfactory agreement.
Cartesian Grid Method for Gas Kinetic Scheme
Chen, Songze; Li, Zhihui
2015-01-01
A Cartesian grid method combined with a simplified gas kinetic scheme is presented for subsonic and supersonic viscous flow simulation on complex geometries. Under the Cartesian mesh, the computational grid points are classified into four different categories, the fluid point, the solid point, the drop point, and the interpolation point. The boundaries are represented by a set of direction-oriented boundary points. A constrained weighted least square method is employed to evaluate the physical quantities at the interpolation points. Different boundary conditions, including isothermal boundary, adiabatic boundary, and Euler slip boundary, are presented by different interpolation strategies. We also propose a simplified gas kinetic scheme as the flux solver for both subsonic and supersonic flow computations. The methodology of constructing a simplified kinetic flux function can be extended to other flow systems. A few numerical examples are used to validate the Cartesian grid method and the simplified flux func...
Efficient estimation of rare-event kinetics
Trendelkamp-Schroer, Benjamin
2014-01-01
The efficient calculation of rare-event kinetics in complex dynamical systems, such as the rate and pathways of ligand dissociation from a protein, is a generally unsolved problem. Markov state models can systematically integrate ensembles of short simulations and thus effectively parallelize the computational effort, but the rare events of interest still need to be spontaneously sampled in the data. Enhanced sampling approaches, such as parallel tempering or umbrella sampling, can accelerate the computation of equilibrium expectations massively - but sacrifice the ability to compute dynamical expectations. In this work we establish a principle to combine knowledge of the equilibrium distribution with kinetics from fast "downhill" relaxation trajectories using reversible Markov models. This approach is general as it does not invoke any specific dynamical model, and can provide accurate estimates of the rare event kinetics. Large gains in sampling efficiency can be achieved whenever one direction of the proces...
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...
Resonance Van Hove Singularities in Wave Kinetics
Shi, Yi-Kang
2015-01-01
Wave kinetic theory has been developed to describe the statistical dynamics of weakly nonlinear, dispersive waves. However, we show that systems which are generally dispersive can have resonant sets of wave modes with identical group velocities, leading to a local breakdown of dispersivity. This shows up as a geometric singularity of the resonant manifold and possibly as an infinite phase measure in the collision integral. Such singularities occur widely for classical wave systems, including acoustical waves, Rossby waves, helical waves in rotating fluids, light waves in nonlinear optics and also in quantum transport, e.g. kinetics of electron-hole excitations (matter waves) in graphene. These singularities are the exact analogue of the critical points found by Van Hove in 1953 for phonon dispersion relations in crystals. The importance of these singularities in wave kinetics depends on the dimension of phase space $D=(N-2)d$ ($d$ physical space dimension, $N$ the number of waves in resonance) and the degree ...
Determination of kinetic parameters for biomass combustion.
Álvarez, A; Pizarro, C; García, R; Bueno, J L; Lavín, A G
2016-09-01
The aim of this work is to provide a wide database of kinetic data for the most common biomass by thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). Due to the characteristic parameters of DTG curves, a two-stage reaction model is proposed and the kinetic parameters obtained from model-based methods with energy activation values for first and second stages in the range 1.75·10(4)-1.55·10(5)J/mol and 1.62·10(4)-2.37·10(5)J/mol, respectively. However, it has been found that Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose model-free methods are not suitable to determine the kinetic parameters of biomass combustion since the assumptions of these two methods were not accomplished in the full range of the combustion process.
Kinetics and thermodynamics of living copolymerization processes
Gaspard, Pierre
2016-11-01
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'.
Wave-kinetic description of nonlinear photons
Marklund, M; Brodin, G; Stenflo, L
2004-01-01
The nonlinear interaction, due to quantum electrodynamical (QED) effects, between photons is investigated using a wave-kinetic description. Starting from a coherent wave description, we use the Wigner transform technique to obtain a set of wave-kinetic equations, the so called Wigner-Moyal equations. These equations are coupled to a background radiation fluid, whose dynamics is determined by an acoustic wave equation. In the slowly varying acoustic limit, we analyse the resulting system of kinetic equations, and show that they describe instabilities, as well as Landau-like damping. The instabilities may lead to break-up and focusing of ultra-high intensity multi-beam systems, which in conjunction with the damping may result in stationary strong field structures. The results could be of relevance for the next generation of laser-plasma systems.
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.
Lattice kinetic simulation of nonisothermal magnetohydrodynamics.
Chatterjee, Dipankar; Amiroudine, Sakir
2010-06-01
In this paper, a lattice kinetic algorithm is presented to simulate nonisothermal magnetohydrodynamics in the low-Mach number incompressible limit. The flow and thermal fields are described by two separate distribution functions through respective scalar kinetic equations and the magnetic field is governed by a vector distribution function through a vector kinetic equation. The distribution functions are only coupled via the macroscopic density, momentum, magnetic field, and temperature computed at the lattice points. The novelty of the work is the computation of the thermal field in conjunction with the hydromagnetic fields in the lattice Boltzmann framework. A 9-bit two-dimensional (2D) lattice scheme is used for the numerical computation of the hydrodynamic and thermal fields, whereas the magnetic field is simulated in a 5-bit 2D lattice. Simulation of Hartmann flow in a channel provides excellent agreement with corresponding analytical results.
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 energy transfer during the tennis serve
C.L. de Subijana
2010-12-01
Full Text Available Several studies have established the pattern used in the over arm hitting and throwing movements, however to date there has not been one which statistically expresses the Kinetic Link Principle of the tennis serve. The main goals of this study were: first to investigate the kinetic energy transmission pattern using a complete mechanical body model and second, to create a tool which could help evaluating the individual technique of a tennis player. This tool was a statistical procedure which expressed the individual technique of a player as a mathematical function. Fourteen and twelve flat tennis serves of two top tennis players landing in an aiming area were recorded with two synchronized video cameras at 125 Hz. The experimental technique was 3D photogrammetry. A 28 points body model with five solid-rigid (the pelvis, the thorax, the upper arms and the racquet was built. The kinetic energies from the body segments were considered the biomechanical parameters. The mean speeds of the balls were 41.9 m/s (150.9 km/hr and 38.1 m/s (137.2 km/hr. A Kinetic Sequential Action Muscle principle based on the kinetic energy transfer was probed statistically by mean a correlation analysis [3]. This pattern showed the existence of a proximal to distal sequence of kinetic energy maximums. A significant (p<0.05 discriminant function for each player could predict the category of the serve (“good” or “bad” in the 78.6% and 100% of the cases. This function facilitated the understanding of the individual technique of a tennis player showing that this could be a tool for the tennis training complementary to the qualitative (observational analysis.
The hydrothermal reaction kinetics of aspartic acid
Cox, Jenny S.; Seward, Terry M.
2007-02-01
Experimental data on the hydrothermal reaction kinetics of aspartic acid were acquired using a custom-built spectrophotometric reaction cell which permits in situ observation under hydrothermal conditions. The results of this study indicate that the reaction kinetics of dilute aspartic acid solutions are significantly different depending on the presence or absence of catalytic surfaces such as standard metal alloys. The spectroscopic data presented here represent the first direct observations, in situ and in real time, of an amino acid reacting in a hydrothermal solution. Quantitative kinetic information, including rate constants, concentration versus time profiles, and calculations of the individual component spectra, was obtained from the data using a chemometric approach based on factor analysis/principle component analysis which treats the rate expressions simultaneously as a system of differential algebraic equations (DAE) of index 1. Identification of the products was confirmed where possible by high pressure anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The reaction kinetics of aspartic acid under hydrothermal conditions was observed to be highly complex, in contrast to previous studies which indicated almost exclusively deamination. At lower temperatures (120-170 °C), several different reaction pathways were observed, including decarboxylation and polymerization, and the catalytic effects of reactor surfaces on the aspartic acid system were clearly demonstrated. At higher temperatures (above 170 °C), aspartic acid exhibited highly complex behaviour, with evidence indicating that it can simultaneously dimerize and cyclize, deaminate (by up to two pathways), and decarboxylate (by up to two pathways). These higher temperature kinetics were not fully resolvable in a quantitative manner due to the complexity of the system and the constraints of UV spectroscopy. The results of this study provide strong evidence that the reaction
Picosecond kinetic measurements of the metalloporphyrin fluorescence
Aaviskoq, Y.Y.; Freiburg, A.M.; Savikhin, S.F.; Stel' makh, G.F.
1986-08-01
The authors attempt to directly measure the deactivation kinetics of the short-lived excited S/sub 2/ and S/sub 1/ states of metalloporphyrins and compare the results with those obtained by other (either direct or indirect) methods. The studies were carried out on diamagnetic metallocomplexes of tetrabenzoporphyrin (MeTBP) exhibiting measurable fluorescence from the S/sub 1/ and S/sub 2/ states. The complexes with Lu, Cd, and Zn in dilute solutions were studied at room temperature. The results of direct kinetic experiments confirm the previously obtained data on picosecond deactivation processes in photoexcited metalloporphyrins.
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.
Kinetics of Nitrogen Diffusion in Granular Manganese
ZHANG Jin-zhu; XU Chu-shao; ZHAO Yue-ping
2008-01-01
The kinetics and the influence of time on granular manganese nitriding were studied by means of a vacuum resistance furnace, X-ray diffraction technique, and LECO TC-436 oxygen/nitrogen determinator. The longer the nitriding time, the more the nitrogen pickup. Except for a trace of oxide MnO that developed, the metal manganese could thoroughly be nitrided to form Mn4N and a little ζ-phase (the stoichiometric components as Mn2N) with the nitriding time lasting. A kinetic model is developed to reveal the nitriding situation and agrees well with the experimental results.
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)
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 quantiti...... in the two pictures, containing different physical information, but the relation between them is well defined. We discuss this relation and illustrate its nature by examples referring to a free particle and to a ground-state hydrogen atom....
Kinetic Alfven wave turbulence in space plasmas
Sharma, R.P. [Plasma Simulation Laboratory, Centre for Energy Studies, Indian Institute of Technology, Delhi-110016, New Delhi (India); Kumar, Sachin, E-mail: dynamicalfven@gmail.co [Plasma Simulation Laboratory, Centre for Energy Studies, Indian Institute of Technology, Delhi-110016, New Delhi (India)
2010-07-26
This work presents the derivation of nonlinear coupled equations for the evolution of solar wind turbulence. These equations are governing the coupled dynamics of kinetic Alfven wave and ion acoustic wave. Numerical simulation of these equations is also presented. The ponderomotive nonlinearity is incorporated in the wave dynamics. Filamentation of kinetic Alfven wave and the turbulent spectra are presented in intermediate-{beta} plasmas at heliocentric distances (0.3 AU{<=}r<1.0 AU). The growing filaments and steeper turbulent spectra (of power law k{sup -S}, 5/3{<=}S{<=}3) can be responsible for plasma heating and particle acceleration in solar wind.
Determination of rate distributions from kinetic experiments.
Steinbach, P J; Chu, K; Frauenfelder, H; Johnson, J B; Lamb, D C; Nienhaus, G U; Sauke, T B; Young, R D
1992-01-01
Rate processes in proteins are often not adequately described by simple exponential kinetics. Instead of modeling the kinetics in the time domain, it can be advantageous to perform a numerical inversion leading to a rate distribution function f(lambda). The features observed in f(lambda) (number, positions, and shapes of peaks) can then be interpreted. We discuss different numerical techniques for obtaining rate distribution functions, with special emphasis on the maximum entropy method. Examples are given for the application of these techniques to flash photolysis data of heme proteins.
Langmuir wave filamentation in the kinetic regime
Silantyev, Denis A; Rose, Harvey A
2016-01-01
Nonlinear Langmuir wave in the kinetic regime $k\\lambda_D\\gtrsim0.2$ has a transverse instability, where $k$ is the wavenumber and $\\lambda_D$ is the Debye length. The nonlinear stage of that instability development leads to the filamentation of Langmuir waves. Here we study the linear stage of transverse instability of both Bernstein-Greene-Kruskal (BGK) modes and dynamically prepared BGK-like initial conditions to find the same instability growth rate suggesting the universal mechanism for the kinetic saturation of stimulated Raman scatter in laser-plasma interaction experiments. Multidimensional Vlasov simulations results are compared to the theoretical predictions.
Concepts of Modern Catalysis and Kinetics
Chorkendorff, I
2003-01-01
Until now, the literature has offered a rather limited approach to the use of fundamental kinetics and their application to catalytic reactions. Subsequently, this book spans the full range from fundamentals of kinetics and heterogeneous catalysis via modern experimental and theoretical results of model studies to their equivalent large-scale industrial production processes. The result is key knowledge for students at technical universities and professionals already working in industry. "...such an enterprise will be of great value to the community, to professionals as well as graduate an
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.
Kinetic models with randomly perturbed binary collisions
Bassetti, Federico; Toscani, Giuseppe
2010-01-01
We introduce a class of Kac-like kinetic equations on the real line, with general random collisional rules, which include as particular cases models for wealth redistribution in an agent-based market or models for granular gases with a background heat bath. Conditions on these collisional rules which guarantee both the existence and uniqueness of equilibrium profiles and their main properties are found. We show that the characterization of these stationary solutions is of independent interest, since the same profiles are shown to be solutions of different evolution problems, both in the econophysics context and in the kinetic theory of rarefied gases.
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
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.
Kinetics of glucose transport in rat muscle
Ploug, Thorkil; Galbo, H; Vinten, J
1987-01-01
-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...
Introducing Michaelis-Menten Kinetics through Simulation
Halkides, Christopher J.; Herman, Russell
2007-01-01
We describe a computer tutorial that introduces the concept of the steady state in enzyme kinetics. The tutorial allows students to produce graphs of the concentrations of free enzyme, enzyme-substrate complex, and product versus time in order to learn about the approach to steady state. By using a range of substrate concentrations and rate…
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...
Enzyme kinetics of conjugating enzymes: PAPS sulfotransferase.
James, Margaret O
2014-01-01
The sulfotransferase (SULT) enzymes catalyze the formation of sulfate esters or sulfamates from substrates that contain hydroxy or amine groups, utilizing 3'-phosphoadenosyl-5'-phosphosulfate (PAPS) as the donor of the sulfonic group. The rate of product formation depends on the concentrations of PAPS and substrate as well as the sulfotransferase enzyme; thus, if PAPS is held constant while varying substrate concentration (or vice versa), the kinetic constants derived are apparent constants. When studied over a narrow range of substrate concentrations, classic Michaelis-Menten kinetics can be observed with many SULT enzymes and most substrates. Some SULT enzymes exhibit positive or negative cooperativity during conversion of substrate to product, and the kinetics fit the Hill plot. A characteristic feature of most sulfotransferase-catalyzed reactions is that, when studied over a wide range of substrate concentrations, the rate of product formation initially increases as substrate concentration increases, then decreases at high substrate concentrations, i.e., they exhibit substrate inhibition or partial substrate inhibition. This chapter gives an introduction to sulfotransferases, including a historical note, the nomenclature, a description of the function of SULTs with different types of substrates, presentation of examples of enzyme kinetics with SULTs, and a discussion of what is known about mechanisms of substrate inhibition in the sulfotransferases.
Kinetics of asphaltene precipitation from crude oils
Maqbool, T.; Hussein, I.A.; Fogler, H.S. [Michigan Univ., Ann Arbor (United States). Dept. of Chemical Engineering
2008-07-01
The kinetics of asphaltene precipitation from crude oils was investigated using n-alkane precipitants. Recent studies have shown that there is a kinetic phenomenon associated with asphaltene precipitation. This study showed that the time needed to precipitate the asphaltenes can vary from a few minutes to several months, depending on the amount of n-alkane precipitant added. As such, the onset of asphaltene precipitation is a function of the concentration of precipitant and time. A technique to quantify the amount of asphaltenes precipitated as a function of time and precipitant concentration was presented. This study also investigated the kinetic effects caused by various precipitants. Optical microscopy was used to monitor the growth of asphaltene aggregates with time. Refractive index measurements provided further insight into the kinetics of asphaltene precipitation. Polarity based fractionation and dielectric constant measurements were used to compare the nature of asphaltenes precipitated early in the precipitation process with the asphaltenes precipitated at later times. It was concluded that asphaltenes precipitating at different times from the same crude oil-precipitant mixture are different from one another. 3 refs.
Collapse of a Bose gas: Kinetic approach
Shyamal Biswas
2012-08-01
We have analytically explored the temperature dependence of critical number of particales for the collapse of a harmonically trapped attractively interacting Bose gas below the condensation point by introducing a kinetic approach within the Hartee-Fock approximation. The temperature dependence obtained by this easy approach is consistant with that obtained from the scaling theory.
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...
Kinetic Equations for Describing Phosphorus Transport
无
2001-01-01
@@Studies on kinetics of adsorption and release of phosphorus by soil,a new field in soil chemistry,began only over ten years ago (He et al.,1989; Wang and Zhu,1988;Zhang and Zhang,1991; Lin,1989; Lin and Xue,1989; Jiang,1993; Xue et al.,1995;LU et al.,1997).
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 eg
Electrode kinetics and double layer structure
Timmer, B.; Sluyters-Rehbach, M.; Sluyters, J.H.
1969-01-01
Several electrochemical methods have been developed in recent years for the study of the kinetic parameters of electrode reactions. These methods have been used for obtaining an abundance of experimental data for the standard heterogeneous rate constant, ksh, of electrode reactions, mostly limited t
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…
Studies on the kinetics of alcoholic fermentation
Godia i Casablancas, F.; Casas Alvero, C.; Sola Ferrando, C.
1984-01-01
Yeast isolated from a must was used to ferment a medium containing 50, 98, 150, or 188 g glucose L and the kinetics of cell growth, EtOH formation, and glucose utilization were determined. The results did not agree with the results obtained using 9 different model equations. The models are therefore unsatisfactory.
Kinetic Analysis of Char Thermal Deactivation
Zolin, Alfredo; Jensen, Anker; Dam-Johansen, Kim
2001-01-01
data for all chars obtained from the TGA, kinetic parameters in an annealing model reported in the literature were determined. A shifted Gamma distribution taking into account a positive activation energy at the beginning of deactivation, as well as a lower bound of char reactivity corresponding...
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...
Chibisov, D. V.; Mikhailenko, V. S.; Stepanov, K. N.
