Kinetics from Replica Exchange Molecular Dynamics Simulations.

PubMed

Stelzl, Lukas S; Hummer, Gerhard

2017-08-08

Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.

Morphology and Kinetics of Growth of CaCO3 Precipitates Formed in Saline Water at 30°C

NASA Astrophysics Data System (ADS)

Sui, Xin; Wang, Baohui; Wu, Haiming

2018-02-01

The crystallization kinetics and morphology of CaCO3 crystals precipitated from the high salinity oilfield water were studied. The crystallization kinetics measurements show that nucleation and nuclei growth obey the first order reaction kinetics. The induction period of precipitation is extended in the high salinity solutions. Morphological studies show that impurity ions remain mostly in the solution phase instead of filling the CaCO3 crystal lattice. The morphology of CaCO3 precipitates can be changed from a smooth surface (calcite) to rough spheres (vaterite), and spindle rod bundles, or spherical, ellipsoid, flowers, plates and other shapes (aragonite).

Investigation of the first-order phase transition kinetics using the method of pulsed photothermal surface deformation: radial measurements

NASA Astrophysics Data System (ADS)

Vintzentz, S. V.; Sandomirsky, V. B.

1992-09-01

An extension of the photothermal surface deformation (PTSD) method to study the macroscopic kinetics of the first-order phase transition (PTr) is given. The movement of the phase interface (PI) over a surface with a PTr locally induced in the subsurface volume by a focused laser pulse is investigated for the first time using radial measurements of the PTSD kinetics. For the known metal-to-semiconductor PTr in VO 2 (a good model system) a procedure is suggested for measuring the maximum size rsm of the "hot" (metal) phase on the surface (a parameter most difficult to determine) as well as for estimating the velocity of the PI movement over the surface, vs, and in the bulk, vb. Besides, it is shown that the PTSD method may be used to determine the "local" threshold energy E0 needed for the laser-induced PTr and the "local" latent heat L of the PTr. This demonstrates the feasibility of scanning surface E0- and L-microscopy.

Kinetic study and mechanism of Niclosamide degradation.

PubMed

Zaazaa, Hala E; Abdelrahman, Maha M; Ali, Nouruddin W; Magdy, Maimana A; Abdelkawy, M

2014-11-11

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Kinetic arrest of field-temperature induced first order phase transition in quasi-one dimensional spin system Ca{sub 3}Co{sub 2}O{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

De, Santanu, E-mail: santanujuphys91@gmail.com; Kumar, Kranti; Banerjee, A.

We have found that the geometrically frustrated spin chain compound Ca{sub 3}Co{sub 2}O{sub 6} belonging to Ising like universality class with uniaxial anisotropy shows kinetic arrest of first order intermediate phase (IP) to ferrimagnetic (FIM) transition. In this system, dc magnetization measurements followed by different protocols suggest the coexistence of high temperature IP with equilibrium FIM phase in low temperature. Formation of metastable state due to hindered first order transition has also been probed through cooling and heating in unequal field (CHUF) protocol. Kinetically arrested high temperature IP appears to persist down to almost the spin freezing temperature in thismore » system.« less

Monte Carlo Simulations of the Kinetics of Protein Adsorption

NASA Astrophysics Data System (ADS)

Zhdanov, V. P.; Kasemo, B.

The past decade has been characterized by rapid progress in Monte Carlo simulations of protein folding in a solution. This review summarizes the main results obtained in the field, as a background to the major topic, namely corresponding advances in simulations of protein adsorption kinetics at solid-liquid interfaces. The latter occur via diffusion in the liquid towards the interface followed by actual adsorption, and subsequent irreversible conformational changes, resulting in more or less pronounced denaturation of the native protein structure. The conventional kinetic models describing these steps are based on the assumption that the denaturation transitions obey the first-order law with a single value of the denaturation rate constant kr. The validity of this assumption has been studied in recent lattice Monte Carlo simulations of denaturation of model protein-like molecules with different types of the monomer-monomer interactions. The results obtained indicate that, due to trapping in metastable states, (i) the transition of a molecule to the denatured state is usually nonexponential in time, i.e. it does not obey the first-order law, and (ii) the denaturation transitions of an ensemble of different molecules are characterized by different time scales, i.e. the denaturation process cannot be described by a single rate constant kr. One should, rather, introduce a distribution of values of this rate constant (physically, different values of kr reflect the fact that the transitions to the altered state occurs via different metastable states). The phenomenological kinetics of irreversible adsorption of proteins with and without a distribution of the denaturation rate constant values have been calculated in the limits where protein diffusion in the solution is, respectively, rapid or slow. In both cases, the adsorption kinetics with a distribution of kr are found to be close to those with a single-valued rate constant kr, provided that the average value of kr in

Determination of Dacarbazine Φ-Order Photokinetics, Quantum Yields, and Potential for Actinometry.

PubMed

Maafi, Mounir; Lee, Lok-Yan

2015-10-01

The characterization of drugs' photodegradation kinetics is more accurately achieved by means of the recently developed Φ-order kinetics than by the zero-, first-, and/or second-order classical treatments. The photodegradation of anti-cancer dacarbazine (DBZ) in ethanol has been investigated and found to obey Φ-order kinetics when subjected to continuous and monochromatic irradiation of various wavelengths. Its photochemical efficiency was proven to be wavelength dependent in the 220-350 nm range, undergoing a 50-fold increase. Albeit this variation was well defined by a sigmoid pattern, the overall photoreactivity of DBZ was proven to depend also on the contributions of reactants and experimental attributes. The usefulness of DBZ to serve as a drug-actinometer has been investigated using the mathematical framework of Φ-order kinetics. It has been shown that DBZ in ethanol can represent a good candidate for reliable actinometry in the range 270-350 nm. A detailed and easy-to-implement procedure has been proposed for DBZ actinometry. This procedure could advantageously be implemented prior to the determination of the photodegradation quantum yields. This approach might be found useful for the development of many drug actinometers as alternatives to quinine hydrochloride. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Theory of First Order Chemical Kinetics at the Critical Point of Solution.

PubMed

Baird, James K; Lang, Joshua R

2017-10-26

Liquid mixtures, which have a phase diagram exhibiting a miscibility gap ending in a critical point of solution, have been used as solvents for chemical reactions. The reaction rate in the forward direction has often been observed to slow down as a function of temperature in the critical region. Theories based upon the Gibbs free energy of reaction as the driving force for chemical change have been invoked to explain this behavior. With the assumption that the reaction is proceeding under relaxation conditions, these theories expand the free energy in a Taylor series about the position of equilibrium. Since the free energy is zero at equilibrium, the leading term in the Taylor series is proportional to the first derivative of the free energy with respect to the extent of reaction. To analyze the critical behavior of this derivative, the theories exploit the principle of critical point isomorphism, which is thought to govern all critical phenomena. They find that the derivative goes to zero in the critical region, which accounts for the slowing down observed in the reaction rate. As has been pointed out, however, most experimental rate investigations have been carried out under irreversible conditions as opposed to relaxation conditions [Shen et al. J. Phys. Chem. A 2015, 119, 8784-8791]. Below, we consider a reaction governed by first order kinetics and invoke transition state theory to take into account the irreversible conditions. We express the apparent activation energy in terms of thermodynamic derivatives evaluated under standard conditions as well as the pseudoequilibrium conditions associated with the reactant and the activated complex. We show that these derivatives approach infinity in the critical region. The apparent activation energy follows this behavior, and its divergence accounts for the slowing down of the reaction rate.

Dynamics of the quantum search and quench-induced first-order phase transitions.

PubMed

Coulamy, Ivan B; Saguia, Andreia; Sarandy, Marcelo S

2017-02-01

We investigate the excitation dynamics at a first-order quantum phase transition (QPT). More specifically, we consider the quench-induced QPT in the quantum search algorithm, which aims at finding out a marked element in an unstructured list. We begin by deriving the exact dynamics of the model, which is shown to obey a Riccati differential equation. Then, we discuss the probabilities of success by adopting either global or local adiabaticity strategies. Moreover, we determine the disturbance of the quantum criticality as a function of the system size. In particular, we show that the critical point exponentially converges to its thermodynamic limit even in a fast evolution regime, which is characterized by both entanglement QPT estimators and the Schmidt gap. The excitation pattern is manifested in terms of quantum domain walls separated by kinks. The kink density is then shown to follow an exponential scaling as a function of the evolution speed, which can be interpreted as a Kibble-Zurek mechanism for first-order QPTs.

Invasion-wave-induced first-order phase transition in systems of active particles.

PubMed

Ihle, Thomas

2013-10-01

An instability near the transition to collective motion of self-propelled particles is studied numerically by Enskog-like kinetic theory. While hydrodynamics breaks down, the kinetic approach leads to steep solitonlike waves. These supersonic waves show hysteresis and lead to an abrupt jump of the global order parameter if the noise level is changed. Thus they provide a mean-field mechanism to change the second-order character of the phase transition to first order. The shape of the wave is shown to follow a scaling law and to quantitatively agree with agent-based simulations.

Semi-local machine-learned kinetic energy density functional with third-order gradients of electron density

NASA Astrophysics Data System (ADS)

Seino, Junji; Kageyama, Ryo; Fujinami, Mikito; Ikabata, Yasuhiro; Nakai, Hiromi

2018-06-01

A semi-local kinetic energy density functional (KEDF) was constructed based on machine learning (ML). The present scheme adopts electron densities and their gradients up to third-order as the explanatory variables for ML and the Kohn-Sham (KS) kinetic energy density as the response variable in atoms and molecules. Numerical assessments of the present scheme were performed in atomic and molecular systems, including first- and second-period elements. The results of 37 conventional KEDFs with explicit formulae were also compared with those of the ML KEDF with an implicit formula. The inclusion of the higher order gradients reduces the deviation of the total kinetic energies from the KS calculations in a stepwise manner. Furthermore, our scheme with the third-order gradient resulted in the closest kinetic energies to the KS calculations out of the presented functionals.

Sorption kinetics of Zn (II) ion by thermally treated rice husk

NASA Astrophysics Data System (ADS)

Ong, K. K.; Tarmizi, A. F. A.; Wan Yunus W. M., Z.; Safidin, K. M.; Fitrianto, A.; Hussin, A. G. A.; Azmi, F. M.

2015-05-01

Agricultural wastes such as orange peels, tea leave waste, rice husk and corn cobs have been widely studied as sorbents for heavy metal ion removal from various wastewaters. In order to understand their sorption mechanism, the adsorption kinetics is studied. This report describes the kinetics study of a thermally treated rice husk to adsorb Zn (II) ion from an aqueous solution. The adsorbent was obtained by heating the rice husk in a furnace at 500°C for two hours. Increase the contact period improved percentage of the removal of Zn (II) ion until an equilibrium was reached. The data obtained showed that the adsorption of Zn (II) ion by thermally treated rice husk obeyed pseudo-second order kinetics model, which is in agreement with chemisorption as the rate limiting mechanism.

Kinetic effects on double hysteresis in spin crossover molecular magnets analyzed with first order reversal curve diagram technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stan, Raluca-Maria; Gaina, Roxana; Enachescu, Cristian, E-mail: cristian.enachescu@uaic.ro, E-mail: radu.tanasa@uaic.ro

2015-05-07

In this paper, we analyze two types of hysteresis in spin crossover molecular magnets compounds in the framework of the First Order Reversal Curve (FORC) method. The switching between the two stable states in these compounds is accompanied by hysteresis phenomena if the intermolecular interactions are higher than a threshold. We have measured the static thermal hysteresis (TH) and the kinetic light induced thermal hysteresis (LITH) major loops and FORCs for the polycrystalline Fe(II) spin crossover compound [Fe{sub 1−x}Zn{sub x}(bbtr){sub 3}](ClO{sub 4}){sub 2} (bbtr = 1,4-di(1,2,3-triazol-1-yl)butane), either in a pure state (x = 0) or doped with Zn ions (x = 0.33) considering different sweeping rates.more » Here, we use this method not only to infer the domains distribution but also to disentangle between kinetic and static components of the LITH and to estimate the changes in the intermolecular interactions introduced by dopants. We also determined the qualitative relationship between FORC distributions measured for TH and LITH.« less

Kinetically Inhibited Order in a Diamond-Lattice Antiferromagnet

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacDougall, Gregory J; Gout, Delphine J; Zarestky, Jerel L

2011-01-01

Frustrated magnetic systems exhibit highly degenerate ground states and strong fluctuations, often leading to new physics. An intriguing example of current interest is the antiferromagnet on a diamond lattice, realized physically in the A-site spinel materials. This is a prototypical system in three dimensions where frustration arises from competing interactions rather than purely geometric constraints, and theory suggests the possibility of novel order at low temperature. Here we present a comprehensive single crystal neutron scattering study CoAl2O4, a highly frustrated A-site spinel. We observe strong diffuse scattering that peaks at wavevectors associated with Neel ordering. Below the temperature T*=6.5K, theremore » is a dramatic change in elastic scattering lineshape accompanied by the emergence of well-defined spin-wave excitations. T* had previously been associated with the onset of glassy behavior. Our new results suggest instead that in fact T* signifies a first-order phase transition, but with true long-range order inhibited by the kinetic freezing of domain walls. This scenario might be expected to occur widely in frustrated systems containing first-order phase transitions and is a natural explanation for existing reports of anomalous glassy behavior in other materials.« less

Numerical study of Potts models with aperiodic modulations: influence on first-order transitions

NASA Astrophysics Data System (ADS)

Branco, Nilton; Girardi, Daniel

2012-02-01

We perform a numerical study of Potts models on a rectangular lattice with aperiodic interactions along one spatial direction. The number of states q is such that the transition is a first-order one for the uniform model. The Wolff algorithm is employed, for many lattice sizes, allowing for a finite-size scaling analyses to be carried out. Three different self-dual aperiodic sequences are employed, such that the exact critical temperature is known: this leads to precise results for the exponents. We analyze models with q=6 and 15 and show that the Harris-Luck criterion, originally introduced in the study of continuous transitions, is obeyed also for first-order ones. The new universality class that emerges for relevant aperiodic modulations depends on the number of states of the Potts model, as obtained elsewhere for random disorder, and on the aperiodic sequence. We determine the occurrence of log-periodic behavior, as expected for models with aperiodic modulated interactions.

Kinetics of Polydomain Ordering at Second-Order Phase Transitions (by the Example of the AuCu3 Alloy)

NASA Astrophysics Data System (ADS)

Feldman, E. P.; Stefanovich, L. I.; Gumennyk, K. V.

2008-08-01

Kinetics of polydomain spinodal ordering is studied in alloys of AuCu3 type. We introduce four non-conserved long-range order parameters whose sum, however, is conserved and, using the statistical approach, follow the temporal evolution of their random spatial distribution after a rapid temperature quench. A system of nonlinear differential equations for correlators of second and third order is derived. Asymptotical analysis of this system allows to investigate the scaling regime, which develops on the late stages of evolution and to extract additional information concerning the rate of decrease of the specific volume of disordered regions and the rate of decrease of the average thickness of antiphase boundaries. Comparison of these results to experimental data is given. The quench below the spinodal and the onset of long-range order may be separated by the incubation time, whose origin is different from that in first-order phase transitions. Numerical integration of equations for correlators shows also, that it is possible to prepare a sample in such a way that its further evolution will go with formation of transient kinetically slowed polydomain structures different from the final L12 structure.

First-order inflation

NASA Technical Reports Server (NTRS)

Kolb, Edward W.

1991-01-01

In the original proposal, inflation occurred in the process of a strongly first-order phase transition. This model was soon demonstrated to be fatally flawed. Subsequent models for inflation involved phase transitions that were second-order, or perhaps weakly first-order; some even involved no phase transition at all. Recently the possibility of inflation during a strongly first-order phase transition has been revived. In this talk I will discuss some models for first-order inflation, and emphasize unique signatures that result if inflation is realized in a first-order transition. Before discussing first-order inflation, I will briefly review some of the history of inflation to demonstrate how first-order inflation differs from other models.

Change of wandering pattern with anisotropy in step kinetics

NASA Astrophysics Data System (ADS)

Sato, Masahide; Uwaha, Makio

1999-03-01

We study the effect of anisotropy in step kinetics on the wandering instability of an isolated step. With the asymmetry of the step kinetics, a straight step becomes unstable for long wavelength fluctuations and wanders when the step velocity exceeds a critical value. Near the threshold of the instability, an isotropic step obeys the Kuramoto-Sivashinsky equation, HT=- HXX- HXXXX+( H2X/2), and shows a chaotic pattern. A step with anisotropic kinetics obeys the Benney equation, HT=- HXX- δHXXX- HXXXX+( H2X/2), and the wandering pattern changes: when the anisotropy is strong, δ≫1, the step shows a regular pattern. Near the threshold of the instability, the anisotropy effect becomes strong while that of the step stiffness becomes weak.

Aspects of reheating in first-order inflation

NASA Technical Reports Server (NTRS)

Watkins, Richard; Widrow, Lawrence M.

1991-01-01

Studied here is reheating in theories where inflation is completed by a first-order phase transition. In the scenarios, the Universe decays from its false vacuum state by bubble nucleation. In the first stage of reheating, vacuum energy is converted into kinetic energy for the bubble walls. To help understand this phase, researchers derive a simple expression for the equation of state of a universe filled with expanding bubbles. Eventually, the bubble walls collide. Researchers present numerical simulations of two-bubble collisions clarifying and extending previous work by Hawking, Moss, and Stewart. The researchers' results indicate that wall energy is efficiently converted into coherent scalar waves. Also discussed is particle production due to quantum effects. These effects lead to the decay of the coherent scalar waves. They also lead to direct particle production during bubble-wall collisions. Researchers calculate particle production for colliding walls in both sine-Gordon and theta (4) theories and show that it is far more efficient in the theta (4) case. The relevance of this work for recently proposed models of first order inflation is discussed.

Influence of thermodynamically unfavorable secondary structures on DNA hybridization kinetics

PubMed Central

Hata, Hiroaki; Kitajima, Tetsuro

2018-01-01

Abstract Nucleic acid secondary structure plays an important role in nucleic acid–nucleic acid recognition/hybridization processes, and is also a vital consideration in DNA nanotechnology. Although the influence of stable secondary structures on hybridization kinetics has been characterized, unstable secondary structures, which show positive ΔG° with self-folding, can also form, and their effects have not been systematically investigated. Such thermodynamically unfavorable secondary structures should not be ignored in DNA hybridization kinetics, especially under isothermal conditions. Here, we report that positive ΔG° secondary structures can change the hybridization rate by two-orders of magnitude, despite the fact that their hybridization obeyed second-order reaction kinetics. The temperature dependence of hybridization rates showed non-Arrhenius behavior; thus, their hybridization is considered to be nucleation limited. We derived a model describing how ΔG° positive secondary structures affect hybridization kinetics in stopped-flow experiments with 47 pairs of oligonucleotides. The calculated hybridization rates, which were based on the model, quantitatively agreed with the experimental rate constant. PMID:29220504

The Kinetics and Inhibition of the Enzyme Methemoglobin Reductase

ERIC Educational Resources Information Center

Splittgerber, A. G.; And Others

1975-01-01

Describes an undergraduate biochemistry experiment which involves the preparation and kinetics of an oxidation-reduction enzyme system, methemoglobin reductase. A crude enzyme extract is prepared and assayed spectrophotometrically. The enzyme system obeys Michaelis-Menton kinetics with respect to both substrate and the NADH cofactor. (MLH)

On the relationships between the Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, J. Y.

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 respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme–substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steadymore » state for the enzyme–substrate complex and that the product genesis from enzyme–substrate complex is much slower than the equilibration between enzyme–substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [ E] T of v with respect the total enzyme concentration [ E] T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [ S] T of v with respect to the total substrate

On the relationships between the Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

DOE PAGES

Tang, J. Y.

2015-12-01

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 respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme–substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steadymore » state for the enzyme–substrate complex and that the product genesis from enzyme–substrate complex is much slower than the equilibration between enzyme–substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [ E] T of v with respect the total enzyme concentration [ E] T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [ S] T of v with respect to the total substrate

Degradation kinetics of gamma-oryzanol in antioxidant-stripped rice bran oil during thermal oxidation.

PubMed

Khuwijitjaru, Pramote; Yuenyong, Thippawan; Pongsawatmanit, Rungnaphar; Adachi, Shuji

2009-01-01

Gamma-oryzanol, a group of phytosterol ferulates found in rice bran, possesses antioxidative activity and other bioactivities. The kinetics of thermal degradation of gamma-oryzanol in stripped rice bran oil (SRBO) were investigated under heating at 132, 160, 192 and 222 degrees C for 480, 140, 60 and 50 h, respectively. Losses of the overall gamma-oryzanol and its components (cycloartenyl ferulate, 24-methylene cycloartanyl ferulate, campesteryl ferulate and beta-sitosteryl ferulate) could be expressed by the first-order kinetics model. The rate constant of thermal degradation of gamma-oryzanol increased with increasing heating temperatures. The temperature dependence of the obtained rate constants was found to obey the Arrhenius equation. Campesteryl ferulate showed slightly more thermally resistant than other components at temperature lower than 160 degrees C. However, the change in the absorbance from 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay as a function of heating time exhibited the same pattern for the SRBO with and without gamma-oryzanol for all studied heating temperatures.

Correlation functions in first-order phase transitions

NASA Astrophysics Data System (ADS)

Garrido, V.; Crespo, D.

1997-09-01

Most of the physical properties of systems underlying first-order phase transitions can be obtained from the spatial correlation functions. In this paper, we obtain expressions that allow us to calculate all the correlation functions from the droplet size distribution. Nucleation and growth kinetics is considered, and exact solutions are obtained for the case of isotropic growth by using self-similarity properties. The calculation is performed by using the particle size distribution obtained by a recently developed model (populational Kolmogorov-Johnson-Mehl-Avrami model). Since this model is less restrictive than that used in previously existing theories, the result is that the correlation functions can be obtained for any dependence of the kinetic parameters. The validity of the method is tested by comparison with the exact correlation functions, which had been obtained in the available cases by the time-cone method. Finally, the correlation functions corresponding to the microstructure developed in partitioning transformations are obtained.

A high-order gas-kinetic Navier-Stokes flow solver

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Qibing, E-mail: lqb@tsinghua.edu.c; Xu Kun, E-mail: makxu@ust.h; Fu Song, E-mail: fs-dem@tsinghua.edu.c

2010-09-20

The foundation for the development of modern compressible flow solver is based on the Riemann solution of the inviscid Euler equations. The high-order schemes are basically related to high-order spatial interpolation or reconstruction. In order to overcome the low-order wave interaction mechanism due to the Riemann solution, the temporal accuracy of the scheme can be improved through the Runge-Kutta method, where the dynamic deficiencies in the first-order Riemann solution is alleviated through the sub-step spatial reconstruction in the Runge-Kutta process. The close coupling between the spatial and temporal evolution in the original nonlinear governing equations seems weakened due to itsmore » spatial and temporal decoupling. Many recently developed high-order methods require a Navier-Stokes flux function under piece-wise discontinuous high-order initial reconstruction. However, the piece-wise discontinuous initial data and the hyperbolic-parabolic nature of the Navier-Stokes equations seem inconsistent mathematically, such as the divergence of the viscous and heat conducting terms due to initial discontinuity. In this paper, based on the Boltzmann equation, we are going to present a time-dependent flux function from a high-order discontinuous reconstruction. The theoretical basis for such an approach is due to the fact that the Boltzmann equation has no specific requirement on the smoothness of the initial data and the kinetic equation has the mechanism to construct a dissipative wave structure starting from an initially discontinuous flow condition on a time scale being larger than the particle collision time. The current high-order flux evaluation method is an extension of the second-order gas-kinetic BGK scheme for the Navier-Stokes equations (BGK-NS). The novelty for the easy extension from a second-order to a higher order is due to the simple particle transport and collision mechanism on the microscopic level. This paper will present a hierarchy to

Higher-order kinetic expansion of quantum dissipative dynamics: mapping quantum networks to kinetic networks.

PubMed

Wu, Jianlan; Cao, Jianshu

2013-07-28

We apply a new formalism to derive the higher-order quantum kinetic expansion (QKE) for studying dissipative dynamics in a general quantum network coupled with an arbitrary thermal bath. The dynamics of system population is described by a time-convoluted kinetic equation, where the time-nonlocal rate kernel is systematically expanded of the order of off-diagonal elements of the system Hamiltonian. In the second order, the rate kernel recovers the expression of the noninteracting-blip approximation method. The higher-order corrections in the rate kernel account for the effects of the multi-site quantum coherence and the bath relaxation. In a quantum harmonic bath, the rate kernels of different orders are analytically derived. As demonstrated by four examples, the higher-order QKE can reliably predict quantum dissipative dynamics, comparing well with the hierarchic equation approach. More importantly, the higher-order rate kernels can distinguish and quantify distinct nontrivial quantum coherent effects, such as long-range energy transfer from quantum tunneling and quantum interference arising from the phase accumulation of interactions.

Proofreading of DNA polymerase: a new kinetic model with higher-order terminal effects

NASA Astrophysics Data System (ADS)

Song, Yong-Shun; Shu, Yao-Gen; Zhou, Xin; Ou-Yang, Zhong-Can; Li, Ming

2017-01-01

The fidelity of DNA replication by DNA polymerase (DNAP) has long been an important issue in biology. While numerous experiments have revealed details of the molecular structure and working mechanism of DNAP which consists of both a polymerase site and an exonuclease (proofreading) site, there were quite a few theoretical studies on the fidelity issue. The first model which explicitly considered both sites was proposed in the 1970s and the basic idea was widely accepted by later models. However, all these models did not systematically investigate the dominant factor on DNAP fidelity, i.e. the higher-order terminal effects through which the polymerization pathway and the proofreading pathway coordinate to achieve high fidelity. In this paper, we propose a new and comprehensive kinetic model of DNAP based on some recent experimental observations, which includes previous models as special cases. We present a rigorous and unified treatment of the corresponding steady-state kinetic equations of any-order terminal effects, and derive analytical expressions for fidelity in terms of kinetic parameters under bio-relevant conditions. These expressions offer new insights on how the higher-order terminal effects contribute substantially to the fidelity in an order-by-order way, and also show that the polymerization-and-proofreading mechanism is dominated only by very few key parameters. We then apply these results to calculate the fidelity of some real DNAPs, which are in good agreements with previous intuitive estimates given by experimentalists.