2011-10-01
An extension of hydrodynamic D'Angelo mode of inhomogeneous sheared plasma flow along the magnetic field into the short wavelength range, where the hydrodynamic treatment is not valid, has been considered. We find that D'Angelo mode in this wavelength range is excited by inverse ion Landau damping and is a shear flow driven ion-kinetic mode.
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...
A microcomputer spreadsheet for aminoglycoside kinetics.
Kiacz, B J
1990-05-01
Development of an aminoglycoside monitoring program need not entail large capital expenditures for pharmacokinetic software. Microsoft's Excel spreadsheet was used to develop a single compartment, first-order kinetics template for individualized aminoglycoside dosing. The formulas employed may be adapted to virtually any other microcomputer spreadsheet package to provide accurate professional results.
Hydrodynamic transport functions from quantum kinetic theory
Calzetta, E A; Ramsey, S
2000-01-01
Starting from the quantum kinetic field theory [E. Calzetta and B. L. Hu, Phys. Rev. D37, 2878 (1988)] constructed from the closed-time-path (CTP), two-particle-irreducible (2PI) effective action we show how to compute from first principles the shear and bulk viscosity functions in the hydrodynamic-thermodynamic regime. For a real scalar field with $\\lambda \\Phi ^{4}$ self-interaction we need to include 4 loop graphs in the equation of motion. This work provides a microscopic field-theoretical basis to the ``effective kinetic theory'' proposed by Jeon and Yaffe [S. Jeon and L. G. Yaffe, Phys. Rev. D53, 5799 (1996)], while our result for the bulk viscosity reproduces their expression derived from linear response theory and the imaginary-time formalism of thermal field theory. Though unavoidably involved in calculations of this sort, we feel that the approach using fundamental quantum kinetic field theory is conceptually clearer and methodically simpler than the effective kinetic theory approach, as the success...
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
Adsorption Kinetics in Nanoscale Porous Coordination Polymers
Nune, Satish K.; Thallapally, Praveen K.; McGrail, Benard Peter; Annapureddy, Harsha V. R.; Dang, Liem X.; Mei, Donghai; Karri, Naveen; Alvine, Kyle J.; Olszta, Matthew J.; Arey, Bruce W.; Dohnalkova, Alice
2015-10-07
Nanoscale porous coordination polymers were synthesized using simple wet chemical method. The effect of various polymer surfactants on colloidal stability and shape selectivity was investigated. Our results suggest that the nanoparticles exhibited significantly improved adsorption kinetics compared to bulk crystals due to decreased diffusion path lengths and preferred crystal plane interaction.
Kinetic properties of fractal stellar media
Chumak, O. V.; Rastorguev, A. S.
2017-01-01
Kinetic processes in fractal stellar media are analysed in terms of the approach developed in our earlier paper involving a generalization of the nearest neighbour and random force distributions to fractal media. Diffusion is investigated in the approximation of scale-dependent conditional density based on an analysis of the solutions of the corresponding Langevin equations. It is shown that kinetic parameters (time-scales, coefficients of dynamic friction, diffusion, etc.) for fractal stellar media can differ significantly both qualitatively and quantitatively from the corresponding parameters for a quasi-uniform random media with limited fluctuations. The most important difference is that in the fractal case, kinetic parameters depend on spatial scalelength and fractal dimension of the medium studied. A generalized kinetic equation for stellar media (fundamental equation of stellar dynamics) is derived in the Fokker-Planck approximation with the allowance for the fractal properties of the spatial stellar density distribution. Also derived are its limit forms that can be used to describe small departures of fractal gravitating medium from equilibrium.
A kinetic model of zircon thermoluminescence
Turkin, A.A.; Es, H.J. van; Vainshtein, D.I.; Hartog, H.W. den
A kinetic model of zircon thermoluminescence (TL) has been constructed to simulate the processes and stages relevant to thermoluminescent dating such as: filling of electron and hole traps during the excitation stage both for natural and laboratory irradiation; the time dependence of fading after
Thermodynamics, Kinetics and Microstructural Evolution during Nitrocarburising
Somers, Marcel A.J.; Du, Hong
2000-01-01
is associated with a strong absorption of carbon from the nitrocarburising gas: the nitrogen contnt in the layer increases gradually, while the carbon content decreases accordingly. Layer growth kinetics depends strongly on the distribution of phases in the compound layer. Fastest growth was observed...
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 tereph
Kinetic modeling of reactions in Foods
Boekel, van M.A.J.S.
2008-01-01
The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to effec
Simulation of Adaptive Kinetic Architectural Structures
Kirkegaard, Poul Henning
2010-01-01
This project deals with shape control of kinetic structures within the field of adaptable architecture. Here a variable geometry truss cantilever structure is analyzed using MATLAB/SIMULINK and the multibody dynamic software MSC Adams. Active shape control of a structure requires that the kinematic...
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 wor
Introducing Michaelis-Menten Kinetics through Simulation
Halkides, Christopher J.; Herman, Russell
2007-01-01
We describe a computer tutorial that introduces the concept of the steady state in enzyme kinetics. The tutorial allows students to produce graphs of the concentrations of free enzyme, enzyme-substrate complex, and product versus time in order to learn about the approach to steady state. By using a range of substrate concentrations and rate…
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
Chemical Dosing and First-Order Kinetics
Hladky, Paul W.
2011-01-01
College students encounter a variety of first-order phenomena in their mathematics and science courses. Introductory chemistry textbooks that discuss first-order processes, usually in conjunction with chemical kinetics or radioactive decay, stop at single, discrete dose events. Although single-dose situations are important, multiple-dose events,…
Nonlinear Kinetic Dynamics of Magnetized Weibel Instability
Palodhi, L; Pegoraro, F
2010-01-01
Kinetic numerical simulations of the evolution of the Weibel instability during the full nonlinear regime are presented. The formation of strong distortions in the electron distribution function resulting in formation of strong peaks in it and their influence on the resulting electrostatic waves are shown.
Enzyme kinetics informatics: from instrument to browser.
Swainston, Neil; Golebiewski, Martin; Messiha, Hanan L; Malys, Naglis; Kania, Renate; Kengne, Sylvestre; Krebs, Olga; Mir, Saqib; Sauer-Danzwith, Heidrun; Smallbone, Kieran; Weidemann, Andreas; Wittig, Ulrike; Kell, Douglas B; Mendes, Pedro; Müller, Wolfgang; Paton, Norman W; Rojas, Isabel
2010-09-01
A limited number of publicly available resources provide access to enzyme kinetic parameters. These have been compiled through manual data mining of published papers, not from the original, raw experimental data from which the parameters were calculated. This is largely due to the lack of software or standards to support the capture, analysis, storage and dissemination of such experimental data. Introduced here is an integrative system to manage experimental enzyme kinetics data from instrument to browser. The approach is based on two interrelated databases: the existing SABIO-RK database, containing kinetic data and corresponding metadata, and the newly introduced experimental raw data repository, MeMo-RK. Both systems are publicly available by web browser and web service interfaces and are configurable to ensure privacy of unpublished data. Users of this system are provided with the ability to view both kinetic parameters and the experimental raw data from which they are calculated, providing increased confidence in the data. A data analysis and submission tool, the kineticswizard, has been developed to allow the experimentalist to perform data collection, analysis and submission to both data resources. The system is designed to be extensible, allowing integration with other manufacturer instruments covering a range of analytical techniques.
Oscillatory quintessence with nonminimal kinetic coupling
Sadjadi, H Mohseni
2013-01-01
The rapid oscillating scalar field is considered as the quintessence in the framework of nonminimal kinetic coupling model. Evolution of dark matter and dark energy in the spatially flat Friedmann-Robertson-Walker universe are studied and the possibility of reentrance of the universe to a normal expansion phase without acceleration, and also the coincidence problem are investigated.
Progress in antenna coupled kinetic inductance detectors
Baryshev, A.; Baselmans, J.J.A.; Freni, A.; Gerini, G.; Hoevers, H.; 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 wo
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...
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...
Solution Kinetics Database on the Web
SRD 40 NDRL/NIST Solution Kinetics Database on the Web (Web, free access) Data for free radical processes involving primary radicals from water, inorganic radicals and carbon-centered radicals in solution, and singlet oxygen and organic peroxyl radicals in various solvents.
Kinetics methods for clinical epidemiology problems.
Corlan, Alexandru Dan; Ross, John
2015-11-17
Calculating the probability of each possible outcome for a patient at any time in the future is currently possible only in the simplest cases: short-term prediction in acute diseases of otherwise healthy persons. This problem is to some extent analogous to predicting the concentrations of species in a reactor when knowing initial concentrations and after examining reaction rates at the individual molecule level. The existing theoretical framework behind predicting contagion and the immediate outcome of acute diseases in previously healthy individuals is largely analogous to deterministic kinetics of chemical systems consisting of one or a few reactions. We show that current statistical models commonly used in chronic disease epidemiology correspond to simple stochastic treatment of single reaction systems. The general problem corresponds to stochastic kinetics of complex reaction systems. We attempt to formulate epidemiologic problems related to chronic diseases in chemical kinetics terms. We review methods that may be adapted for use in epidemiology. We show that some reactions cannot fit into the mass-action law paradigm and solutions to these systems would frequently exhibit an antiportfolio effect. We provide a complete example application of stochastic kinetics modeling for a deductive meta-analysis of two papers on atrial fibrillation incidence, prevalence, and mortality.
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...
A multigrid method applied to reactor kinetics
Nguyen, T.S
2006-07-01
The control and safety analysis of a nuclear reactor strongly relies on numerical simulation of reactor dynamics, in which the neutronics computation is one of the most important tasks. It is necessary to utilize a full three-dimensional model of neutron kinetics for satisfactory results but this requires an extensive computation. The purpose of this research is to explore an efficient method for accurate solution of the spatial neutron kinetics problem. The kinetics of neutrons in a nuclear reactor of practical interest is adequately represented by the few-group diffusion equations with delayed neutron effects taken into account. For solving such a space-time equation system, finite difference methods, though the simplest, must work with a very fine-mesh grid, resulting in an extremely large algebraic system whose solution by basic numerical methods encounters inefficiency. Coarse-mesh methods increase computational efficiency by reducing the number of discretized equations. However, by adding more complexity and limitations, the coarse-mesh computation is still rather time-consuming. Multigrid methods may provide an optimal solution for a large, sparse algebraic system arising from discretization of a partial differential equation or system but have not found many applications in reactor physics due to inherent difficulties. In this research, a finite difference method is used for discretization of the kinetics equations and a multigrid solver is developed to solve the discretized equation system. The Additive Correction Multigrid, the simplest and cheapest method in the multigrid family, is used for grid coarsening, allowing for reaching the coarsest grid without any difficulties. By avoiding the singularity and indefiniteness of the discretized system, the Red-Black Gauss-Seidel method is suited for multigrid smoothing and favours an implementation of parallel computation. Numerical experiments show that our multigrid solver is not only much faster than any
Preformed Seeds Modulate Native Insulin Aggregation Kinetics.
Dutta, Colina; Yang, Mu; Long, Fei; Shahbazian-Yassar, Reza; Tiwari, Ashutosh
2015-12-10
Insulin aggregates under storage conditions via disulfide interchange reaction. It is also known to form aggregates at the site of repeated injections in diabetes patients, leading to injection amyloidosis. This has fueled research in pharmaceutical and biotechnology industry as well as in academia to understand factors that modulate insulin stability and aggregation. The main aim of this study is to understand the factors that modulate aggregation propensity of insulin under conditions close to physiological and measure effect of "seeds" on aggregation kinetics. We explored the aggregation kinetics of insulin at pH 7.2 and 37 °C in the presence of disulfide-reducing agent dithiothreitol (DTT), using spectroscopy (UV-visible, fluorescence, and Fourier transform infrared spectroscopy) and microscopy (scanning electron microscopy, atomic force microscopy) techniques. We prepared insulin "seeds" by incubating disulfide-reduced insulin at pH 7.2 and 37 °C for varying lengths of time (10 min to 12 h). These seeds were added to the native protein and nucleation-dependent aggregation kinetics was measured. Aggregation kinetics was fastest in the presence of 10 min seeds suggesting they were nascent. Interestingly, intermediate seeds (30 min to 4 h incubation) resulted in formation of transient fibrils in 4 h that converted to amorphous aggregates upon longer incubation of 24 h. Overall, the results show that insulin under disulfide reducing conditions at pH and temperature close to physiological favors amorphous aggregate formation and seed "maturity" plays an important role in nucleation dependent aggregation kinetics.
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.
Nariyuki, Y; Nariyuki, Yasuhiro; Hada, Tohru
2006-01-01
Parametric instabilities of parallel propagating,circularly polarized Alfv\\'en waves in a uniform background plasma is studied, within a framework of one-dimensional Vlasov equation for ions and massless electron fluid, so that kinetic perturbations in the longitudinal direction (ion Landau damping) are included. The present formulation also includes the Hall effect. The obtained results agree well with relevant analysis in the past, suggesting that kinetic effects in the longitudinal direction play essential roles in the parametric instabilities of Alfven waves when the kinetic effects react "passively". Furthermore, existence of the kinetic parametric instabilities is confirmed for the regime with small wave number daughter waves. Growth rates of these instabilities are sensitive to ion temperature.
Fransson, Ann-Britt L; Borén, Linnéa; Pàmies, Oscar; Bäckvall, Jan-E
2005-04-01
[reaction: see text] An efficient kinetic resolution of racemic gamma-hydroxy amides 1 was performed via Pseudomas cepacia lipase (PS-C)-catalyzed transesterification. The enzyme PS-C tolerates both variation in the chain length and different functionalities giving good to high enantioselectivity (E values of up to >250). The combination of enzymatic kinetic resolution with a ruthenium-catalyzed racemization led to a dynamic kinetic resolution. The use of 2,4-dimethyl-3-pentanol as a hydrogen source to suppress ketone formation in the dynamic kinetic resolution yields the corresponding acetates in good yield and good to high enantioselectivity (ee's up to 98%). The synthetic utility of this procedure was illustrated by the practical synthesis of the versatile intermediate gamma-lactone (R)-5-methyltetrahydrofuran-2-one.
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 and Thermodynamic Studies of Charge-Transfer Complex ...
Kinetic and Thermodynamic Studies of Charge-Transfer Complex Formation ... The activation parameters, i.e. activation energy, enthalpy, and entropy of ... KEYWORDS Charge-transfer complex, imipramine, DDQ, ionization potential, kinetic, ...
Mathematical Modelling of Thermal Degradation Kinetics of Ascorbic ...
However, adequate study has not been conducted to exploit the potential of this ... of ascorbic acid in yeabesha gomen fitted first-order reaction kinetic model ... Activation energy for ascorbic degeneration kinetics of yeabesha gomen was ...
A Comparative Kinetic Study of Acidic Hydrolysis of Wastes ...
A Comparative Kinetic Study of Acidic Hydrolysis of Wastes Cellulose from Agricultural Derived Biomass. ... fuels and chemicals offers potential economical, environmental and strategic ... Keywords: Agricultural wastes; cellulose; acid hydrolysis; first-order rate kinetics; activation energy, Arrhenius equation ... Article Metrics.
Comparison of kinetic characteristics of xylanases from Aspergillus ...
LAB
2013-05-08
May 8, 2013 ... Commercial pure xylanase was derived from genetically modified microorganism ... Kinetic and thermodynamic studies of the xylanases. The kinetic ..... Effect of corn cobs concentration on xylanase ... Food Chem. 44:.
Copolymerization Kinetics of Ethylene Oxide and Propylene Oxide
尹红; 陈志荣
2002-01-01
The copolymerization kinetics of ethylene oxide and propylene oxide in an atomizing-circulation reactorunder semi-continuous operation is studied which is of great importance for molecular designation. The kineticparameters are obtained by numerical optimization of the kinetic model.
Deconvolution of ultrafast kinetic data with inverse filtering
Banyasz, Akos [Department of Physical Chemistry, Eoetvoes University, P.O. Box 32, H-1518 Budapest 112 (Hungary); Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Matyus, Edit [Department of Physical Chemistry, Eoetvoes University, P.O. Box 32, H-1518 Budapest 112 (Hungary); Keszei, Erno [Department of Physical Chemistry, Eoetvoes University, P.O. Box 32, H-1518 Budapest 112 (Hungary)]. E-mail: keszei@chem.elte.hu
2005-02-01
Due to limitations of pulse widths in ultrafast laser or electron pulse kinetic measurements, in the case of subpicosecond characteristic times of the studied reactions, deconvolution with the pulses always distorts the kinetic signal. Here, we describe inverse filtering based on Fourier transformations to deconvolve measured ultrafast kinetic data without evoking a particular kinetic mechanism. Deconvolution methods using additional Wiener filtering or two-parameter regularization are found to give reliable results for simulated as well as experimental data.
A Century of Enzyme Kinetic Analysis, 1913 to 2013
Johnson, Kenneth A.
2013-01-01
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. ...
Investigation of the Kinetic Energy Characterization of Advanced Ceramics
2015-04-01
ARL-TR-7263 ● APR 2015 US Army Research Laboratory Investigation of the Kinetic Energy Characterization of Advanced Ceramics ...Kinetic Energy Characterization of Advanced Ceramics by Tyrone L Jones Weapons and Materials Research Directorate, ARL...Kinetic Energy Characterization of Advanced Ceramics 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Tyrone L
KINETICS OF QUERCETIN NITRATIO N BY HORSERADISH PEROXIDASE
Andrija Šmelcerović
2013-03-01
Full Text Available In this study we investigated the kinetics of the nitration of quercetin by horseradish peroxidase. Quercetin nitration reaction was followed by recording the spectral changes over the time at 380 nm. The reaction rate increases with increasing of the quercetin concentration and follows the Michaelis-Menten type kinetics. Kinetic parameters of the studied enzymatic reaction were determined.
Modelling dimercaptosuccinic acid (DMSA) plasma kinetics in humans
van Eijkeren, Jan C H; Olie, J Daniël N; Bradberry, Sally M; Vale, J Allister; de Vries, Irma; Meulenbelt, Jan; Hunault, Claudine C
2016-01-01
CONTEXT: No kinetic models presently exist which simulate the effect of chelation therapy on lead blood concentrations in lead poisoning. OBJECTIVE: Our aim was to develop a kinetic model that describes the kinetics of dimercaptosuccinic acid (DMSA; succimer), a commonly used chelating agent, that c
Mathematics analysis of polymerase chain reaction kinetic curves.
Sochivko, D G; Fedorov, A A; Varlamov, D A; Kurochkin, V E; Petrov, R V
2016-01-01
The paper reviews different approaches to the mathematical analysis of polymerase chain reaction (PCR) kinetic curves. The basic principles of PCR mathematical analysis are presented. Approximation of PCR kinetic curves and PCR efficiency curves by various functions is described. Several PCR models based on chemical kinetics equations are suggested. Decision criteria for an optimal function to describe PCR efficiency are proposed.
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.
Kinetic titration series with biolayer interferometry.
Daniel Frenzel
Full Text Available 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.
Perspective: Stochastic algorithms for chemical kinetics.
Gillespie, Daniel T; Hellander, Andreas; Petzold, Linda R
2013-05-01
We outline our perspective on stochastic chemical kinetics, paying particular attention to numerical simulation algorithms. We first focus on dilute, well-mixed systems, whose description using ordinary differential equations has served as the basis for traditional chemical kinetics for the past 150 years. For such systems, we review the physical and mathematical rationale for a discrete-stochastic approach, and for the approximations that need to be made in order to regain the traditional continuous-deterministic description. We next take note of some of the more promising strategies for dealing stochastically with stiff systems, rare events, and sensitivity analysis. Finally, we review some recent efforts to adapt and extend the discrete-stochastic approach to systems that are not well-mixed. In that currently developing area, we focus mainly on the strategy of subdividing the system into well-mixed subvolumes, and then simulating diffusional transfers of reactant molecules between adjacent subvolumes together with chemical reactions inside the subvolumes.
Influence of surface charge on wetting kinetics.
Puah, Lee San; Sedev, Rossen; Fornasiero, Daniel; Ralston, John; Blake, Terry
2010-11-16
The wettability of a titania surface, partially covered with octadecyltrihydrosilane, has been investigated as a function of solution pH. The results show that surface charge affects both static wettability and wetting kinetics. The static contact angle decreases above and below the point of zero charge of the titania surface in a Lippman-like manner as the pH is altered. The dependence of dynamic contact angle on velocity is also affected by pH. The molecular-kinetic theory (MKT) is used to interpret the dynamic contact angle data. The frequency of molecular displacement κ(0) strongly varies with surface charge, whereas the mean molecular displacement length λ is essentially unaffected. There is an exponential dependence of contact-line friction upon work of adhesion, which is varied simply by altering the pH.
Kinetic and hydrodynamic models of chemotactic aggregation
Chavanis, Pierre-Henri
2007-01-01
We derive general kinetic and hydrodynamic models of chemotactic aggregation that describe certain features of the morphogenesis of biological colonies (like bacteria, amoebae, endothelial cells or social insects). Starting from a stochastic model defined in terms of N coupled Langevin equations, we derive a nonlinear mean field Fokker-Planck equation governing the evolution of the distribution function of the system in phase space. By taking the successive moments of this kinetic equation and using a local thermodynamic equilibrium condition, we derive a set of hydrodynamic equations involving a damping term. In the limit of small frictions, we obtain a hyperbolic model describing the formation of network patterns (filaments) and in the limit of strong frictions we obtain a parabolic model which is a generalization of the standard Keller-Segel model describing the formation of clusters (clumps). Our approach connects and generalizes several models introduced in the chemotactic literature. We discuss the anal...
Kinetics of Leaching Calcium from Dolomite
Azizi, A.
2011-06-01
Full Text Available Magnesia is obtained from magnesite ore and the production process applied should remove accompanying minerals that reduce its refractoriness. Given that magnesite reservoirs are more exploited and largely exhausted, there is a growing need for production of magnesia on the basis of other magnesium minerals. Dolomite is a promising source of magnesia because it forms large deposits, is easy to exploit, and generally contains a small quantity of impurities.The kinetics of calcium leaching from dolomite by magnesium-nitrate solution has been studied. The research program included the influence of temperature, mass fraction of magnesium nitrate in solution, dolomite particle size and leaching time. Time dependence of calcium leaching is described by relevant kinetic equations. Rate coefficients, their temperature dependence and Arrhenius activation energy have been determined.
Thermal Decomposition Kinetics of Triethylene Glycol Dinitrate
CHEN,Pei(陈沛); ZHAO,Feng-Qi(赵凤起); LUO,Yang(罗阳); HU,Rong-Zu(胡荣祖); LI,Shang-Wen(李上文); GAO,Yin(高茵)
2004-01-01
The thermal behavior and kinetic parameters of the decomposition reaction of triethylene glycol dinitrate (TEGDN) in a temperature-programmed mode at different pressures (0.1, 2, 4 and 6 MPa) have been investigated by means of DSC and TG-DTG. The results show that the properties of the thermal decomposition of TEGDN are affected by the change of pressure, and the kinetic model function, the apparent activation energy Ea and TEGDN obtained by the values Teo and Tpo of the onset temperature Te and the peak temperature TP when the heating rate tends to zero are 191.05,209.86 ℃ at 0.1 MPa, 207.59 and 221.65 ℃ at 2 MPa, respectively.
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 begun...... immediately by artificial ventilation and simultaneous external chest compressions. Epinephrine was administered after 8 min of CPR. One group (n = 5) of animals received no buffer treatment while another (n = 5) received an infusion of 75 mmol sodium bicarbonate and a third group (n = 5) received...... an equivalent amount of tris-buffer mixture. The results of these experiments, as well as previously described circulatory variables during CPR, were analyzed using a computer model describing the CO2 kinetics of the pig. Our main finding was that PaCO2 was positively correlated to cardiac output during CPR...
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.
Adsorption kinetics of methyl violet onto perlite.
Doğan, Mehmet; Alkan, Mahir
2003-01-01
This study examines adsorption kinetics and activation parameters of methyl violet on perlite. The effect of process parameters like contact time, concentration of dye, temperature and pH on the extent of methyl violet adsorption from solution has been investigated. Results of the kinetic studies show that the adsorption reaction is first order with respect to dye solution concentration with activation energy of 13.2 kJ mol(-1). This low activation energy value indicates that the adsorption reaction is diffusion controlled. The activation parameters using Arrhenius and Eyring equations have been calculated. Adsorption increases with increase of variables such as contact time, initial dye concentration, temperature and pH.
Gaussian kinetic model for granular gases.
Dufty, James W; Baskaran, Aparna; Zogaib, Lorena
2004-05-01
A kinetic model for the Boltzmann equation is proposed and explored as a practical means to investigate the properties of a dilute granular gas. It is shown that all spatially homogeneous initial distributions approach a universal "homogeneous cooling solution" after a few collisions. The homogeneous cooling solution (HCS) is studied in some detail and the exact solution is compared with known results for the hard sphere Boltzmann equation. It is shown that all qualitative features of the HCS, including the nature of overpopulation at large velocities, are reproduced by the kinetic model. It is also shown that all the transport coefficients are in excellent agreement with those from the Boltzmann equation. Also, the model is specialized to one having a velocity independent collision frequency and the resulting HCS and transport coefficients are compared to known results for the Maxwell model. The potential of the model for the study of more complex spatially inhomogeneous states is discussed.
A KINETIC DATABASE FOR ASTROCHEMISTRY (KIDA)
Wakelam, V.; Pavone, B.; Hebrard, E.; Hersant, F. [University of Bordeaux, LAB, UMR 5804, F-33270 Floirac (France); Herbst, E. [Departments of Physics, Astronomy, and Chemistry, The Ohio State University, Columbus, OH 43210 (United States); Loison, J.-C.; Chandrasekaran, V.; Bergeat, A. [University of Bordeaux, ISM, CNRS UMR 5255, F-33400 Talence (France); Smith, I. W. M. [University Chemical Laboratories, Lensfield Road, Cambridge CB2 1EW (United Kingdom); Adams, N. G. [Department of Chemistry, University of Georgia, Athens, GA 30602 (United States); Bacchus-Montabonel, M.-C. [LASIM, CNRS-UMR5579, Universite de Lyon (Lyon I), 43 Bvd. 11 Novembre 1918, F-69622 Villeurbanne Cedex (France); Beroff, K. [Institut des Sciences Moleculaires d' Orsay, CNRS and Universite Paris-Sud, F-91405 Orsay Cedex (France); Bierbaum, V. M. [Department of Chemistry and Biochemistry, Center for Astrophysics and Space Astronomy, University of Colorado, Boulder, CO 80309 (United States); Chabot, M. [Intitut de Physique Nucleaire d' Orsay, IN2P3-CNRS and Universite Paris-Sud, F-91406 Orsay Cedex (France); Dalgarno, A. [Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138 (United States); Van Dishoeck, E. F. [Leiden Observatory, Leiden University, P.O. Box 9513, NL-2300 RA Leiden (Netherlands); Faure, A. [UJF-Grenoble 1/CNRS, Institut de Planetologie et d' Astrophysique de Grenoble (IPAG) UMR 5274, F-38041 Grenoble (France); Geppert, W. D. [Department of Physics, University of Stockholm, Roslagstullbacken 21, S-10691 Stockholm (Sweden); Gerlich, D. [Technische Universitaet Chemnitz, Department of Physics, D-09107 Chemnitz (Germany); Galli, D. [INAF-Osservatorio Astrofisico di Arcetri, Largo E. Fermi 5, I-50125 Firenze (Italy); and others
2012-03-01
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.
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.
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
Energy transfer and kinetics in mechanochemistry.
Chen, Zhiliang; Lu, Shengyong; Mao, Qiongjing; Buekens, Alfons; Wang, Yuting; Yan, Jianhua
2017-09-13
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.
Sigmoid kinetics of protein crystal nucleation
Nanev, Christo N.; Tonchev, Vesselin D.
2015-10-01
A non-linear differential equation expressing the new phase nucleation rate in the different steps of the process (non-stationary and stationary nucleation and in the plateau region) is derived from basic principles of the nucleation theory. It is shown that one and the same sigmoid (logistic) function describes both nucleation scenarios: the one according to the classical theory, and the other according to the modern two-stage mechanism of protein crystal formation. Comparison to experimental data on both insulin crystal nucleation kinetics and on bovine β-lactoglobulin crystallization indicates a good agreement with the sigmoidal prediction. Experimental data for electrochemical nucleation and glass crystallization obey the same sigmoid time dependence, and suggest universality of this nucleation kinetics law.
Transport Reversal during Heteroexchange: A Kinetic Study
V. Makarov
2013-01-01
Full Text Available It is known that secondary transporters, which utilize transmembrane ionic gradients to drive their substrates up a concentration gradient, can reverse the uptake and instead release their substrates. Unfortunately, the Michaelis-Menten kinetic scheme, which is popular in transporter studies, does not include transporter reversal, and it completely neglects the possibility of equilibrium between the substrate concentrations on both sides of the membrane. We have developed a complex two-substrate kinetic model that includes transport reversal. This model allows us to construct analytical formulas allowing the calculation of a “heteroexchange” and “transacceleration” using standard Michaelis coefficients for respective substrates. This approach can help to understand how glial and other cells accumulate substrates without synthesis and are able to release such substrates and gliotransmitters.
Perspective: Stochastic algorithms for chemical kinetics
Gillespie, Daniel T.; Hellander, Andreas; Petzold, Linda R.
2013-05-01
We outline our perspective on stochastic chemical kinetics, paying particular attention to numerical simulation algorithms. We first focus on dilute, well-mixed systems, whose description using ordinary differential equations has served as the basis for traditional chemical kinetics for the past 150 years. For such systems, we review the physical and mathematical rationale for a discrete-stochastic approach, and for the approximations that need to be made in order to regain the traditional continuous-deterministic description. We next take note of some of the more promising strategies for dealing stochastically with stiff systems, rare events, and sensitivity analysis. Finally, we review some recent efforts to adapt and extend the discrete-stochastic approach to systems that are not well-mixed. In that currently developing area, we focus mainly on the strategy of subdividing the system into well-mixed subvolumes, and then simulating diffusional transfers of reactant molecules between adjacent subvolumes together with chemical reactions inside the subvolumes.
Kinetic study and mechanism of Niclosamide degradation
Zaazaa, Hala E.; Abdelrahman, Maha M.; Ali, Nouruddin W.; Magdy, Maimana A.; Abdelkawy, M.
2014-11-01
A spectrophotometric kinetic study of Niclosamide alkaline degradation as a function of drug concentration, alkaline concentration and temperature has been established utilizing double divisor-ratio spectra spectrophotometric method. The developed method allowed determination of Niclosamide in presence of its alkaline degradation products; namely; 2-chloro-4-nitro aniline (DEG I) and 5-chloro salicylic acid (DEG II) with characterization of its degradation mechanism. It was found that degradation kinetic of Niclosamide followed pseudo-first order under the established experimental conditions with a degradation rate constant (k) of 0.0829 mol/h and half life (t1/2) of 8.35 h. The overall degradation rate constant as a function of the temperature under the given conditions obeyed Arrhenius equation where the activation energy was calculated to be 3.41 kcal/mol.
Foot kinematics and kinetics during adolescent gait.
MacWilliams, Bruce A; Cowley, Matthew; Nicholson, Diane E
2003-06-01
Gait analysis models typically analyze the ankle joint complex and treat the foot as a rigid segment. Such models are inadequate for clinical decision making for patients with foot impairments. While previous multisegment foot models have been presented, no comprehensive kinematic and kinetic databases for normal gait exist. This study provides normative foot joint angles, moments and powers during adolescent gait. Eighteen subjects were evaluated using 19 retroreflective markers, six cameras, a pressure platform and a force plate. A nine-segment model determined 3D angles, 3D moments, and powers in eight joints or joint complexes. A complete sets of sagittal, coronal and frontal plane results are presented. Results indicate that single link models of the foot significantly overestimate ankle joint powers during gait. Understanding normal joint kinematics and kinetics during gait will provide a baseline for documenting impairments in patients with foot disorders.
Inflation Rates, Car Devaluation, and Chemical Kinetics
Pogliani, Lionello; Berberan-Santos, Màrio N.
1996-10-01
The inflation rate problem of a modern economy shows quite interesting similarities with chemical kinetics and especially with first-order chemical reactions. In fact, capital devaluation during periods of rather low inflation rates or inflation measured over short periods shows a dynamics formally similar to that followed by first-order chemical reactions and they can thus be treated by the aid of the same mathematical formalism. Deviations from this similarity occurs for higher inflation rates. The dynamics of price devaluation for two different types of car, a compact car and a luxury car, has been followed for seven years long and it has been established that car devaluation is a process that is formally similar to a zeroth-order chemical kinetic process disregarding the type of car, if car devaluation is much faster than money devaluation. In fact, expensive cars devaluate with a faster rate than inexpensive cars.
Reduced Chemical Kinetic Model for Titan Entries
Romain Savajano
2011-01-01
Full Text Available A reduced chemical kinetic model for Titan's atmosphere has been developed. This new model with 18 species and 28 reactions includes the mainfeatures of a more complete scheme, respecting the radiative fluxes. It has been verified against three key elements: a sensitivity analysis, the equilibrium chemical composition using shock tube simulations in CHEMKIN, and the results of computational fluid dynamics (CFDs simulations.
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.
Kinetics of hole nucleation in biomembrane rupture
Evans, Evan [Biomedical Engineering, Boston University, Boston, MA 02215 (United States); Smith, Benjamin A, E-mail: evanse@bu.edu [Departments of Physics and Pathology, University of British Columbia, Vancouver, BC, V6T 2A6 (Canada)
2011-09-15
The core component of a biological membrane is a fluid-lipid bilayer held together by interfacial-hydrophobic and van der Waals interactions, which are balanced for the most part by acyl chain entropy confinement. If biomembranes are subjected to persistent tensions, an unstable (nanoscale) hole will emerge at some time to cause rupture. Because of the large energy required to create a hole, thermal activation appears to be requisite for initiating a hole and the activation energy is expected to depend significantly on mechanical tension. Although models exist for the kinetic process of hole nucleation in tense membranes, studies of membrane survival have failed to cover the ranges of tension and lifetime needed to critically examine nucleation theory. Hence, rupturing giant ({approx}20 {mu}m) membrane vesicles ultra-slowly to ultra-quickly with slow to fast ramps of tension, we demonstrate a method to directly quantify kinetic rates at which unstable holes form in fluid membranes, at the same time providing a range of kinetic rates from <0.01 to >100 s{sup -1}. Measuring lifetimes of many hundreds of vesicles, each tensed by precision control of micropipette suction, we have determined the rates of failure for vesicles made from several synthetic phospholipids plus 1:1 mixtures of phospho- and sphingo-lipids with cholesterol, all of which represent prominent constituents of eukaryotic cell membranes. Plotted on a logarithmic scale, the failure rates for vesicles are found to rise dramatically with an increase in tension. Converting the experimental profiles of kinetic rates into changes of activation energy versus tension, we show that the results closely match expressions for thermal activation derived from a combination of meso-scale theory and molecular-scale simulations of hole formation. Moreover, we demonstrate a generic approach to transform analytical fits of activation energies obtained from rupture experiments into energy landscapes characterizing the
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.
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.
Enolisation Kinetics of m-Nitro Acetophenone
Swati Malhotra
2014-03-01
Full Text Available m-Nitroacetophenone was chosen for the study of kinetics of enolisation. The rate of the reaction was studied by iodination. The kinetics of the reaction was monitored under several conditions of variation of ketone concentration, dielectric constant of the medium , temperature, effect of catalyst etc. In addition to this four different amino acids viz. β-alanin, DL-alanin, L-alanin and Glycine were tested as catalyst for the enolisation process. The rate of enolisation was found to increase with the increase in then ketone concentration , percentage composition of the solvent mixture and also with the increase in the dipole moments of the amino acids. Pseudofirst order rate kinetics was operational and the rate constants were found to increase with the increase in the amino acid molarity. Linear plots obtained for log of rate constants versus reciprocal of temperature which were in good agreement with Arrhenius equation. The values of thermodynamic parameters like Entropy (∆S≠ , Enthalpy (∆H≠, energy of activation (∆Ea and Free energy(∆F≠ were calculated and were found to be 2.6186 e.u. , 20.85 e.u. ,23.46 k cal mol-1 and 20.0 k cal mol-1 respectively. © 2014 BCREC UNDIP. All rights reservedReceived: 31st July 2013; Revised: 8th November 2013; Accepted: 21st November 2013[How to Cite: Malhotra, S., Jaspal, D. (2014. Kinetics of the Enolisation Reaction of m-Nitro Acetophe-none Catalyzed by Amino Acids. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 16-22. (doi:10.9767/bcrec.9.1.5258.16-22][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.1.5258.16-22
Kinetics of metal salt vapor lasers
Kazarian, M.A.; Trofimov, A.N.