Investigating the kinetics of the enzymatic depolymerization of polygalacturonic acid in continuous UF-membrane reactors.

PubMed

Gallifuoco, Alberto; Cantarella, Maria; Marucci, Mariagrazia

2007-01-01

A stirred tank membrane reactor is used to study the kinetics of polygalacturonic acid (PGA) enzymatic hydrolysis. The reactor operates in semicontinuous configuration: the native biopolymer is loaded at the initial time and the system is continuously fed with the buffer. The effect of retention time (from 101 to 142 min) and membrane molecular weight cutoff (from 1 to 30 kDa) on the rate of permeable oligomers production is investigated. Reaction products are clustered in two different classes, those sized below the membrane cutoff and those above. The reducing power measured in the permeate is used as an estimate of total product concentration. The characteristic breakdown times range from 40 to 100 min. The overall kinetics obeys a first-order law with a characteristic time estimated to 24 min. New mathematical data handling are developed and illustrated using the experimental data obtained. Finally, the body of the experimental results suggests useful indications (reactor productivity, breakdown induction period) for implementing the bioprocess at the industrial scale.

Thermodynamic Analysis of Chemically Reacting Mixtures-Comparison of First and Second Order Models.

PubMed

Pekař, Miloslav

2018-01-01

Recently, a method based on non-equilibrium continuum thermodynamics which derives thermodynamically consistent reaction rate models together with thermodynamic constraints on their parameters was analyzed using a triangular reaction scheme. The scheme was kinetically of the first order. Here, the analysis is further developed for several first and second order schemes to gain a deeper insight into the thermodynamic consistency of rate equations and relationships between chemical thermodynamic and kinetics. It is shown that the thermodynamic constraints on the so-called proper rate coefficient are usually simple sign restrictions consistent with the supposed reaction directions. Constraints on the so-called coupling rate coefficients are more complex and weaker. This means more freedom in kinetic coupling between reaction steps in a scheme, i.e., in the kinetic effects of other reactions on the rate of some reaction in a reacting system. When compared with traditional mass-action rate equations, the method allows a reduction in the number of traditional rate constants to be evaluated from data, i.e., a reduction in the dimensionality of the parameter estimation problem. This is due to identifying relationships between mass-action rate constants (relationships which also include thermodynamic equilibrium constants) which have so far been unknown.

First-order kinetic gas generation model parameters for wet landfills.

PubMed

Faour, Ayman A; Reinhart, Debra R; You, Huaxin

2007-01-01

Landfill gas collection data from wet landfill cells were analyzed and first-order gas generation model parameters were estimated for the US EPA landfill gas emissions model (LandGEM). Parameters were determined through statistical comparison of predicted and actual gas collection. The US EPA LandGEM model appeared to fit the data well, provided it is preceded by a lag phase, which on average was 1.5 years. The first-order reaction rate constant, k, and the methane generation potential, L(o), were estimated for a set of landfills with short-term waste placement and long-term gas collection data. Mean and 95% confidence parameter estimates for these data sets were found using mixed-effects model regression followed by bootstrap analysis. The mean values for the specific methane volume produced during the lag phase (V(sto)), L(o), and k were 33 m(3)/Megagrams (Mg), 76 m(3)/Mg, and 0.28 year(-1), respectively. Parameters were also estimated for three full scale wet landfills where waste was placed over many years. The k and L(o) estimated for these landfills were 0.21 year(-1), 115 m(3)/Mg, 0.11 year(-1), 95 m(3)/Mg, and 0.12 year(-1) and 87 m(3)/Mg, respectively. A group of data points from wet landfills cells with short-term data were also analyzed. A conservative set of parameter estimates was suggested based on the upper 95% confidence interval parameters as a k of 0.3 year(-1) and a L(o) of 100 m(3)/Mg if design is optimized and the lag is minimized.

Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

NASA Astrophysics Data System (ADS)

Wang, Hai-Feng; Lin, Zhen-Quan; Kong, Xiang-Mu

2006-12-01

Two catalyzed-birth models of n-species (n>=2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates Amk and Amj of the same species with the rate kernels Km(k,j) = Kmkj (m = 1,2,...,n, n>=2), and aggregates of An species catalyze a monomer-birth of Al species (l = 1,2,...,n-1) with the catalysis rate kernel Jl(k,j) = Jlkjυ. The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution alk(t) of Al species depends crucially on the value of the catalysis rate parameter υ: (i) alk(t) obeys the conventional scaling law in the case of υ<=0, (ii) alk(t) satisfies a modified scaling form in the case of υ>0. In the second model, the mechanism of monomer-birth of An-species catalyzed by Al species is added on the basis of the first model, that is, the aggregates of Al and An species catalyze each other to cause monomer-birth. The kinetic behaviors of Al and An species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ<=0, (ii) gelling at finite time with υ>0.

Kinetics of Methylmercury Production Revisited

DOE PAGES

Olsen, Todd A.; Muller, Katherine A.; Painter, Scott L.; ...

2018-01-27

Laboratory measurements of the biologically mediated methylation of mercury (Hg) to the neurotoxin monomethylmercury (MMHg) often exhibit kinetics that are inconsistent with first-order kinetic models. Using time-resolved measurements of filter passing Hg and MMHg during methylation/demethylation assays, a multisite kinetic sorption model, and reanalyses of previous assays, we show in this paper that competing kinetic sorption reactions can lead to time-varying availability and apparent non-first-order kinetics in Hg methylation and MMHg demethylation. The new model employing a multisite kinetic sorption model for Hg and MMHg can describe the range of behaviors for time-resolved methylation/demethylation data reported in the literature includingmore » those that exhibit non-first-order kinetics. Additionally, we show that neglecting competing sorption processes can confound analyses of methylation/demethylation assays, resulting in rate constant estimates that are systematically biased low. Finally, simulations of MMHg production and transport in a hypothetical periphyton biofilm bed illustrate the implications of our new model and demonstrate that methylmercury production may be significantly different than projected by single-rate first-order models.« less

Rate kernel theory for pseudo-first-order kinetics of diffusion-influenced reactions and application to fluorescence quenching kinetics.

PubMed

Yang, Mino

2007-06-07

Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.

Parameter estimation and order selection for an empirical model of VO2 on-kinetics.

PubMed

Alata, O; Bernard, O

2007-04-27

In humans, VO2 on-kinetics are noisy numerical signals that reflect the pulmonary oxygen exchange kinetics at the onset of exercise. They are empirically modelled as a sum of an offset and delayed exponentials. The number of delayed exponentials; i.e. the order of the model, is commonly supposed to be 1 for low-intensity exercises and 2 for high-intensity exercises. As no ground truth has ever been provided to validate these postulates, physiologists still need statistical methods to verify their hypothesis about the number of exponentials of the VO2 on-kinetics especially in the case of high-intensity exercises. Our objectives are first to develop accurate methods for estimating the parameters of the model at a fixed order, and then, to propose statistical tests for selecting the appropriate order. In this paper, we provide, on simulated Data, performances of Simulated Annealing for estimating model parameters and performances of Information Criteria for selecting the order. These simulated Data are generated with both single-exponential and double-exponential models, and noised by white and Gaussian noise. The performances are given at various Signal to Noise Ratio (SNR). Considering parameter estimation, results show that the confidences of estimated parameters are improved by increasing the SNR of the response to be fitted. Considering model selection, results show that Information Criteria are adapted statistical criteria to select the number of exponentials.

Adsorptive removal of direct azo dye from aqueous phase onto coal based sorbents: a kinetic and mechanistic study.

PubMed

Venkata Mohan, S; Chandrasekhar Rao, N; Karthikeyan, J

2002-03-01

This communication presents the results pertaining to the investigation conducted on color removal of trisazo direct dye, C.I. Direct Brown 1:1 by adsorption onto coal based sorbents viz. charfines, lignite coal, bituminous coal and comparing results with activated carbon (Filtrasorb-400). The kinetic sorption data indicated the sorption capacity of the different coal based sorbents. The sorption interaction of direct dye on to coal based sorbents obeys first-order irreversible rate equation and activated carbon fits with the first-order reversible rate equation. Intraparticle diffusion studies revealed the dye sorption interaction was complex and intraparticle diffusion was not only the rate limiting step. Isothermal data fit well with the rearranged Langmuir adsorption model. R(L) factor revealed the favorable nature of the isotherm of the dye-coal system. Neutral solution pH yielded maximum dye color removal. Desorption and interruption studies further indicated that the coal based sorbents facilitated chemisorption in the process of dye sorption while, activated carbon resulted in physisorption interaction.

Application of first order rate kinetics to explain changes in bloom toxicity—the importance of understanding cell toxin quotas

NASA Astrophysics Data System (ADS)

Orr, Philip T.; Willis, Anusuya; Burford, Michele A.

2018-04-01

Cyanobacteria are oxygenic photosynthetic Gram-negative bacteria that can form potentially toxic blooms in eutrophic and slow flowing aquatic ecosystems. Bloom toxicity varies spatially and temporally, but understanding the mechanisms that drive these changes remains largely a mystery. Changes in bloom toxicity may result from changes in intracellular toxin pool sizes of cyanotoxins with differing molecular toxicities, and/or from changes in the cell concentrations of toxic and non-toxic cyanobacterial species or strains within bloom populations. We show here how first-order rate kinetics at the cellular level can be used to explain how environmental conditions drive changes in bloom toxicity at the ecological level. First order rate constants can be calculated for changes in cell concentration (μ c: specific cell division rate) or the volumetric biomass concentration (μ g: specific growth rate) between short time intervals throughout the cell cycle. Similar first order rate constants can be calculated for changes in nett volumetric cyanotoxin concentration (μ tox: specific cyanotoxin production rate) over similar time intervals. How μ c (or μ g ) covaries with μ tox over the cell cycle shows conclusively when cyanotoxins are being produced and metabolised, and how the toxicity of cells change in response to environment stressors. When μ tox/μ c>1, cyanotoxin cell quotas increase and individual cells become more toxic because the nett cyanotoxin production rate is higher than the cell division rate. When μ tox/μ c=1, cell cyanotoxin quotas remains fixed because the nett cyanotoxin production rate matches the cell division rate. When μ tox/μ c<1, the cyanotoxin cell quota decreases because either the nett cyanotoxin production rate is lower than the cell division rate, or metabolic breakdown and/or secretion of cyanotoxins is occurring. These fundamental equations describe cyanotoxin metabolism dynamics at the cellular level and provide the necessary

Two-order parameters theory of the metal-insulator phase transition kinetics in the magnetic field

NASA Astrophysics Data System (ADS)

Dubovskii, L. B.

2018-05-01

The metal-insulator phase transition is considered within the framework of the Ginzburg-Landau approach for the phase transition described with two coupled order parameters. One of the order parameters is the mass density which variation is responsible for the origin of nonzero overlapping of the two different electron bands and the appearance of free electron carriers. This transition is assumed to be a first-order phase one. The free electron carriers are described with the vector-function representing the second-order parameter responsible for the continuous phase transition. This order parameter determines mostly the physical properties of the metal-insulator transition and leads to a singularity of the surface tension at the metal-insulator interface. The magnetic field is involved into the consideration of the system. The magnetic field leads to new singularities of the surface tension at the metal-insulator interface and results in a drastic variation of the phase transition kinetics. A strong singularity in the surface tension results from the Landau diamagnetism and determines anomalous features of the metal-insulator transition kinetics.

Kinetics of pulse photothermal surface deformation as a method of studying the phase interface movement in a first-order phase transition

NASA Astrophysics Data System (ADS)

Vintzentz, S. V.; Kiselev, V. F.; Levshin, N. L.; Sandomirskii, V. B.

1991-01-01

The photothermal surface deformation (PTSD) method is used for characterization of the first-order phase transition (PT) for the first time. The advantages of the method are demonstrated experimentally for the well known metal-to-semiconductor PT in VO 2. It is found that near the PT temperature the PTSD pulse in a VO 2 film has a sign opposite to that of the thermoelastic response. The conclusion is drawn that this phenomenon is determined primarily by the contribution of the decrease in the specific volume (Δ V/ V) of the substance involved in the semiconductor-to-metal PT. The sign of Δ V/ V for a submicron polycrystalline VO 2 film is determined. Besides, analysis shows that in the PTSD kinetics measured as a whole we can "separate" a law for the metal-semicon- ductor interface movement (i.e. the interface moves towards the interior of the film when the latter is heated and back towards the surface when it is cooling down). The relative density change due to the PT is estimated based on this law.

Continuum theory of phase separation kinetics for active Brownian particles.

PubMed

Stenhammar, Joakim; Tiribocchi, Adriano; Allen, Rosalind J; Marenduzzo, Davide; Cates, Michael E

2013-10-04

Active Brownian particles (ABPs), when subject to purely repulsive interactions, are known to undergo activity-induced phase separation broadly resembling an equilibrium (attraction-induced) gas-liquid coexistence. Here we present an accurate continuum theory for the dynamics of phase-separating ABPs, derived by direct coarse graining, capturing leading-order density gradient terms alongside an effective bulk free energy. Such gradient terms do not obey detailed balance; yet we find coarsening dynamics closely resembling that of equilibrium phase separation. Our continuum theory is numerically compared to large-scale direct simulations of ABPs and accurately accounts for domain growth kinetics, domain topologies, and coexistence densities.

CO₂ sorption kinetics of scaled-up polyethylenimine-functionalized mesoporous silica sorbent.

PubMed

Al-Marri, M J; Khader, M M; Tawfik, M; Qi, G; Giannelis, E P

2015-03-31

Two CO2 solid sorbents based on polyethylenimine, PEI (M(n) ∼ 423 and 10K), impregnated into mesoporous silica (MPS) foam prepared in kilogram quantities via a scale-up process were synthesized and systematically characterized by a range of analytical and surface techniques. The mesoporous silica sorbent impregnated with lower molecular weight PEI, PEI-423/MPS, showed higher capacity toward CO2 sorption than the sorbent functionalized with the higher molecular weight PEI (PEI-10K/MPS). On the other hand, PEI-10K/MPS exhibited higher thermal stability than PEI-423/MPS. The kinetics of CO2 adsorption on both PEI/MPS fitted well with a double-exponential model. According to this model CO2 adsorption can be divided into two steps: the first is fast and is attributed to CO2 adsorption on the sorbent surface; the second is slower and can be related to the diffusion of CO2 within and between the mesoporous particles. In contrast, the desorption process obeyed first-order kinetics with activation energies of 64.3 and 140.7 kJ mol(-1) for PEI-423/MPS and PEI-10K/MPS, respectively. These studies suggest that the selection of amine is critical as it affects not only sorbent capacity and stability but also the energy penalty associated with sorbent regeneration.

Order-disorder transition of intrinsically disordered kinase inducible transactivation domain of CREB

NASA Astrophysics Data System (ADS)

Liu, Hao; Guo, Xiang; Han, Jingcheng; Luo, Ray; Chen, Hai-Feng

2018-06-01

Transcription factor cyclic Adenosine monophosphate response-element binding protein plays a critical role in the cyclic AMP response pathway via its intrinsically disordered kinase inducible transactivation domain (KID). KID is one of the most studied intrinsically disordered proteins (IDPs), although most previous studies focus on characterizing its disordered state structures. An interesting question that remains to be answered is how the order-disorder transition occurs at experimental conditions. Thanks to the newly developed IDP-specific force field ff14IDPSFF, the quality of conformer sampling for IDPs has been dramatically improved. In this study, molecular dynamics (MD) simulations were used to study the order-to-disorder transition kinetics of KID based on the good agreement with the experiment on its disordered-state properties. Specifically, we tested four force fields, ff99SBildn, ff99IDPs, ff14IDPSFF, and ff14IDPs in the simulations of KID and found that ff14IDPSFF can generate more diversified disordered conformers and also reproduce more accurate experimental secondary chemical shifts. Kinetics analysis of MD simulations demonstrates that the order-disorder transition of KID obeys the first-order kinetics, and the transition nucleus is I127/L128/L141. The possible transition pathways from the nucleus to the last folded residues were identified as I127-R125-L138-L141-S143-A145 and L128-R125-L138-L141-S143-A145 based on a residue-level dynamical network analysis. These computational studies not only provide testable prediction/hypothesis on the order-disorder transition of KID but also confirm that the ff14IDPSFF force field can be used to explore the correlation between the structure and function of IDPs.

Ergodicity convergence test suggests telomere motion obeys fractional dynamics

NASA Astrophysics Data System (ADS)

Kepten, E.; Bronshtein, I.; Garini, Y.

2011-04-01

Anomalous diffusion, observed in many biological processes, is a generalized description of a wide variety of processes, all obeying the same law of mean-square displacement. Identifying the basic mechanisms of these observations is important for deducing the nature of the biophysical systems measured. We implement a previously suggested method for distinguishing between fractional Langevin dynamics, fractional Brownian motion, and continuous time random walk based on the ergodic nature of the data. We apply the method together with the recently suggested P-variation test and the displacement correlation to the lately measured dynamics of telomeres in the nucleus of mammalian cells and find strong evidence that the telomeres motion obeys fractional dynamics. The ergodic dynamics are observed experimentally to fit fractional Brownian or Langevin dynamics.

Chaotic orbits obeying one isolating integral in a four-dimensional map

NASA Astrophysics Data System (ADS)

Muzzio, J. C.

2018-02-01

We have recently presented strong evidence that chaotic orbits that obey one isolating integral besides energy exist in a toy Hamiltonian model with three degrees of freedom and are bounded by regular orbits that isolate them from the Arnold web. The interval covered by those numerical experiments was equivalent to about one million Hubble times in a galactic context. Here, we use a four-dimensional map to confirm our previous results and to extend that interval 50 times. We show that, at least within that interval, features found in lower dimension Hamiltonian systems and maps are also present in our study, e.g. within the phase space occupied by a chaotic orbit that obeys one integral there are subspaces where that orbit does not enter and are, instead, occupied by regular orbits that, if tori, bound other chaotic orbits obeying one integral and, if cantori, produce stickiness. We argue that the validity of our results might exceed the time intervals covered by the numerical experiments.

First-order inflation. [in cosmology

NASA Technical Reports Server (NTRS)

Kolb, Edward W.

1991-01-01

In the original proposal, inflation occurred in the process of a strongly first-order phase transition. This model was soon demonstrated to be fatally flawed. Subsequent models for inflation involved phase transitions that were second-order, or perhaps weakly first-order; some even involved no phase transition at all. Recently the possibility of inflation during a strongly first-order phase transition has been revived. In this paper, some models for first-order inflation are discussed, and unique signatures that result if inflation is realized in a first-order transition are emphasized. Some of the history of inflation is reviewed to demonstrate how first-order inflation differs from other models.

Enzymatic Kinetic Isotope Effects from First-Principles Path Sampling Calculations.

PubMed

Varga, Matthew J; Schwartz, Steven D

2016-04-12

In this study, we develop and test a method to determine the rate of particle transfer and kinetic isotope effects in enzymatic reactions, specifically yeast alcohol dehydrogenase (YADH), from first-principles. Transition path sampling (TPS) and normal mode centroid dynamics (CMD) are used to simulate these enzymatic reactions without knowledge of their reaction coordinates and with the inclusion of quantum effects, such as zero-point energy and tunneling, on the transferring particle. Though previous studies have used TPS to calculate reaction rate constants in various model and real systems, it has not been applied to a system as large as YADH. The calculated primary H/D kinetic isotope effect agrees with previously reported experimental results, within experimental error. The kinetic isotope effects calculated with this method correspond to the kinetic isotope effect of the transfer event itself. The results reported here show that the kinetic isotope effects calculated from first-principles, purely for barrier passage, can be used to predict experimental kinetic isotope effects in enzymatic systems.

Energy Stable Flux Formulas For The Discontinuous Galerkin Discretization Of First Order Nonlinear Conservation Laws

NASA Technical Reports Server (NTRS)

Barth, Timothy; Charrier, Pierre; Mansour, Nagi N. (Technical Monitor)

2001-01-01

We consider the discontinuous Galerkin (DG) finite element discretization of first order systems of conservation laws derivable as moments of the kinetic Boltzmann equation. This includes well known conservation law systems such as the Euler For the class of first order nonlinear conservation laws equipped with an entropy extension, an energy analysis of the DG method for the Cauchy initial value problem is developed. Using this DG energy analysis, several new variants of existing numerical flux functions are derived and shown to be energy stable.

Analytical solution of Luedeking-Piret equation for a batch fermentation obeying Monod growth kinetics.

PubMed

Garnier, Alain; Gaillet, Bruno

2015-12-01

Not so many fermentation mathematical models allow analytical solutions of batch process dynamics. The most widely used is the combination of the logistic microbial growth kinetics with Luedeking-Piret bioproduct synthesis relation. However, the logistic equation is principally based on formalistic similarities and only fits a limited range of fermentation types. In this article, we have developed an analytical solution for the combination of Monod growth kinetics with Luedeking-Piret relation, which can be identified by linear regression and used to simulate batch fermentation evolution. Two classical examples are used to show the quality of fit and the simplicity of the method proposed. A solution for the combination of Haldane substrate-limited growth model combined with Luedeking-Piret relation is also provided. These models could prove useful for the analysis of fermentation data in industry as well as academia. © 2015 Wiley Periodicals, Inc.

Molecular Robots Obeying Asimov's Three Laws of Robotics.

PubMed

Kaminka, Gal A; Spokoini-Stern, Rachel; Amir, Yaniv; Agmon, Noa; Bachelet, Ido

2017-01-01

Asimov's three laws of robotics, which were shaped in the literary work of Isaac Asimov (1920-1992) and others, define a crucial code of behavior that fictional autonomous robots must obey as a condition for their integration into human society. While, general implementation of these laws in robots is widely considered impractical, limited-scope versions have been demonstrated and have proven useful in spurring scientific debate on aspects of safety and autonomy in robots and intelligent systems. In this work, we use Asimov's laws to examine these notions in molecular robots fabricated from DNA origami. We successfully programmed these robots to obey, by means of interactions between individual robots in a large population, an appropriately scoped variant of Asimov's laws, and even emulate the key scenario from Asimov's story "Runaround," in which a fictional robot gets into trouble despite adhering to the laws. Our findings show that abstract, complex notions can be encoded and implemented at the molecular scale, when we understand robots on this scale on the basis of their interactions.

A first approximation kinetic model to predict methane generation from an oil sands tailings settling basin.

PubMed

Siddique, Tariq; Gupta, Rajender; Fedorak, Phillip M; MacKinnon, Michael D; Foght, Julia M

2008-08-01

A small fraction of the naphtha diluent used for oil sands processing escapes with tailings and supports methane (CH(4)) biogenesis in large anaerobic settling basins such as Mildred Lake Settling Basin (MLSB) in northern Alberta, Canada. Based on the rate of naphtha metabolism in tailings incubated in laboratory microcosms, a kinetic model comprising lag phase, rate of hydrocarbon metabolism and conversion to CH(4) was developed to predict CH(4) biogenesis and flux from MLSB. Zero- and first-order kinetic models, respectively predicted generation of 5.4 and 5.1 mmol CH(4) in naphtha-amended microcosms compared to 5.3 (+/-0.2) mmol CH(4) measured in microcosms during 46 weeks of incubation. These kinetic models also predicted well the CH(4) produced by tailings amended with either naphtha-range n-alkanes or BTEX compounds at concentrations similar to those expected in MLSB. Considering 25% of MLSB's 200 million m(3) tailings volume to be methanogenic, the zero- and first-order kinetic models applied over a wide range of naphtha concentrations (0.01-1.0 wt%) predicted production of 8.9-400 million l CH(4) day(-1) from MLSB, which exceeds the estimated production of 3-43 million l CH(4) day(-1). This discrepancy may result from heterogeneity and density of the tailings, presence of nutrients in the microcosms, and/or overestimation of the readily biodegradable fraction of the naphtha in MLSB tailings.

First-order particle acceleration in magnetically driven flows

DOE PAGES

Beresnyak, Andrey; Li, Hui

2016-03-02

In this study, we demonstrate that particles are regularly accelerated while experiencing curvature drift in flows driven by magnetic tension. Some examples of such flows include spontaneous turbulent reconnection and decaying magnetohydrodynamic turbulence, where a magnetic field relaxes to a lower-energy configuration and transfers part of its energy to kinetic motions of the fluid. We show that this energy transfer, which normally causes turbulent cascade and heating of the fluid, also results in a first-order acceleration of non-thermal particles. Since it is generic, this acceleration mechanism is likely to play a role in the production of non-thermal particle distribution inmore » magnetically dominant environments such as the solar chromosphere, pulsar magnetospheres, jets from supermassive black holes, and γ-ray bursts.« less

Polarimetric signatures of a canopy of dielectric cylinders based on first and second order vector radiative transfer theory

NASA Technical Reports Server (NTRS)

Tsang, Leung; Chan, Chi Hou; Kong, Jin AU; Joseph, James

1992-01-01

Complete polarimetric signatures of a canopy of dielectric cylinders overlying a homogeneous half space are studied with the first and second order solutions of the vector radiative transfer theory. The vector radiative transfer equations contain a general nondiagonal extinction matrix and a phase matrix. The energy conservation issue is addressed by calculating the elements of the extinction matrix and the elements of the phase matrix in a manner that is consistent with energy conservation. Two methods are used. In the first method, the surface fields and the internal fields of the dielectric cylinder are calculated by using the fields of an infinite cylinder. The phase matrix is calculated and the extinction matrix is calculated by summing the absorption and scattering to ensure energy conservation. In the second method, the method of moments is used to calculate the elements of the extinction and phase matrices. The Mueller matrix based on the first order and second order multiple scattering solutions of the vector radiative transfer equation are calculated. Results from the two methods are compared. The vector radiative transfer equations, combined with the solution based on method of moments, obey both energy conservation and reciprocity. The polarimetric signatures, copolarized and depolarized return, degree of polarization, and phase differences are studied as a function of the orientation, sizes, and dielectric properties of the cylinders. It is shown that second order scattering is generally important for vegetation canopy at C band and can be important at L band for some cases.

First-order inflation. [in cosmology

NASA Technical Reports Server (NTRS)

Turner, Michael S.

1992-01-01

I discuss the most recent model of inflation. In first-order inflation the inflationary epoch is associated with a first-order phase transition, with the most likely candidate being GUT symmetry breaking. The transition from the false-vacuum inflationary phase to the true-vacuum radiation-dominated phase proceeds through the nucleation and percolation of true-vacuum bubbles. The first successful and simplest model of first-order inflation, extended inflation, is discussed in some detail: evolution of the cosmic-scale factor, reheating, density perturbations, and the production of gravitational waves both from quantum fluctuations and bubble collisions. Particular attention is paid to the most critical issue in any model of first-order inflation: the requirements on the nucleation rate to ensure a graceful transition from the inflationary phase to the radiation-dominated phase.

Using a Datalogger to Determine First-Order Kinetics and Calcium Carbonate in Eggshells

ERIC Educational Resources Information Center

Choi, Martin M. F.; Pui Shan Wong

2004-01-01

The applications of a Pasco CI-6532 pressure sensor used in conjunction with a datalogger to monitor the liberation of carbon dioxide in the reaction CaCO3(s) + 2H(super +)(aq) --> Ca(super 2+)(aq) + CO2 (g) + H2O(I) are described. The method serves for the determination of the chemical kinetics of the reaction and also can be extended to…

An Example of Following Second-Order Kinetics by Simple Laboratory Means

ERIC Educational Resources Information Center

Schreiber, Gisela

1976-01-01

Describes a procedure for studying the kinetics of the second-order hydrolysis of ethylene bromohydrine in alkaline medium by incorporating a substance that changes color as one of the reacting components is depleted. (MLH)

First- and second-order metal-insulator phase transitions and topological aspects of a Hubbard-Rashba system

NASA Astrophysics Data System (ADS)

Marcelino, Edgar

2017-05-01

This paper considers a model consisting of a kinetic term, Rashba spin-orbit coupling and short-range Coulomb interaction at zero temperature. The Coulomb interaction is decoupled by a mean-field approximation in the spin channel using field theory methods. The results feature a first-order phase transition for any finite value of the chemical potential and quantum criticality for vanishing chemical potential. The Hall conductivity is also computed using the Kubo formula in a mean-field effective Hamiltonian. In the limit of infinite mass the kinetic term vanishes and all the phase transitions are of second order; in this case the spontaneous symmetry-breaking mechanism adds a ferromagnetic metallic phase to the system and features a zero-temperature quantization of the Hall conductivity in the insulating one.

Optimization and adsorption kinetic studies of aqueous manganese ion removal using chitin extracted from shells of edible Philippine crabs

NASA Astrophysics Data System (ADS)

Quimque, Mark Tristan J.; Jimenez, Marvin C.; Acas, Meg Ina S.; Indoc, Danrelle Keth L.; Gomez, Enjelyn C.; Tabuñag, Jenny Syl D.

2017-01-01

Manganese is a common contaminant in drinking water along with other metal pollutants. This paper investigates the use of chitin, extracted from crab shells obtained as restaurant throwaway, as an adsorbent in removing manganese ions from aqueous medium. In particular, this aims to optimize the adsorption parameters and look into the kinetics of the process. The adsorption experiments done in this study employed the batch equilibration method. In the optimization, the following parameters were considered: pH and concentration of Mn (II) sorbate solution, particle size and dosage of adsorbent chitin, and adsorbent-adsorbate contact time. At the optimal condition, the order of the adsorption reaction was estimated using kinetic models which describes the process best. It was found out that the adsorption of aqueous Mn (II) ions onto chitin obeys the pseudo-second order model. This model assumes that the adsorption occurred via chemisorption

A family of high-order gas-kinetic schemes and its comparison with Riemann solver based high-order methods

NASA Astrophysics Data System (ADS)

Ji, Xing; Zhao, Fengxiang; Shyy, Wei; Xu, Kun

2018-03-01

Most high order computational fluid dynamics (CFD) methods for compressible flows are based on Riemann solver for the flux evaluation and Runge-Kutta (RK) time stepping technique for temporal accuracy. The advantage of this kind of space-time separation approach is the easy implementation and stability enhancement by introducing more middle stages. However, the nth-order time accuracy needs no less than n stages for the RK method, which can be very time and memory consuming due to the reconstruction at each stage for a high order method. On the other hand, the multi-stage multi-derivative (MSMD) method can be used to achieve the same order of time accuracy using less middle stages with the use of the time derivatives of the flux function. For traditional Riemann solver based CFD methods, the lack of time derivatives in the flux function prevents its direct implementation of the MSMD method. However, the gas kinetic scheme (GKS) provides such a time accurate evolution model. By combining the second-order or third-order GKS flux functions with the MSMD technique, a family of high order gas kinetic methods can be constructed. As an extension of the previous 2-stage 4th-order GKS, the 5th-order schemes with 2 and 3 stages will be developed in this paper. Based on the same 5th-order WENO reconstruction, the performance of gas kinetic schemes from the 2nd- to the 5th-order time accurate methods will be evaluated. The results show that the 5th-order scheme can achieve the theoretical order of accuracy for the Euler equations, and present accurate Navier-Stokes solutions as well due to the coupling of inviscid and viscous terms in the GKS formulation. In comparison with Riemann solver based 5th-order RK method, the high order GKS has advantages in terms of efficiency, accuracy, and robustness, for all test cases. The 4th- and 5th-order GKS have the same robustness as the 2nd-order scheme for the capturing of discontinuous solutions. The current high order MSMD GKS is a

First-principles studies of Te line-ordered alloys in a MoS2 monolayer

NASA Astrophysics Data System (ADS)

Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

2018-04-01

The thermodynamic stability, structural and electronic properties of Te line-ordered alloys are investigated using density functional theory (DFT) methods. Thirty four possible Te line-ordered alloy configurations are found in a 5×5 supercell of a MoS2 monolayer. The calculated formation energies show that the Te line-ordered alloy configurations are thermodynamically stable at 0 K and agree very well with the random alloys. The lowest energy configurations at each concentration correspond to the configuration where the Te atom rows are far apart from each other (avoiding clustering) within the supercell. The variation of the lattice constant at different concentrations obey Vegard's law. The Te line-ordered alloys fine tune the band gap of a MoS2 monolayer although deviating from linearity behavior. Our results suggest that the Te line-ordered alloys can be an effective way to modulate the band gap of a MoS2 monolayer for nanoelectronic, optoelectronic and nanophotonic applications.

Describing the dynamics of processes consisting simultaneously of Poissonian and non-Poissonian kinetics

NASA Astrophysics Data System (ADS)

Eule, S.; Friedrich, R.

2013-03-01

Dynamical processes exhibiting non-Poissonian kinetics with nonexponential waiting times are frequently encountered in nature. Examples are biochemical processes like gene transcription which are known to involve multiple intermediate steps. However, often a second process, obeying Poissonian statistics, affects the first one simultaneously, such as the degradation of mRNA in the above example. The aim of the present article is to provide a concise treatment of such random systems which are affected by regular and non-Poissonian kinetics at the same time. We derive the governing master equation and provide a controlled approximation scheme for this equation. The simplest approximation leads to generalized reaction rate equations. For a simple model of gene transcription we solve the resulting equation and show how the time evolution is influenced significantly by the type of waiting time distribution assumed for the non-Poissonian process.

Can eustatic charts go beyond first-order? Insights from the Permo-Triassic

NASA Astrophysics Data System (ADS)

Guillaume, Benjamin; Monteux, Julien; Pochat, Stéphane; Husson, Laurent; Choblet, Gaël

2016-04-01

To the first order, eustatic charts are in accord with our understanding of the geodynamic processes that control sea level. By extrapolation, second-order features are also thought to obey to the same rules, and are thus often taken for granted. But this assumption may be jeopardized by a close examination of a characteristic example. The Permo-Triassic period is characteristic for both its purported eustatic signal and its geodynamic and climatic setting are well defined and contrasted. Both the fragmentation of the Pangean supercontinent and the late Paleozoic melting of ice sheets argue for a rise of the eustatic sea level (ESL) whereas eustatic charts show the opposite. Here we review the possible mechanisms that could explain the apparent sea level low, and find that some of them do lower the ESL while others instead only modify the referential, either uplifting continents or tilting the margins where the control points are located. In the first category, we find that (i) dynamic deflections of the Earth surface above subduction zones and their location with respect to continents primarily control absolute sea level while the Pangean supercontinent forms and breaks up, (ii) endorheism that ubiquitously developed at the time of Pangean aggregation also contributed to lowering the ESL by storing water out of the oceanic reservoir. In the second category, we show that (i) the thermal uplift associated to supercontinental insulation and (ii) the dynamic uplift associated with the emplacement of a superplume both give rates of change in the range of long-term changes of ESL. We also show that (iii) the dynamic tilting of continental margins not only produces apparent sea level changes, but also modifies the absolute sea level, which in turn may end up in the paradoxical situation wherein fingerprints of ESL drop are found in the geological record whereas ESL is actually rising. We conclude that the establishment of second to third order absolute sea level changes

Kinetics of moisture loss and oil uptake during deep fat frying of Gethi (Dioscorea kamoonensis Kunth) strips.

PubMed

Manjunatha, S S; Ravi, N; Negi, P S; Raju, P S; Bawa, A S

2014-11-01

Investigation was carried out to study kinetics of moisture loss, oil uptake and tristimulus colour during deep fat frying of Gethi (Dioscorea kamoonensis kunth) strips. Deep fat frying of Gethi strips of size 6 × 6 × 40 mm was carried out in a laboratory scale fryer at different temperatures ranging from 120 to 180 °C. The investigation showed that the moisture loss and oil uptake followed the first order kinetics equation (r > 0.95, p < 0.05). The kinetic coefficients for moisture loss and oil uptake increased significantly (p < 0.05) with temperature from 0.166 to 0.889 min(-1) and 0.139 to 0.430 min(-1) respectively. The temperature dependency of rate constants for moisture loss and oil uptake values was described using Arrhenius equation (r > 0.99, p < 0.01). The activation energies for moisture loss and oil uptake were found to be 41.53 KJ/mol and 27.12 KJ/mol respectively. The hunter colour parameters were significantly affected by frying temperature and frying time. The hunter lightness (L) value increased with respect to frying time initially, followed by decline and same trend was observed at higher temperatures of frying with elevated rate, whereas hunter redness (a) value increased significantly (p < 0.01) with time as well as temperature of frying and obeyed zero order rate equation. The temperature dependency kinetic coefficients of Hunter (a) value were described by Arrhenius equation and the energy of activation for change in hunter redness was found to be 42.41 KJ/mol (r > 0.99, p < 0.01). The other hunter colour parameters such as chroma, hue angle and total colour difference were markedly affected by frying temperature as well as frying time.

An efficient and accurate two-stage fourth-order gas-kinetic scheme for the Euler and Navier-Stokes equations

NASA Astrophysics Data System (ADS)

Pan, Liang; Xu, Kun; Li, Qibing; Li, Jiequan

2016-12-01

provides a dynamic process of evolution from the kinetic scale particle free transport to the hydrodynamic scale wave propagation, which provides the physics for the non-equilibrium numerical shock structure construction to the near equilibrium NS solution. As a result, with the implementation of the fifth-order WENO initial reconstruction, in the smooth region the current two-stage GKS provides an accuracy of O ((Δx) 5 ,(Δt) 4) for the Euler equations, and O ((Δx) 5 ,τ2 Δt) for the NS equations, where τ is the time between particle collisions. Many numerical tests, including difficult ones for the Navier-Stokes solvers, have been used to validate the current method. Perfect numerical solutions can be obtained from the high Reynolds number boundary layer to the hypersonic viscous heat conducting flow. Following the two-stage time-stepping framework, the third-order GKS flux function can be used as well to construct a fifth-order method with the usage of both first-order and second-order time derivatives of the flux function. The use of time-accurate flux function may have great advantages on the development of higher-order CFD methods.

Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods.

PubMed

Ho, Yuh-Shan

2006-01-01

A comparison was made of the linear least-squares method and a trial-and-error non-linear method of the widely used pseudo-second-order kinetic model for the sorption of cadmium onto ground-up tree fern. Four pseudo-second-order kinetic linear equations are discussed. Kinetic parameters obtained from the four kinetic linear equations using the linear method differed but they were the same when using the non-linear method. A type 1 pseudo-second-order linear kinetic model has the highest coefficient of determination. Results show that the non-linear method may be a better way to obtain the desired parameters.

Kinetic transition in the order-disorder transformation at a solid/liquid interface

NASA Astrophysics Data System (ADS)

Galenko, P. K.; Nizovtseva, I. G.; Reuther, K.; Rettenmayr, M.

2018-01-01

Phase-field analysis for the kinetic transition in an ordered crystal structure growing from an undercooled liquid is carried out. The results are interpreted on the basis of analytical and numerical solutions of equations describing the dynamics of the phase field, the long-range order parameter as well as the atomic diffusion within the crystal/liquid interface and in the bulk crystal. As an example, the growth of a binary A50B50 crystal is described, and critical undercoolings at characteristic changes of growth velocity and the long-range order parameter are defined. For rapidly growing crystals, analogies and qualitative differences are found in comparison with known non-equilibrium effects, particularly solute trapping and disorder trapping. The results and model predictions are compared qualitatively with results of the theory of kinetic phase transitions (Chernov 1968 Sov. Phys. JETP 26, 1182-1190) and with experimental data obtained for rapid dendritic solidification of congruently melting alloy with order-disorder transition (Hartmann et al. 2009 Europhys. Lett. 87, 40007 (doi:10.1209/0295-5075/87/40007)). This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

Low Temperature Kinetics of the First Steps of Water Cluster Formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bourgalais, J.; Roussel, V.; Capron, M.

2016-03-01

We present a combined experimental and theoretical low temperature kinetic study of water cluster formation. Water cluster growth takes place in low temperature (23-69 K) supersonic flows. The observed kinetics of formation of water clusters are reproduced with a kinetic model based on theoretical predictions for the first steps of clusterization. The temperature-and pressure-dependent association and dissociation rate coefficients are predicted with an ab initio transition state theory based master equation approach over a wide range of temperatures (20-100 K) and pressures (10(-6) - 10 bar).

Obeying patient's rights on the basis of maternity ward.

PubMed

Leszczyńska, K; Dymczyk, K; Wac, K; Krajewska, K

2005-01-01

This work is an attempt to evaluate the extent of knowledge concerning patient's rights and chances to execute these rights in everyday hospital reality. We have collected opinions of the patients from the maternity ward of Independent Central Public Clinical Hospital of Medical University of Silesia in Katowice. We also interested in participation of medical staff in respecting and realization of patient's rights it has become the main objective of this work. To collect the patient's opinions we used a specially prepared questionnaire which has measured obeying patient's rights in the following aspects: the rights to make decisions, the rights to information including the right to inspect medical data, the right to respect privacy and dignity, the right to treatment and care, the right to be in touch with relatives, the right the priest's care, the rights to file a complaint, the right to obey patient's rights. Patient's rights in a delivery room and a maternity ward are not respected to a satisfactory extent which is confirmed by the research results. During the hospitalization the patients aren't informed and they do not acquire almost any knowledge concerning their rights. The patient staying in a maternity ward is in most cases only a passive receiver of medical service.

Dynamo onset as a first-order transition: lessons from a shell model for magnetohydrodynamics.

PubMed

Sahoo, Ganapati; Mitra, Dhrubaditya; Pandit, Rahul

2010-03-01

We carry out systematic and high-resolution studies of dynamo action in a shell model for magnetohydrodynamic (MHD) turbulence over wide ranges of the magnetic Prandtl number PrM and the magnetic Reynolds number ReM. Our study suggests that it is natural to think of dynamo onset as a nonequilibrium first-order phase transition between two different turbulent, but statistically steady, states. The ratio of the magnetic and kinetic energies is a convenient order parameter for this transition. By using this order parameter, we obtain the stability diagram (or nonequilibrium phase diagram) for dynamo formation in our MHD shell model in the (PrM-1,ReM) plane. The dynamo boundary, which separates dynamo and no-dynamo regions, appears to have a fractal character. We obtain a hysteretic behavior of the order parameter across this boundary and suggestions of nucleation-type phenomena.

First order ball bearing kinematics

NASA Technical Reports Server (NTRS)

Kingbury, E.

1984-01-01

Two first order equations are given connecting geometry and internal motions in an angular contact ball bearing. Total speed, kinematic equivalence, basic speed ratio, and modal speed ratio are defined and discussed; charts are given for the speed ratios covering all bearings and all rotational modes. Instances where specific first order assumptions might fail are discussed, and the resulting effects on bearing performance reviewed.

Organic Lecture Demonstrations of Common-Ion Effect, Ionizing Power of Solvents, and First-Order Reaction Kinetics.

ERIC Educational Resources Information Center

Danen, Wayne C.; Blecha, M. Therese, Sr.

1982-01-01

Background information and experimental procedures are provided for three lecture-demonstrations (involving hydrolysis of tetra-butyl chloride) illustrating: (1) common-ion or mass law effect; (2) effect of changing ionizing power of a solvent on a solvolysis reaction; and (3) collecting/plotting data to illustrate a first-order reaction.…

Dike intrusions during rifting episodes obey scaling relationships similar to earthquakes.

PubMed

Passarelli, L; Rivalta, E; Shuler, A

2014-01-28

As continental rifts evolve towards mid-ocean ridges, strain is accommodated by repeated episodes of faulting and magmatism. Discrete rifting episodes have been observed along two subaerial divergent plate boundaries, the Krafla segment of the Northern Volcanic Rift Zone in Iceland and the Manda-Hararo segment of the Red Sea Rift in Ethiopia. In both cases, the initial and largest dike intrusion was followed by a series of smaller intrusions. By performing a statistical analysis of these rifting episodes, we demonstrate that dike intrusions obey scaling relationships similar to earthquakes. We find that the dimensions of dike intrusions obey a power law analogous to the Gutenberg-Richter relation, and the long-term release of geodetic moment is governed by a relationship consistent with the Omori law. Due to the effects of magma supply, the timing of secondary dike intrusions differs from that of the aftershocks. This work provides evidence of self-similarity in the rifting process.

Dike intrusions during rifting episodes obey scaling relationships similar to earthquakes

PubMed Central

L., Passarelli; E., Rivalta; A., Shuler

2014-01-01

As continental rifts evolve towards mid-ocean ridges, strain is accommodated by repeated episodes of faulting and magmatism. Discrete rifting episodes have been observed along two subaerial divergent plate boundaries, the Krafla segment of the Northern Volcanic Rift Zone in Iceland and the Manda-Hararo segment of the Red Sea Rift in Ethiopia. In both cases, the initial and largest dike intrusion was followed by a series of smaller intrusions. By performing a statistical analysis of these rifting episodes, we demonstrate that dike intrusions obey scaling relationships similar to earthquakes. We find that the dimensions of dike intrusions obey a power law analogous to the Gutenberg-Richter relation, and the long-term release of geodetic moment is governed by a relationship consistent with the Omori law. Due to the effects of magma supply, the timing of secondary dike intrusions differs from that of the aftershocks. This work provides evidence of self-similarity in the rifting process. PMID:24469260

A Classical Based Derivation of Time Dilation Providing First Order Accuracy to Schwarzschild's Solution of Einstein's Field Equations

NASA Astrophysics Data System (ADS)

Austin, Rickey W.

In Einstein's theory of Special Relativity (SR), one method to derive relativistic kinetic energy is via applying the classical work-energy theorem to relativistic momentum. This approach starts with a classical based work-energy theorem and applies SR's momentum to the derivation. One outcome of this derivation is relativistic kinetic energy. From this derivation, it is rather straight forward to form a kinetic energy based time dilation function. In the derivation of General Relativity a common approach is to bypass classical laws as a starting point. Instead a rigorous development of differential geometry and Riemannian space is constructed, from which classical based laws are derived. This is in contrast to SR's approach of starting with classical laws and applying the consequences of the universal speed of light by all observers. A possible method to derive time dilation due to Newtonian gravitational potential energy (NGPE) is to apply SR's approach to deriving relativistic kinetic energy. It will be shown this method gives a first order accuracy compared to Schwarzschild's metric. The SR's kinetic energy and the newly derived NGPE derivation are combined to form a Riemannian metric based on these two energies. A geodesic is derived and calculations compared to Schwarzschild's geodesic for an orbiting test mass about a central, non-rotating, non-charged massive body. The new metric results in high accuracy calculations when compared to Einsteins General Relativity's prediction. The new method provides a candidate approach for starting with classical laws and deriving General Relativity effects. This approach mimics SR's method of starting with classical mechanics when deriving relativistic equations. As a compliment to introducing General Relativity, it provides a plausible scaffolding method from classical physics when teaching introductory General Relativity. A straight forward path from classical laws to General Relativity will be derived. This derivation

Asymptotic orderings and approximations of the Master kinetic equation for large hard spheres systems

NASA Astrophysics Data System (ADS)

Tessarotto, Massimo; Asci, Claudio

2017-05-01

In this paper the problem is posed of determining the physically-meaningful asymptotic orderings holding for the statistical description of a large N-body system of hard spheres, i.e., formed by N ≡1/ε ≫ 1 particles, which are allowed to undergo instantaneous and purely elastic unary, binary or multiple collisions. Starting point is the axiomatic treatment recently developed [Tessarotto et al., 2013-2016] and the related discovery of an exact kinetic equation realized by Master equation which advances in time the 1-body probability density function (PDF) for such a system. As shown in the paper the task involves introducing appropriate asymptotic orderings in terms of ε for all the physically-relevant parameters. The goal is that of identifying the relevant physically-meaningful asymptotic approximations applicable for the Master kinetic equation, together with their possible relationships with the Boltzmann and Enskog kinetic equations, and holding in appropriate asymptotic regimes. These correspond either to dilute or dense systems and are formed either by small-size or finite-size identical hard spheres, the distinction between the various cases depending on suitable asymptotic orderings in terms of ε.

Thermodynamic and Kinetic Properties of Metal Hydrides from First-Principles Calculations

NASA Astrophysics Data System (ADS)

Michel, Kyle Jay

In an effort to minimize the worldwide dependence on fossil fuels, much research has focused on the development of hydrogen fuel cell vehicles. Among the many challenges currently facing the transition to such an alternative energy economy is the storage of hydrogen in an economical and practical way. One class of materials that has presented itself as a possible candidate is solid metal hydrides. These materials chemically bind hydrogen and on heating, release the gas which can then be used to generate power as needed for the vehicle. In order to meet guidelines that have been set for such a storage system, hydrogen must be released rapidly in a narrow temperature range of -40 to 80°C with all reactions being reversible. This sets both thermodynamic and kinetic requirements for the design of candidate metal hydrides. First-principles calculations are well-suited for the task of exploring reactions involving metal hydrides. Here, density-functional theory is used to calculate properties of these materials at the quantum mechanical level of accuracy. In particular, three systems have been investigated: 1. Li-Mg-N-H. Reactions between all known compounds in this system are systematically investigated in order to predict thermodynamically allowed reactions that release hydrogen. The properties of these reactions are compared to the requirements set for hydrogen storage systems. Additionally, ground-state structures are predicted for Li2Mg(NH)2 and Li 4Mg(NH)3. 2. Na-Al-H. The kinetics of mass transport during the (de)hydrogenation of the well-known metal hydride NaAlH4 are investigated. A model is developed to study the flux of native defects through phases involved in these reactions. Since it is also known that titanium is an effective catalyst for both dehydrogenation and rehydrogenation, the effect of Ti substitution in bulk lattices on the kinetics of mass transport is investigated. Results are compared to experiments in order to determine if mass transport

Second order kinetic theory of parallel momentum transport in collisionless drift wave turbulence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yang, E-mail: lyang13@mails.tsinghua.edu.cn; Southwestern Institute of Physics, Chengdu 610041; Gao, Zhe

A second order kinetic model for turbulent ion parallel momentum transport is presented. A new nonresonant second order parallel momentum flux term is calculated. The resonant component of the ion parallel electrostatic force is the momentum source, while the nonresonant component of the ion parallel electrostatic force compensates for that of the nonresonant second order parallel momentum flux. The resonant component of the kinetic momentum flux can be divided into three parts, including the pinch term, the diffusive term, and the residual stress. By reassembling the pinch term and the residual stress, the residual stress can be considered as amore » pinch term of parallel wave-particle resonant velocity, and, therefore, may be called as “resonant velocity pinch” term. Considering the resonant component of the ion parallel electrostatic force is the transfer rate between resonant ions and waves (or, equivalently, nonresonant ions), a conservation equation of the parallel momentum of resonant ions and waves is obtained.« less

Joint experimental and DFT study of the gas-phase unimolecular elimination kinetic of methyl trifluoropyruvate.

PubMed

Tosta, María M; Mora, José R; Córdova, Tania; Chuchani, Gabriel

2010-08-05

The elimination kinetics of methyl trifluoropyruvate in the gas phase was determined in a static system, where the reaction vessel was always deactivated with allyl bromide, and in the presence of at least a 3-fold excess of the free-radical chain inhibitor toluene. The working temperature range was 388.5-430.1 degrees C, and the pressure range was 38.6-65.8 Torr. The reaction was found to be homogeneous and unimolecular and to obey a first-order rate law. The products of the reaction are methyl trifluoroacetate and CO gas. The Arrhenius equation of this elimination was found to be as follows: log k(1) (s(-1)) = (12.48 +/- 0.32) - (204.2 +/- 4.2) kJ mol(-1)(2.303RT)(-1) (r = 0.9994). The theoretical calculation of the kinetic and thermodynamic parameters and the mechanism of this reaction were carried out at the B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), MPW1PW91/6-31G(d,p), MPW1PW91/6-31++G(d,p), PBEPBE/6-31G(d,p), and PBEPBE/6-31G++(d,p) levels of theory. The theoretical study showed that the preferred reaction channel is a 1,2-migration of OCH(3) involving a three-membered cyclic transition state in the rate-determining step.