1979-02-01
A kinetic model is constructed for lasers operating on metal salt vapors. Different operating regimes of these lasers are considered, and it is shown that during transition from double-pulse regime to pulse-train regime or regular-pulse regime it is necessary to take into account accumulation effects. Numerical calculations for copper halogenides are carried out. It is shown how different operating regimes have widely different lasing conditions. This is due to the accumulation effects mentioned above.
Kinetics of the Double Carbonylation of Benzylchloride
无
2000-01-01
It is a multi-phase-catalyzed reaction to produce calcium phenylpyruvate by double carbonylation of benzylchloride. Based on the analysis of the reaction mechanism, a kinetic model of the carbonylation reaction was obtained. The model was verified through experiments in which the diffusion effect was neglected with the appropriate operation manner. But it is inevitable that the carbonylation process is controlled by diffusion as the autoclave scaling up.
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
Desulfurizer desulphurization kinetics by the injection method
Zhijun Han; Yanbin Hu; Wei Wu
2008-01-01
To obtain a better desulphurization effect in hot metal, suitable desulfurizers should be selected first according to thermodynamics. However, the effect of desulphurization is also strongly affected by kinetics. The conditions of different desulfurizers (Mg, CaC2, and lime) penetrating into hot metal, the rising up velocity in iron melt, residence time, and dissolving time are theoretically calculated and analyzed. The results are helpful to select the desulphurization process and equipment and to improve the desulphurization effect.
Kinetics of dimethoate biodegradation in bacterial system
Manisha DebMandal; Shyamapada Mandal; Nishith Kumar Pal
2011-01-01
The present study is an investigation on the kinetics of dimethoate biodegradation and an estimation of residual dimethoate in bacterial culture by spectrophotometry. The methylene chloride extract of the culture medium was used for determination of dimethoate through its reaction with 1 chloro-2, 4 dinitrobenzene to produce methylamine whose absorbance at 505 nm gave an estimation of dimethoate content. The dimethoate standard curve follows Beer’s law at 505 nm with a slope of 0.0129 absorba...
Catechol biodegradation kinetics using Candida parapsilopsis
Maurício Rigo; Ranulfo Monte Alegre; José Raniere Mazile Vidal Bezerra; Narjara Coelho; Reinaldo Gaspar Bastos
2010-01-01
This study evaluated the biodegradation of catechol by a yeast strain of Candida parapsilopsis in standard medium in Erlenmeyer flasks. Results shown that the highest concentration of catechol caused the longer lag period, demonstrating that acclimatized cultures could completely degrade an initial catechol concentration of 910 mg/L within 48 h. Haldane's model validated the experimental data adequately for growth kinetics over the studied catechol concentration ranges of 36 to 910 mg/L. The ...
A kinetic model of plasma turbulence
Servidio, S.; Valentini, F.; Perrone, D.; Greco, A.; Califano, F.; Matthaeus, W. H.; Veltri, P.
2015-01-01
A Hybrid Vlasov-Maxwell (HVM) model is presented and recent results about the link between kinetic effects and turbulence are reviewed. Using five-dimensional (2D in space and 3D in the velocity space) simulations of plasma turbulence, it is found that kinetic effects (or non-fluid effects) manifest through the deformation of the proton velocity distribution function (DF), with patterns of non-Maxwellian features being concentrated near regions of strong magnetic gradients. The direction of the proper temperature anisotropy, calculated in the main reference frame of the distribution itself, has a finite probability of being along or across the ambient magnetic field, in general agreement with the classical definition of anisotropy T ⊥/T ∥ (where subscripts refer to the magnetic field direction). Adopting the latter conventional definition, by varying the global plasma beta (β) and fluctuation level, simulations explore distinct regions of the space given by T ⊥/T ∥ and β∥, recovering solar wind observations. Moreover, as in the solar wind, HVM simulations suggest that proton anisotropy is not only associated with magnetic intermittent events, but also with gradient-type structures in the flow and in the density. The role of alpha particles is reviewed using multi-ion kinetic simulations, revealing a similarity between proton and helium non-Maxwellian effects. The techniques presented here are applied to 1D spacecraft-like analysis, establishing a link between non-fluid phenomena and solar wind magnetic discontinuities. Finally, the dimensionality of turbulence is investigated, for the first time, via 6D HVM simulations (3D in both spaces). These preliminary results provide support for several previously reported studies based on 2.5D simulations, confirming several basic conclusions. This connection between kinetic features and turbulence open a new path on the study of processes such as heating, particle acceleration, and temperature
Kinetics of Dyes Adsorbed by Chitosan
CHEN Liang; CHEN Dong-hui; GAO Liang
2002-01-01
A study on adsorption of Acidic Blue RAWL and Cationic Blue X-GRRL dyes by chitosan have been conducted.The adsorption kinetic parameters including adsorption rate K and effective diffusing coefficient D'i under the optimal pH ranges have been determined. Analysis through the enthalpy calculation reveals a substantial thermodynamic difference between the adsorption processes of the two dyes, which helps to understand the adsorption mechanism by chitosan.
Autoxidation kinetics of aqueous nitric oxide
1993-01-01
Reports on the kinetics of the autoxidation of aqueous nitric oxide are discussed. It is concluded that the correct rate law is -d[NO]/dt = 4kaq[NO]2 [O2] with kaq = 2 × 106 M-2 · s-1 at 25°C and that a recent report of a rate law zero order in NO is incorrect. © 1993.
Self-consistent kinetic lattice Monte Carlo
Horsfield, A.; Dunham, S.; Fujitani, Hideaki
1999-07-01
The authors present a brief description of a formalism for modeling point defect diffusion in crystalline systems using a Monte Carlo technique. The main approximations required to construct a practical scheme are briefly discussed, with special emphasis on the proper treatment of charged dopants and defects. This is followed by tight binding calculations of the diffusion barrier heights for charged vacancies. Finally, an application of the kinetic lattice Monte Carlo method to vacancy diffusion is presented.
Kinetic reduction of mill scale via hydrogen
Gaballah N.M.
2014-01-01
Full Text Available Mill scale is very attractive industrial waste since it is rich in iron (about = 72 % Fe and it is suiTab. for direct recycling to the blast furnace via sintering plant. In this paper the characterizations of raw materials were studied by different methods of analyses. The produced briquettes were reduced with different amounts of hydrogen at varying temperatures, and the reduction kinetics was determined. Two models were applied and the energy of activation was calculated.
Kinetics of human sperm acrosomal exocytosis.
Sosa, C M; Pavarotti, M A; Zanetti, M N; Zoppino, F C M; De Blas, G A; Mayorga, L S
2015-03-01
The acrosome reaction is a unique event in the lifespan of sperm characterized by the exocytosis of the acrosomal content and the release of hybrid vesicles formed by patches of the outer acrosomal membrane and the plasma membrane. This unique regulated exocytosis is mediated by essentially the same membrane fusion machinery present in neuroendocrine cells. However, whereas secretion in neuroendocrine cells occurs in less than a second, the acrosome reaction is normally assessed after several minutes of incubation with inducers. In this report, we measured the kinetics of human sperm exocytosis triggered by two stimuli (calcium ionophore and progesterone) by using electron microscopy and three different approaches based on the incorporation of fluorescent Pisum sativum agglutinin into the acrosome upon opening of fusion pores connecting the extracellular medium with the acrosomal lumen. The results with the different methods are consistent with a slow kinetics (t½ = 14 min). We also manipulated the system to measure different steps of the process. We observed that cytosolic calcium increased with a relatively fast kinetics (t½ = 0.1 min). In contrast, the swelling of the acrosomal granule that precedes exocytosis was a slow process (t½ = 13 min). When swelling was completed, the fusion pore opening was fast (t½ = 0.2 min). The results indicate that acrosomal swelling is the slowest step and it determines the kinetics of the acrosome reaction. After the swelling is completed, the efflux of calcium from intracellular stores triggers fusion pores opening and the release of hybrid vesicles in seconds.
75 FR 28665 - Kinetics Mutual Funds, Inc., et al.; Notice of Application
2010-05-21
... COMMISSION Kinetics Mutual Funds, Inc., et al.; Notice of Application May 17, 2010. AGENCY: Securities and... the Act to invest in certain financial instruments. ] APPLICANTS: Kinetics Mutual Funds, Inc. (``Company''), Kinetics Portfolios Trust (``Trust''), Kinetics Asset Management, Inc. (``Adviser''),...
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.
Crystallization: Key thermodynamic, kinetic and hydrodynamic aspects
Sreepriya Vedantam; Vivek V Ranade
2013-12-01
Crystallization is extensively used in different industrial applications, including the production of a wide range of materials such as fertilizers, detergents, food and pharmaceutical products, as well as in the mineral processing industries and treatment of waste effluents. In spite of the wide-spread use of crystallization, a clear understanding of the thermodynamic, kinetic and hydrodynamic aspects of the design methodologies are not yet well established. More often than not crystallization is still considered an art especially in fine-chemicals, pharmaceuticals and life-sciences sector. It is essential to understand and relate key thermodynamic, kinetic and hydrodynamic aspects to crystallizer performance, not just in terms of yield but also in terms of product quality (characterized by particle size distribution, morphology, polymorphism and the amount of strain as well as the uptake of solvent or impurities in the crystal lattice). This paper attempts to do that by critically reviewing published experimental and modelling studies on establishing and enhancing state-of-the-art thermodynamic, kinetic and hydrodynamic aspects of crystallization. Efforts are made to discuss and raise points for emerging modelling tools needed for a flexible design and operation of crystallizers and crystallization processes that are needed to meet the ever increasing demand on precise product specifications. Focus is on bringing out the trends which can be used as perspectives for future studies in this field.
Capillary instabilities in thin films. II. Kinetics
Srolovitz, D.J.; Safran, S.A.
1986-07-01
We consider the kinetic evolution of perturbations to thin films. Since all small (nonsubstrate intersecting) perturbations to the film surface decay, we consider the evolution of large perturbations, in the form of a single hole which exposes the substrate. For large holes, the hole radius increases at a constant rate under the assumption of evaporation/condensation kinetics. When the dominant transport mode is surface diffusion, large holes grow with a rate proportional to t/sup -3/4/ (log/sup 3/(t/ rho/sup 4//sub c/)). Small holes with a radii less than rho/sub c/ shrink, where rho/sub c/ is the film thickness divided by the tangent of the equilibrium wetting angle. The growth of these holes eventually leads to hole impingement which ruptures the film, creating a set of disconnected islands. The relaxation time for these islands to go to their equilibrium shape and size (rho/sub eq/) scales as rho/sup 2//sub eq/ or rho/sup 4//sub eq/ for evaporation/condensation or surface diffusion kinetics, respectively.
Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation
Silke, E J; Pitz, W J; Westbrook, C K; Ribaucour, M
2006-11-10
A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O{sub 2} through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO{sub 2} from RO{sub 2} is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O{sub 2}QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.
The kinetics of sulfation of calcium oxide
Sarofim, A.F.; Longwell, J.P.
1990-01-01
The rate of sulfation of a CaO surface is rapid at first, limited by the intrinsic kinetics, but slows down with increasing conversion as a consequence of the increased resistance to diffusion through the product layer. The objectives of this study are to determine the intrinsic kinetics and the product layer diffusion pate by minimizing the resistances to gas-phase pore diffusion, and eliminating complications due to pore filling. This is achieved by the use of nonporous CaO. A wide range of particle sizes are used to change the relative importance of the regimes in which the intrinsic kinetics and product layer diffusion control. The assumption of constant product layer diffusivity can then be tested and the variables that determine this diffusivity independently studied. Information on product layer diffusion can also be obtained from studies of porous particles after the pore mouths are all plugged and a uniform surface coating is obtained. This information on diffusion rate and intrinsic reactivity can then be combined with a geometrical model to describe the rate of reaction over the entire range of conversions and is particularly useful in treating the effect of particle size on conversion history.
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
Drying kinetics of some building materials
A. Moropoulou
2005-06-01
Full Text Available Moisture is one of the most deteriorating factors of buildings. The deteriorating effect of moisture occurs mainly during the drying phase, and not in the wetting phase. Appropriate parameters of the drying kinetics are required for the building materials. Environmental factors, such as air temperature, air humidity, and air velocity affect drying. An experimental air dryer of controlled drying air conditions was used to investigate the drying performance of 4 stone materials, 2 bricks and 7 plasters. Drying kinetics was examined at 4 air temperatures, 6 air humidities, and 3 air velocities. A first-order kinetics model was obtained, in which the drying time constant was a function of the drying conditions, and the equilibrium material moisture content was described by the Oswin equation. The parameters of the proposed model were found to be affected strongly by the material and the drying air conditions. The results obtained are very useful in selecting the appropriate plaster to protect existing historic buildings.
Computational model for Halorhodopsin photocurrent kinetics
Bravo, Jaime; Stefanescu, Roxana; Talathi, Sachin
2013-03-01
Optogenetics is a rapidly developing novel optical stimulation technique that employs light activated ion channels to excite (using channelrhodopsin (ChR)) or suppress (using halorhodopsin (HR)) impulse activity in neurons with high temporal and spatial resolution. This technique holds enormous potential to externally control activity states in neuronal networks. The channel kinetics of ChR and HR are well understood and amenable for mathematical modeling. Significant progress has been made in recent years to develop models for ChR channel kinetics. To date however, there is no model to mimic photocurrents produced by HR. Here, we report the first model developed for HR photocurrents based on a four-state model of the HR photocurrent kinetics. The model provides an excellent fit (root-mean-square error of 3.1862x10-4, to an empirical profile of experimentally measured HR photocurrents. In combination, mathematical models for ChR and HR photocurrents can provide effective means to design test light based control systems to regulate neural activity, which in turn may have implications for the development of novel light based stimulation paradigms for brain disease control. I would like to thank the University of Florida and the Physics Research Experience for Undergraduates (REU) program, funded through NSF DMR-1156737. This research was also supported through start-up funds provided to Dr. Sachin Talathi
Neptunium Binding Kinetics with Arsenazo(III)
Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Johnson, Aaron T. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stephen P. [Idaho National Lab. (INL), Idaho Falls, ID (United States)
2014-08-01
This document has been prepared to meet FCR&D level 2 milestone M2FT-14IN0304021, “Report on the results of actinide binding kinetics with aqueous phase complexants” This work was carried out under the auspices of the Thermodynamics and Kinetics of Advanced Separations Systems FCR&D work package. The report details kinetics experiments that were performed to measure rates of aqueous phase complexation for pentavalent neptunium with the chromotropic dye Arsenazo III (AAIII). The studies performed were designed to determine how pH, ionic strength and AAIII concentration may affect the rate of the reaction. A brief comparison with hexavalent neptunium is also made. It was identified that as pH was increased the rate of reaction also increased, however increasing the ionic strength and concentration of AAIII had the opposite effect. Interestingly, the rate of reaction of Np(VI) with AAIII was found to be slower than that of the Np(V) reaction.
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.
Optimization of KINETICS Chemical Computation Code
Donastorg, Cristina
2012-01-01
NASA JPL has been creating a code in FORTRAN called KINETICS to model the chemistry of planetary atmospheres. Recently there has been an effort to introduce Message Passing Interface (MPI) into the code so as to cut down the run time of the program. There has been some implementation of MPI into KINETICS; however, the code could still be more efficient than it currently is. One way to increase efficiency is to send only certain variables to all the processes when an MPI subroutine is called and to gather only certain variables when the subroutine is finished. Therefore, all the variables that are used in three of the main subroutines needed to be investigated. Because of the sheer amount of code that there is to comb through this task was given as a ten-week project. I have been able to create flowcharts outlining the subroutines, common blocks, and functions used within the three main subroutines. From these flowcharts I created tables outlining the variables used in each block and important information about each. All this information will be used to determine how to run MPI in KINETICS in the most efficient way possible.
Thermodynamics and Kinetics of Calcium Sulphoaluminate
GUO Huiling; XIE Junlin
2011-01-01
The formation process of calcium suphoaluminate(C4A3S)was investigated by the X-ray diffraction technique and then the thermodynamics was analyzed,finally the kinetics of which was studied by SC-132.XRD results show that the formation of C4A3S is accomplished in three different kinds of ways:one is by solid reaction of Ca(OH)2/CaO,Al2O3 and CaSO4,other two ways are through such interstitial products as ℃ and increases as temperature rising;the quantity of reaches the highest at 1300 ℃-1350 ℃ and then falls at >1350℃.Kinetics study shows that the formation rate of C4A3S can be described as first-order kinetics at high temperature,and it belongs to the random nucleation growth mechanism.The apparent activation energy is 456.37 kJ·mol-1 and pre-exponential factor is 1.545×1012.
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.
Estimation of turbulent kinetic energy dissipation
Chen, Huey-Long; Hondzo, Miki; Rao, A. Ramachandra
2001-06-01
The kinetic energy dissipation rate is one of the key intrinsic fluid flow parameters in environmental fluid dynamics. In an indirect method the kinetic energy dissipation rate is estimated from the Batchelor spectrum. Because the Batchelor spectrum has a significant difference between the highest and lowest spectral values, the spectral bias in the periodogram causes the lower spectral values at higher frequencies to increase. Consequently, the accuracy in fitting the Batchelor spectrum is affected. In this study, the multitaper spectral estimation method is compared to conventional methods in estimating the synthetic temperature gradient spectra. It is shown in the results that the multitaper spectra have less bias than the Hamming window smoothed spectra and the periodogram in estimating the synthetic temperature gradient spectra. The results of fitting the Batchelor spectrum based on four error functions are compared. When the theoretical noise spectrum is available and delineated at the intersection of the estimated spectrum, the fitting results of the kinetic energy dissipation rate corresponding to the four error functions do not have significant differences. However, when the noise spectrum is unknown and part of the Batchelor spectrum overlaps the region where the noise spectrum dominates, the weighted chi-square distributed error function has the best fitting results.