Kinetic Modeling of the Release of Ethylene Oxide from Sterilized Plastic Containers and its Interaction with Monoclonal Antibodies.

PubMed

Yu, Bryan Lei; Han, Jun; Hammond, Matthew; Wang, Xuemei; Zhang, Qingchun; Clausen, Andrew; Forster, Ronald; Eu, Mingda

2016-12-14

Ethylene oxide (ETO) is commonly used to sterilize plastic containers, but the effects of residual amounts left after sterilization on protein therapeutics are still not well understood. Here we focus primarily on the factors that influence concentrations of ETO migrating from ETO-treated plastic containers. A study was designed to investigate the kinetics of this process at various temperatures, and the kinetic data could be fit with a model based on a combination of Fickean diffusion and first order chemical reaction (to account for observed hydrolysis of ETO). The diffusion and reaction rate constants thus obtained obey Arrhenius-like temperature dependence. These results indicate that even with the use of an effective extraction protocol and sensitive analytical method, measurements of residual ETO in a container must account for the effects of ETO hydrolysis. Further, the effects of salt concentration and pH of the fluid in the container on accumulated ETO levels were explored. Finally, interactions of ETO with anti-streptavidin (AntiSA) IgG1 and IgG2 antibodies were studied, with ETO adducts found on all methionine residues when incubated in solutions spiked with ETO at concentrations that could be reached (based on the kinetic studies) in ETO-treated plastic vials. Overall, the likelihood of observable ETO-protein modifications upon storage in ETO-sterilized containers will depend on a complex interplay of protein properties, formulation details, storage conditions, and amount of residual ETO initially in the container. Copyright © 2016, Parenteral Drug Association.

The kinetics of cooked meat haemoprotein formation in meat and model systems.

PubMed

Geileskey, A; King, R D; Corte, D; Pinto, P; Ledward, D A

1998-03-01

The rate of cooked meat haemoprotein formation (measured as the rate of loss of myoglobin solubility) was found, at least initially, to obey first order kinetics in meat, aqueous muscle extracts and mixtures of myoglobin and bovine serum albumin. In meat at 60 °C the rate was dependent on the species, (the pigment was formed significantly faster in lamb m. longissimus dorsi than in beef m. longissimus dorsi) and anatomical location (cooked meat haemoprotein was formed in beef m. 1. dorsi about twice as rapidly as in both beef shin and chuck (shoulder) muscle of similar pH). The rate of formation was similar in aqueous muscle extracts to that found in meat and in these systems increased with decreasing pH. The activation energies for all beef systems studied were similar and typical of those associated with protein denaturation (~300 KJ mol(-1)); however, that from lamb appeared to be lower (~200 KJ mol(-1)). The problems of using colour as an index of temperature reached, either for microbial safety (E. Coli 0157:H7 destruction) or quality are discussed in the light of these results.

Fourth-Order Vibrational Transition State Theory and Chemical Kinetics

NASA Astrophysics Data System (ADS)

Stanton, John F.; Matthews, Devin A.; Gong, Justin Z.

2015-06-01

Second-order vibrational perturbation theory (VPT2) is an enormously successful and well-established theory for treating anharmonic effects on the vibrational levels of semi-rigid molecules. Partially as a consequence of the fact that the theory is exact for the Morse potential (which provides an appropriate qualitative model for stretching anharmonicity), VPT2 calculations for such systems with appropriate ab initio potential functions tend to give fundamental and overtone levels that fall within a handful of wavenumbers of experimentally measured positions. As a consequence, the next non-vanishing level of perturbation theory -- VPT4 -- offers only slight improvements over VPT2 and is not practical for most calculations since it requires information about force constants up through sextic. However, VPT4 (as well as VPT2) can be used for other applications such as the next vibrational correction to rotational constants (the ``gammas'') and other spectroscopic parameters. In addition, the marriage of VPT with the semi-classical transition state theory of Miller (SCTST) has recently proven to be a powerful and accurate treatment for chemical kinetics. In this talk, VPT4-based SCTST tunneling probabilities and cumulative reaction probabilities are give for the first time for selected low-dimensional model systems. The prospects for VPT4, both practical and intrinsic, will also be discussed.

The initial value problem in Lagrangian drift kinetic theory

NASA Astrophysics Data System (ADS)

Burby, J. W.

2016-06-01

> Existing high-order variational drift kinetic theories contain unphysical rapidly varying modes that are not seen at low orders. These unphysical modes, which may be rapidly oscillating, damped or growing, are ushered in by a failure of conventional high-order drift kinetic theory to preserve the structure of its parent model's initial value problem. In short, the (infinite dimensional) system phase space is unphysically enlarged in conventional high-order variational drift kinetic theory. I present an alternative, `renormalized' variational approach to drift kinetic theory that manifestly respects the parent model's initial value problem. The basic philosophy underlying this alternate approach is that high-order drift kinetic theory ought to be derived by truncating the all-orders system phase-space Lagrangian instead of the usual `field particle' Lagrangian. For the sake of clarity, this story is told first through the lens of a finite-dimensional toy model of high-order variational drift kinetics; the analogous full-on drift kinetic story is discussed subsequently. The renormalized drift kinetic system, while variational and just as formally accurate as conventional formulations, does not support the troublesome rapidly varying modes.

A third-order gas-kinetic CPR method for the Euler and Navier-Stokes equations on triangular meshes

NASA Astrophysics Data System (ADS)

Zhang, Chao; Li, Qibing; Fu, Song; Wang, Z. J.

2018-06-01

A third-order accurate gas-kinetic scheme based on the correction procedure via reconstruction (CPR) framework is developed for the Euler and Navier-Stokes equations on triangular meshes. The scheme combines the accuracy and efficiency of the CPR formulation with the multidimensional characteristics and robustness of the gas-kinetic flux solver. Comparing with high-order finite volume gas-kinetic methods, the current scheme is more compact and efficient by avoiding wide stencils on unstructured meshes. Unlike the traditional CPR method where the inviscid and viscous terms are treated differently, the inviscid and viscous fluxes in the current scheme are coupled and computed uniformly through the kinetic evolution model. In addition, the present scheme adopts a fully coupled spatial and temporal gas distribution function for the flux evaluation, achieving high-order accuracy in both space and time within a single step. Numerical tests with a wide range of flow problems, from nearly incompressible to supersonic flows with strong shocks, for both inviscid and viscous problems, demonstrate the high accuracy and efficiency of the present scheme.

The reversibility and first-order nature of liquid–liquid transition in a molecular liquid

PubMed Central

Kobayashi, Mika; Tanaka, Hajime

2016-01-01

Liquid–liquid transition is an intriguing phenomenon in which a liquid transforms into another liquid via the first-order transition. For molecular liquids, however, it always takes place in a supercooled liquid state metastable against crystallization, which has led to a number of serious debates concerning its origin: liquid–liquid transition versus unusual nano-crystal formation. Thus, there have so far been no single example free from such debates, to the best of our knowledge. Here we show experimental evidence that the transition is truly liquid–liquid transition and not nano-crystallization for a molecular liquid, triphenyl phosphite. We kinetically isolate the reverse liquid-liquid transition from glass transition and crystallization with a high heating rate of flash differential scanning calorimetry, and prove the reversibility and first-order nature of liquid–liquid transition. Our finding not only deepens our physical understanding of liquid–liquid transition but may also initiate a phase of its research from both fundamental and applications viewpoints. PMID:27841349

Adolescents' as active agents in the socialization process: legitimacy of parental authority and obligation to obey as predictors of obedience.

PubMed

Darling, Nancy; Cumsille, Patricio; Martínez, M Loreto

2007-04-01

Adolescents' agreement with parental standards and beliefs about the legitimacy of parental authority and their own obligation to obey were used to predict adolescents' obedience, controlling for parental monitoring, rules, and rule enforcement. Hierarchical linear models were used to predict both between-adolescent and within-adolescent, issue-specific differences in obedience in a sample of 703 Chilean adolescents (M age=15.0 years). Adolescents' global agreement with parents and global beliefs about their obligation to obey predicted between-adolescent obedience, controlling for parental monitoring, age, and gender. Adolescents' issue-specific agreement, legitimacy beliefs, and obligation to obey predicted issue-specific obedience, controlling for rules and parents' reports of rule enforcement. The potential of examining adolescents' agreement and beliefs about authority as a key link between parenting practices and adolescents' decisions to obey is discussed.

Photocatalytic degradation of carbofuran by TiO2-coated activated carbon: Model for kinetic, electrical energy per order and economic analysis.

PubMed

Vishnuganth, M A; Remya, Neelancherry; Kumar, Mathava; Selvaraju, N

2016-10-01

The photocatalytic removal of carbofuran (CBF) from aqueous solution in the presence of granular activated carbon supported TiO2 (GAC-TiO2) catalyst was investigated under batch-mode experiments. The presence of GAC enhanced the photocatalytic efficiency of the TiO2 catalyst. Experiments were conducted at different concentrations of CBF to clarify the dependence of apparent rate constant (kapp) in the pseudo first-order kinetics on CBF photodegradation. The general relationship between the adsorption equilibrium constant (K) and reaction rate constant (kr) were explained by using the modified Langmuir-Hinshelwood (L-H) model. From the observed kinetics, it was observed that the surface reaction was the rate limiting step in the GAC-TiO2 catalyzed photodegradation of CBF. The values of K and kr for this pseudo first-order reaction were found to be 0.1942 L  mg(-1) and 1.51 mg L(-1) min(-1), respectively. In addition, the dependence of kapp on the half-life time was determined by calculating the electrical energy per order experimentally (EEO experimental) and also by modeling (EEO model). The batch-mode experimental outcomes revealed the possibility of 100% CBF removal (under optimized conditions and at an initial concentration of 50 mg L(-1) and 100 mg L(-1)) at a contact time of 90 min and 120 min, respectively. Both L-H kinetic model and EEO model fitted well with the batch-mode experimental data and also elucidated successfully the phenomena of photocatalytic degradation in the presence of GAC-TiO2 catalyst. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-order continuum kinetic method for modeling plasma dynamics in phase space

DOE PAGES

Vogman, G. V.; Colella, P.; Shumlak, U.

2014-12-15

Continuum methods offer a high-fidelity means of simulating plasma kinetics. While computationally intensive, these methods are advantageous because they can be cast in conservation-law form, are not susceptible to noise, and can be implemented using high-order numerical methods. Advances in continuum method capabilities for modeling kinetic phenomena in plasmas require the development of validation tools in higher dimensional phase space and an ability to handle non-cartesian geometries. To that end, a new benchmark for validating Vlasov-Poisson simulations in 3D (x,v x,v y) is presented. The benchmark is based on the Dory-Guest-Harris instability and is successfully used to validate a continuummore » finite volume algorithm. To address challenges associated with non-cartesian geometries, unique features of cylindrical phase space coordinates are described. Preliminary results of continuum kinetic simulations in 4D (r,z,v r,v z) phase space are presented.« less

Kinetic theory of Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Leegwater, Jan A.

1991-12-01

A kinetic theory that describes the time evolution of a fluid consisting of Lennard-Jones particles at all densities is proposed. The kinetic equation assumes binary collisions, but takes into account the finite time duration of a collision. Furthermore, it is an extension of a kinetic equation for the square well fluid as well as the hard sphere Enskog theory. In the low density limit, the Boltzmann theory is obtained. It is shown that the proposed theory obeys all the conservation laws. The exchange of potential and kinetic energies is studied and it is shown that at high density this is a fast process. The dominant mechanism for energy exchange is found to be collisions at the strongly repulsive part of the potential that are disturbed by third particles. The kinetic equation is also used to calculate the Green-Kubo integrands for shear viscosity and heat conductivity. The major structures found in molecular dynamics simulations are reproduced at intermediate densities quantitatively and at high density semiquantitatively. It is found that at high density, not only correlated collisions have to be taken into account, but that even the concept of collisions in the sense of sudden changes in the velocity is no longer useful.

Pseudo second order kinetics and pseudo isotherms for malachite green onto activated carbon: comparison of linear and non-linear regression methods.

PubMed

Kumar, K Vasanth; Sivanesan, S

2006-08-25

Pseudo second order kinetic expressions of Ho, Sobkowsk and Czerwinski, Blanachard et al. and Ritchie were fitted to the experimental kinetic data of malachite green onto activated carbon by non-linear and linear method. Non-linear method was found to be a better way of obtaining the parameters involved in the second order rate kinetic expressions. Both linear and non-linear regression showed that the Sobkowsk and Czerwinski and Ritchie's pseudo second order model were the same. Non-linear regression analysis showed that both Blanachard et al. and Ho have similar ideas on the pseudo second order model but with different assumptions. The best fit of experimental data in Ho's pseudo second order expression by linear and non-linear regression method showed that Ho pseudo second order model was a better kinetic expression when compared to other pseudo second order kinetic expressions. The amount of dye adsorbed at equilibrium, q(e), was predicted from Ho pseudo second order expression and were fitted to the Langmuir, Freundlich and Redlich Peterson expressions by both linear and non-linear method to obtain the pseudo isotherms. The best fitting pseudo isotherm was found to be the Langmuir and Redlich Peterson isotherm. Redlich Peterson is a special case of Langmuir when the constant g equals unity.

First- and second-order processing in transient stereopsis.

PubMed

Edwards, M; Pope, D R; Schor, C M

2000-01-01

Large-field stimuli were used to investigate the interaction of first- and second-order pathways in transient-stereo processing. Stimuli consisted of sinewave modulations in either the mean luminance (first-order stimulus) or the contrast (second-order stimulus) of a dynamic-random-dot field. The main results of the present study are that: (1) Depth could be extracted with both the first-order and second-order stimuli; (2) Depth could be extracted from dichoptically mixed first- and second-order stimuli, however, the same stimuli, when presented as a motion sequence, did not result in a motion percept. Based upon these findings we conclude that the transient-stereo system processes both first- and second-order signals, and that these two signals are pooled prior to the extraction of transient depth. This finding of interaction between first- and second-order stereoscopic processing is different from the independence that has been found with the motion system.

In vitro dissolution kinetic study of theophylline from hydrophilic and hydrophobic matrices.

PubMed

Maswadeh, Hamzah M; Semreen, Mohammad H; Abdulhalim, Abdulatif A

2006-01-01

Oral dosage forms containing 300 mg theophylline in matrix type tablets, were prepared by direct compression method using two kinds of matrices, glycerylbehenate (hydrophobic), and (hydroxypropyl)methyl cellulose (hydrophilic). The in vitro release kinetics of these formulations were studied at pH 6.8 using the USP dissolution apparatus with the paddle assemble. The kinetics of the dissolution process were studied by analyzing the dissolution data using four kinetic equations, the zero-order equation, the first-order equation, the Higuchi square root equation and the Hixson-Crowell cube root law. The analysis of the dissolution kinetic data for the theophylline preparations in this study shows that it follows the first order kinetics and the release process involves erosion / diffusion and an alteration in the surface area and diameter of the matrix system, as well as in the diffusion path length from the matrix drug load during the dissolution process. This relation is best described by the use of both the first-order equation and the Hixson-Crowell cube root law.

Adsorption kinetics of NO on ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC)

NASA Astrophysics Data System (ADS)

Chen, Jinghuan; Cao, Feifei; Chen, Songze; Ni, Mingjiang; Gao, Xiang; Cen, Kefa

2014-10-01

Ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC) were prepared using evaporation-induced self-assembly (EISA) method and used to adsorb NO. N2 sorption, X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to confirm their structures. The results showed that the ordered and uniform structures were successfully synthesized and with the introduction of cerium pore properties were not significantly changed. The NO adsorption capacity of OMC was two times larger than that of activated carbon (AC). With the introduction of cerium both the adsorption capacity and the adsorption rate were improved. The effects of residence time and oxygen concentration on NO adsorption were also investigated. Oxygen played an important role in the NO adsorption (especially in the form of chemisorption) and residence time had small influence on the NO adsorption capacity. The NO adsorption kinetics was analyzed using pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion models. The results indicated that the NO adsorption process can be divided into rapid adsorption period, slow adsorption period, and equilibrium adsorption period. The pseudo-second-order model was the most suitable model for NO adsorption on OMC and Ce-OMC. The rate controlling step was the intraparticle diffusion together with the adsorption reaction.

First kinetic discrimination between carbon and oxygen reactivity of enols.

PubMed

García-Río, Luis; Mejuto, Juan C; Parajó, Mercedes; Pérez-Lorenzo, Moisés

2008-11-07

Nitrosation of enols shows a well-differentiated behavior depending on whether the reaction proceeds through the carbon (nucleophilic catalysis is observed) or the oxygen atom (general acid-base catalysis is observed). This is due to the different operating mechanisms for C- and O-nitrosation. Nitrosation of acetylacetone (AcAc) shows a simultaneous nucleophilic and acid-base catalysis. This simultaneous catalysis constitutes the first kinetic evidence of two independent reactions on the carbon and oxygen atom of an enol. The following kinetic study allows us to determine the rate constants for both reaction pathways. A similar reactivity of the nucleophilic centers with the nitrosonium ion is observed.

BTE-OX biodegradation kinetics with MTBE through bioaugmentation.

PubMed

Acuna-Askar, K; Villarreal-Chiu, J F; Gracia-Lozano, M V; Garza-Gonzalez, M T; Chavez-Gomez, B; Rodriguez-Sanchez, I P; Barrera-Saldana, H A

2004-01-01

The biodegradation kinetics of BTE-oX and MTBE, mixed all together, in the presence of bioaugmented bacterial populations as high as 880 mg/L VSS was evaluated. The effect of soil in aqueous samples and the effect of Tergitol NP-10 on substrate biodegradation rates were also evaluated. Biodegradation kinetics was evaluated for 36 hours, every 6 hours. Benzene and o-xylene biodegradation followed a first-order one-phase kinetic model, whereas toluene and ethylbenzene biodegradation was well described by a first-order two-phase kinetic model in all samples. MTBE followed a zero-order removal kinetic model in all samples. The presence of soil in aqueous samples retarded BTE-oX removal rates, with the highest negative effect on o-xylene. The presence of soil enhanced MTBE removal rate. The addition of Tergitol NP-10 to aqueous samples containing soil had a positive effect on substrate removal rate in all samples. Substrate percent removals ranged from 95.4-99.7% for benzene, toluene and ethylbenzene. O-xylene and MTBE percent removals ranged from 55.9-90.1% and 15.6-30.1%, respectively.

Equilibrium, kinetics and mechanism of Au3+, Pd2+ and Ag+ ions adsorption from aqueous solutions by graphene oxide functionalized persimmon tannin.

PubMed

Wang, Zhongmin; Li, Xiaojuan; Liang, Haijun; Ning, Jingliang; Zhou, Zhide; Li, Guiyin

2017-10-01

In this study, a novel bio-adsorbent (PT-GO) was prepared by functionalization persimmon tannin (PT) with graphene oxide (GO) and the effective adsorption behaviors of Au 3+ , Pd 2+ and Ag + ions from aqueous solution was investigated. The PT-GO was characterized by Fourier transform infrared spectrometer (FTIR), scanning electronic microscope (SEM), thermogravimetric analysis (TGA) and Zeta potential. Many influence factors such as pH value, bio-adsorbent dosage, initial concentration of metal ions and contact time were optimized. The maximum adsorption capacity for Au 3+ , Pd 2+ and Ag + was 1325.09mg/g, 797.66mg/g and 421.01mg/g, respectively. The equilibrium isotherm for the adsorption of Au 3+ and Ag + on PT-GO were found to obey the Langmuir model, while the Freundlich model fitted better for Pd 2+ . The adsorption process of Au 3+ , Pd 2+ presented relatively fast adsorption kinetics with pseudo-second-order equation as the best fitting model, while the pseudo-first-order kinetic model was suitable for describing the adsorption of Ag + . Combination of ion exchange, electrostatic interaction and physical adsorption was the mechanism for adsorption of Au 3+ , Pd 2+ and Ag + onto PT-GO bio-adsorbent. Therefore, the PT-GO bio-adsorbent would be an ideal adsorbent for removal of precious metal ions and broaden the potential applications of persimmon tannin in environmental research. Copyright © 2017 Elsevier B.V. All rights reserved.

Discriminating between first- and second-order cognition in first-episode paranoid schizophrenia.

PubMed

Bliksted, Vibeke; Samuelsen, Erla; Sandberg, Kristian; Bibby, Bo Martin; Overgaard, Morten Storm

2017-03-01

An impairment of visually perceiving backward masked stimuli is commonly observed in patients with schizophrenia, yet it is unclear whether this impairment is the result of a deficiency in first or higher order processing and for which subtypes of schizophrenia it is present. Here, we compare identification (first order) and metacognitive (higher order) performance in a visual masking paradigm between a highly homogenous group of young first-episode patients diagnosed with paranoid schizophrenia (N = 11) to that of carefully matched healthy controls (N = 13). We find no difference across groups in first-order performance, but find a difference in metacognitive performance, particularly for stimuli with relatively high visibility. These results indicate that the masking deficit is present in first-episode patients with paranoid schizophrenia, but that it is primarily an impairment of metacognition.

Generalized quantum kinetic expansion: Higher-order corrections to multichromophoric Förster theory

NASA Astrophysics Data System (ADS)

Wu, Jianlan; Gong, Zhihao; Tang, Zhoufei

2015-08-01

For a general two-cluster energy transfer network, a new methodology of the generalized quantum kinetic expansion (GQKE) method is developed, which predicts an exact time-convolution equation for the cluster population evolution under the initial condition of the local cluster equilibrium state. The cluster-to-cluster rate kernel is expanded over the inter-cluster couplings. The lowest second-order GQKE rate recovers the multichromophoric Förster theory (MCFT) rate. The higher-order corrections to the MCFT rate are systematically included using the continued fraction resummation form, resulting in the resummed GQKE method. The reliability of the GQKE methodology is verified in two model systems, revealing the relevance of higher-order corrections.

Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

PubMed

Kumar, K Vasanth

2006-10-11

Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

Individual Differences in Adolescents' Beliefs about the Legitimacy of Parental Authority and Their Own Obligation to Obey: A Longitudinal Investigation

ERIC Educational Resources Information Center

Darling, Nancy; Cumsille, Patricio; Martinez, M. Loreto

2008-01-01

Adolescents' beliefs about the legitimacy of parental authority and obligation to obey were examined in 568 Chilean adolescents (11-14 years old at Wave 1), followed once a year for 4 years. Adolescents' beliefs about parental legitimacy and obligation to obey declined with age. The steepest decline occurred during early adolescence, particularly…

Rarefied gas flow simulations using high-order gas-kinetic unified algorithms for Boltzmann model equations

NASA Astrophysics Data System (ADS)

Li, Zhi-Hui; Peng, Ao-Ping; Zhang, Han-Xin; Yang, Jaw-Yen

2015-04-01

This article reviews rarefied gas flow computations based on nonlinear model Boltzmann equations using deterministic high-order gas-kinetic unified algorithms (GKUA) in phase space. The nonlinear Boltzmann model equations considered include the BGK model, the Shakhov model, the Ellipsoidal Statistical model and the Morse model. Several high-order gas-kinetic unified algorithms, which combine the discrete velocity ordinate method in velocity space and the compact high-order finite-difference schemes in physical space, are developed. The parallel strategies implemented with the accompanying algorithms are of equal importance. Accurate computations of rarefied gas flow problems using various kinetic models over wide ranges of Mach numbers 1.2-20 and Knudsen numbers 0.0001-5 are reported. The effects of different high resolution schemes on the flow resolution under the same discrete velocity ordinate method are studied. A conservative discrete velocity ordinate method to ensure the kinetic compatibility condition is also implemented. The present algorithms are tested for the one-dimensional unsteady shock-tube problems with various Knudsen numbers, the steady normal shock wave structures for different Mach numbers, the two-dimensional flows past a circular cylinder and a NACA 0012 airfoil to verify the present methodology and to simulate gas transport phenomena covering various flow regimes. Illustrations of large scale parallel computations of three-dimensional hypersonic rarefied flows over the reusable sphere-cone satellite and the re-entry spacecraft using almost the largest computer systems available in China are also reported. The present computed results are compared with the theoretical prediction from gas dynamics, related DSMC results, slip N-S solutions and experimental data, and good agreement can be found. The numerical experience indicates that although the direct model Boltzmann equation solver in phase space can be computationally expensive

Effect of electrolyte nature on kinetics of remazol yellow G removal by electrocoagulation

NASA Astrophysics Data System (ADS)

Rajabi, M.; Bagheri-Roochi, M.; Asghari, A.

2011-10-01

The present study describes an electrocoagulation process for the removal of remazol yellow G from dye solutions using Iron as the anode and Steel as the cathode. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to analyze the kinetic data obtained at different concentrations in different conditions. The adsorption kinetics was well described by the pseudo-second-order kinetic model.

Modelling nifedipine photodegradation, photostability and actinometric properties.

PubMed

Maafi, Wassila; Maafi, Mounir

2013-11-01

The photodegradation of drugs obeying unimolecular mechanisms such as that of nifedipine (NIF) were usually characterised in the literature by zero-, first- and second-order kinetics. This approach has been met with varying success. This paper addresses this issue and proposes a novel approach for unimolecular photodegradation kinetics. The photodegradation of the cardiovascular drug nifedipine is investigated within this framework. Experimental kinetic data of nifedipine photodegradation were obtained by continuous monochromatic irradiation and DAD analysis. Fourth-order Runge-Kutta calculated kinetic data served for the validation of the new semi-empirical integrated rate-law model proposed in this study. A new model equation has been developed and proposed which faithfully describes the kinetic behaviour of NIF in solution for non-isosbestic irradiations at wavelengths where both NIF and its photoproduct absorb. NIF absolute quantum yield values were determined and found to increase with irradiation wavelength according to a defined sigmoid relationship. The effects of increasing NIF or excipients' concentrations on NIF kinetics were successfully modelled and found to improve NIF photostability. The potential of NIF for actinometry has been explored and evaluated. A new reaction order (the so-called Φ-order) has been identified and specifically proposed for unimolecular photodegradation reactions. The semi-empirical and integrated rate-law models facilitated reliable kinetic studies of NIF photodegradation as an example of AB(1Φ) unimolecular reactions. It allowed filling a gap in kinetic studies of drugs since, thus far, thermal first-order or a combination of first- and zero- order kinetic equations were generally applied for drug photoreactions in the literature. Also, a new reaction order, the "Φ-order", has been evidenced and proposed as a specific alternative for photodegradation kinetics. Copyright © 2013 Elsevier B.V. All rights reserved.

Fast and calibration free determination of first order reaction kinetics in API synthesis using in-situ ATR-FTIR.

PubMed

Rehbein, Moritz C; Husmann, Sascha; Lechner, Christian; Kunick, Conrad; Scholl, Stephan

2018-05-01

In early stages of drug development only sparse amounts of the key substances are available, which is problematic for the determination of important process data like reaction kinetics. Therefore, it is important to perform experiments as economically as possible, especially in regards to limiting compounds. Here we demonstrate the use of a temperature step experiment enabling the determination of complete reaction kinetics in a single non-isothermal experiment. In contrast to the traditionally used HPLC, the method takes advantage of the high measuring rate and the low amount of labor involved in using in-situ ATR-FTIR to determine time-dependent concentration-equivalent data. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparative evaluation of adsorption kinetics of diclofenac and isoproturon by activated carbon.

PubMed

Torrellas, Silvia A; Rodriguez, Araceli R; Escudero, Gabriel O; Martín, José María G; Rodriguez, Juan G

2015-01-01

Adsorption mechanism of diclofenac and isoproturon onto activated carbon has been proposed using Langmuir and Freundlich isotherms. Adsorption capacity and optimum adsorption isotherms were predicted by nonlinear regression method. Different kinetic equations, pseudo-first-order, pseudo-second-order, intraparticle diffusion model and Bangham kinetic model, were applied to study the adsorption kinetics of emerging contaminants on activated carbon in two aqueous matrices.

Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations

DOE PAGES

Ji, Ho-Il; Davenport, Timothy C.; Gopal, Chirranjeevi Balaji; ...

2016-07-18

The redox kinetics of undoped ceria (CeO 2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO 2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant k chem is found to obey the correlation log(k chem/cm s -1) = (0.84 ± 0.02) × log(pO 2/atm) - (0.99 ± 0.05) and increases withmore » oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.« less

Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations.

PubMed

Ji, Ho-Il; Davenport, Timothy C; Gopal, Chirranjeevi Balaji; Haile, Sossina M

2016-08-03

The redox kinetics of undoped ceria (CeO2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant kchem is found to obey the correlation log(kchem/cm s(-1)) = (0.84 ± 0.02) × log(pO2/atm) - (0.99 ± 0.05) and increases with oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.

Mechanism of alpha-amino acids decomposition in the gas phase. experimental and theoretical study of the elimination kinetics of N-benzyl glycine ethyl ester.

PubMed

Tosta, Maria; Oliveros, Jhenny C; Mora, Jose R; Córdova, Tania; Chuchani, Gabriel

2010-02-25

The gas-phase elimination kinetics of N-benzylglycine ethyl ester was examined in a static system, seasoned with allyl bromide, and in the presence of the free chain radical suppressor toluene. The working temperature and pressure range were 386.4-426.7 degrees C and 16.7-40.0 torr, respectively. The reaction showed to be homogeneous, unimolecular, and obeys a first-order rate law. The elimination products are benzylglycine and ethylene. However, the intermediate benzylglycine is unstable under the reaction conditions decomposing into benzyl methylamine and CO(2) gas. The variation of the rate coefficients with temperature is expressed by the following Arrhenius equation: log k(1) (s(-1)) = (11.83 +/- 0.52) - (190.3 +/- 6.9) kJ mol(-1) (2.303RT)(-1). The theoretical calculation of the kinetic parameters and mechanism of elimination of this ester were performed at B3LYP/6-31G*, B3LYP/6-31+G**, MPW1PW91/6-31G*, and MPW1PW91/6-31+G** levels of theory. The calculation results suggest a molecular mechanism of a concerted nonsynchronous six-membered cyclic transition state process. The analysis of bond order and natural bond orbital charges implies that the bond polarization of C(=O)O-C, in the sense of C(=O)O(delta-)...C(delta+), is rate determining. The experimental and theoretical parameters have been found to be in reasonable agreement.

Second-order Kinetics of DTPA and Plutonium in Rat Plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Guthrie; Poudel, Deepesh; Klumpp, John Allan

We report that in 2008, Serandour et al. reported on their in vitro experiment involving rat plasma samples obtained after an intravenous intake of plutonium citrate. Different amounts of DTPA were added to the plasma samples and the percentage of low-molecular-weight plutonium measured. Only when the DTPA dosage was three orders of magnitude greater than the recommended 30 μmol/kg was 100% of the plutonium apparently in the form of chelate. These data were modeled assuming three competing chemical reactions with other molecules that bind with plutonium. Here, time-dependent second-order kinetics of these reactions are calculated, intended eventually to become partmore » of a complete biokinetic model of DTPA action on actinides in laboratory animals or humans. The probability distribution of the ratio of stability constants for the reactants was calculated using Markov Chain Monte Carlo. In conclusion, these calculations substantiate that the inclusion of more reactions is needed in order to be in agreement with known stability constants.« less

Second-order Kinetics of DTPA and Plutonium in Rat Plasma

DOE PAGES

Miller, Guthrie; Poudel, Deepesh; Klumpp, John Allan; ...

2017-11-15

We report that in 2008, Serandour et al. reported on their in vitro experiment involving rat plasma samples obtained after an intravenous intake of plutonium citrate. Different amounts of DTPA were added to the plasma samples and the percentage of low-molecular-weight plutonium measured. Only when the DTPA dosage was three orders of magnitude greater than the recommended 30 μmol/kg was 100% of the plutonium apparently in the form of chelate. These data were modeled assuming three competing chemical reactions with other molecules that bind with plutonium. Here, time-dependent second-order kinetics of these reactions are calculated, intended eventually to become partmore » of a complete biokinetic model of DTPA action on actinides in laboratory animals or humans. The probability distribution of the ratio of stability constants for the reactants was calculated using Markov Chain Monte Carlo. In conclusion, these calculations substantiate that the inclusion of more reactions is needed in order to be in agreement with known stability constants.« less

Thermo-kinetics of lipase-catalyzed synthesis of 6-O-glucosyldecanoate.

PubMed

Gumel, A M; Annuar, M S M; Heidelberg, T; Chisti, Y

2011-10-01

Lipase-catalyzed synthesis of 6-O-glucosyldecanoate from d-glucose and decanoic acid was performed in dimethyl sulfoxide (DMSO), a mixture of DMSO and tert-butanol and tert-butanol alone with a decreasing order of polarity. The highest conversion yield (> 65%) of decanoic acid was obtained in the blended solvent of intermediate polarity mainly because it could dissolve relatively large amounts of both the reactants. The reaction obeyed Michaelis-Menten type of kinetics. The affinity of the enzyme towards the limiting substrate (decanoic acid) was not affected by the polarity of the solvent, but increased significantly with temperature. The esterification reaction was endothermic with activation energy in the range of 60-67 kJ mol⁻¹. Based on the Gibbs energy values, in the solvent blend of DMSO and tert-butanol the position of the equilibrium was shifted more towards the products compared to the position in pure solvents. Monoester of glucose was the main product of the reaction. Copyright © 2011 Elsevier Ltd. All rights reserved.

Kinetics of a Migration-Driven Aggregation-Fragmentation Process

NASA Astrophysics Data System (ADS)

Zhuang, You-Yi; Lin, Zhen-Quan; Ke, Jian-Hong

2003-08-01

We propose a reversible model of the migration-driven aggregation-fragmentation process with the symmetric migration rate kernels K(k;j)=K^'(k;j)=λ kj^v and the constant aggregation rates I1, I2 and fragmentation rates J1, J2. Based on the mean-field theory, we investigate the evolution behavior of the aggregate size distributions in several cases with different values of index υ. We find that the fragmentation reaction plays a more important role in the kinetic behaviors of the system than the aggregation and migration. When J1=0 and J2 =0, the aggregate size distributions ak(t) and bk(t) obey the conventional scaling law, while when J1>0 and J2>0, they obey the modified scaling law with an exponential scaling function. The total mass of either species remains conserved. The project supported by National Natural Science Foundation of China under Grant Nos. 10275048 and 10175008, and Natural Science Foundation of Zhejiang Province of China under Grant No. 102067

Desorption Kinetics of Methanol, Ethanol, and Water from Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

2014-09-18

The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water the first and second layers are not resolved. At low water coverages (< 1 ML) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10 to 100 ML), the desorption leading edges are in alignmentmore » throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the non-alignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.« less

Desorption kinetics of methanol, ethanol, and water from graphene.

PubMed

Smith, R Scott; Matthiesen, Jesper; Kay, Bruce D

2014-09-18

The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water, the first and second layers are not resolved. At low water coverages (<1 monolayer (ML)) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10-100 ML), the desorption leading edges are in alignment throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the nonalignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.

Effect of soil and a nonionic surfactant on BTE-oX and MTBE biodegradation kinetics.

PubMed

Acuna-Askar, K; Gracia-Lozano, M V; Villarreal-Chiu, J F; Marmolejo, J G; Garza-Gonzalez, M T; Chavez-Gomez, B

2005-01-01

The biodegradation kinetics of BTE-oX and MTBE, mixed all together, in the presence of 905 mg/L VSS of BTEX-acclimated biomass was evaluated. Effects of soil and Tergitol NP-10 in aqueous samples on substrate biodegradation rates were also evaluated. Biodegradation kinetics was evaluated for 36 hours, every 6 hours. MTBE biodegradation followed a first-order one-phase kinetic model in all samples, whereas benzene, toluene and ethylbenzene biodegradation followed a first-order two-phase kinetic model in all samples. O-xylene biodegradation followed a first-order two-phase kinetic model in the presence of biomass only. Interestingly, o-xylene biodegradation was able to switch to a first-order one-phase kinetic model when either soil or soil and Tergitol NP-10 were added. The presence of soil in aqueous samples retarded benzene, toluene and ethylbenzene removal rates. O-xylene and MTBE removal rates were enhanced by soil. The addition of Tergitol NP-10 to aqueous samples containing soil had a positive effect on substrate removal rate in all samples. Substrate percent removals ranged 77-99.8% for benzene, toluene and ethylbenzene. O-xylene and MTBE percent removals ranged 50.1-65.3% and 9.9-43.0%, respectively.

Individual differences in adolescents' beliefs about the legitimacy of parental authority and their own obligation to obey: a longitudinal investigation.

PubMed

Darling, Nancy; Cumsille, Patricio; Martínez, M Loreto

2008-01-01

Adolescents' beliefs about the legitimacy of parental authority and obligation to obey were examined in 568 Chilean adolescents (11-14 years old at Wave 1), followed once a year for 4 years. Adolescents' beliefs about parental legitimacy and obligation to obey declined with age. The steepest decline occurred during early adolescence, particularly in the personal domain. Adolescents who were uninvolved in problem behavior and perceived their parents to be supportive or high in monitoring at Wave 1 were more likely to endorse parental legitimacy and obligation to obey over time. There was little evidence that parenting or problem behavior moderated the normative decline in adolescents' beliefs about parental authority. Findings concerning individual differences in adolescents' endorsement of parental authority are highlighted in this study.

A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies

DOE PAGES

Hoffmann, Max J.; Bligaard, Thomas

2018-01-22

Here, mean-field microkinetic models in combination with Brønsted–Evans–Polanyi like scaling relations have proven highly successful in identifying catalyst materials with good or promising reactivity and selectivity. Analysis of the microkinetic model by means of lattice kinetic Monte Carlo promises a faithful description of a range of atomistic features involving short-range ordering of species in the vicinity of an active site. In this paper, we use the “fruit fly” example reaction of CO oxidation on fcc(111) transition and coinage metals to motivate and develop a lattice kinetic Monte Carlo solver suitable for the numerically challenging case of vastly disparate rate constants.more » As a result, we show that for the case of infinitely fast diffusion and absence of adsorbate-adsorbate interaction it is, in fact, possible to match the prediction of the mean-field-theory method and the lattice kinetic Monte Carlo method. As a corollary, we conclude that lattice kinetic Monte Carlo simulations of surface chemical reactions are most likely to provide additional insight over mean-field simulations if diffusion limitations or adsorbate–adsorbate interactions have a significant influence on the mixing of the adsorbates.« less

A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, Max J.; Bligaard, Thomas

Here, mean-field microkinetic models in combination with Brønsted–Evans–Polanyi like scaling relations have proven highly successful in identifying catalyst materials with good or promising reactivity and selectivity. Analysis of the microkinetic model by means of lattice kinetic Monte Carlo promises a faithful description of a range of atomistic features involving short-range ordering of species in the vicinity of an active site. In this paper, we use the “fruit fly” example reaction of CO oxidation on fcc(111) transition and coinage metals to motivate and develop a lattice kinetic Monte Carlo solver suitable for the numerically challenging case of vastly disparate rate constants.more » As a result, we show that for the case of infinitely fast diffusion and absence of adsorbate-adsorbate interaction it is, in fact, possible to match the prediction of the mean-field-theory method and the lattice kinetic Monte Carlo method. As a corollary, we conclude that lattice kinetic Monte Carlo simulations of surface chemical reactions are most likely to provide additional insight over mean-field simulations if diffusion limitations or adsorbate–adsorbate interactions have a significant influence on the mixing of the adsorbates.« less

First-order metal-insulator transitions in vanadates from first principles

NASA Astrophysics Data System (ADS)

Kumar, Anil; Rabe, Karin

2013-03-01

Materials that exhibit first-order metal-insulator transitions, with the accompanying abrupt change in the conductivity, have potential applications as switches in future electronic devices. Identification of materials and exploration of the atomic-scale mechanisms for switching between the two electronic states is a focus of current research. In this work, we search for first-order metal-insulator transitions in transition metal compounds, with a particular focus on d1 and d2 systems, by using first principles calculations to screen for an alternative low-energy state having not only a electronic character opposite to that of the ground state, but a distinct structure and/or magnetic ordering which would permit switching by an applied field or stress. We will present the results of our investigation of the perovskite compounds SrVO3, LaVO3, CaVO3, YVO3, LaTiO3 and related layered phase, including superlattices and Ruddlesden-Popper phases. While the pure compounds do not satisfy the search criteria, the layered phases show promising results.

Investigating local network interactions underlying first- and second-order processing.

PubMed

Ellemberg, Dave; Allen, Harriet A; Hess, Robert F

2004-01-01

We compared the spatial lateral interactions for first-order cues to those for second-order cues, and investigated spatial interactions between these two types of cues. We measured the apparent modulation depth of a target Gabor at fixation, in the presence and the absence of horizontally flanking Gabors. The Gabors' gratings were either added to (first-order) or multiplied with (second-order) binary 2-D noise. Apparent "contrast" or modulation depth (i.e., the perceived difference between the high and low luminance regions for the first-order stimulus, or between the high and low contrast regions for the second-order stimulus) was measured with a modulation depth-matching paradigm. For each observer, the first- and second-order Gabors were equated for apparent modulation depth without the flankers. Our results indicate that at the smallest inter-element spacing, the perceived reduction in modulation depth is significantly smaller for the second-order than for the first-order stimuli. Further, lateral interactions operate over shorter distances and the spatial frequency and orientation tuning of the suppression effect are broader for second- than first-order stimuli. Finally, first- and second-order information interact in an asymmetrical fashion; second-order flankers do not reduce the apparent modulation depth of the first-order target, whilst first-order flankers reduce the apparent modulation depth of the second-order target.

Kinetics, Thermodynamics and Modelling of Amido Black Dye Photodegradation in Water Using Co/TiO2 Nanoparticles.

PubMed

Ali, Imran; M L Alharbi, Omar; A Alothman, Zeid; Badjah, Ahmad Yacine

2018-05-16

Titanium oxide nanoparticles were doped with copper and characterized by XRD, FT-IR, TEM and SEM. The surface morphology was spherical with 15-26 nm as particle size. The doped titanium oxide (Co/TiO 2 ) nanomaterial was used for photodegradation of amido black dye in water. The maximum photodegradation of amido black obtained was 90%. The values of free energy, and enthalpy were negative, indicating spontaneous photodegradation of amido black dye. The photodegradation of amido black dye obeyed first order kinetic model. The photodegradation mechanism of amido black involved adsorption of the dye on the surface of cobalt doped titanium oxide and its degradation under UV radiation. The electron (e - ) and hole (h + ) pairs are generated by Co/TiO 2 , which consequently generated superoxide oxygen anion and hydroxyl free radical. These species degraded amido black dye. The reported method is fast, effective and economic, which may be utilized to remove amido black in water. The doped TiO 2 catalyst was quite stable and can be used up to 5 cycles. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

CHLORINE DEMAND AND TTHM FORMATION KINETICS: A SECOND-ORDER MODEL

EPA Science Inventory

Much effort has been expended in attempting to develop mathematical models for chlorine demand in water and wastewater. Most of these efforts have centered around the use of first-order functions or modifications of first-order functions. Recently there has also been interest i...

Biotransformation of trace organic chemicals during groundwater recharge: How useful are first-order rate constants?

PubMed

Regnery, J; Wing, A D; Alidina, M; Drewes, J E

2015-08-01

This study developed relationships between the attenuation of emerging trace organic chemicals (TOrC) during managed aquifer recharge (MAR) as a function of retention time, system characteristics, and operating conditions using controlled laboratory-scale soil column experiments simulating MAR. The results revealed that MAR performance in terms of TOrC attenuation is primarily determined by key environmental parameters (i.e., redox, primary substrate). Soil columns with suboxic and anoxic conditions performed poorly (i.e., less than 30% attenuation of moderately degradable TOrC) in comparison to oxic conditions (on average between 70-100% attenuation for the same compounds) within a residence time of three days. Given this dependency on redox conditions, it was investigated if key parameter-dependent rate constants are more suitable for contaminant transport modeling to properly capture the dynamic TOrC attenuation under field-scale conditions. Laboratory-derived first-order removal kinetics were determined for 19 TOrC under three different redox conditions and rate constants were applied to MAR field data. Our findings suggest that simplified first-order rate constants will most likely not provide any meaningful results if the target compounds exhibit redox dependent biotransformation behavior or if the intention is to exactly capture the decline in concentration over time and distance at field-scale MAR. However, if the intention is to calculate the percent removal after an extended time period and subsurface travel distance, simplified first-order rate constants seem to be sufficient to provide a first estimate on TOrC attenuation during MAR. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydrolysis kinetics in anaerobic degradation of particulate organic material: an overview.

PubMed

Vavilin, V A; Fernandez, B; Palatsi, J; Flotats, X

2008-01-01

The applicability of different kinetics to the hydrolysis of particulate organic material in anaerobic digestion is discussed. Hydrolysis has traditionally been modelled according to the first-order kinetics. For complex substrate, the first-order kinetics should be modified in order to take into account hardly degradable material. It has been shown that models in which hydrolysis is coupled to the growth of hydrolytic bacteria work well at high or at fluctuant organic loading. In particular, the surface-related two-phase and the Contois models showed good fits to experimental data from a wide range of organic waste. Both models tend to the first-order kinetics at a high biomass-to-waste ratio and, for this reason, they can be considered as more general models. Examples on different inhibition processes that might affect the degradation of solid waste are reported. Acetogenesis or methanogenesis might be the rate-limiting stages in complex waste. In such cases, stimulation of hydrolysis (mechanically, chemically or biologically) may lead to a further inhibition of these stages, which ultimately affects hydrolysis as well. Since the hydrolysis process is characterized by surface and transport phenomena, new developments in spatially distributed models are considered fundamental to provide new insights in this complex process.

Kinetic model of turbulence in an incompressible fluid

NASA Technical Reports Server (NTRS)

Tchen, C. M.

1978-01-01

A statistical description of turbulence in an incompressible fluid obeying the Navier-Stokes equations is proposed, where pressure is regarded as a potential for the interaction between fluid elements. A scaling procedure divides a fluctuation into three ranks representing the three transport processes of macroscopic evolution, transport property, and relaxation. Closure is obtained by relaxation, and a kinetic equation is obtained for the fluctuation of the macroscopic rank of the distribution function. The solution gives the transfer function and eddy viscosity. When applied to the inertia subrange of the energy spectrum the analysis recovers the Kolmogorov law and its numerical coefficient.

Kinetic effects in thermal explosion with oscillating ambient conditions.

PubMed

Novozhilov, Vasily

2018-03-05

Thermal explosion problem for a medium with oscillating ambient temperature at its boundaries is a new problem which was introduced in the preceding publication by the present author. It is directly applicable to a range of practical fire autoignition scenarios (e.g. in the storages of organic matter, explosives, propellants, etc.). Effects of kinetic mechanisms, however, need be further investigated as they are expected to alter critical conditions of thermal explosion. We consider several global kinetic mechanisms: first order reaction, second order reaction, and first order autocatalysis. It is demonstrated that kinetic effects related to reactants consumption do indeed shift respective critical boundaries. Effect of kinetics on oscillatory development of thermal explosion is of particular interest. In line with conclusions of the preceding publication, it is confirmed that temperature oscillations may develop during induction phase of thermal explosion when the effect of reactants consumption is properly taken into account. Moreover, development of thermal explosion instability through the prior oscillations is an inevitable and natural scenario. This fact is confirmed by a number of examples. Besides, effects of the other relevant parameter, Zeldovich number on critical conditions are also investigated.

A first principles study of the oxidation energetics and kinetics of realgar

NASA Astrophysics Data System (ADS)

Renock, Devon; Becker, Udo

2010-08-01

Quantum-mechanical calculations allow resolving and quantifying in detail important aspects of reaction mechanisms such as spin transitions and oxygen dissociation that can be the major rate-limiting steps in redox processes on sulfide and oxide surfaces. In addition, this knowledge can help experimentalists in setting up the framework of rate equations that can be used to describe the kinetics of, e.g., oxidation processes. The unique molecular crystal structure of realgar, As 4S 4 clusters held together by van der Waals bonds, allows for a convenient quantum-mechanical (q.m.) cluster approach to investigate the thermodynamics and kinetic pathways of oxidation. The interaction of As 4S 4 clusters with oxygen and co-adsorbed ions provides a model system for understanding the molecular-scale processes that underpin empirically-derived rate expressions, and provides clues to the oxidation mechanisms of other sulfides and oxides. Two activated processes are shown to dominate the kinetics of oxidation by molecular oxygen: (i) a paramagnetic 3O to diamagnetic 1O spin transition and (ii) oxygen dissociation on the surface, in that order. The activation energies for the spin transition and O 2 dissociation step were determined to be 1.1 eV (106 kJ/mol) and 0.9 eV (87 kJ/mol), respectively, if molecular oxygen is the only reactant on the surface. In the case of As 4S 4, q.m. calculations reveal that 3O transfers its spin to the cluster and forms a low-spin, peroxo intermediate on the surface before dissociating. The adsorption of a hydroxide ion on the surface proximate to the 3O adsorption site changes the adsorption mechanism by lowering the activation energy barriers for both the spin transition (0.30 eV/29 kJ/mol) and the O 2 dissociation step (0.72 eV/69 kJ/mol). Thus, while spin transition is rate limiting for oxidation with O 2 alone, dissociation becomes the rate-limiting step for oxidation with co-adsorption of OH -. First-principles, periodic calculations of the

Photodegradation kinetics, transformation, and toxicity prediction of ketoprofen, carprofen, and diclofenac acid in aqueous solutions.

PubMed

Li, Jian; Ma, Li-Yun; Li, Lu-Shuang; Xu, Li

2017-12-01

Photodegradation of 3 commonly used nonsteroidal anti-inflammatory drugs, ketoprofen, carprofen, and diclofenac acid, was conducted under ultraviolet (UV) irradiation. The kinetic results showed that the 3 pharmaceuticals obeyed the first-order reaction with decreasing rate constants of 1.54 × 10 -4 , 5.91 × 10 -5 , and 7.78 × 10 -6  s -1 for carprofen, ketoprofen, and diclofenac acid, respectively. Moreover, the main transformation products were identified by ion-pair liquid-liquid extraction combined with injection port derivatization-gas chromatography-mass spectrometry and high-performance liquid chromatography-quadrupole-time of flight mass spectrometric analysis. There were 8, 3, and 6 transformation products identified for ketoprofen, carprofen, and diclofenac acid, respectively. Decarboxylation, dechlorination, oxidation, demethylation, esterification, and cyclization were proposed to be associated with the transformation of the 3 pharmaceuticals. Toxicity prediction of the transformation products was conducted on the EPI Suite software based on ECOSAR model, and the results indicate that some of the transformation products were more toxic than the parent compounds. The present study provides the foundation to understand the transformation behavior of the studied pharmaceuticals under UV irradiation. Environ Toxicol Chem 2017;36:3232-3239. © 2017 SETAC. © 2017 SETAC.

Improved first-order uncertainty method for water-quality modeling

USGS Publications Warehouse

Melching, C.S.; Anmangandla, S.

1992-01-01

Uncertainties are unavoidable in water-quality modeling and subsequent management decisions. Monte Carlo simulation and first-order uncertainty analysis (involving linearization at central values of the uncertain variables) have been frequently used to estimate probability distributions for water-quality model output due to their simplicity. Each method has its drawbacks: Monte Carlo simulation's is mainly computational time; and first-order analysis are mainly questions of accuracy and representativeness, especially for nonlinear systems and extreme conditions. An improved (advanced) first-order method is presented, where the linearization point varies to match the output level whose exceedance probability is sought. The advanced first-order method is tested on the Streeter-Phelps equation to estimate the probability distribution of critical dissolved-oxygen deficit and critical dissolved oxygen using two hypothetical examples from the literature. The advanced first-order method provides a close approximation of the exceedance probability for the Streeter-Phelps model output estimated by Monte Carlo simulation using less computer time - by two orders of magnitude - regardless of the probability distributions assumed for the uncertain model parameters.