Kinetics for a membrane reactor reducing perchlorate.
Padhye, Lokesh; Rainwater, Ken; Jackson, W Andrew; Morse, Audra
2007-02-01
The major objectives of this work were to operate and construct an autohydrogenotrophic reactor and estimate perchlorate degradation kinetics. The results show that autohydrogenotrophic bacteria were cultured in the reactor and capable of removing 3.6 mg/d of perchlorate in the presence of excess hydrogen (99% removal). The reactor was successful in treating the average influent perchlorate concentration of 532 microg/L to the level of 3 microg/L. A first-order relationship was obtained between the concentration of active biomass in the reactor and the hydraulic retention time for the given amount of substrate. During the kinetic loading study, perchlorate removal ranged from 100 to 50%. The kinetic rate of perchlorate degradation observed in this study was 1.62 hr(-1). The significant degradation of perchlorate in these samples indicates the ubiquity of perchlorate-reducing organisms. Additionally, nitrate was simultaneously removed during water treatment (greater than 90% removal). Because of the excess levels of hydrogen, simultaneous removal of nitrate was not believed to significantly affect perchlorate removal. The area of concern was the lack of complete control over biological treatment. The growth of sulfate-reducing organisms in the reactor negatively affected perchlorate removal efficiency. There were no significant effects observed on the dissolved organic carbon and total suspended solids concentration of the effluent, suggesting that the treatment did not produce a large amount of biomass washout.
A Century of Enzyme Kinetic Analysis, 1913 to 2013
Johnson, Kenneth A.
2013-01-01
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. PMID:23850893
Gas transport in tight porous media Gas kinetic approach
Shapiro, Alexander; Wesselingh, Johannes
2008-01-01
We describe the flow of gas in a porous medium in the kinetic regime, where the viscous flow structure is not formed in separate pores. Special attention is paid to the dense kinetic regime, where the interactions within the gas are as important as the interaction with the porous medium....... The transport law for this regime is derived by means of the gas kinetic theory, in the framework of the model of "heavy gas in light one". The computations of the gas kinetic theory are confirmed by the dimension analysis and a simplified derivation revealing the considerations behind the kinetic derivation...
A note on the maintenance of the atmospheric kinetic energy
Chen, T.-C.; Lee, Y.-H.
1982-01-01
The winter simulations of the GLAS climate model and the NCAR community climate model are used to examine the maintenance of the atmospheric kinetic energy. It is found that the kinetic energy is generated in the lower latitudes south of the maximum westerlies, transported northward and then, destroyed in the midlatitudes north of the maximum westerlies. Therefore, the atmospheric kinetic energy is maintained by the counterbalance between the divergence (convergence) of kinetic energy flux and generation (destruction) of kinetic energy in lower (middle) latitudes.
Kinetics study on biomass pyrolysis for fuel gas production
无
2003-01-01
Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The kinetic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into primary products (tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.
Kinetics study on biomass pyrolysis for fuel gas production
陈冠益; 方梦祥; ANDRIES，J.; 骆仲泱; SPLIETHOFF,H.; 岑可法
2003-01-01
Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The ki-netic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into pri-mary products ( tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.
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.
A note on the maintenance of the atmospheric kinetic energy
Chen, T.-C.; Lee, Y.-H.
1982-01-01
The winter simulations of the GLAS climate model and the NCAR community climate model are used to examine the maintenance of the atmospheric kinetic energy. It is found that the kinetic energy is generated in the lower latitudes south of the maximum westerlies, transported northward and then, destroyed in the midlatitudes north of the maximum westerlies. Therefore, the atmospheric kinetic energy is maintained by the counterbalance between the divergence (convergence) of kinetic energy flux and generation (destruction) of kinetic energy in lower (middle) latitudes.
Kinetic investigation for slow combustion of biomass
Haykiri-Acma, H.; Yaman, S. [Istanbul Technical Univ., Istanbul (Turkey). Dept. of Chemical Engineering, Faculty of Chemical and Metallurgical Engineering
2006-07-01
The renewed interest in biomass as a renewable, clean, and inexpensive fuel was discussed. Many different mechanisms take place simultaneously during biomass combustion and also during other thermal processes such as gasification, pyrolysis or carbonization. These mechanisms have a pronounced influence on the design and operation of thermal conversion processes. In addition, product yields and product distributions from the thermal processes are sensitive to the kinetic properties of biomass. In order to evaluate the combustion mechanisms and the combustion kinetics of biomass, the behavior of these constituents under combustion conditions were properly evaluated. In this study, combustion of biomass samples was carried out in a thermogravimetric analyzer by heating them from ambient to 1173 K with heating rates of 5 K/min and 10 K/min under dynamic dry air atmosphere of 40 mL/min. The biomass samples included olive refuse, sunflower seed shell, rapeseed, grape seed, and hybrid poplar. The purpose of the study was to examine the kinetic properties of biomass during slow combustion for the overall combustion process as well as for some definite temperature intervals at which different combustion mechanisms are present according to the type and complexity of biomass used. Derivative thermogravimetric analysis (DTG) curves were derived, and data obtained from these curves were used to compute the kinetic parameters such as activation energy, pre-exponential factor, and governing mechanisms for the combustion processes. The governing mechanisms for individual temperature intervals were examined along with the overall combustion process. The study showed that at lower temperature intervals, the combustion process was controlled primarily by the chemical reaction. At least 3 sequential mechanisms may occur at different temperature intervals during combustion of biomass. Activation energy and pre-exponential factors were determined for each temperature interval
Yuki, Dai; Kikuchi, Akira; Miura, Naoki; Kakehi, Aoi; Onozawa, Masahiro
2013-11-01
This study investigated the relationship between plasma and saliva cotinine kinetics after smoking one cigarette and the relationship between cotinine kinetics and estimated nicotine intake, which was calculated as mouth level exposure (MLE) of nicotine, from smoking two test cigarettes with different nicotine yields. This study was conducted in 16 healthy adult Japanese smokers, who did not have null nor reduced-activity alleles of CYP2A6, with a quasi-randomized crossover design of smoking a low-tar cigarette or a high-tar cigarette. Saliva cotinine showed similar concentration profiles to plasma cotinine, and all of the calculated pharmacokinetic parameters of cotinine showed the same values in plasma and saliva. The Cmax and AUC of cotinine showed almost the same dose-responsiveness to the estimated MLE of nicotine between plasma and saliva, but the tmax and t1/2 of cotinine were not affected by the estimated MLE of nicotine in either plasma or saliva. The results show that saliva cotinine kinetics reflects plasma cotinine kinetics, and measurement of saliva cotinine concentration gives the same information as plasma cotinine on the nicotine intake. Thus, saliva cotinine would be a good and less-invasive exposure marker of cigarette smoke, reflecting the plasma cotinine concentration and kinetics.
Quantum kinetics derivation as generalization of the quantum hydrodynamics method
Andreev, Pavel A
2012-01-01
We present a new way of quantum kinetic equation derivation. This method appears as a natural generalization of the many-particle quantum hydrodynamic method. Kinetic equations are derived for different system of particles. First of all we consider quantum plasma and pay special attention to the spin evolution. We show that we need a set of two kinetic equations for description of spinning particles. One of these equations is the equation for distribution function, however this equation contains new function, even in the self-consistent field approximation. This is a spin-distribution function introduced in the paper. Therefore we have to derive kinetic equation for spin distribution function evolution, which is presented here and used to construct a closed set of kinetic equations. We also present kinetic equation for system of neutral particles with a short-range interaction in the first order by the interaction radius approximation. We derive a set of kinetic equations for particles having electric dipole ...
Simulation of the kinetics of oxygen complexes in crystalline silicon
Joo Lee, Young; von Boehm, J.; Nieminen, R. M.
2002-10-01
The formation kinetics of thermal double donors (TDD's) is studied by a general kinetic model with parameters based on accurate ab initio total-energy calculations. The kinetic model includes all relevant association, dissociation, and restructuring processes. The simulated kinetics agrees qualitatively and in most cases quantitatively with the experimentally found consecutive kinetics of TDD's. It also supports our earlier assignments of the ring-type oxygen chains to TDD's [Pesola et al., Phys. Rev. Lett. 84, 5343 (2000)]. We demonstrate with the kinetic model that the most common assumption that only the O2 dimer acts as a fast diffusing species would lead to an unrealistic steady increase of the concentration of O3. The neglect of restructuring processes leads to an anomalous increase of oxygen dimers and negligible concentrations of TDD's. The capture of interstitial oxygens by diffusing oxygen chains and the escaping of interstitial oxygens from the chains fully dominate the formation kinetics.
Self-Propulsion of Pure Water Droplets by Spontaneous Marangoni-Stress-Driven Motion
Izri, Ziane; van der Linden, Marjolein N.; Michelin, Sébastien; Dauchot, Olivier
2014-12-01
We report spontaneous motion in a fully biocompatible system consisting of pure water droplets in an oil-surfactant medium of squalane and monoolein. Water from the droplet is solubilized by the reverse micellar solution, creating a concentration gradient of swollen reverse micelles around each droplet. The strong advection and weak diffusion conditions allow for the first experimental realization of spontaneous motion in a system of isotropic particles at sufficiently large Péclet number according to a straightforward generalization of a recently proposed mechanism [S. Michelin, E. Lauga, and D. Bartolo, Phys. Fluids 25, 061701 (2013); S. Michelin and E. Lauga, J. Fluid Mech. 747, 572 (2014)]. Experiments with a highly concentrated solution of salt instead of water, and tetradecane instead of squalane, confirm the above mechanism. The present swimming droplets are able to carry external bodies such as large colloids, salt crystals, and even cells.
Steullet, P; Cabungcal, J-H; Coyle, J; Didriksen, M; Gill, K; Grace, A A; Hensch, T K; LaMantia, A-S; Lindemann, L; Maynard, T M; Meyer, U; Morishita, H; O'Donnell, P; Puhl, M; Cuenod, M; Do, K Q
2017-01-01
Parvalbumin inhibitory interneurons (PVIs) are crucial for maintaining proper excitatory/inhibitory balance and high-frequency neuronal synchronization. Their activity supports critical developmental trajectories, sensory and cognitive processing, and social behavior. Despite heterogeneity in the etiology across schizophrenia and autism spectrum disorder, PVI circuits are altered in these psychiatric disorders. Identifying mechanism(s) underlying PVI deficits is essential to establish treatments targeting in particular cognition. On the basis of published and new data, we propose oxidative stress as a common pathological mechanism leading to PVI impairment in schizophrenia and some forms of autism. A series of animal models carrying genetic and/or environmental risks relevant to diverse etiological aspects of these disorders show PVI deficits to be all accompanied by oxidative stress in the anterior cingulate cortex. Specifically, oxidative stress is negatively correlated with the integrity of PVIs and the extracellular perineuronal net enwrapping these interneurons. Oxidative stress may result from dysregulation of systems typically affected in schizophrenia, including glutamatergic, dopaminergic, immune and antioxidant signaling. As convergent end point, redox dysregulation has successfully been targeted to protect PVIs with antioxidants/redox regulators across several animal models. This opens up new perspectives for the use of antioxidant treatments to be applied to at-risk individuals, in close temporal proximity to environmental impacts known to induce oxidative stress. PMID:28322275
Optimal bounds with semidefinite programming: an application to stress driven shear flows
Fantuzzi, G
2015-01-01
We introduce an innovative numerical technique based on convex optimization to solve a range of infinite dimensional variational problems arising from the application of the background method to fluid flows. In contrast to most existing schemes, we do not consider the Euler-Lagrange equations for the minimizer. Instead, we use series expansions to formulate a finite dimensional semidefinite program (SDP) whose solution converges to that of the original variational problem. The formulation is rigorous, meaning that a solution of the SDP gives a certifiably feasible solution for the infinite dimensional problem. Moreover, SDPs can be easily formulated when the fluid is subject to imposed boundary fluxes, which pose a challenge for the traditional methods. We apply this technique to compute rigorous and near-optimal upper bounds on the dissipation coefficient for flows driven by a surface stress. We improve previous analytical bounds by more than 10 times, and show that the bounds become independent of the domai...
Biaxial-stress-driven full spin polarization in ferromagnetic hexagonal chromium telluride
Xiao, Xiang-Bo; Li, Jun; Liu, Bang-Gui
2017-03-01
It is important to spintronics to achieve fully-spin-polarized magnetic materials that are stable and can be easily fabricated. Here, through systematical density-functional-theory investigations, we achieve high and even full spin polarization for carriers in the ground-state phase of CrTe by applying tensile biaxial stress. The resulting strain is tensile in the xy plane and compressive in the z axis. With the in-plane tensile strain increasing, the ferromagnetic order is stable against antiferromagnetic fluctuations, and a half-metallic ferromagnetism is achieved at an in-plane strain of 4.8%. With the spin-orbit coupling taken into account, the spin polarization is equivalent to 97% at the electronic transition point, and then becomes 100.0% at the in-plane strain of 6.0%. These make us believe that the full-spin-polarized ferromagnetism in this stable and easily-realizable hexagonal phase could be realized soon, and applied in spintronics.
Atypical cytochrome p450 kinetics: implications for drug discovery.
Tracy, Timothy S
2006-01-01
The Michaelis-Menten model is commonly used to estimate a drug's potential in vivo hepatic clearance based on in vitro data obtained during drug discovery and development. This paradigm assumes that the drug obeys 'typical' enzyme kinetics and thus can be described by this model. However, it is increasingly being recognised that a number of drugs metabolised not only by the cytochrome P450 enzymes but also by other enzymes and transporters can exhibit atypical kinetic profiles, and thus are not accurately modeled with the Michaelis-Menten model. Application of an incorrect model can then lead to mis-estimation of in vitro intrinsic clearance and thus affect the prediction of in vivo clearance. This review discusses several types of atypical kinetic profiles that may be observed, including examples of homotropic cooperativity (i.e. sigmoidal kinetics, biphasic kinetics and substrate inhibition kinetics) as well as heterotropic cooperativity (i.e. activation). Application of the incorrect kinetic model may profoundly affect estimations of intrinsic clearance. For example, incorrectly applying the Michaelis-Menten model to a kinetic profile exhibiting substrate inhibition kinetics will result in an underestimation of Km (Michaelis-Menten constant) and V(max) (maximal velocity), whereas application of the Michaelis-Menten model to sigmoidal kinetic data typically results in an overestimation of Km and V(max) at the lower substrate concentrations that are typically therapeutically relevant. One must also be careful of potential artefactual causes of atypical kinetic profiles, such as enzyme activation by solvents, buffer dependent kinetic profiles, or altered kinetic parameter estimates due to nonspecific binding of the substrate to proteins. Despite a plethora of data on the effects of atypical kinetic profiles in vitro, only modest effects have been noted in vivo (with the exception of substrate dependent inhibition). Thus, the clinical relevance of these phenomena
Large-scale epitaxial growth kinetics of graphene: A kinetic Monte Carlo study
Jiang, Huijun; Hou, Zhonghuai, E-mail: hzhlj@ustc.edu.cn [Department of Chemical Physics and Hefei National Laboratory for Physical Sciences at Microscales, University of Science and Technology of China, Hefei, Anhui 230026 (China)
2015-08-28
Epitaxial growth via chemical vapor deposition is considered to be the most promising way towards synthesizing large area graphene with high quality. However, it remains a big theoretical challenge to reveal growth kinetics with atomically energetic and large-scale spatial information included. Here, we propose a minimal kinetic Monte Carlo model to address such an issue on an active catalyst surface with graphene/substrate lattice mismatch, which facilitates us to perform large scale simulations of the growth kinetics over two dimensional surface with growth fronts of complex shapes. A geometry-determined large-scale growth mechanism is revealed, where the rate-dominating event is found to be C{sub 1}-attachment for concave growth-front segments and C{sub 5}-attachment for others. This growth mechanism leads to an interesting time-resolved growth behavior which is well consistent with that observed in a recent scanning tunneling microscopy experiment.
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.
The thermodynamic driving force for kinetics in general and enzyme kinetics in particular.
Pekař, Miloslav
2015-03-16
The thermodynamic driving force of a reaction is usually taken as the chemical potential difference between products and reactants. The forward and backward reaction rates are then related to this force. This procedure is of very limited validity, as the resulting expression contains no kinetic factor and gives little information on reaction kinetics. The transformation of the reaction rate as a function of concentration (and temperature) into a function of chemical potential should be more properly performed, as illustrated by a simple example of an enzymatic reaction. The proper thermodynamic driving force is the difference between the exponentials of the totaled chemical potentials of reactants and products.
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.
Sorption kinetics of hexadecyltrimethylammonium on natural clinoptilolite
Li, Z.
1999-09-14
Sorption kinetics of hexadecyltrimethylammonium (HDTMA) chloride on a natural clinoptilolite was studied in this research. The amount of HDTMA sorbed is a function of the initial HDTMA input and the sorption time. When the initial HDTMA input is less than the external cation-exchange capacity of the clinoptilolite, the HDTMA sorption is fast and equilibrium can be established in 1 h. As the initial HDTMA input is greater than the external cation-exchange capacity of clinoptilolite, which will result in more than a monolayer HDTMA surface coverage, the time for HDTMA sorption to reach equilibrium increases exponentially. The HDTMA sorption maximum on clinoptilolite increases logarithmically with mixing time. The counterion solution concentration data suggest that at the initial stage HDTMA molecules sorb on the zeolite via micelle forms, which is manifested by a decrease in chloride solution concentration with time. When HDTMA solution concentration is depleted to less than its critical micelle concentration, the adsorbed micelles (admicelles) rearrange themselves to a more stable monolayer or bilayer configuration, which is reflected by an increase in counterion solution concentration due to the desorption of chloride from admicelles. The time required for the surface rearrangement increases exponentially as the HDTMA input increases. The data of HDTMA sorption kinetics were fitted to different kinetic models, and the parabolic diffusion model fits the data best for the HDTMA sorption, counterion sorption at the initial stage and counterion desorption at the rearrangement stage. Thus, the sorption of HDTMA on clinoptilolite surfaces is diffusion controlled. The results also indicate that it is incomplete to discuss surfactant sorption without counterion concentration data.