Evaluation of the cure kinetics of the wood/pMDI bondline

Treesearch

David P. Harper; Michael P. Wolcott; Timothy G. Rials

2001-01-01

Micro-dielectric analysis (µDEA) and differentia1 scanning calorimetry (DSC) were used to monitor cure of polymeric diphenyl-methane diisocyanate (pMDI) resin with wood strands in a saturated steam environment. A first-order autocatalyzed kinetic model was employed to determine kinetic parameters. The kinetics were found to follow an Arrhenius relation. A single ramp...

Superposition-Based Analysis of First-Order Probabilistic Timed Automata

NASA Astrophysics Data System (ADS)

Fietzke, Arnaud; Hermanns, Holger; Weidenbach, Christoph

This paper discusses the analysis of first-order probabilistic timed automata (FPTA) by a combination of hierarchic first-order superposition-based theorem proving and probabilistic model checking. We develop the overall semantics of FPTAs and prove soundness and completeness of our method for reachability properties. Basically, we decompose FPTAs into their time plus first-order logic aspects on the one hand, and their probabilistic aspects on the other hand. Then we exploit the time plus first-order behavior by hierarchic superposition over linear arithmetic. The result of this analysis is the basis for the construction of a reachability equivalent (to the original FPTA) probabilistic timed automaton to which probabilistic model checking is finally applied. The hierarchic superposition calculus required for the analysis is sound and complete on the first-order formulas generated from FPTAs. It even works well in practice. We illustrate the potential behind it with a real-life DHCP protocol example, which we analyze by means of tool chain support.

Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

PubMed

Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

2014-07-01

Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

Charge transfer kinetics at the solid-solid interface in porous electrodes

NASA Astrophysics Data System (ADS)

Bai, Peng; Bazant, Martin Z.

2014-04-01

Interfacial charge transfer is widely assumed to obey the Butler-Volmer kinetics. For certain liquid-solid interfaces, the Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-LixFePO4) interface rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidsey’s method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modelling batteries and other electrochemical systems.

Modeling the degradation kinetics of ascorbic acid.

PubMed

Peleg, Micha; Normand, Mark D; Dixon, William R; Goulette, Timothy R

2018-06-13

Most published reports on ascorbic acid (AA) degradation during food storage and heat preservation suggest that it follows first-order kinetics. Deviations from this pattern include Weibullian decay, and exponential drop approaching finite nonzero retention. Almost invariably, the degradation rate constant's temperature-dependence followed the Arrhenius equation, and hence the simpler exponential model too. A formula and freely downloadable interactive Wolfram Demonstration to convert the Arrhenius model's energy of activation, E a , to the exponential model's c parameter, or vice versa, are provided. The AA's isothermal and non-isothermal degradation can be simulated with freely downloadable interactive Wolfram Demonstrations in which the model's parameters can be entered and modified by moving sliders on the screen. Where the degradation is known a priori to follow first or other fixed order kinetics, one can use the endpoints method, and in principle the successive points method too, to estimate the reaction's kinetic parameters from considerably fewer AA concentration determinations than in the traditional manner. Freeware to do the calculations by either method has been recently made available on the Internet. Once obtained in this way, the kinetic parameters can be used to reconstruct the entire degradation curves and predict those at different temperature profiles, isothermal or dynamic. Comparison of the predicted concentration ratios with experimental ones offers a way to validate or refute the kinetic model and the assumptions on which it is based.

Second-order advantage obtained from standard addition first-order instrumental data and multivariate curve resolution-alternating least squares. Calculation of the feasible bands of results.

PubMed

Mohseni, Naimeh; Bahram, Morteza; Olivieri, Alejandro C

2014-03-25

In order to achieve the second-order advantage, second-order data per sample is usually required, e.g., kinetic-spectrophotometric data. In this study, instead of monitoring the time evolution of spectra (and collecting the kinetic-spectrophotometric data) replicate spectra are used to build a virtual second order data. This data matrix (replicate mode×λ) is rank deficient. Augmentation of these data with standard addition data [or standard sample(s)] will break the rank deficiency, making the quantification of the analyte of interest possible. The MCR-ALS algorithm was applied for the resolution and quantitation of the analyte in both simulated and experimental data sets. In order to evaluate the rotational ambiguity in the retrieved solutions, the MCR-BANDS algorithm was employed. It has been shown that the reliability of the quantitative results significantly depends on the amount of spectral overlap in the spectral region of occurrence of the compound of interest and the remaining constituent(s). Copyright © 2013 Elsevier B.V. All rights reserved.

First-principles-based kinetic Monte Carlo studies of diffusion of hydrogen in Ni–Al and Ni–Fe binary alloys

DOE PAGES

Tafen, De Nyago

2015-02-14

The diffusion of dilute hydrogen in fcc Ni–Al and Ni–Fe binary alloys was examined using kinetic Monte Carlo method with input kinetic parameters obtained from first-principles density functional theory. The simulation involves the implementation of computationally efficient energy barrier model that describes the configuration dependence of the hydrogen hopping. The predicted hydrogen diffusion coefficients in Ni and Ni 89.4Fe 10.6 are compared well with the available experimental data. In Ni–Al, the model predicts lower hydrogen diffusivity compared to that in Ni. Overall, diffusion prefactors and the effective activation energies of H in Ni–Fe and Ni–Al are concentration dependent of themore » alloying element. Furthermore, the changes in their values are the results of the short-range order (nearest-neighbor) effect on the interstitial diffusion of hydrogen in fcc Ni-based alloys.« less

Kinetic parameter estimation model for anaerobic co-digestion of waste activated sludge and microalgae.

PubMed

Lee, Eunyoung; Cumberbatch, Jewel; Wang, Meng; Zhang, Qiong

2017-03-01

Anaerobic co-digestion has a potential to improve biogas production, but limited kinetic information is available for co-digestion. This study introduced regression-based models to estimate the kinetic parameters for the co-digestion of microalgae and Waste Activated Sludge (WAS). The models were developed using the ratios of co-substrates and the kinetic parameters for the single substrate as indicators. The models were applied to the modified first-order kinetics and Monod model to determine the rate of hydrolysis and methanogenesis for the co-digestion. The results showed that the model using a hyperbola function was better for the estimation of the first-order kinetic coefficients, while the model using inverse tangent function closely estimated the Monod kinetic parameters. The models can be used for estimating kinetic parameters for not only microalgae-WAS co-digestion but also other substrates' co-digestion such as microalgae-swine manure and WAS-aquatic plants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetic Equation for an Unstable Plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balescu, R.

1963-01-01

A kinetic equation is derived for the description of the evolution in time of the distribution of velocities in a spatially homogeneous ionized gas that, at the initial time, is able to sustain exponentially growing oscillations. This equation is expressed in terms of a functional of the distribution finction that obeys the same integral equation as in the stable case. Although the method of solution used in the stable case breaks down, the equation can still be solved in closed form under unstable conditions, and hence an explicit form of the kinetic equation is obtained. The latter contains the normalmore » collision term and a new additional term describing the stabilization of the plasma. The latter acts through friction and diffusion and brings the plasma into a state of neutral stability. From there on the system evolves toward thermal equilibrium under the action of the normal collision term as well as of an additional Fokker-Planck- like term with timedependent coefficients, which however becomes less and less efficient as the plasma approaches equilibrium.« less

Kinetic degradation of guar gum in oilfield wastewater by photo-Fenton process.

PubMed

Wang, Shunwu; Li, Ziwang; Yu, Qinglong

2017-01-01

Guar gum is considered as a main component of oilfield wastewater. This work is intended to optimize the experimental conditions (H 2 O 2 dosage, Fe 2+ dosage, initial concentration of organics, initial pH and temperature) for the maximum oxidative degradation of guar gum by Fenton's reagent. The kinetics of guar gum removal were evaluated by means of the chemical oxygen demand (COD) and the absorbance measurements. The batch experiment results showed that the optimum conditions were: H 2 O 2 dosage, 10,000 mg/L; Fe 2+ dosage, 2,000 mg/L; initial concentration of organics, 413 mg/L; pH, 3 and temperature, 35 °C, under which the COD removal could reach 61.07% and fairly good stability could be obtained. Under the optimum experimental conditions, using UV irradiation to treat the wastewater, the photo-Fenton systems can successfully eliminate COD from guar gum solution. The COD removal always obeyed a pseudo-first-order kinetics and the degradation rate (k app ) was increased by 25.7% in the photo-Fenton process compared to the Fenton process. The photo-Fenton system needed less time and consequently less quantity of H 2 O 2 to obtain the same results as the Fenton process. The photo-Fenton process needs a dose of H 2 O 2 20.46% lower than that used in the Fenton process to remove 79.54% of COD. The cost of the photo/Fenton process amounted to RMB9.43/m 3 , which was lower than that of the classic Fenton process alone (RMB10.58/m 3 ) and the overall water quality of the final effluent could meet the class Ι national wastewater discharge standard for the petrochemical industry of China.

46 CFR 5.569 - Selection of an appropriate order.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Administrative Law Judge, subject to appeal and review. The investigating officer and the respondent may suggest... guidance of Administrative Law Judges and is intended to promote uniformity in orders rendered. This table... obey master's/ship officer's order 1-3. Failure to comply with U.S. law or regulations 1-3. Possession...

Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maggi, F.M.; Riley, W.J.

2009-06-01

The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O productionmore » and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.« less

Explicit integration with GPU acceleration for large kinetic networks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brock, Benjamin; Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37830; Belt, Andrew

2015-12-01

We demonstrate the first implementation of recently-developed fast explicit kinetic integration algorithms on modern graphics processing unit (GPU) accelerators. Taking as a generic test case a Type Ia supernova explosion with an extremely stiff thermonuclear network having 150 isotopic species and 1604 reactions coupled to hydrodynamics using operator splitting, we demonstrate the capability to solve of order 100 realistic kinetic networks in parallel in the same time that standard implicit methods can solve a single such network on a CPU. This orders-of-magnitude decrease in computation time for solving systems of realistic kinetic networks implies that important coupled, multiphysics problems inmore » various scientific and technical fields that were intractable, or could be simulated only with highly schematic kinetic networks, are now computationally feasible.« less

Explicit integration with GPU acceleration for large kinetic networks

DOE PAGES

Brock, Benjamin; Belt, Andrew; Billings, Jay Jay; ...

2015-09-15

In this study, we demonstrate the first implementation of recently-developed fast explicit kinetic integration algorithms on modern graphics processing unit (GPU) accelerators. Taking as a generic test case a Type Ia supernova explosion with an extremely stiff thermonuclear network having 150 isotopic species and 1604 reactions coupled to hydrodynamics using operator splitting, we demonstrate the capability to solve of order 100 realistic kinetic networks in parallel in the same time that standard implicit methods can solve a single such network on a CPU. In addition, this orders-of-magnitude decrease in computation time for solving systems of realistic kinetic networks implies thatmore » important coupled, multiphysics problems in various scientific and technical fields that were intractable, or could be simulated only with highly schematic kinetic networks, are now computationally feasible.« less

Quantitative kinetic theory of active matter

NASA Astrophysics Data System (ADS)

Ihle, Thomas; Chou, Yen-Liang

2014-03-01

Models of self-driven agents similar to the Vicsek model [Phys. Rev. Lett. 75 (1995) 1226] are studied by means of kinetic theory. In these models, particles try to align their travel directions with the average direction of their neighbours. At strong alignment a globally ordered state of collective motion forms. An Enskog-like kinetic theory is derived from the exact Chapman-Kolmogorov equation in phase space using Boltzmann's mean-field approximation of molecular chaos. The kinetic equation is solved numerically by a nonlocal Lattice-Boltzmann-like algorithm. Steep soliton-like waves are observed that lead to an abrupt jump of the global order parameter if the noise level is changed. The shape of the wave is shown to follow a novel scaling law and to quantitatively agree within 3 % with agent-based simulations at large particle speeds. This provides a mean-field mechanism to change the second-order character of the flocking transition to first order. Diagrammatic techniques are used to investigate small particle speeds, where the mean-field assumption of Molecular Chaos is invalid and where correlation effects need to be included.

Evaluation of the kinetic oxidation of aqueous volatile organic compounds by permanganate.

PubMed

Mahmoodlu, Mojtaba G; Hassanizadeh, S Majid; Hartog, Niels

2014-07-01

The use of permanganate solutions for in-situ chemical oxidation (ISCO) is a well-established groundwater remediation technology, particularly for targeting chlorinated ethenes. The kinetics of oxidation reactions is an important ISCO remediation design aspect that affects the efficiency and oxidant persistence. The overall rate of the ISCO reaction between oxidant and contaminant is typically described using a second-order kinetic model while the second-order rate constant is determined experimentally by means of a pseudo first order approach. However, earlier studies of chlorinated hydrocarbons have yielded a wide range of values for the second-order rate constants. Also, there is limited insight in the kinetics of permanganate reactions with fuel-derived groundwater contaminants such as toluene and ethanol. In this study, batch experiments were carried out to investigate and compare the oxidation kinetics of aqueous trichloroethylene (TCE), ethanol, and toluene in an aqueous potassium permanganate solution. The overall second-order rate constants were determined directly by fitting a second-order model to the data, instead of typically using the pseudo-first-order approach. The second-order reaction rate constants (M(-1) s(-1)) for TCE, toluene, and ethanol were 8.0×10(-1), 2.5×10(-4), and 6.5×10(-4), respectively. Results showed that the inappropriate use of the pseudo-first-order approach in several previous studies produced biased estimates of the second-order rate constants. In our study, this error was expressed as a function of the extent (P/N) in which the reactant concentrations deviated from the stoichiometric ratio of each oxidation reaction. The error associated with the inappropriate use of the pseudo-first-order approach is negatively correlated with the P/N ratio and reached up to 25% of the estimated second-order rate constant in some previous studies of TCE oxidation. Based on our results, a similar relation is valid for the other volatile

First and Higher Order Effects on Zero Order Radiative Transfer Model

NASA Astrophysics Data System (ADS)

Neelam, M.; Mohanty, B.

2014-12-01

Microwave radiative transfer model are valuable tool in understanding the complex land surface interactions. Past literature has largely focused on local sensitivity analysis for factor priotization and ignoring the interactions between the variables and uncertainties around them. Since land surface interactions are largely nonlinear, there always exist uncertainties, heterogeneities and interactions thus it is important to quantify them to draw accurate conclusions. In this effort, we used global sensitivity analysis to address the issues of variable uncertainty, higher order interactions, factor priotization and factor fixing for zero-order radiative transfer (ZRT) model. With the to-be-launched Soil Moisture Active Passive (SMAP) mission of NASA, it is very important to have a complete understanding of ZRT for soil moisture retrieval to direct future research and cal/val field campaigns. This is a first attempt to use GSA technique to quantify first order and higher order effects on brightness temperature from ZRT model. Our analyses reflect conditions observed during the growing agricultural season for corn and soybeans in two different regions in - Iowa, U.S.A and Winnipeg, Canada. We found that for corn fields in Iowa, there exist significant second order interactions between soil moisture, surface roughness parameters (RMS height and correlation length) and vegetation parameters (vegetation water content, structure and scattering albedo), whereas in Winnipeg, second order interactions are mainly due to soil moisture and vegetation parameters. But for soybean fields in both Iowa and Winnipeg, we found significant interactions only to exist between soil moisture and surface roughness parameters.

The effect of the textile industry dye bath additive EDTMPA on colour removal characteristics by ozone oxidation.

PubMed

Olmez, T; Kabdaşli, I; Tünay, O

2007-01-01

In this study, the effects of the phosphonic acid based sequestering agent EDTMPA used in the textile dye baths on colour and organic matter removal by ozone oxidation was experimentally investigated. Procion Navy HEXL dyestuff that has been commonly used for the reactive dyeing of cellulose fibers was selected as the model component. The organic matter oxidation by ozone was determined to obey the pseudo-first order kinetics as they are treated singly or in combination. COD removal rates obtained from pseudo-first order reaction kinetics showed that oxidation of Navy HEXL alone (0.0947 L/min) was faster than that of EDTMPA (0.0171 L/min) and EDTMPA with dye (0.0155 L/min) at pH 3.0. It was also found that reaction rates of single EDTMPA removal and EDTMPA and dye mixture removal increased as the reaction pH was increased from 3.0 to 10.5.

Effects of Transition-Metal Mixing on Na Ordering and Kinetics in Layered P 2 Oxides

NASA Astrophysics Data System (ADS)

Zheng, Chen; Radhakrishnan, Balachandran; Chu, Iek-Heng; Wang, Zhenbin; Ong, Shyue Ping

2017-06-01

Layered P 2 oxides are promising cathode materials for rechargeable sodium-ion batteries. In this work, we systematically investigate the effects of transition-metal (TM) mixing on Na ordering and kinetics in the NaxCo1 -yMnyO2 model system using density-functional-theory (DFT) calculations. The DFT-predicted 0-K stability diagrams indicate that Co-Mn mixing reduces the energetic differences between Na orderings, which may account for the reduction of the number of phase transformations observed during the cycling of mixed-TM P 2 layered oxides compared to a single TM. Using ab initio molecular-dynamics simulations and nudged elastic-band calculations, we show that the TM composition at the Na(1) (face-sharing) site has a strong influence on the Na site energies, which in turn impacts the kinetics of Na diffusion towards the end of the charge. By employing a site-percolation model, we establish theoretical upper and lower bounds for TM concentrations based on their effect on Na(1) site energies, providing a framework to rationally tune mixed-TM compositions for optimal Na diffusion.

Static and dynamic dielectric properties of strongly polar liquids in the vicinity of first order and weakly first order phase transitions

NASA Astrophysics Data System (ADS)

Jadżyn, Jan; Czechowski, Grzegorz; Legrand, Christian; Douali, Redouane

2003-04-01

The paper presents the results of measurements of the linear dielectric properties of the compounds from the homologous series of alkylcyanobiphenyls (CnH2n+1PhPhCN, nCB) in the vicinity of the first order transition (from the isotropic liquid to the crystalline phase) of nonmesogenic nCB’s (n=2 4) and the weakly first order transition (from the isotropic liquid to the nematic phase) of 5CB. The experimental method for the separation of the critical part of the static permittivity derivative and the activation energy for rotation of the mesogenic molecules, in the vicinity of weakly first order phase transition, is proposed. It is shown that the critical temperature dependence of the permittivity and the activation energy can be described with a function of (T-T*)-α type, with the same values of the temperature of virtual transition of the second order (T*) and the critical exponent (α).

First-principles-based kinetic Monte Carlo simulation of nitric oxide decomposition over Pt and Rh surfaces under lean-burn conditions

NASA Astrophysics Data System (ADS)

Mei, Donghai; Ge, Qingfeng; Neurock, Matthew; Kieken, Laurent; Lerou, Jan

First-principles-based kinetic Monte Carlo simulation was used to track the elementary surface transformations involved in the catalytic decomposition of NO over Pt(100) and Rh(100) surfaces under lean-burn operating conditions. Density functional theory (DFT) calculations were carried out to establish the structure and energetics for all reactants, intermediates and products over Pt(100) and Rh(100). Lateral interactions which arise from neighbouring adsorbates were calculated by examining changes in the binding energies as a function of coverage and different coadsorbed configurations. These data were fitted to a bond order conservation (BOC) model which is subsequently used to establish the effects of coverage within the simulation. The intrinsic activation barriers for all the elementary reaction steps in the proposed mechanism of NO reduction over Pt(100) were calculated by using DFT. These values are corrected for coverage effects by using the parametrized BOC model internally within the simulation. This enables a site-explicit kinetic Monte Carlo simulation that can follow the kinetics of NO decomposition over Pt(100) and Rh(100) in the presence of excess oxygen. The simulations are used here to model various experimental protocols including temperature programmed desorption as well as batch catalytic kinetics. The simulation results for the temperature programmed desorption and decomposition of NO over Pt(100) and Rh(100) under vacuum condition were found to be in very good agreement with experimental results. NO decomposition is strongly tied to the temporal number of sites that remain vacant. Experimental results show that Pt is active in the catalytic reaction of NO into N2 and NO2 under lean-burn conditions. The simulated reaction orders for NO and O2 were found to be +0.9 and -0.4 at 723 K, respectively. The simulation also indicates that there is no activity over Rh(100) since the surface becomes poisoned by oxygen.

Entanglement scaling at first order quantum phase transitions

NASA Astrophysics Data System (ADS)

Yuste, A.; Cartwright, C.; De Chiara, G.; Sanpera, A.

2018-04-01

First order quantum phase transitions (1QPTs) are signalled, in the thermodynamic limit, by discontinuous changes in the ground state properties. These discontinuities affect expectation values of observables, including spatial correlations. When a 1QPT is crossed in the vicinity of a second order one, due to the correlation length divergence of the latter, the corresponding ground state is modified and it becomes increasingly difficult to determine the order of the transition when the size of the system is finite. Here we show that, in such situations, it is possible to apply finite size scaling (FSS) to entanglement measures, as it has recently been done for the order parameters and the energy gap, in order to recover the correct thermodynamic limit (Campostrini et al 2014 Phys. Rev. Lett. 113 070402). Such a FSS can unambiguously discriminate between first and second order phase transitions in the vicinity of multicritical points even when the singularities displayed by entanglement measures lead to controversial results.

Explicit solution of integrated 1 - exp equation for predicting accumulation and decline of concentrations for drugs obeying nonlinear saturation kinetics.

PubMed

Keller, Frieder; Hartmann, Bertram; Czock, David

2009-12-01

To describe nonlinear, saturable pharmacokinetics, the Michaelis-Menten equation is frequently used. However, the Michaelis-Menten equation has no integrated solution for concentrations but only for the time factor. Application of the Lambert W function was proposed recently to obtain an integrated solution of the Michaelis-Menten equation. As an alternative to the Michaelis-Menten equation, a 1 - exp equation has been used to describe saturable kinetics, with the advantage that the integrated 1 - exp equation has an explicit solution for concentrations. We used the integrated 1 - exp equation to predict the accumulation kinetics and the nonlinear concentration decline for a proposed fictive drug. In agreement with the recently proposed method, we found that for the integrated 1 - exp equation no steady state is obtained if the maximum rate of change in concentrations (Vmax) within interval (Tau) is less than the difference between peak and trough concentrations (Vmax x Tau < C peak - C trough).

Kinetic study on UV-absorber photodegradation under different conditions

NASA Astrophysics Data System (ADS)

Bubev, Emil; Georgiev, Anton; Machkova, Maria

2016-09-01

The photodegradation kinetics of two benzophenone derivative UV-absorbers (UVAs)-BP-4 (benzophenone-4) and 4-HBP (4-hydroxybenzophenone), as additives in polyvinyl acetate (PVAc) films, were studied. Solution-processed PVAc films were irradiated in different environments in order to study oxygen and atmospheric humidity influence on UVA photodegradation. Photodegradation was traced by absorption intensity loss via UV-vis spectroscopy. Both UVAs exhibited excellent photostability in an inert atmosphere. Rate constants showed that BP-4 has better permanence in absence of oxygen. Both film types experienced rapid absorption loss, when irradiated in an oxygen containing atmosphere. UVA degradation was treated as a two-stage process. The photodegradation kinetics in the first stage agreed with the adopted complex rate law, but the second stage was best described by pseudo-first order kinetics. BP-4 exhibited better stability. Oxygen was established as the main accelerating factor for photodegradation of benzophenone derivatives UV-absorbers in thin PVAc films.

Experimental demonstration that a free-falling aerosol particle obeys a fluctuation theorem

NASA Astrophysics Data System (ADS)

Wong, Chun-Shang; Goree, J.; Gopalakrishnan, Ranganathan

2018-05-01

We investigate the fluctuating motion of an aerosol particle falling in air. Using a Millikan-like setup, we tracked a 1-μ m sphere falling at its terminal velocity. We observe occurrences of particles undergoing upward displacements against the force of gravity, so that negative work is done briefly. These negative-work events have a probability that is shown to obey the work fluctuation theorem. This experimental confirmation of the theorem's applicability to aerosols leads us to develop and demonstrate an application: an in situ measurement of an aerosol particle's mass.

Statistical correlations in an ideal gas of particles obeying fractional exclusion statistics.

PubMed

Pellegrino, F M D; Angilella, G G N; March, N H; Pucci, R

2007-12-01

After a brief discussion of the concepts of fractional exchange and fractional exclusion statistics, we report partly analytical and partly numerical results on thermodynamic properties of assemblies of particles obeying fractional exclusion statistics. The effect of dimensionality is one focal point, the ratio mu/k_(B)T of chemical potential to thermal energy being obtained numerically as a function of a scaled particle density. Pair correlation functions are also presented as a function of the statistical parameter, with Friedel oscillations developing close to the fermion limit, for sufficiently large density.

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.

2015-08-07

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

Kinetics of Alcohol Dehydrogenase-Catalyzed Oxidation of Ethanol Followed by Visible Spectroscopy

ERIC Educational Resources Information Center

Bendinskas, Kestutis; DiJiacomo, Christopher; Krill, Allison; Vitz, Ed

2005-01-01

The effect of substrate concentration on the rate of enzymatic reaction was investigated and typical Michaelis-Mentin kinetics was observed during the first week. The first order reaction at relatively low concentrations of ethanol and the pseudo zero-order reaction at high concentrations of ethanol were emphasized.

First passage times for multiple particles with reversible target-binding kinetics

NASA Astrophysics Data System (ADS)

Grebenkov, Denis S.

2017-10-01

We investigate the first passage problem for multiple particles that diffuse towards a target, partially adsorb there, and then desorb after a finite exponentially distributed residence time. We search for the first time when m particles undergoing such reversible target-binding kinetics are found simultaneously on the target that may trigger an irreversible chemical reaction or a biophysical event. Even if the particles are independent, the finite residence time on the target yields an intricate temporal coupling between particles. We compute analytically the mean first passage time (MFPT) for two independent particles by mapping the original problem to higher-dimensional surface-mediated diffusion and solving the coupled partial differential equations. The respective effects of the adsorption and desorption rates on the MFPT are revealed and discussed.

First off-time treatment prostate-specific antigen kinetics predicts survival in intermittent androgen deprivation for prostate cancer.

PubMed

Sanchez-Salas, Rafael; Olivier, Fabien; Prapotnich, Dominique; Dancausa, José; Fhima, Mehdi; David, Stéphane; Secin, Fernando P; Ingels, Alexandre; Barret, Eric; Galiano, Marc; Rozet, François; Cathelineau, Xavier

2016-01-01

Prostate-specific antigen (PSA) doubling time is relying on an exponential kinetic pattern. This pattern has never been validated in the setting of intermittent androgen deprivation (IAD). Objective is to analyze the prognostic significance for PCa of recurrent patterns in PSA kinetics in patients undergoing IAD. A retrospective study was conducted on 377 patients treated with IAD. On-treatment period (ONTP) consisted of gonadotropin-releasing hormone agonist injections combined with oral androgen receptor antagonist. Off-treatment period (OFTP) began when PSA was lower than 4 ng/ml. ONTP resumed when PSA was higher than 20 ng/ml. PSA values of each OFTP were fitted with three basic patterns: exponential (PSA(t) = λ.e(αt)), linear (PSA(t) = a.t), and power law (PSA(t) = a.t(c)). Univariate and multivariate Cox regression model analyzed predictive factors for oncologic outcomes. Only 45% of the analyzed OFTPs were exponential. Linear and power law PSA kinetics represented 7.5% and 7.7%, respectively. Remaining fraction of analyzed OFTPs (40%) exhibited complex kinetics. Exponential PSA kinetics during the first OFTP was significantly associated with worse oncologic outcome. The estimated 10-year cancer-specific survival (CSS) was 46% for exponential versus 80% for nonexponential PSA kinetics patterns. The corresponding 10-year probability of castration-resistant prostate cancer (CRPC) was 69% and 31% for the two patterns, respectively. Limitations include retrospective design and mixed indications for IAD. PSA kinetic fitted with exponential pattern in approximately half of the OFTPs. First OFTP exponential PSA kinetic was associated with a shorter time to CRPC and worse CSS. © 2015 Wiley Periodicals, Inc.

Zero-Order Chemical Kinetics as a Context to Investigate Student Understanding of Catalysts and Half-Life

ERIC Educational Resources Information Center

Bain, Kinsey; Rodriguez, Jon-Marc G.; Towns, Marcy H.

2018-01-01

Zero-order systems provide an interesting opportunity for students to think about the underlying mechanism behind the physical phenomena being modeled. The work reported here is part of a larger study that seeks to characterize how students integrate chemistry and mathematics in the context of chemical kinetics. Thirty-six general chemistry…

Thermodynamics versus Kinetics Dichotomy in the Linear Self-Assembly of Mixed Nanoblocks.

PubMed

Ruiz, L; Keten, S

2014-06-05

We report classical and replica exchange molecular dynamics simulations that establish the mechanisms underpinning the growth kinetics of a binary mix of nanorings that form striped nanotubes via self-assembly. A step-growth coalescence model captures the growth process of the nanotubes, which suggests that high aspect ratio nanostructures can grow by obeying the universal laws of self-similar coarsening, contrary to systems that grow through nucleation and elongation. Notably, striped patterns do not depend on specific growth mechanisms, but are governed by tempering conditions that control the likelihood of depropagation and fragmentation.

Bioethics in Denmark. Moving from first- to second-order analysis?

PubMed

Nielsen, Morten Ebbe Juul; Andersen, Martin Marchman

2014-07-01

This article examines two current debates in Denmark--assisted suicide and the prioritization of health resources--and proposes that such controversial bioethical issues call for distinct philosophical analyses: first-order examinations, or an applied philosophy approach, and second-order examinations, what might be called a political philosophical approach. The authors argue that although first-order examination plays an important role in teasing out different moral points of view, in contemporary democratic societies, few, if any, bioethical questions can be resolved satisfactorily by means of first-order analyses alone, and that bioethics needs to engage more closely with second-order enquiries and the question of legitimacy in general.

Temporal Frequency Modulates Reaction Time Responses to First-Order and Second-Order Motion

ERIC Educational Resources Information Center

Hutchinson, Claire V.; Ledgeway, Tim

2010-01-01

This study investigated the effect of temporal frequency and modulation depth on reaction times for discriminating the direction of first-order (luminance-defined) and second-order (contrast-defined) motion, equated for visibility using equal multiples of direction-discrimination threshold. Results showed that reaction times were heavily…

Adsorption kinetic and desorption studies of Cd2+ on Multi-Carboxylic-Functionalized Silica Gel

NASA Astrophysics Data System (ADS)

Li, Min; Wei, Jian; Meng, Xiaojing; Wu, Zhuqiang; Liang, Xiuke

2018-01-01

In the present study, the adsorption behavior of cadmium (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of contact time on adsorption capacity of cadmium (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. And the adsorption mechanism of the process was studied by intra-particle and film diffusion, it was found out that the adsorption rate was governed primarily by film diffusion to the adsorption onto the SG-MCF. In addition, column experiments were conducted to assess the effects initial inlet concentration and the flow rate on breakthrough time and adsorption capacity ascertaining the practical applicability of the adsorbent. The results suggest that the total amount of adsorbed cadmium (II) ion increased with declined flow rate and increased the inlet concentration. The adsorption-desorption experiment confirmed that adsorption capacity of cadmium (II) ion didn’t present an obvious decrease after five cycles.

Adsorption kinetic and desorption studies of Cu2+ on Multi-Carboxylic-Functionalized Silica Gel

NASA Astrophysics Data System (ADS)

Li, Min; Meng, Xiaojing; Liu, Yushuang; Hu, Xinju; Liang, Xiuke

2018-01-01

In the present study, the adsorption behavior of copper (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of contact time on adsorption capacity of copper (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. And the adsorption mechanism of the process was studied by intra-particle and film diffusion, it was found out that the adsorption rate was governed primarily by film diffusion to the adsorption onto the SG-MCF. In addition, column experiments were conducted to assess the effects initial inlet concentration and the flow rate on breakthrough time and adsorption capacity ascertaining the practical applicability of the adsorbent. The results suggest that the total amount of adsorbed copper (II) ion increased with declined flow rate and increased the inlet concentration. The adsorption-desorption experiment confirmed that adsorption capacity of copper (II) ion didn’t present an obvious decrease after five cycles.

Quantitative Analysis of Clopidogrel Bisulphate and Aspirin by First Derivative Spectrophotometric Method in Tablets

PubMed Central

Game, Madhuri D.; Gabhane, K. B.; Sakarkar, D. M.

2010-01-01

A simple, accurate and precise spectrophotometric method has been developed for simultaneous estimation of clopidogrel bisulphate and aspirin by employing first order derivative zero crossing method. The first order derivative absorption at 232.5 nm (zero cross point of aspirin) was used for clopidogrel bisulphate and 211.3 nm (zero cross point of clopidogrel bisulphate) for aspirin.Both the drugs obeyed linearity in the concentration range of 5.0 μg/ml to 25.0 μg/ml (correlation coefficient r2<1). No interference was found between both determined constituents and those of matrix. The method was validated statistically and recovery studies were carried out to confirm the accuracy of the method. PMID:21969765

Cooperative ordering and kinetics of cellulose nanocrystal alignment in a magnetic field

DOE PAGES

De France, Kevin J.; Yager, Kevin G.; Hoare, Todd; ...

2016-07-13

Cellulose nanocrystals (CNCs) are emerging nanomaterials that form chiral nematic liquid crystals above a critical concentration (C*) and additionally orient within electromagnetic fields. The control over CNC alignment is significant for materials processing and end use; to date, magnetic alignment has been demonstrated using only strong fields over extended or arbitrary time scales. This work investigates the effects of comparatively weak magnetic fields (0–1.2 T) and CNC concentration (1.65–8.25 wt %) on the kinetics and degree of CNC ordering using small-angle X-ray scattering. Interparticle spacing, correlation length, and orientation order parameters (η and S) increased with time and field strengthmore » following a sigmoidal profile. In a 1.2 T magnetic field for CNC suspensions above C*, partial alignment occurred in under 2 min followed by slower cooperative ordering to achieve nearly perfect alignment in under 200 min (S = –0.499 where S = –0.5 indicates perfect antialignment). At 0.56 T, nearly perfect alignment was also achieved, yet the ordering was 36% slower. Outside of a magnetic field, the order parameter plateaued at 52% alignment (S = –0.26) after 5 h, showcasing the drastic effects of relatively weak magnetic fields on CNC alignment. For suspensions below C*, no magnetic alignment was detected.« less

On the relationships between Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, Equilibrium Chemistry Approximation kinetics and quadratic kinetics

DOE PAGES

Tang, J. Y.

2015-09-03

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 respond to changes in substrate abundance. However, the criteria of when to use which of the two are often ambiguous. Here I show that these two kinetics are special approximations to the Equilibrium Chemistry Approximation kinetics, which is the first order approximation to the quadratic kinetics that solves the equation of enzyme-substrate complex exactly for a single enzyme single substrate biogeochemical reaction with the law of mass action and the assumption of quasi-steady-state formore » the enzyme-substrate complex and that the product genesis from enzyme-substrate complex is much slower than the equilibration between enzyme-substrate complexes, substrates and enzymes. In particular, I showed that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in the Equilibrium Chemistry Approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln [ E ] T of v with respect the total enzyme concentration [ E ] T and persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln [ S ] T of v with respect to the total substrate concentration [ S ] T

Variational energy principle for compressible, baroclinic flow. 1: First and second variations of total kinetic action

NASA Technical Reports Server (NTRS)

Schmid, L. A.

1977-01-01

The case of a cold gas in the absence of external force fields is considered. Since the only energy involved is kinetic energy, the total kinetic action (i.e., the space-time integral of the kinetic energy density) should serve as the total free-energy functional in this case, and as such should be a local minimum for all possible fluctuations about stable flow. This conjecture is tested by calculating explicit, manifestly covariant expressions for the first and second variations of the total kinetic action in the context of Lagrangian kinematics. The general question of the correlation between physical stability and the convexity of any action integral that can be interpreted as the total free-energy functional of the flow is discussed and illustrated for the cases of rectillinear and rotating shearing flows.

Ordering kinetics in the long-period superlattice alloy Cu0.79 Pd0.21

NASA Astrophysics Data System (ADS)

Wang, X.; Mainville, J.; Ludwig, K.; Flament, X.; Finel, A.; Caudron, R.

2005-07-01

The kinetics of long-period superlattice (LPS) formation from the disordered state has been examined in a Cu0.79Pd0.21 alloy that exhibits a one-dimensional LPS ordered state. Time-resolved x-ray scattering shows that, following a rapid temperature quench from the disordered state into the LPS region of the phase diagram, the satellite peaks initially grow more quickly than do the central integer-order superlattice peaks. During this process, the satellite peak position, which is inversely related to the average modulation wavelength 2M , initially decreases rapidly, then reaches a minimum and relaxes slowly back toward its new equilibrium position. In the later stages of the LPS formation process, the satellite and central integer-order superlattice peaks narrow in a manner consistent with t1/2 domain coarsening. A simple stochastic model of the partially ordered structure was developed to better understand the relationships between peak widths.

First-Order Frameworks for Managing Models in Engineering Optimization

NASA Technical Reports Server (NTRS)

Alexandrov, Natlia M.; Lewis, Robert Michael

2000-01-01

Approximation/model management optimization (AMMO) is a rigorous methodology for attaining solutions of high-fidelity optimization problems with minimal expense in high- fidelity function and derivative evaluation. First-order AMMO frameworks allow for a wide variety of models and underlying optimization algorithms. Recent demonstrations with aerodynamic optimization achieved three-fold savings in terms of high- fidelity function and derivative evaluation in the case of variable-resolution models and five-fold savings in the case of variable-fidelity physics models. The savings are problem dependent but certain trends are beginning to emerge. We give an overview of the first-order frameworks, current computational results, and an idea of the scope of the first-order framework applicability.

Photocatalytic activity enhancement of anatase-graphene nanocomposite for methylene removal: Degradation and kinetics.

PubMed

Rezaei, Mostafa; Salem, Shiva

2016-10-05

In the present research, the TiO2-graphene nanocomposite was synthesized by an eco-friendly method. The blackberry juice was introduced to graphene oxide (GO) as a reducing agent to produce the graphene nano-sheets. The nanocomposite of anatase-graphene was developed as a photocatalyst for the degradation of methylene blue, owing to the larger specific surface area and synergistic effect of reduced graphene oxide (RGO). The UV spectroscopy measurements showed that the prepared nanocomposite exhibited an excellent photocatalytic activity toward the methylene blue degradation. The rate of electron transfer of redox sheets is much higher than that observed on GO, indicating the applicability of proposed method for the production of anatase-RGO nanocomposite for treatment of water contaminated by cationic dye. The prepared materials were characterized with Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller surface area measurement, scanning electron microscopy and transmission electron microscopy. A facile and rapid route was applied for the uniform deposition of anatase nanoparticles on the sheets. The resulting nanocomposite contained nanoparticles with a mean diameter of 10nm. A mechanism for the photocatalytic activity of nanocomposite was suggested and the degradation reaction obeyed the second-order kinetics. It was concluded that the degradation kinetics is changed due to the reduction of GO in the presence of blackberry juice. Copyright © 2016 Elsevier B.V. All rights reserved.

Photocatalytic activity enhancement of anatase-graphene nanocomposite for methylene removal: Degradation and kinetics

NASA Astrophysics Data System (ADS)

Rezaei, Mostafa; Salem, Shiva

2016-10-01

In the present research, the TiO2-graphene nanocomposite was synthesized by an eco-friendly method. The blackberry juice was introduced to graphene oxide (GO) as a reducing agent to produce the graphene nano-sheets. The nanocomposite of anatase-graphene was developed as a photocatalyst for the degradation of methylene blue, owing to the larger specific surface area and synergistic effect of reduced graphene oxide (RGO). The UV spectroscopy measurements showed that the prepared nanocomposite exhibited an excellent photocatalytic activity toward the methylene blue degradation. The rate of electron transfer of redox sheets is much higher than that observed on GO, indicating the applicability of proposed method for the production of anatase-RGO nanocomposite for treatment of water contaminated by cationic dye. The prepared materials were characterized with Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller surface area measurement, scanning electron microscopy and transmission electron microscopy. A facile and rapid route was applied for the uniform deposition of anatase nanoparticles on the sheets. The resulting nanocomposite contained nanoparticles with a mean diameter of 10 nm. A mechanism for the photocatalytic activity of nanocomposite was suggested and the degradation reaction obeyed the second-order kinetics. It was concluded that the degradation kinetics is changed due to the reduction of GO in the presence of blackberry juice.

Contrast gain control in first- and second-order motion perception.

PubMed

Lu, Z L; Sperling, G

1996-12-01

A novel pedestal-plus-test paradigm is used to determine the nonlinear gain-control properties of the first-order (luminance) and the second-order (texture-contrast) motion systems, that is, how these systems' responses to motion stimuli are reduced by pedestals and other masking stimuli. Motion-direction thresholds were measured for test stimuli consisting of drifting luminance and texture-contrast-modulation stimuli superimposed on pedestals of various amplitudes. (A pedestal is a static sine-wave grating of the same type and same spatial frequency as the moving test grating.) It was found that first-order motion-direction thresholds are unaffected by small pedestals, but at pedestal contrasts above 1-2% (5-10 x pedestal threshold), motion thresholds increase proportionally to pedestal amplitude (a Weber law). For first-order stimuli, pedestal masking is specific to the spatial frequency of the test. On the other hand, motion-direction thresholds for texture-contrast stimuli are independent of pedestal amplitude (no gain control whatever) throughout the accessible pedestal amplitude range (from 0 to 40%). However, when baseline carrier contrast increases (with constant pedestal modulation amplitude), motion thresholds increase, showing that gain control in second-order motion is determined not by the modulator (as in first-order motion) but by the carrier. Note that baseline contrast of the carrier is inherently independent of spatial frequency of the modulator. The drastically different gain-control properties of the two motion systems and prior observations of motion masking and motion saturation are all encompassed in a functional theory. The stimulus inputs to both first- and second-order motion process are normalized by feedforward, shunting gain control. The different properties arise because the modulator is used to control the first-order gain and the carrier is used to control the second-order gain.

First-Order System Least-Squares for Second-Order Elliptic Problems with Discontinuous Coefficients

NASA Technical Reports Server (NTRS)

Manteuffel, Thomas A.; McCormick, Stephen F.; Starke, Gerhard

1996-01-01

The first-order system least-squares methodology represents an alternative to standard mixed finite element methods. Among its advantages is the fact that the finite element spaces approximating the pressure and flux variables are not restricted by the inf-sup condition and that the least-squares functional itself serves as an appropriate error measure. This paper studies the first-order system least-squares approach for scalar second-order elliptic boundary value problems with discontinuous coefficients. Ellipticity of an appropriately scaled least-squares bilinear form of the size of the jumps in the coefficients leading to adequate finite element approximation results. The occurrence of singularities at interface corners and cross-points is discussed. and a weighted least-squares functional is introduced to handle such cases. Numerical experiments are presented for two test problems to illustrate the performance of this approach.

Disproportionation of rosin on an industrial Pd/C catalyst: reaction pathway and kinetic model discrimination.

PubMed

Souto, Juan Carlos; Yustos, Pedro; Ladero, Miguel; Garcia-Ochoa, Felix

2011-02-01

In this work, a phenomenological study of the isomerisation and disproportionation of rosin acids using an industrial 5% Pd on charcoal catalyst from 200 to 240°C is carried out. Medium composition is determined by elemental microanalysis, GC-MS and GC-FID. Dehydrogenated and hydrogenated acid species molar amounts in the final product show that dehydrogenation is the main reaction. Moreover, both hydrogen and non-hydrogen concentration considering kinetic models are fitted to experimental data using a multivariable non-linear technique. Statistical discrimination among the proposed kinetic models lead to the conclusion hydrogen considering models fit much better to experimental results. The final kinetic model involves first-order isomerisation reactions of neoabietic and palustric acids to abietic acid, first-order dehydrogenation and hydrogenation of this latter acid, and hydrogenation of pimaric acids. Hydrogenation reactions are partial first-order regarding the acid and hydrogen. Copyright © 2010 Elsevier Ltd. All rights reserved.

Kinetics of the Fading of Phenolphthalein in Alkaline Solution.

ERIC Educational Resources Information Center

Nicholson, Lois

1989-01-01

Described is an experiment which illustrates pseudo-first-order kinetics in the fading of a common indicator in an alkaline solution. Included are background information, details of materials used, laboratory procedures, and sample results. (CW)

Second-order motions contribute to vection.

PubMed

Gurnsey, R; Fleet, D; Potechin, C

1998-09-01

First- and second-order motions differ in their ability to induce motion aftereffects (MAEs) and the kinetic depth effect (KDE). To test whether second-order stimuli support computations relating to motion-in-depth we examined the vection illusion (illusory self motion induced by image flow) using a vection stimulus (V, expanding concentric rings) that depicted a linear path through a circular tunnel. The set of vection stimuli contained differing amounts of first- and second-order motion energy (ME). Subjects reported the duration of the perceived MAEs and the duration of their vection percept. In Experiment 1 both MAEs and vection durations were longest when the first-order (Fourier) components of V were present in the stimulus. In Experiment 2, V was multiplicatively combined with static noise carriers having different check sizes. The amount of first-order ME associated with V increases with check size. MAEs were found to increase with check size but vection durations were unaffected. In general MAEs depend on the amount of first-order ME present in the signal. Vection, on the other hand, appears to depend on a representation of image flow that combines first- and second-order ME.

Hydrolysis kinetics of secoisolariciresinol diglucoside oligomers from flaxseed.

PubMed

Yuan, Jian-Ping; Li, Xin; Xu, Shi-Ping; Wang, Jiang-Hai; Liu, Xin

2008-11-12

Flaxseed is the richest dietary source of the lignan secoisolariciresinol diglucoside (SDG) and contains the largest amount of SDG oligomers, which are often hydrolyzed to break the ester linkages for the release of SDG and the glycosidic bonds for the release of secoisolariciresinol (SECO). The alkaline hydrolysis reaction kinetics of SDG oligomers from flaxseed and the acid hydrolysis process of SDG and other glucosides were investigated. For the kinetic modeling, a pseudo-first-order reaction was assumed. The results showed that the alkaline hydrolysis of SDG oligomers followed first-order reaction kinetics under mild alkaline hydrolytic conditions and that the concentration of sodium hydroxide had a strong influence on the activation energy of the alkaline hydrolysis of SDG oligomers. The results also indicated that the main acid hydrolysates of SDG included secoisolariciresinol monoglucoside (SMG), SECO, and anhydrosecoisolariciresinol (anhydro-SECO) and that the extent and the main hydrolysates of the acid hydrolysis reaction depended on the acid concentration, hydrolysis temperature, and time. In addition, the production and change of p-coumaric acid glucoside, ferulic acid glucoside and their methyl esters and p-coumaric acid, ferulic acid, and their methyl esters during the process of hydrolysis was also investigated.

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes.

PubMed

Wang, Dawei; Kou, Ronghui; Ren, Yang; Sun, Cheng-Jun; Zhao, Hu; Zhang, Ming-Jian; Li, Yan; Huq, Ashifia; Ko, J Y Peter; Pan, Feng; Sun, Yang-Kook; Yang, Yong; Amine, Khalil; Bai, Jianming; Chen, Zonghai; Wang, Feng

2017-10-01

Nickel-rich layered transition metal oxides, LiNi 1- x (MnCo) x O 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7 Mn 0.15 Co 0.15 O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Dawei; Kou, Ronghui; Ren, Yang

Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-2 (1-x >= 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationicmore » ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.« less

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Dawei; Kou, Ronghui; Ren, Yang

Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

DOE PAGES

Wang, Dawei; Kou, Ronghui; Ren, Yang; ...

2017-08-25

Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

Study on kinetics of adsorption of humic acid modified by ferric chloride on U(VI)

NASA Astrophysics Data System (ADS)

Zhang, Y. Y.; Lv, J. W.; Song, Y.; Dong, X. J.; Fang, Q.

2017-11-01

In order to reveal the adsorption mechanism of the ferric chloride modified humic acid on uranium, the influence of pH value and contact time of adsorption on uranium was studied through a series of batch experiments. Meanwhile, the adsorption kinetics was analyzed with pseudo-first order kinetic model and pseudo-second order kinetic model. The results show that adsorption is affected by the pH value of the solution and by contract time, and the best condition for adsorption on uranium is at pH=5 and the adsorption equilibrium time is about 80 min. Kinetics of HA-Fe adsorption on uranium accords with pseudo-second order kinetic model. The adsorption is mainly chemical adsorption, and complexes were produced by the reaction between uranium ions and the functional groups on the surface of HA-Fe, which can provide reference for further study of humic acid effecting on the migration of U(VI) in soil.

Kinetic theory of two-temperature polyatomic plasmas

NASA Astrophysics Data System (ADS)

Orlac'h, Jean-Maxime; Giovangigli, Vincent; Novikova, Tatiana; Roca i Cabarrocas, Pere

2018-03-01

We investigate the kinetic theory of two-temperature plasmas for reactive polyatomic gas mixtures. The Knudsen number is taken proportional to the square root of the mass ratio between electrons and heavy-species, and thermal non-equilibrium between electrons and heavy species is allowed. The kinetic non-equilibrium framework also requires a weak coupling between electrons and internal energy modes of heavy species. The zeroth-order and first-order fluid equations are derived by using a generalized Chapman-Enskog method. Expressions for transport fluxes are obtained in terms of macroscopic variable gradients and the corresponding transport coefficients are expressed as bracket products of species perturbed distribution functions. The theory derived in this paper provides a consistent fluid model for non-thermal multicomponent plasmas.

Sorption kinetics of diuron on volcanic ash derived soils.

PubMed

Cáceres-Jensen, Lizethly; Rodríguez-Becerra, Jorge; Parra-Rivero, Joselyn; Escudey, Mauricio; Barrientos, Lorena; Castro-Castillo, Vicente

2013-10-15

Diuron sorption kinetic was studied in Andisols, Inceptisol and Ultisols soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Two types of kinetic models were used to fit the experimental dates: those that allow to establish principal kinetic parameters and modeling of sorption process (pseudo-first-order, pseudo-second-order), and some ones frequently used to describe solute transport mechanisms of organic compounds on different sorbents intended for remediation purposes (Elovich equation, intraparticle diffusion, Boyd, and two-site nonequilibrium models). The best fit was obtained with the pseudo-second-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the behavior of Diuron in each soil, in Andisols were observed the highest values for both parameters. The application of the models to describe solute transport mechanisms allowed establishing that in all soils the mass transfer controls the sorption kinetic across the boundary layer and intraparticle diffusion into macropores and micropores. The slowest sorption rate was observed on Ultisols, behavior which must be taken into account when the leaching potential of Diuron is considered. Copyright © 2013 Elsevier B.V. All rights reserved.

46 CFR 502.210 - Refusal to comply with orders to answer or produce documents; sanctions; enforcement.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., inferences will be drawn adverse to the person or party refusing to obey such order; (3) An order striking... failure to comply. A private party shall advise the Commission five (5) days (excluding Saturdays, Sundays...

46 CFR 502.210 - Refusal to comply with orders to answer or produce documents; sanctions; enforcement.

Code of Federal Regulations, 2011 CFR

2011-10-01

..., inferences will be drawn adverse to the person or party refusing to obey such order; (3) An order striking... or failure to comply. A private party shall advise the Commission five (5) days (excluding Saturdays...

Second-order numerical solution of time-dependent, first-order hyperbolic equations

NASA Technical Reports Server (NTRS)

Shah, Patricia L.; Hardin, Jay

1995-01-01

A finite difference scheme is developed to find an approximate solution of two similar hyperbolic equations, namely a first-order plane wave and spherical wave problem. Finite difference approximations are made for both the space and time derivatives. The result is a conditionally stable equation yielding an exact solution when the Courant number is set to one.