Kinetic simulation of hydrodynamic equivalent capsule implosions
Kwan, Thomas; Le, Ari; Schmitt, Mark; Herrmann, Hans
2016-10-01
We have carried out simulations of direct-drive hydrodynamic equivalent capsule implosion experiments conducted on Omega laser facility at the Laboratory of Laser Energetics of the University of Rochester. The capsules had a glass shell (SiO2) 4.87 μm with an inner diameter of 1086 μm. One was filled with deuterium (D) and tritium (T) at 6.635 and 2.475 atmospheric pressure respectively. The other capsule with D, T, and He-3 at 2.475, 2.475, and 5.55 atmospheric pressure respectively. The capsules were imploded with 60 laser beams with a square pulse length of 0.6ns of total energy of 15.6 kJ. One-dimensional radiation hydrodynamic calculations with HYDRA and kinetic particle/hybrid simulations with LSP are carried out for the post-shot analysis. HYDRA outputs at 0.6ns are linked to LSP, in which the electrons are treated as a fluid while all the ion dynamics is simulated by the standard particle-in-cell technique. Additionally, simulations with the new photon package in LSP are initiated at the beginning of the implosion to include the implosion phase of the capsule. The simulation results of density, temperature, and velocity profiles of the electrons, D, T, He-3, and SiO2species are compared with HYDRA. Detail comparisons among the kinetic simulations, rad-hydro simulations, and experimental results of neutron yield, yield ratio, fusion burn histories, and shell convergence will be presented to assess plasma kinetic effects. Work performed under the auspices of the US DOE by the Los Alamos National Laboratory under Contract No. W7405-ENG-36.
Kinetic vs. Thermodynamic Control of Bacteriorhodopsin Pumping
Gunner, Marilyn
2011-03-01
Bacteriorhodopsin is a transmembrane proton pump that converts light energy to a transmembrane electrochemical gradient. Retinal, bound in the center of the protein, absorbs light and isomerizes from the all-trans to 13-cis configuration. A series of conformational changes and proton transfers then restores the structure to the all-trans ground state while pumping one proton from the high pH cell interior to the low pH exterior, saving energy in an electrochemical gradient. Poorly understood gating elements control key steps where incorrect proton transfer would return the protein to the ground state without pumping. The gate's barrier height determines how much the pump leaks. Analysis of high-resolution structures trapped in different intermediates has produced ideas for how bacteriorhodopsin ensures pumping. There are two contrasting strategies, one primarily thermodynamic and the other relying on kinetic control to ensure that protons are moved uphill. With thermodynamic control, residue protonation states always remain in quasi-equilibrium. Relatively slow conformational changes shift the energy landscape modifying site pKas. Residues then change ionization remaining in equilibrium in each metastable intermediate. The sequence of intermediates imparts the directionality to the transfers. Alternatively, the direction of transfer is determined by the accessibility of low energy pathways so is thus is under kinetic control. We will discuss which steps in the bacteriorhodopsin photocycle are under thermodynamic or under kinetic control. The role of three specific conformational changes (retinal isomerization, Arg82 reorientation and Glu194 and 204 separations) on the degree of proton transfer will be described. Supported by NFS MCB 1022208. Carried out with Yifan Song now at the University of Washington Department of Biochemistry.
Kinetics of dodecanedioic acid triglyceride in rats.
de Gaetano, A; Mingrone, G; Castagneto, M; Benedetti, G; Greco, A V; Gasbarrini, G
1999-03-01
The kinetics of the triglyceride of dodecanedioic acid (TGDA) has been investigated in 30 male Wistar rats after a rapid intravenous bolus injection. TGDA and its product of hydrolysis, nonesterified dodecanedioic acid (NEDA), were measured in plasma samples taken at different times using an improved high-performance liquid chromatographic method. The 24-h urinary excretion of TGDA was 1.54 +/- 0.37 micromol, corresponding to approximately 0.67% of the administered amount. Several kinetics models were considered, including central and peripheral compartments for the triglyceride and the free forms and expressing transports between compartments with combinations of linear, carrier-limited, or time-varying mechanisms. The parameter estimates of the kinetics of TGDA and of NEDA were finally obtained using a three-compartment model in which the transfer of TGDA to NEDA was assumed to be linear, through a peripheral compartment, and the tissue uptake of NEDA was assumed to be carrier limited. TGDA had a large volume of distribution ( approximately 0.5 l/kg body wt) with a fast disappearance rate from plasma (0.42 min-1), whereas NEDA had a very small volume of distribution ( approximately 0.04 l/kg body wt) and a tissue uptake with maximal transport rate of 0.636 mM/min. In conclusion, this first study on the triglyceride form of dodecanedioic acid indicates that it is rapidly hydrolyzed and that both triglyceride and nonesterified forms are excreted in the urine to a very low extent. The tissue uptake rate of NEDA is consistent with the possibility of achieving substantial energy delivery, should it be added to parenteral nutrition formulations. Furthermore, the amount of sodium administered with the triglyceride form is one-half of that necessary with the free diacid.
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.
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.)
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) 2 tabs., 2 ills.; 20 refs.
Kinetics and Hydrodynamics of Silver Ion Flotation
2012-01-01
This paper studies and determines the dispersion properties (Jg, Eg and Db), kinetics parameters and hydrodynamics of the process and its effect on the recovery of silver contained in spent diluted fixers by techniques of ion flotation in columns. The experimental results show silver recoveries of 97 % using sodium isopropyl xanthate (SIX) 0.06 g·L-1 and 0.04 g·L-1 of frother, at a Jg of 1.0 cm·s-1 and Jl of 0.72 cm·s-1. Xanthate-promoter combinations do not improve the separation; however, r...
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
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.
A kinetic approach to granular gases
Puglisi, A.; Loreto, V.; Marconi, U. Marini Bettolo; Vulpiani, A.
1998-01-01
We address the problem of the so-called ``granular gases'', i.e. gases of massive particles in rapid movement undergoing inelastic collisions. We introduce a class of models of driven granular gases for which the stationary state is the result of the balance between the dissipation and the random forces which inject energies. These models exhibit a genuine thermodynamic limit, i.e. at fixed density the mean values of kinetic energy and dissipated energy per particle are independent of the num...
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.
Kinetics Analysis of Coconut Shell Pyrolysis
LIU; Xue-mei; JIANG; Jian-chun; SUN; Kang; XU; Fan; XU; Yu
2012-01-01
[Objective] The paper aimed to study kinetics analysis of coconut shell pyrolysis. [Method] Thermo gravimetric analysis was used to study the pyrolysis characteristic of coconut shell at different pyrolysis rates (5, 10, 20 K/min). [Result] The pyrolysis process included 3 stages, water loss, pyrolysis, and thermal condensation. The pyrolysis process can be described through first-order reaction model. With the increasing pyrolysis rate, activation energy in the first stage rose, but activation energy in the second stage reduced. [Conclusion] The study provided theoretical basis for the promotion and application of biomass energy.
Kinetic treatment of radiation reaction effects
Noble, Adam; Gratus, Jonathan; Burton, David; Ersfeld, Bernhard; Islam, M. Ranaul; Kravets, Yevgen; Raj, Gaurav; Jaroszynski, Dino
2011-05-01
Modern accelerators and light sources subject bunches of charged particles to quasiperiodic motion in extremely high electric fields, under which they may emit a substantial fraction of their energy. To properly describe the motion of these particle bunches, we require a kinetic theory of radiation reaction. We develop such a theory based on the notorious Lorentz-Dirac equation, and explore how it reduces to the usual Vlasov theory in the appropriate limit. As a simple illustration of the theory, we explore the radiative damping of Langmuir waves.
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...... explanation using the finite field of residual classes of integers modulo 5: F 5 = ℤ/5ℤ. We show also an isomorphism between the set of complex operations on the kinetic Voronoi diagram of points and open oriented line segments and the set of differences of new and deleted Quad-Edge edges induced...
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.
Stress enhanced calcium kinetics in a neuron.
Kant, Aayush; Bhandakkar, Tanmay K; Medhekar, Nikhil V
2017-08-23
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.
Spectrum Analysis of Some Kinetic Equations
Yang, Tong; Yu, Hongjun
2016-11-01
We analyze the spectrum structure of some kinetic equations qualitatively by using semigroup theory and linear operator perturbation theory. The models include the classical Boltzmann equation for hard potentials with or without angular cutoff and the Landau equation with {γ≥q-2}. As an application, we show that the solutions to these two fundamental equations are asymptotically equivalent (mod time decay rate {t^{-5/4}}) as {tto∞} to that of the compressible Navier-Stokes equations for initial data around an equilibrium state.
Folding Kinetics of Riboswitch Transcriptional Terminators
Sauerwine, Benjamin; Widom, Michael
2009-03-01
Riboswitches control the expression of genes in bacteria by halting gene transcription or allowing it to proceed based on the presence of ligands in solution. A key feature of every riboswitch is a transcriptional terminator in which the messenger RNA folds into a secondary structure with the stem-loop structure of a hairpin. Through kinetic Monte Carlo simulation we show that terminators have been naturally selected to fold with high reliability on the time-scale of gene transcription. This efficient folding behavior is preserved among two classes of riboswitch and among two species of bacteria.
Thermodynamics, Kinetics and Microstructural Evolution during Nitrocarburising
Somers, Marcel A.J.; Du, Hong
2000-01-01
for compound layers where epsilon carbonitride phase is the dominant phase and extends from the surface to the interface with the substrate. Both cementite and gamma' phase, with narrow composition ranges, reduce the growth rate. Modelling of the microstructure evolution during nitrocarburising is hindered......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...
Reaction kinetic analysis of reactor surveillance data
Yoshiie, T.; Kinomura, A.; Nagai, Y.
2017-02-01
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.
Catalytic pyrolysis of tars. A kinetic approach
Faundez, J.; Garcia, X.; Gordon, A. [Universidad de Concepcion (Chile). Dept. de Ingeniera Quimica
1997-12-31
A kinetic model to describe the catalytic pyrolysis of tars is proposed and validated through pyrolysis of two tars of different characteristics and origin. Calcinated limestone (11 m{sup 2}/g) was used as catalyst. The model assumes that tars are composed of two pseudo-components: (i) heavy tar, and (ii) light tar. Tar pyrolysis is described by two simultaneous chemical reactions; catalyst deactivation due to carbon deposition is also considered. After mathematical resolution, expressions for product`s concentration as functions of residence time, selectivity and the deactivation were obtained. (orig.)
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.
Thermodynamic and kinetic modelling: creep resistant materials
Hald, John; Korcakova, L.; Danielsen, Hilmar Kjartansson
2008-01-01
particles and coarsening of MX, M23C6 and Laves phase particles. The modelling provided new insight into the long term stability of new steels. Modelling of the detrimental precipitation of Z phase Cr(V,Nb)N is described, which points to new approaches in alloy development for higher temperatures......The use of thermodynamic and kinetic modelling of microstructure evolution in materials exposed to high temperatures in power plants is demonstrated with two examples. Precipitate stability in martensitic 9–12%Cr steels is modelled including equilibrium phase stability, growth of Laves phase...
Bao, Jiayin; Krylova, Svetlana M; Reinstein, Oren; Johnson, Philip E; Krylov, Sergey N
2011-11-15
Here we demonstrate a label-free solution-based approach for studying the kinetics of biopolymer-small molecule interactions. The approach utilizes kinetic capillary electrophoresis (KCE) separation and UV light absorption detection of the unlabeled small molecule. In this proof-of-concept work, we applied KCE-UV to study kinetics of interaction between a small molecule and a DNA aptamer. From the kinetic analysis of a series of aptamers, we found that dissociation rather than binding controls the stability of the complex. Because of its label-free features and generic nature, KCE-UV promises to become a practical tool for challenging kinetic studies of biopolymer-small molecule interactions.
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.
Vlasov simulations of Kinetic Alfv\\'en Waves at proton kinetic scales
Vasconez, C L; Camporeale, E; Veltri, P
2014-01-01
Kinetic 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 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 Alfv\\'en waves at proton kinetic scales, in typical conditions of the solar wind environment. 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 $d_p$ and proton plasma beta $\\bet...
Reinisch, Guillaume; Leyssale, Jean-Marc; Vignoles, Gérard L.
2010-10-01
We present an extension of some popular hindered rotor (HR) models, namely, the one-dimensional HR (1DHR) and the degenerated two-dimensional HR (d2DHR) models, allowing for a simple and accurate treatment of internal rotations. This extension, based on the use of a variable kinetic function in the Hamiltonian instead of a constant reduced moment of inertia, is extremely suitable in the case of rocking/wagging motions involved in dissociation or atom transfer reactions. The variable kinetic function is first introduced in the framework of a classical 1DHR model. Then, an effective temperature and potential dependent constant is proposed in the cases of quantum 1DHR and classical d2DHR models. These methods are finally applied to the atom transfer reaction SiCl3+BCl3→SiCl4+BCl2. We show, for this particular case, that a proper accounting of internal rotations greatly improves the accuracy of thermodynamic and kinetic predictions. Moreover, our results confirm (i) that using a suitably defined kinetic function appears to be very adapted to such problems; (ii) that the separability assumption of independent rotations seems justified; and (iii) that a quantum mechanical treatment is not a substantial improvement with respect to a classical one.
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...
Kinetic study of biological hydrogen production by anaerobic fermentation
Sangeetha, R. [Annamalai Univ., Chidambaram (India). Dept. of Chemical Engineering; Karunanithi, T. [Annamalai Univ., Tamilnadu (India). Dept. of Chemical Engineering
2009-07-01
This study examined the kinetics of batch biohydrogen production from glucose. Clostridium pasteurianum was used to produce biohydrogen by dark anaerobic fermentation. The initial substrate concentration, initial pH and temperature were optimized for biohydrogen production. The maximum production of hydrogen under optimum conditions was found to be 5.376 l/l. The kinetic parameters were determined for the optimized medium and conditions in the batch reactor. The by product was expressed as total acidic equivalent. This presentation discussed the logistic equation that was used to model the growth of the organism and described how the kinetic parameters were calculated. The Leudeking piret kinetic model was used to express the hydrogen production and substrate use because it combines both growth associated and non associated contributions. It was concluded the production of biohydrogen can be predicted well using the logistic model for cell growth kinetics and the logistic incorporated Leudeking Piret model for product and substrate utilization kinetics.
Computer prediction system on solid/solid reaction kinetics
无
2001-01-01
A computer software system of kinetic predication of solid/solid reaction, KinPreSSR, was developed using Visual C++ and FoxPro. It includes two main modules, REACTION and DIFFUSION. KinPreSSR deals with the kinetics on the diffusion in solids as well as solid/solid reactions. The REACTION module in KinPreSSR was mainly described, which has organized the commonly recognized kinetic models, parameters, and employed both numerical and graphical methods for data analyses. The proper combination between the kinetic contents and the analytical methods enables users to use KinPreSSR for the evaluation and prediction of solid/solid reactions interested. As an example to show some of functions of KinPreSSR, the kinetics analysis for the reaction between SrCO3 and TiO2 powders to form SrTiO3 with a series of kinetic data from isothermal measurements was demonstrated.
Experimental Studies on Turbulence Kinetic Energy in Confined Vortex Flows
L.Yan; G.H.Vatistas; 等
2000-01-01
Turbulence kinetic energies in confined vortex flows have been studied.The studies were based on the experiments performed in a vortex chamber,In the experiments,a Laser Doppler Anemometry(LDA) was used to perform flow measurements inside the vortex chamber,which provided the data for the kinetic energy analysis.The studies concentrated on the influences of the contraction ratio and the inlet air flow rate on the kinetic energy,and analyzed the characteristics of the kinetic energy in the confined vortex flows,including the distributions of the tangential component,radial component and total turbulence kinetic energy,In the paper,both the experimental techniques and the experimental results were presented.Based on a similarity analyis and the experimental data,an empirical scaling formula was proposed so that the tangential component of the turbulence kinetic energy was dependent only on the parameter of the contraction ratio.
Hydrolysis kinetics of atrazine and influence factors
无
2001-01-01
The hydrolysis kinetics of atrazine in distilled water and leaching water from soil, and their influence factors were studied by incubation at 35℃ and HPLC analysis method in this paper. The kinetic process of atrazine hydrolysis can be described by the first-order reaction law. The results showed that the hydrolysis rate constants k in leaching water and distilled water were 1.606x10-3/d and 1.055x10-3/d, respectively; the half-life of atrazine hydrolysis in distilled water at pH 3, pH 4.5 and pH 8 were 373 days, 522 days and 657 days respectively. The results also showed that the proton in reaction solution can catalyze the atrazine hydrolysis; humic acid and NH4+ etc. substances in aqueous solution can facilitate atrazine hydrolysis; rate constants of atrazine hydrolysis with humic acid and NH4NO3 were 2.431x10-3/d and 1.498x10-3/d respectively which were 2.3 and 1.42 times of control(1.055x10-3/d); anion NO3- can inhibit catalysis of humic acid to atrazine hydrolysis.
Population balance modeling of antibodies aggregation kinetics.
Arosio, Paolo; Rima, Simonetta; Lattuada, Marco; Morbidelli, Massimo
2012-06-21
The aggregates morphology and the aggregation kinetics of a model monoclonal antibody under acidic conditions have been investigated. Growth occurs via irreversible cluster-cluster coagulation forming compact, fractal aggregates with fractal dimension of 2.6. We measured the time evolution of the average radius of gyration, , and the average hydrodynamic radius, , by in situ light scattering, and simulated the aggregation kinetics by a modified Smoluchowski's population balance equations. The analysis indicates that aggregation does not occur under diffusive control, and allows quantification of effective intermolecular interactions, expressed in terms of the Fuchs stability ratio (W). In particular, by introducing a dimensionless time weighed on W, the time evolutions of measured under various operating conditions (temperature, pH, type and concentration of salt) collapse on a single master curve. The analysis applies also to data reported in the literature when growth by cluster-cluster coagulation dominates, showing a certain level of generality in the antibodies aggregation behavior. The quantification of the stability ratio gives important physical insights into the process, including the Arrhenius dependence of the aggregation rate constant and the relationship between monomer-monomer and cluster-cluster interactions. Particularly, it is found that the reactivity of non-native monomers is larger than that of non-native aggregates, likely due to the reduction of the number of available hydrophobic patches during aggregation.
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.
Kinetic theory of diffusion-limited nucleation
Philippe, T.; Bonvalet, M.; Blavette, D.
2016-05-01
We examine binary nucleation in the size and composition space {R,c} using the formalism of the multivariable theory [N. V. Alekseechkin, J. Chem. Phys. 124, 124512 (2006)]. We show that the variable c drops out of consideration for very large curvature of the new phase Gibbs energy with composition. Consequently nuclei around the critical size have the critical composition, which is derived from the condition of criticality for the canonical variables and is found not to depend on surface tension. In this case, nucleation kinetics can be investigated in the size space only. Using macroscopic kinetics, we determine the general expression for the condensation rate when growth is limited by bulk diffusion, which accounts for both diffusion and capillarity and exhibits a different dependence with the critical size, as compared with the interface-limited regime. This new expression of the condensation rate for bulk diffusion-limited nucleation is the counterpart of the classical interface-limited result. We then extend our analysis to multicomponent solutions.
PBXN-9 Ignition Kinetics and Deflagration Rates
Glascoe, E; Maienschein, J; Burnham, A; Koerner, J; Hsu, P; Wemhoff, A
2008-04-24
The ignition kinetics and deflagration rates of PBXN-9 were measured using specially designed instruments at LLNL and compared with previous work on similar HMX based materials. Ignition kinetics were measured based on the One Dimensional Time-to-Explosion combined with ALE3D modeling. Results of these experiments indicate that PBXN-9 behaves much like other HMX based materials (i.e. LX-04, LX-07, LX-10 and PBX-9501) and the dominant factor in these experiments is the type of explosive, not the type of binder/plasticizer. In contrast, the deflagration behavior of PBXN-9 is quite different from similar high weight percent HMX based materials (i.e LX-10, LX-07 and PBX-9501). PBXN-9 burns in a laminar manner over the full pressure range studied (0-310 MPa) unlike LX-10, LX-07, and PBX-9501. The difference in deflagration behavior is attributed to the nature of the binder/plasticizer alone or in conjunction with the volume of binder present in PBXN-9.
Pozzolanic Reaction Kinetics of Coal Ashes
ZHENG Hongwei; WANG Zhijuan; QIAN Jueshi; SONG Yuanming; WANG Zhi
2009-01-01
The pozzolanic reactivity was determined by the hydration kinetics of pozzolanic reaction based on the fact that the hydration products of active SiO_2 and Al_2O_3 with lime were soluble in dilute hydrochloric acid.The results show that the pozzolanic reaction of active SiO_2 and Al2O3 of coal ashes follows apparent first-order kinetics.The reaction rate constant of FBC ashes is greater than that of PC ashes,while the activation energy of the former is lower than that of the latter.It is confirmed that the pozzolanic activity of fluidized bed combustion(FBC)ashes is significantly higher than that of PC ashes,and the reaction barrier of the former is lower than that of the latter,because the microstructures of FBC ashes,such as mineralogical composition,morphology and polymerization degree of [SiO_4]and[AlO_6]are more favorable to the pozzolanic activity development than those of PC ashes.
Thermodynamic and kinetic modeling of transcriptional pausing.
Tadigotla, Vasisht R; O Maoiléidigh, Dáibhid; Sengupta, Anirvan M; Epshtein, Vitaly; Ebright, Richard H; Nudler, Evgeny; Ruckenstein, Andrei E
2006-03-21
We present a statistical mechanics approach for the prediction of backtracked pauses in bacterial transcription elongation derived from structural models of the transcription elongation complex (EC). Our algorithm is based on the thermodynamic stability of the EC along the DNA template calculated from the sequence-dependent free energy of DNA-DNA, DNA-RNA, and RNA-RNA base pairing associated with (i) the translocational and size fluctuations of the transcription bubble; (ii) changes in the associated DNA-RNA hybrid; and (iii) changes in the cotranscriptional RNA secondary structure upstream of the RNA exit channel. The calculations involve no adjustable parameters except for a cutoff used to discriminate paused from nonpaused complexes. When applied to 100 experimental pauses in transcription elongation by Escherichia coli RNA polymerase on 10 DNA templates, the approach produces statistically significant results. We also present a kinetic model for the rate of recovery of backtracked paused complexes. A crucial ingredient of our model is the incorporation of kinetic barriers to backtracking resulting from steric clashes of EC with the cotranscriptionally generated RNA secondary structure, an aspect not included explicitly in previous attempts at modeling the transcription elongation process.
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.
Kinetics of zeolite dealumination in steam
Hughes, C.D.; Labouriau, A.; Crawford, S.N.; Romero, R.; Quirin, J.; Earl, W.L.
1998-08-01
Zeolite dealumination is a well known phenomenon that contributes to the deactivation or activation of catalysts in several different applications. The most obvious effect is in acid catalysis where dealumination under reaction conditions removes the Broensted sites, thus deactivating the catalyst. The authors are interested in the use of cation exchanged zeolites as selective reduction catalysts for removal of NO{sub x} from exhaust streams, particularly from automotive exhaust. In this case, copper exchanged ZSM-5 has been shown to be an effective catalyst for the generic reaction of NO{sub x} with hydrocarbons. However, high temperature and steam in combustion exhaust causes dealumination and consequent migration of copper out of the zeolite structure resulting in rapid deactivation of the catalyst. Dealumination of zeolites has been reported by many authors in uncountable papers and cannot be reviewed here. However, to the authors` knowledge there are no reports on the kinetics of dealumination under varying conditions of temperature and steam. By measuring the kinetics of dealumination with different zeolites and exchange cations they expect to develop working models of the dealumination process that will allow control of zeolite deactivation. This manuscript is a description of the basic techniques used and a progress report on the very beginning of this study.
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.
Kinetics of virus entry by endocytosis
Zhdanov, Vladimir P.
2015-04-01
Entry of virions into the host cells is either endocytotic or fusogenic. In both cases, it occurs via reversible formation of numerous relatively weak bonds resulting in wrapping of a virion by the host membrane with subsequent membrane rupture or scission. The corresponding kinetic models are customarily focused on the formation of bonds and do not pay attention to the energetics of the whole process, which is crucially dependent, especially in the case of endocytosis, on deformation of actin filaments forming the cytoskeleton of the host cell. The kinetic model of endocytosis, proposed by the author, takes this factor into account and shows that the whole process can be divided into a rapid initial transient stage and a long steady-state stage. The entry occurs during the latter stage and can be described as a first-order reaction. Depending on the details of the dependence of the grand canonical potential on the number of bonds, the entry can be limited either by the interplay of bond formation and membrane rupture (or scission) or by reaching a maximum of this potential.
Kinetic Analysis of tRNA Methylfransferases
Hou, Ya-Ming; Masuda, Isao
2016-01-01
Transfer RNA (tRNA) molecules contain many chemical modifications that are introduced after transcription. A major form of these modifications is methyl transfer to bases and backbone groups, using S-adenosyl methionine (AdoMet) as the methyl donor. Each methylation confers a specific advantage to tRNA in structure or in function. A remarkable methylation is to the G37 base on the 3' side of the anticodon to generate m1G37-tRNA, which suppresses frameshift errors during protein synthesis and is therefore essential for cell growth in all three domains of life. This methylation is catalyzed by TrmD in bacteria and by Trm5 in eukaryotes and archaea. Although TrmD and Trm5 catalyze the same methylation reaction, kinetic analysis reveal that these two enzymes are unrelated to each other and are distinct in their reaction mechanism. This chapter summarizes the kinetic assays that are used to reveal the distinction between TrmD and Trm5. Three types of assays are described, the steady-state, the pre-steady-state, and the single turnover assays, which collectively provide the basis for mechanistic investigation of AdoMet-dependent methyl transfer reactions. PMID:26253967
Quantum kinetic theories in degenerate plasmas
Brodin, Gert; Ekman, Robin; Zamanian, Jens
2017-01-01
In this review we give an overview of the recent work on quantum kinetic theories of plasmas. We focus, in particular, on the case where the electrons are fully degenerate. For such systems, perturbation methods using the distribution function can be problematic. Instead we present a model that considers the dynamics of the Fermi surface. The advantage of this model is that, even though the value of the distribution function can be greatly perturbed outside the equilibrium Fermi surface, deformation of the Fermi surface is small up to very large amplitudes. Next, we investigate the short-scale dynamics for which the Wigner-Moyal equation replaces the Vlasov equation. In particular, we study wave-particle interaction, and deduce that new types of wave damping can occur due to the simultaneous absorption (or emission) of multiple wave quanta. Finally, we consider exchange effects within a quantum kinetic formalism to find a model that is more accurate than those using exchange potentials from density functional theory. We deduce the exchange corrections to the dispersion relations for Langmuir and ion-acoustic waves. In comparison to results based on exchange potentials deduced from density functional theory we find that the latter models are reasonably accurate for Langmuir waves, but rather inaccurate for ion acoustic waves.
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).
Kinetic transport simulation of energetic particles
Sheng, He; Waltz, R. E.
2016-05-01
A kinetic transport code (EPtran) is developed for the transport of the energetic particles (EPs). The EPtran code evolves the EP distribution function in radius, energy, and pitch angle phase space (r, E, λ) to steady state with classical slowing down, pitch angle scattering, as well as radial and energy transport of the injected EPs (neutral beam injection (NBI) or fusion alpha). The EPtran code is illustrated by treating the transport of NBI fast ions from high-n ITG/TEM micro-turbulence and EP driven unstable low-n Alfvén eigenmodes (AEs) in a well-studied DIII-D NBI heated discharge with significant AE central core loss. The kinetic transport code results for this discharge are compared with previous study using a simple EP density moment transport code ALPHA (R.E. Waltz and E.M. Bass 2014 Nucl. Fusion 54 104006). The dominant EP-AE transport is treated with a local stiff critical EP density (or equivalent pressure) gradient radial transport model modified to include energy-dependence and the nonlocal effects EP drift orbits. All previous EP transport models assume that the EP velocity space distribution function is not significantly distorted from the classical ‘no transport’ slowing down distribution. Important transport distortions away from the slowing down EP spectrum are illustrated by a focus on the coefficient of convection: EP energy flux divided by the product of EP average energy and EP particle flux.
Coal char oxidation kinetics in air medium
Korotkikh Alexander G.
2017-01-01
Full Text Available Study of oxidation kinetics for three types of coal char with different carbon content in air is presented. The coal char powders of anthracite, bituminous T-grade coal and 2B-grade lignite with particle size less than 80 μm were tested. The coal char oxidation was researched by isothermal method via simultaneous TG-DSC analyzer Netzsch STA 449 Jupiter F3 in the temperature range of 1000–1200 °C. Measurements were carried out at ambient pressure. Volumetric flow rate of oxidizing medium into analyser chamber was 250 ml/min. Flow consisted of air and argon with volumetric ratio 24/1. Carbon average rate of oxidation reaction at each temperature were defined based on experimental results. Kinetic constants (the frequency factor and activation energy were defined for Arrhenius equation modified with three submodels: volumetric model, shrinking core model and random pore model. The activation energy values for anthracite are 1,6-1,7 times higher than for chars of bituminous coal and lignite.
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.
Accelerated simulation methods for plasma kinetics
Caflisch, Russel
2016-11-01
Collisional kinetics is a multiscale phenomenon due to the disparity between the continuum (fluid) and the collisional (particle) length scales. This paper describes a class of simulation methods for gases and plasmas, and acceleration techniques for improving their speed and accuracy. Starting from the Landau-Fokker-Planck equation for plasmas, the focus will be on a binary collision model that is solved using a Direct Simulation Monte Carlo (DSMC) method. Acceleration of this method is achieved by coupling the particle method to a continuum fluid description. The velocity distribution function f is represented as a combination of a Maxwellian M (the thermal component) and a set of discrete particles fp (the kinetic component). For systems that are close to (local) equilibrium, this reduces the number N of simulated particles that are required to represent f for a given level of accuracy. We present two methods for exploiting this representation. In the first method, equilibration of particles in fp, as well as disequilibration of particles from M, due to the collision process, is represented by a thermalization/dethermalization step that employs an entropy criterion. Efficiency of the representation is greatly increased by inclusion of particles with negative weights. This significantly complicates the simulation, but the second method is a tractable approach for negatively weighted particles. The accelerated simulation method is compared with standard PIC-DSMC method for both spatially homogeneous problems such as a bump-on-tail and inhomogeneous problems such as nonlinear Landau damping.
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 energy decomposition scheme based on information theory.
Imamura, Yutaka; Suzuki, Jun; Nakai, Hiromi
2013-12-15
We proposed a novel kinetic energy decomposition analysis based on information theory. Since the Hirshfeld partitioning for electron densities can be formulated in terms of Kullback-Leibler information deficiency in information theory, a similar partitioning for kinetic energy densities was newly proposed. The numerical assessments confirm that the current kinetic energy decomposition scheme provides reasonable chemical pictures for ionic and covalent molecules, and can also estimate atomic energies using a correction with viral ratios.
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/O
Karanicolas, John; Brooks, Charles L
2004-03-09
Because of the association of beta-sheet formation with the initiation and propagation of amyloid diseases, model systems have been sought to further our understanding of this process. WW domains have been proposed as one such model system. Whereas the folding of the WW domains from human Yes-associated protein (YAP) and Pin have been shown to obey single-exponential kinetics, the folding of the WW domain from formin-binding protein (FBP) 28 has been shown to proceed via biphasic kinetics. From an analysis of free-energy landscapes from atomic-level molecular dynamics simulations, the biphasic folding kinetics observed in the FBP WW domain may be traced to the ability of this WW domain to adopt two slightly different forms of packing in its hydrophobic core. This conformational change is propagated along the peptide backbone and affects the position of a tryptophan residue shown in other WW domains to play a key role in binding. The WW domains of Pin and YAP do not support more than one type of packing each, leading to monophasic folding kinetics. The ability of the FBP WW domain to assume two different types of packing may, in turn, explain the capacity of this WW domain to bind two classes of ligand, a property that is not shared by other WW domains. These findings lead to the hypothesis that lability with respect to conformations separated by an observable barrier as a requirement for function is incompatible with the ability of a protein to fold via single-exponential kinetics.
Stochastic optimization-based study of dimerization kinetics
Srijeeta Talukder; Shrabani Sen; Ralf Metzler; Suman K Banik; Pinaki Chaudhury
2013-11-01
We investigate the potential of numerical algorithms to decipher the kinetic parameters involved in multi-step chemical reactions. To this end, we study dimerization kinetics of protein as a model system. We follow the dimerization kinetics using a stochastic simulation algorithm and combine it with three different optimization techniques (genetic algorithm, simulated annealing and parallel tempering) to obtain the rate constants involved in each reaction step. We find good convergence of the numerical scheme to the rate constants of the process. We also perform a sensitivity test on the reaction kinetic parameters to see the relative effects of the parameters for the associated profile of the monomer/dimer distribution.
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
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.
Kinetics of Cyclohexanone Ammoximation over Titanium Silicate Molecular Sieves
李永祥; 吴巍; 闵恩泽
2005-01-01
An intrinsic kinetics of cyclohexanone ammoximation in the liquid phase over titanium silicate molecular sieves is investigated in an isothermal slurry reactor at different initial reactant concentrations, catalyst loading,and reaction temperature. The rate equations are developed by analyzing data of kinetic measurements. More than 10 side reactions were found. H202 decomposition reaction Inust be considered and other side reactions can be neglected in the kinetic modeling. The predicted values of reaction rates based on the kinetic models are almost consistent with experimental ones. The models have guidance to the selection of reactor types and they are useful to the design and operation of reactor used.
Effect of interface kinetics on the eutectic growth
LI Jinfu; ZHOU Yaohe
2005-01-01
The atom-attachment kinetics at the solid-liquid interface was incorporated into the eutectic growth theory. The dependence of kinetic undercooling on the structure of the eutectic phases was investigated. Due to the introduction of the kinetic effect, the coupled eutectic growth can proceed in a wider undercooling range, but the growth velocity decreases while the minimum eutectic lamellar spacing remains unchanged. The proportion of kinetic undercooling to the total undercooling is dependent not only on the growth velocity, but also on the phase diagram. Calculation indicated that the proportion decreases as the crystallization temperature range of single eutectic phase at the eutectic composition enlarges.
Kinetic modelling of coupled transport across biological membranes.
Korla, Kalyani; Mitra, Chanchal K
2014-04-01
In this report, we have modelled a secondary active co-transporter (symport and antiport), based on the classical kinetics model. Michaelis-Menten model of enzyme kinetics for a single substrate, single intermediate enzyme catalyzed reaction was proposed more than a hundred years ago. However, no single model for the kinetics of co-transport of molecules across a membrane is available in the literature We have made several simplifying assumptions and have followed the basic Michaelis-Menten approach. The results have been simulated using GNU Octave. The results will be useful in general kinetic simulations and modelling.
Probability representation of kinetic equation for open quantum system
Man'ko, V I; Shchukin, E V
2003-01-01
The tomographic probability distribution is used to decribe the kinetic equations for open quantum systems. Damped oscillator is studied. Purity parameter evolution for different damping regime is considered.
Stiripentol kinetics in epilepsy: nonlinearity and interactions.
Levy, R H; Loiseau, P; Guyot, M; Blehaut, H M; Tor, J; Moreland, T A
1984-11-01
Stiripentol kinetics during oral therapy were assessed in six patients with epilepsy who were receiving other antiepileptic drugs. Steady-state levels at 600, 1200, and 2400 mg/day increased in a nonlinear fashion, indicating Michaelis-Menten kinetics. Oral clearance of stiripentol at 600 mg/day was 41.5 +/- 23.4 l/day/kg (mean +/- SD), greater than that at 1200 mg/day (20.3 +/- 8.8 l/day/kg; P less than 0.05) or 2400 mg/day (8.5 +/- 3.8 l/day/kg; P less than 0.01). The apparent in vivo Michaelis-Menten parameters were determined from three mean steady-state concentrations. The average velocity of conversion of stiripentol to its metabolites (Vm), Michaelis constant (Km), and the ratio Vm/Km were 49.3 +/- 13.1 mg/day/kg, 1.35 +/- 1.08 mg/l, and 50.2 +/- 27.5 l/day/kg. Stiripentol reduced the elimination clearances of concomitant antiepileptic drugs. Phenytoin clearance was reduced in all five subjects who received this drug, from a mean control of 29.5 +/- 13.4 l/day to 18.5 +/- 4.6 l/day at a stiripentol dose of 1200 mg/day (P = 0.05) and to 6.48 +/- 2.59 l/day at 2400 mg/day (P less than 0.01). Stiripentol reduced the clearance of carbamazepine in one subject from a control value of 209 l/day to 128 l/day (1200 mg/day) and 61 l/day (2400 mg/day). Stiripentol reduced phenobarbital clearance in two subjects from 3.8 and 5.1 l/day to 2.3 and 3.4 l/day (2400 mg/day). The Michaelis-Menten kinetics of stiripentol, as well as its interactions with other antiepileptic drugs, have important implications in the designing of controlled clinical trials.
Chemical Kinetic Modeling of Biofuel Combustion
Sarathy, Subram Maniam
Bioalcohols, such as bioethanol and biobutanol, are suitable replacements for gasoline, while biodiesel can replace petroleum diesel. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This study's contribution is experimentally validated chemical kinetic combustion mechanisms for biobutanol and biodiesel. Fundamental combustion data and chemical kinetic mechanisms are presented and discussed to improve our understanding of biofuel combustion. The net environmental impact of biobutanol (i.e., n-butanol) has not been studied extensively, so this study first assesses the sustainability of n-butanol derived from corn. The results indicate that technical advances in fuel production are required before commercializing biobutanol. The primary contribution of this research is new experimental data and a novel chemical kinetic mechanism for n-butanol combustion. The results indicate that under the given experimental conditions, n-butanol is consumed primarily via abstraction of hydrogen atoms to produce fuel radical molecules, which subsequently decompose to smaller hydrocarbon and oxygenated species. The hydroxyl moiety in n-butanol results in the direct production of the oxygenated species such as butanal, acetaldehyde, and formaldehyde. The formation of these compounds sequesters carbon from forming soot precursors, but they may introduce other adverse environmental and health effects. Biodiesel is a mixture of long chain fatty acid methyl esters derived from fats and oils. This research study presents high quality experimental data for one large fatty acid methyl ester, methyl decanoate, and models its combustion using an improved skeletal mechanism. The results indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which ultimately lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular
Catalyst Kinetics Analytical Method Study of Ruthenium
Kou ming-ze; Zhan hui-ying; Kou zong-yan
2004-01-01
Color reactions are used to determine ruthenium utilizing spectrophotometer, but the process need high temperature, long time pyrogenation and miscellaneous extraction and it contaminates the enviroment. As the sensitive degree and simple apparatus of catalyst kinetics analytical method, it was extensively attentcd. The fundmental principle means to determinn a certain chemistry reaction rate accelerated by homogeneous catalyst and determine substantial content using the function of the numerical value of of its and the catalyst concentration. Color acid double azo-reagents (chloro-phosphor group, arsenic group and carboxylic acid group) are sensitive color reagent determining uranium and thorium of lanthanon, but the report is few that it is used to determine ruthenium. Since 1990s, the author studied that the ruthenium was possessed evident catalysis to the fade reaction of oxidant (KIO4, KBrO3) oxidating color acid double azo-reagent in acitidy medium and provided the catalyst kinetics analytical method to determine trace ruthenium.sensitive degree was increased 1 ～2 amount than color reaction. The reaction as:The original concentration of color acid double azo-reagents is A. The instantaneous absorbency after t reaction time is At. In homogeneous catalyst reaction: log(A0/At) = KCRu3+t. Reaction time t is invarible, so log(A0/At) = K' CRu3+t.Color acid double azo-reagents, such as: chlor-azochlorphosphor(CPA-TC),bromic-azochlorphosphor (CPA-TB), DBS-azochlorphosphor(DBS-CPA), DBC-azochlorphosphor (DBC-CPA), DBOK-azochlorpho sphor (DBOK-CPA), p-iodineazochlorphosphor(CPA-PI),p-acetylazochlorphosphor (CPA-PA), azochlorpho sphorⅢ(CPAⅢ), chlor-azoarsenic (TC-AsA),bromic-azoarsenic (TB-AsA), DBS-azoarsenic(DCS-AsA), DCS-azoarsenic(DCS-AsA),azoarsenicⅢ(AsAⅢ), bromicnityrlazoarsenic (DBN-AsA), P-acetylcarboxy lazo-p,P-acetylcarboxylazo, were utilized in catalyst kinetics system. The author obtains the satisfactory results that color acid double azo-rea gents
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
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 begun...... immediately by artificial ventilation and simultaneous external chest compressions. Epinephrine was administered after 8 min of CPR. One group (n = 5) of animals received no buffer treatment while another (n = 5) received an infusion of 75 mmol sodium bicarbonate and a third group (n = 5) received......, bicarbonate and tris-buffer mixture both quickly passed through the blood-brain barrier. When buffer treatment is indicated during CPR, a buffer which does not increase tissue PCO2 may be the drug of choice....
Neutrino quantum kinetic equations: The collision term
Blaschke, Daniel N.; Cirigliano, Vincenzo
2016-08-01
We derive the collision term relevant for neutrino quantum kinetic equations in the early universe and compact astrophysical objects, displaying its full matrix structure in both flavor and spin degrees of freedom. We include in our analysis neutrino-neutrino processes, scattering and annihilation with electrons and positrons, and neutrino scattering off nucleons (the latter in the low-density limit). After presenting the general structure of the collision terms, we take two instructive limiting cases. The one-flavor limit highlights the structure in helicity space and allows for a straightforward interpretation of the off-diagonal entries in terms of the product of scattering amplitudes of the two helicity states. The isotropic limit is relevant for studies of the early universe: in this case the terms involving spin coherence vanish and the collision term can be expressed in terms of two-dimensional integrals, suitable for computational implementation.
Kinetic intermittency in magnetized plasma turbulence
Teaca, Bogdan; Told, Daniel; Jenko, Frank
2016-01-01
We employ magnetized plasma turbulence, described by a gyrokinetic formalism in an interval ranging from the end of the fluid scales to the electron gyroradius, to introduce the first study of kinetic intermittency, in which nonlinear structures formed directly in the distribution functions are analyzed by accounting for velocity space correlations generated by linear (Landau resonance) and nonlinear phase mixing. Electron structures are found to be strongly intermittent and dominated by linear phase mixing, while nonlinear phase mixing dominates the weakly intermittent ions. This is the first time spatial intermittency and linear phase mixing are shown to be self-consistently linked for the electrons and, as the magnetic field follows the intermittency of the electrons at small scales, explain why magnetic islands are places dominated by Landau damping in steady state turbulence.
Kinetics and mass transfer of atrazine ozonation
Bruno Abreu Calfa
2010-08-01
Full Text Available The kinetics of the atrazine oxidation in aqueous solution by ozone was studied under different initial pH conditions and in the presence of a hydroxyl radical scavenger at pH 2.8. It was verified that the process took place mainly through radical reaction, even in acid medium. Therefore, a relatively high value of 26.4 L/(mol.s for the rate constant of the direct reaction between molecular ozone and atrazine was found. After 10 minutes of oxidation, the degradation of the herbicide was more effective for pH 10.30 than for pHs 6.25 and 2.80. The mass transfer of ozone from the gas phase to the liquid phase was strongly affected by the oxygen flowrate and to a lesser extent by the stirring speed.
PYROLYSIS KINETICS OF WASHED PRECIPITATED LIGNIN
Christina Gustafsson
2009-02-01
Full Text Available This article describes the pyrolysis behavior of precipitated washed lignin in a Laminar Entrained Flow Reactor between 700 and 1000°C and at different residence times. Lignin was precipitated by acidification of softwood black liquor using CO2. After acid washing, the solid material was dried and sieved (80-100 μm. This material was then fed into the reactor at a rate of about 0.1 g/min. The formed gases were analyzed with respect to CO, CO2, and CH4, and char was collected and weighed. A traditional first order Arrhenius kinetic expression, based on the temperature of the particles with respect to residence time, was adapted to the experimental results. The activation energy was found to be 32.1 kJ/mol. The low ash content in the washed lignin gave a very low solid material residue after the reactor.
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 growth regimes with 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.
Revisiting the flocculation kinetics of destabilized asphaltenes.
Vilas Bôas Fávero, Cláudio; Maqbool, Tabish; Hoepfner, Michael; Haji-Akbari, Nasim; Fogler, H Scott
2017-06-01
A comprehensive review of the recently published work on asphaltene destabilization and flocculation kinetics is presented. Four different experimental techniques were used to study asphaltenes undergoing flocculation process in crude oils and model oils. The asphaltenes were destabilized by different n-alkanes and a geometric population balance with the Smoluchowski collision kernel was used to model the asphaltene aggregation process. Additionally, by postulating a relation between the aggregation collision efficiency and the solubility parameter of asphaltenes and the solution, a unified model of asphaltene aggregation model was developed. When the aggregation model is applied to the experimental data obtained from several different crude oil and model oils, the detection time curves collapsed onto a universal single line, indicating that the model successfully captures the underlying physics of the observed process. Copyright © 2016 Elsevier B.V. All rights reserved.
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.
Neutrino Quantum Kinetic Equations: The Collision Term
Blaschke, Daniel N
2016-01-01
We derive the collision term relevant for neutrino quantum kinetic equations in the early universe and compact astrophysical objects, displaying its full matrix structure in both flavor and spin degrees of freedom. We include in our analysis neutrino-neutrino processes, scattering and annihilation with electrons and positrons, and neutrino scattering off nucleons (the latter in the low-density limit). After presenting the general structure of the collision terms, we take two instructive limiting cases. The one-flavor limit highlights the structure in helicity space and allows for a straightforward interpretation of the off-diagonal entries in terms of the product of scattering amplitudes of the two helicity states. The isotropic limit is relevant for studies of the early universe: in this case the terms involving spin coherence vanish and the collision term can be expressed in terms of two-dimensional integrals, suitable for computational implementation.
Numerical Simulation of Solitary Kinetic Alfven Waves
DING Jian; LI Yi; WANG Shui
2008-01-01
Using the two-fluid model in the case of α1 (α=β/2Q, β is the ratio of thermal pressure to magnetic pressure, and Q=m,e/m,I), we numerically investigate the interactions between two solitary kinetic Alfven waves (SKAWs) and between an SKAW and a density discontinuity. The results show that the two SKAWs would remain in their original shapes and propagate at their initiating speeds, which indicates that SKAWs behave just like standard solitons. The simulation also shows that SKAWs will reflect and refract when crossing a discontinuity and propagating into a higher density region. The transmission wave is an SKAW with increasing density, and the reverberation is a disturbance with lower amplitude.
Active biopolymers confer fast reorganization kinetics.
Swanson, Douglas; Wingreen, Ned S
2011-11-18
Many cytoskeletal biopolymers are "active," consuming energy in large quantities. In this Letter, we identify a fundamental difference between active polymers and passive, equilibrium polymers: for equal mean lengths, active polymers can reorganize faster than equilibrium polymers. We show that equilibrium polymers are intrinsically limited to linear scaling between mean lifetime (or mean first-passage time, or MFPT) and mean length, MFPT∼, by analogy to 1D Potts models. By contrast, we present a simple active-polymer model that improves upon this scaling, such that MFPT∼(1/2). Since, to be biologically useful, structural biopolymers must typically be many monomers long yet respond dynamically to the needs of the cell, the difference in reorganization kinetics may help to justify the active polymers' greater energy cost.
Nonlinear theory of kinetic instabilities near threshold
Berk, H.L.; Pekker, M.S. [Univ. of Texas, Austin, TX (United States). Inst. for Fusion Studies; Breizman, B.N. [Texas Univ., Austin, TX (United States). Inst. for Fusion Studies]|[Budker Inst. of Nuclear Physics, Novosibirsk (Russian Federation)
1997-05-01
A new nonlinear equation has been derived and solved for the evolution of an unstable collective mode in a kinetic system close to the threshold of linear instability. The resonant particle response produces the dominant nonlinearity, which can be calculated iteratively in the near-threshold regime as long as the mode doe snot trap resonant particles. With sources and classical relaxation processes included, the theory describes both soft nonlinear regimes, where the mode saturation level is proportional to an increment above threshold, and explosive nonlinear regimes, where the mode grows to a level that is independent of the closeness to threshold. The explosive solutions exhibit mode frequency shifting. For modes that exist in the absence of energetic particles, the frequency shift is both upward and downward. For modes that require energetic particles for their existence, there is a preferred direction of the frequency shift. The frequency shift continues even after the mode traps resonant particles.
Carbon monoxide kinetics following simulated cigarette smoking
Karnik, A.S. (Wayne State Univ., Detroit, MI); Coin, E.J.
1980-05-01
Carbon monoxide kinetics were measured in the blood (% carboxyhemoglobin) and alveolar phase (ppM carbon monoxide) after simulated cigarette smoking. Cigarette smoking was siumlated using the same amount of carbon monoxide that 2R1F cigarettes manufactured by the Tobacco Research Institute would contain. Ten boluses of air containing carbon monoxide equivalent to smoking one cigarette were inhaled by six healthy nonsmoker volunteers. Carbon monoxide in the air phase was measured by an Ecolyzer and carboxyhemoglobin was measured by a CO-Oximeter. The mean rise in alveolar carbon monoxide immediately and 20 min after inhaling the last bolus was 3.3 and 3.1 ppM, respectively (p<.005). The mean rise in carboxyhemoglobin immediately and 20 min after inhalation of the last bolus was 0.8 and 0.5% respectively (P<.005). The changes in carboxyhemoglobin were found to be similar to changes that occur when one cigarette is actually smoked.
4-wave dynamics in kinetic wave turbulence
Chibbaro, Sergio; Rondoni, Lamberto
2016-01-01
A general Hamiltonian wave system with quartic resonances is considered, in the standard kinetic limit of a continuum of weakly interacting dispersive waves with random phases. The evolution equation for the multimode characteristic function $Z$ is obtained within an "interaction representation" and a perturbation expansion in the small nonlinearity parameter. A frequency renormalization is performed to remove linear terms that do not appear in the 3-wave case. Feynman-Wyld diagrams are used to average over phases, leading to a first order differential evolution equation for $Z$. A hierarchy of equations, analogous to the Boltzmann hierarchy for low density gases is derived, which preserves in time the property of random phases and amplitudes. This amounts to a general formalism for both the $N$-mode and the 1-mode PDF equations for 4-wave turbulent systems, suitable for numerical simulations and for investigating intermittency.
Analysis of lipid peroxidation kinetics. I
Doktorov, Alexander B.; Lukzen, Nikita N.; Pedersen, Jørgen Boiden
2008-01-01
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......· , but not for the peroxyl radicals LO·2 as assumed in previous works. The method allows us to derive manageable analytical expressions. Based on literature values of the rate constants we are able to intro- duce speciﬁc simpliﬁcations that allow us to obtain simple analytical expressions for the time dependence of all...
Genuinely Multidimensional Kinetic Scheme For Euler Equations
Tiwari, Praveer
2015-01-01
A new framework based on Boltzmann equation which is genuinely multidimensional and mesh-less is developed for solving Euler's equations. The idea is to use the method of moment of Boltzmann equation to operate in multidimensions using polar coordinates. The aim is to develop a framework which is genuinely multidimensional and can be implemented with different methodologies, no matter whether it is in finite difference, finite volume or finite element form. There is a considerable improvement in capturing shocks and other discontinuities. Also, since the method is multidimensional, the flow features are captured isotropically. The method is further extended to second order using 'Arc of Approach' concept. The framework is developed as a finite difference method (called as GINEUS) and is tested on the benchmark test cases. The results are compared against Kinetic Flux Vector Splitting Method.
Coalescence Kinetics of Lipid Based Bicelles
Hu, Andrew; Fan, Tai-Hsi; Katsaras, John; Xia, Yan; Li, Ming; Nieh, Mu-Ping
2014-03-01
Uniform nanodisc can be self-assembled from lipid mixtures of dimyristoyl phosphatidylcholine (DMPC), dimyristoyl phosphatidylglycerol (DMPG), and dihexanoyl phosphatidylcholine (DHPC). This study focuses on the theoretical and experimental growth kinetics of phospholipid based nanodiscs. Motivation for this project comes from the nanodisc's small size and their potential use as a carrier for drug delivery. It was observed that at high total lipid concentration the nanodiscs are stable at approximately 10 nm. However, growth of these nanodiscs is observed at relatively low total lipid concentrations. Dynamic light scattering (DLS) is used to monitor the size and growth rate of these nanodiscs at different solution conditions. The growth at low concentrations is caused by to the transfer of charged lipid (DMPG) from the discs to the solution, reducing the Columbic interaction. The growth of nanodisc as a function of size and surface potential is modeled using the Smoluchowski transport equation with transport-limited boundary conditions.
Electroreduction Kinetics for Molten Oxide Slags
GAO Yun-ming; CHOU Kuo-chih; GUO Xing-min; WANG Wei
2007-01-01
The oxygen-ion conductor, the reducing agent, and the molten oxide slag containing electroactive matter were used as constituent of a galvanic cell. Metal was directly electroreduced from molten slag using a short-circuit galvanic cell. The following galvanic cell was assembled in the present experiment: graphite rod, [O]Fe-C saturated|ZrO2(MgO)|Cu(l)+(FeO)(slag), and molybdenum wire. The FeO electroreduction reaction was studied through measuring short circuit current by controlling factors such as temperature, the FeO content in molten slags, and the external circuit resistance. An overall kinetics model was developed to describe the process of FeO electroreduction. It was found that the modeled curves were in good agreement with the experimental values. The new oxide reduction method in the metallurgy with controlled oxygen flow was proposed and the metallurgical theory with controlled oxygen flow was developed.
Kinetic fluorimetric determination of gliadins in foods.
Gala, B; Gómez-Hens, A; Pérez-Bendito, D
1996-08-01
Kinetic methodology was applied for the first time to the determination of gliadin proteins by using a stopped-flow mixing technique. The method is based on two simultaneous processes: the reaction between gliadins and sodium dodecyl sulfate and the elimination of the quenching caused by this surfactant of the fluorescence of Cresyl Violet. Thus, the increase in fluorescence intensity with time is directly related to gliadin concentration. The use of this oxazine dye allows dynamic fluorescence measurements at long wavelengths, which avoids potential interferences from the sample matrix. The reaction rate is measured within 5 s, so the method is very suitable for the routine determination of gliadins in food samples. The dynamic range of the calibration graph was 0.5-50 micrograms ml-1 and the LOD was 0.25 microgram ml-1. The RSD was 1.6%. The method was applied to different food samples and the analytical recoveries were 88-107%.