Kinetics, Reaction Orders, Rate Laws, and Their Relation to Mechanisms: A Hands-On Introduction for High School Students Using Portable Spectrophotometry

ERIC Educational Resources Information Center

Carraher, Jack M.; Curry, Sarah M.; Tessonnier, Jean-Philippe

2016-01-01

Teaching complex chemistry concepts such as kinetics using inquiry-based learning techniques can be challenging in a high school classroom setting. Access to expensive laboratory equipment such as spectrometers is typically limited and most reaction kinetics experiments have been designed for advanced placement (AP) or first-year undergraduate…

OPAC (orange peel activated carbon) derived from waste orange peel for the adsorption of chlorophenoxyacetic acid herbicides from water: Adsorption isotherm, kinetic modelling and thermodynamic studies.

PubMed

Pandiarajan, Aarthi; Kamaraj, Ramakrishnan; Vasudevan, Sudharshan; Vasudevan, Subramanyan

2018-08-01

This study presents the orange peel activated carbon (OPAC), derived from biowaste precursor (orange peel) by single step pyrolysis method and its application for the adsorption of chlorophenoxyacetic acid herbicides from the water. The OPAC exhibited the surface area of 592.471 m 2  g -1 , pore volume and pore diameter of 0.242 cc g -1 and 1.301 nm respectively. The adsorption kinetics and thermodynamic equilibrium modelling for all chlorophenoxyacetic acid herbicides were investigated. The various parametric effects such as pH and temperature were evaluated. A pseudo-second-order kinetic model was well fitted for all the herbicides. The Langmuir isotherm was obeyed for all the herbicides and the maximum Langmuir capacity of 574.71 mg g -1 was achieved. The thermodynamic studies revealed that the adsorption increases with increase in temperature. The results shows that the orange peel derived carbon (OPAC) as effective and efficient adsorbent material for the removal of chlorophenoxyacid herbicides from the water. Copyright © 2018 Elsevier Ltd. All rights reserved.

A Reduced-order NLTE Kinetic Model for Radiating Plasmas of Outer Envelopes of Stellar Atmospheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Munafò, Alessandro; Mansour, Nagi N.; Panesi, Marco, E-mail: munafo@illinois.edu, E-mail: nagi.n.mansour@nasa.gov, E-mail: m.panesi@illinois.edu

The present work proposes a self-consistent reduced-order NLTE kinetic model for radiating plasmas found in the outer layers of stellar atmospheres. A detailed collisional-radiative kinetic mechanism is constructed by leveraging the most up-to-date set of ab initio and experimental data available in the literature. This constitutes the starting point for the derivation of a reduced-order model, obtained by lumping the bound energy states into groups. In order to determine the needed thermo-physical group properties, uniform and Maxwell–Boltzmann energy distributions are used to reconstruct the energy population of each group. Finally, the reduced set of governing equations for the material gasmore » and the radiation field is obtained based on the moment method. Applications consider the steady flow across a shock wave in partially ionized hydrogen. The results clearly demonstrate that adopting a Maxwell–Boltzmann grouping allows, on the one hand, for a substantial reduction of the number of unknowns and, on the other, to maintain accuracy for both gas and radiation quantities. Also, it is observed that, when neglecting line radiation, the use of two groups already leads to a very accurate resolution of the photo-ionization precursor, internal relaxation, and radiative cooling regions. The inclusion of line radiation requires adopting just one additional group to account for optically thin losses in the α , β , and γ lines of the Balmer and Paschen series. This trend has been observed for a wide range of shock wave velocities.« less

Disproportionation of a crystalline citrate salt of a developmental pharmaceutical compound: characterization of the kinetics using pH monitoring and online Raman spectroscopy plus quantitation of the crystalline free base form in binary physical mixtures using FT-Raman, XRPD and DSC.

PubMed

Skrdla, Peter J; Zhang, Dan

2014-03-01

The crystalline citrate salt (CS) of a developmental pharmaceutical compound, MK-Q, was investigated in this work from two different, but related, perspectives. In the first part of the paper, the apparent disproportionation kinetics were surveyed using two different slurry systems, one containing water and the other a pH 6.9 phosphate buffer, using time-dependent measurements of the solution pH or by acquiring online Raman spectra of the solids. While the CS is generally stable when stored as a solid under ambient conditions of temperature and humidity, its low pHmax (<3) facilitates rapid disproportionation in aqueous solution, particularly at higher pH values. The rate of disappearance of the CS was found to obey first-order (Noyes-Whitney/dissolution rate-limited) kinetics, however, the formation of the crystalline product form in the slurry system was observed to exhibit kinetics consistent with a heterogeneous nucleation-and-growth mechanism. In the second part of this paper, more sensitive offline measurements made using XRPD, DSC and FT-Raman spectroscopy were applied to the characterization of binary physical mixtures of the CS and free base (FB) crystalline forms of MK-Q to obtain a calibration curve for each technique. It was found that all calibration plots exhibited good linearity of response, with the limit of detection (LOD) for each technique estimated to be ≤7 wt% FB. While additional calibration curves would need to be constructed to allow for accurate quantitation in various slurry systems, the general feasibility of these techniques is demonstrated for detecting low levels of CS disproportionation. Copyright © 2013 Elsevier B.V. All rights reserved.

Kinetics and mechanism of permanganate oxidation of iota- and lambda-carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions.

PubMed

Hassan, Refat M; Fawzy, Ahmed; Ahmed, Gamal A; Zaafarany, Ishaq A; Asghar, Basim H; Takagi, Hideo D; Ikeda, Yasuhisa

2011-10-18

The kinetics of oxidation of iota- and lambda-carrageenan as sulfated carbohydrates by permanganate ion in aqueous perchlorate solutions at a constant ionic strength of 2.0 mol dm(-3) have been investigated spectrophotometrically. The pseudo-first-order plots were found to be of inverted S-shape throughout the entire courses of reactions. The initial rates were found to be relatively slow in the early stages, followed by an increase in the oxidation rates over longer time periods. The experimental observations showed first-order dependences in permanganate and fractional first-order kinetics with respect to both carrageenans concentration for both the induction and autoacceleration periods. The results obtained at various hydrogen ion concentrations showed that the oxidation processes in these redox systems are acid-catalyzed throughout the two stages of oxidation reactions. The added salts lead to the prediction that Mn(III) is the reactive species throughout the autoacceleration periods. Kinetic evidence for the formation of 1:1 intermediate complexes was revealed. The kinetic parameters have been evaluated and tentative reaction mechanisms in good agreement with the kinetic results are discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

Kinetic Modeling of a Heterogeneous Fenton Oxidative Treatment of Petroleum Refining Wastewater

PubMed Central

Basheer Hasan, Diya'uddeen; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2014-01-01

The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k 2′), their final oxidation step (k 1′), and the direct conversion to endproducts step (k 3′) were 10.12, 3.78, and 0.24 min−1 for GKM; 0.98, 0.98, and nil min−1 for GLKM; and nil, nil, and >0.005 min−1 for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics. PMID:24592152

Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling.

PubMed

Schaefer, C; Jansen, A P J

2013-02-07

We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

Computer Calculation of First-Order Rate Constants

ERIC Educational Resources Information Center

Williams, Robert C.; Taylor, James W.

1970-01-01

Discusses the computer program used to calculate first-order rate constants. Discussion includes data preparation, weighting options, comparison techniques, infinity point adjustment, least-square fit, Guggenheim calculation, and printed outputs. Exemplifies the utility of the computer program by two experiments: (1) the thermal decomposition of…

Fe-vacancy ordering in superconducting K 1–xFe 2–ySe 2: First-principles calculations and Monte Carlo simulations

DOE PAGES

Fang, Yong; Tai, Yuan -Yen; Deng, Junkai; ...

2015-07-20

Fe vacancies in the 33 K superconductor K 1–xFe 2–ySe 2 show ordering schemes that may be correlated with its superconducting properties. First-principles calculations and kinetic Monte Carlo simulations lead to a very simple model for vacancy ordering. Repulsive dipolar interactions between Fe vacancies show three ground states: amore » $$\\sqrt{8}\\times \\sqrt{10}$$ rhombus-ordered structure for 12.5% vacancies, a $$\\sqrt{5}\\times \\sqrt{5}$$ squared lattice for 20% vacancies, and a $$\\sqrt{5}\\times \\sqrt{5}$$ rhombus-ordered structure for 25% vacancies. Other structural states are derived from these three ground states and may contain additional disordered spatial regions. As a result, the repulsive interaction between Fe vacancies arises from enhanced Fe–Se covalent bonds, which differs from the well-known attractive interaction of Fe vacancies in body-centered cubic Fe.« less

Rules, Legitimacy of Parental Authority, and Obligation to Obey in Chile, the Philippines, and the United States

ERIC Educational Resources Information Center

Darling, Nancy; Cumsille, Patricio; Pena-Alampay, Liane

2005-01-01

With age, Chilean, Filipino, and U.S. youth come to believe that fewer issues are legitimately within the control of parents and that they are less obliged to obey parental rules. These beliefs vary across domains and countries, providing insight into parent-adolescent conflict and the development of autonomy. (Contains 2 figures.)

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

NASA Astrophysics Data System (ADS)

Khan, Sameera Razi; Ashfaq, Maria; Mubashir; Masood, Summyia

2016-05-01

The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298-318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy ( E a), enthalpy change (Δ H*), free energy change (Δ G*), and entropy change (Δ S*) have also been evaluated.

Adsorption of saturated fatty acid in urea complexation: Kinetics and equilibrium studies

NASA Astrophysics Data System (ADS)

Setyawardhani, Dwi Ardiana; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

2018-02-01

Urea complexation is fractionation process for concentrating poly-unsaturated fatty acids (PUFAs) from vegetable oil or animal fats. For process design and optimization in commercial industries, it is necessary to provide kinetics and equilibrium data. Urea inclusion compounds (UICs) as the product is a unique complex form which one molecule (guest) is enclosed within another molecule (host). In urea complexation, the guest-host bonding exists between saturated fatty acids (SFAs) and crystalline urea. This research studied the complexation is analogous to an adsorption process. The Batch adsorption process was developed to obtain the experimental data. The ethanolic urea solution was mixed with SFA in certain compositions and adsorption times. The mixture was heated until it formed homogenous and clear solution, then it cooled very slowly until the first numerous crystal appeared. Adsorption times for the kinetic data were determined since the crystal formed. The temperature was maintained constant at room temperature. Experimental sets of data were observed with adsorption kinetics and equilibrium models. High concentration of saturated fatty acid (SFA) was used to represent adsorption kinetics and equilibrium parameters. Kinetic data were examined with pseudo first-order, pseudo second-order and intra particle diffusion models. Linier, Freundlich and Langmuir isotherm were used to study the equilibrium model of this adsorption. The experimental data showed that SFA adsorption in urea crystal followed pseudo second-order model. The compatibility of the data with Langmuir isotherm showed that urea complexation was a monolayer adsorption.

The kinetics of the O2/CO2 reaction in molten carbonate - Reaction orders for O2 and CO2 on NiO. [in fuel cells

NASA Technical Reports Server (NTRS)

Winnick, J.; Ross, P. N.

1980-01-01

The kinetics of the O2/CO2 reaction in molten carbonate is investigated using paste electrolytes and nickel sinter electrodes. A two-step approach to the determination of reaction orders is employed. First, exchange currents at various P(CO2) and P(O2) were measured using the low polarization method. Second, alpha(+) and alpha(-) values were obtained from the slope of the Allen-Hickling plot for current densities low enough so that concentration polarization within the electrode can be neglected. The reaction orders are + 1/4 in CO2 and + 5/8 in O2 in the cathodic direction, and - 3/4 in CO2 and + 1/8 in O2 in the anodic direction.

Consciousness of the first order in blindsight

PubMed Central

Sahraie, Arash; Hibbard, Paul B.; Trevethan, Ceri T.; Ritchie, Kay L.; Weiskrantz, Lawrence

2010-01-01

At suprathreshold levels, detection and awareness of visual stimuli are typically synonymous in nonclinical populations. But following postgeniculate lesions, some patients may perform above chance in forced-choice detection paradigms, while reporting not to see the visual events presented within their blind field. This phenomenon, termed “blindsight,” is intriguing because it demonstrates a dissociation between detection and perception. It is possible, however, for a blindsight patient to have some “feeling” of the occurrence of an event without seeing per se. This is termed blindsight type II to distinguish it from the type I, defined as discrimination capability in the total absence of any acknowledged awareness. Here we report on a well-studied patient, D.B., whose blindsight capabilities have been previously documented. We have found that D.B. is capable of detecting visual patterns defined by changes in luminance (first-order gratings) and those defined by contrast modulation of textured patterns (textured gratings; second-order stimuli) while being aware of the former but reporting no awareness of the latter. We have systematically investigated the parameters that could lead to visual awareness of the patterns and show that mechanisms underlying the subjective reports of visual awareness rely primarily on low spatial frequency, first-order spatial components of the image. PMID:21078979

Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors.

PubMed

Hassan, Refat M; Zaafarany, Ishaq A

2013-06-17

Corrosion inhibition of aluminum (Al) in hydrochloric acid by anionic polyeletrolyte pectates (PEC) as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper.

First-order error budgeting for LUVOIR mission

NASA Astrophysics Data System (ADS)

Lightsey, Paul A.; Knight, J. Scott; Feinberg, Lee D.; Bolcar, Matthew R.; Shaklan, Stuart B.

2017-09-01

Future large astronomical telescopes in space will have architectures that will have complex and demanding requirements to meet the science goals. The Large UV/Optical/IR Surveyor (LUVOIR) mission concept being assessed by the NASA/Goddard Space Flight Center is expected to be 9 to 15 meters in diameter, have a segmented primary mirror and be diffraction limited at a wavelength of 500 nanometers. The optical stability is expected to be in the picometer range for minutes to hours. Architecture studies to support the NASA Science and Technology Definition teams (STDTs) are underway to evaluate systems performance improvements to meet the science goals. To help define the technology needs and assess performance, a first order error budget has been developed. Like the JWST error budget, the error budget includes the active, adaptive and passive elements in spatial and temporal domains. JWST performance is scaled using first order approximations where appropriate and includes technical advances in telescope control.

A Study on the Kinetics of a Disorder-to-Order Transition Induced by Alkyne/Azide Click Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

X Wei; L Li; J Kalish

2011-12-31

The kinetics of binary blends of poly(ethylene oxide)-block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) diblock copolymer and Rhodamine B azide was investigated during a disorder-to-order transition induced by alkyne/azide click reaction. The change in the domain spacing and conversion of reactants as a function of annealing time were investigated by in situ small-angle X-ray scattering (SAXS) and infrared spectroscopy (IR), suggesting several kinetic processes with different time scales during thermal annealing. While a higher conversion can be realized by extending the annealing time, the microphase-separated morphology is independent of the annealing conditions, as long as both the reagents and final products have enoughmore » mobility.« less

Kinetics and Equilibrium of Fe3+ Ions Adsorption on Carbon Nanofibers

NASA Astrophysics Data System (ADS)

Alimin; Agusu, La; Ahmad, L. O.; Kadidae, L. O.; Ramadhan, L.; Nurdin, M.; Isdayanti, N.; Asria; Aprilia M, P.; Hasrudin

2018-05-01

Generally, the interaction between metal ions and adsorbent is governed by many factors including; concentration of metal ions, interaction time and solution pH. In this work, we applied liquid phase adsorption for studying the interaction between Fe3+ ions and Carbon Nanofibers (CNFs) irradiated by ultrasonic waves. Kinetics and isotherms model of the Fe3+ ion adsorption was investigated by varying contact time and pH. We found that the Fe3+ ions were efficiently adsorbed on CNFs for 0.5 h in acidic pH of around 5. In order to obtain the best-fitted isotherms model, Langmuir and Freundlich’s isotherms were used in this work. The adsorption equilibrium Fe3+ metal ions on CNFs tend to follow Langmuir. Adsorption kinetics of Fe3+ ions on CNFs were investigated by using both pseudo-first and pseudo-second orders. The adsorption kinetics coincided well with the pseudo-second-order.

Kinetic sorption of contaminants of emerging concern by a palygorskite-montmorillonite filter medium.

PubMed

Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D

2017-06-01

Kinetic sorption of bisphenol A (BPA), carbamazepine (CMZ) and ciprofloxacin (CIP) by three palygorskite-montmorillonite (Pal-Mt) granule sizes was studied. For BPA, CMZ and CIP, apparent sorption equilibrium was reached within about 3, 5 and 16 h, respectively. The highest and the lowest sorption capacities were by the small and the large granule sizes, respectively. Experimental results were compared to various sorption kinetics models to gain insights regarding the sorption processes and achieve a predictive capacity. The pseudo-second order (PSO) and the Elovich models performed the best while the pseudo-first order (PFO) model was only adequate for CMZ. The intraparticle-diffusion (IPD) model showed a two-step linear plot of BPA, CMZ and CIP sorption versus square root of time that was indicative of surface-sorption followed by IPD as a rate-limiting process before equilibrium was reached. Using the pseudo-first order (PFO) and the pseudo-second order (PSO) rate constants combined with previously-established Langmuir equilibrium sorption models, the kinetic sorption (k a ) and desorption (k d ) Langmuir kinetic rate constants were theoretically calculated for BPA and CIP. Kinetic sorption was then simulated using these theoretically calculated k a and k d values, and the simulations were compared to the observed behavior. The simulations fit the observed sorbed concentrations better during the early part of the experiments; the observed sorption during later times occurred more slowly than expected, supporting the hypothesis that IPD becomes a rate-limiting process during the course of the experiment. Copyright © 2017 Elsevier Ltd. All rights reserved.

IMPLEMENTATION OF FIRST-PASSAGE TIME APPROACH FOR OBJECT KINETIC MONTE CARLO SIMULATIONS OF IRRADIATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.

2014-06-30

The objective of the work is to implement a first-passage time (FPT) approach to deal with very fast 1D diffusing SIA clusters in KSOME (kinetic simulations of microstructural evolution) [1] to achieve longer time-scales during irradiation damage simulations. The goal is to develop FPT-KSOME, which has the same flexibility as KSOME.

Enhanced electron transfer kinetics through hybrid graphene-carbon nanotube films.

PubMed

Henry, Philémon A; Raut, Akshay S; Ubnoske, Stephen M; Parker, Charles B; Glass, Jeffrey T

2014-11-01

We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k 0 , approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film.

Removal of humic acid from aqueous solution using dual PMMA/PVDF composite nanofiber: kinetics study

NASA Astrophysics Data System (ADS)

Zulfikar, M. A.; Afrianingsih, I.; Bahri, A.; Nasir, M.; Alni, A.; Setiyanto, H.

2018-05-01

The removal of humic acid from aqueous solution using dual poly(methyl methacrylate)/polyvinyl difluoride composite nanofiber under the influence of concentration has been studied. The experiments were performed using humic acid (HA) as an adsorbate at concentration in the range of 50-200 mg/L. Pseudo-first-order, pseudo-second-order, and intra-particle diffusion models were used to describe the kinetic data and the rate constants were evaluated. It was observed that the amount of humic acid removed decrease with increasing concentration. The kinetic study revealed that pseudo-second order model fitted well the kinetic data, while the external diffusion or boundary layer diffusion was the main rate determining step in the removal process.

General and specific consciousness: a first-order representationalist approach

PubMed Central

Mehta, Neil; Mashour, George A.

2013-01-01

It is widely acknowledged that a complete theory of consciousness should explain general consciousness (what makes a state conscious at all) and specific consciousness (what gives a conscious state its particular phenomenal quality). We defend first-order representationalism, which argues that consciousness consists of sensory representations directly available to the subject for action selection, belief formation, planning, etc. We provide a neuroscientific framework for this primarily philosophical theory, according to which neural correlates of general consciousness include prefrontal cortex, posterior parietal cortex, and non-specific thalamic nuclei, while neural correlates of specific consciousness include sensory cortex and specific thalamic nuclei. We suggest that recent data support first-order representationalism over biological theory, higher-order representationalism, recurrent processing theory, information integration theory, and global workspace theory. PMID:23882231

Thermodynamic evidence of first-order melting of Xe on graphite

NASA Astrophysics Data System (ADS)

Jin, A. J.; Bjurstrom, M. R.; Chan, M. H. W.

1989-03-01

Precision heat-capacity and vapor-pressure isotherm measurements indicate that the melting of monolayer Xe on graphite is always first order. This conclusion is consistent with the results of simulation studies but in sharp contrast with the claim advanced in a series of x-ray studies of a crossover from first-order to continuous Kosterlitz-Thouless-Halperin-Nelson-Young melting.

Kinetic intermediates of unfolding of dimeric prostatic phosphatase.

PubMed

Kuciel, Radosława; Mazurkiewicz, Aleksandra; Dudzik, Paulina

2007-01-01

Kinetics of guanidine hydrochloride (GdnHCl)-induced unfolding of human prostatic acid phosphatase (hPAP), a homodimer of 50 kDa subunit molecular mass was investigated with enzyme activity measurements, capacity for binding an external hydrophobic probe, 1-anilinonaphtalene-8-sulfonate (ANS), accessibility of thiols to reaction with 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) and 2-(4'-maleimidylanilino)naphthalene-6-sulfonate (MIANS) and ability to bind Congo red dye. Kinetic analysis was performed to describe a possible mechanism of hPAP unfolding and dissociation that leads to generation of an inactive monomeric intermediate that resembles, in solution of 1.25 M GdnHCl pH 7.5, at 20 degrees C, in equilibrium, a molten globule state. The reaction of hPAP inactivation in 1.25 M GdnHCl followed first order kinetics with the reaction rate constant 0.0715 +/- 0.0024 min(-1) . The rate constants of similar range were found for the pseudo-first-order reactions of ANS and Congo red binding: 0.0366 +/- 0.0018 min(-1) and 0.0409 +/- 0.0052 min(-1), respectively. Free thiol groups, inaccessible in the native protein, were gradually becoming, with the progress of unfolding, exposed for the reactions with DTNB and MIANS, with the pseudo-first-order reaction rate constants 0.327 +/- 0.014 min(-1) and 0.216 +/- 0.010 min(-1), respectively. The data indicated that in the course of hPAP denaturation exposure of thiol groups to reagents took place faster than the enzyme inactivation and exposure of the protein hydrophobic surface. This suggested the existence of a catalytically active, partially unfolded, but probably dimeric kinetic intermediate in the process of hPAP unfolding. On the other hand, the protein inactivation was accompanied by exposure of a hydrophobic, ANS-binding surface, and with an increased capacity to bind Congo red. Together with previous studies these results suggest that the stability of the catalytically active conformation of the enzyme depends mainly on

Universal first-order reliability concept applied to semistatic structures

NASA Technical Reports Server (NTRS)

Verderaime, V.

1994-01-01

A reliability design concept was developed for semistatic structures which combines the prevailing deterministic method with the first-order reliability method. The proposed method surmounts deterministic deficiencies in providing uniformly reliable structures and improved safety audits. It supports risk analyses and reliability selection criterion. The method provides a reliability design factor derived from the reliability criterion which is analogous to the current safety factor for sizing structures and verifying reliability response. The universal first-order reliability method should also be applicable for air and surface vehicles semistatic structures.

Universal first-order reliability concept applied to semistatic structures

NASA Astrophysics Data System (ADS)

Verderaime, V.

1994-07-01

A reliability design concept was developed for semistatic structures which combines the prevailing deterministic method with the first-order reliability method. The proposed method surmounts deterministic deficiencies in providing uniformly reliable structures and improved safety audits. It supports risk analyses and reliability selection criterion. The method provides a reliability design factor derived from the reliability criterion which is analogous to the current safety factor for sizing structures and verifying reliability response. The universal first-order reliability method should also be applicable for air and surface vehicles semistatic structures.

Parallel Coding of First- and Second-Order Stimulus Attributes by Midbrain Electrosensory Neurons

PubMed Central

McGillivray, Patrick; Vonderschen, Katrin; Fortune, Eric S.; Chacron, Maurice J.

2015-01-01

Natural stimuli often have time-varying first-order (i.e., mean) and second-order (i.e., variance) attributes that each carry critical information for perception and can vary independently over orders of magnitude. Experiments have shown that sensory systems continuously adapt their responses based on changes in each of these attributes. This adaptation creates ambiguity in the neural code as multiple stimuli may elicit the same neural response. While parallel processing of first- and second-order attributes by separate neural pathways is sufficient to remove this ambiguity, the existence of such pathways and the neural circuits that mediate their emergence have not been uncovered to date. We recorded the responses of midbrain electrosensory neurons in the weakly electric fish Apteronotus leptorhynchus to stimuli with first- and second-order attributes that varied independently in time. We found three distinct groups of midbrain neurons: the first group responded to both first- and second-order attributes, the second group responded selectively to first-order attributes, and the last group responded selectively to second-order attributes. In contrast, all afferent hindbrain neurons responded to both first- and second-order attributes. Using computational analyses, we show how inputs from a heterogeneous population of ON- and OFF-type afferent neurons are combined to give rise to response selectivity to either first- or second-order stimulus attributes in midbrain neurons. Our study thus uncovers, for the first time, generic and widely applicable mechanisms by which parallel processing of first- and second-order stimulus attributes emerges in the brain. PMID:22514313

Municipal Leachate Treatment by Fenton Process: Effect of Some Variable and Kinetics

PubMed Central

Ahmadian, Mohammad; Reshadat, Sohyla; Yousefi, Nader; Mirhossieni, Seyed Hamed; Zare, Mohammad Reza; Ghasemi, Seyed Ramin; Rajabi Gilan, Nader; Khamutian, Razieh; Fatehizadeh, Ali

2013-01-01

Due to complex composition of leachate, the comprehensive leachate treatment methods have been not demonstrated. Moreover, the improper management of leachate can lead to many environmental problems. The aim of this study was application of Fenton process for decreasing the major pollutants of landfill leachate on Kermanshah city. The leachate was collected from Kermanshah landfill site and treated by Fenton process. The effect of various parameters including solution pH, Fe2+ and H2O2 dosage, Fe2+/H2O2 molar ratio, and reaction time was investigated. The result showed that with increasing Fe2+ and H2O2 dosage, Fe2+/H2O2 molar ratio, and reaction time, the COD, TOC, TSS, and color removal increased. The maximum COD, TOC, TSS, and color removal were obtained at low pH (pH: 3). The kinetic data were analyzed in term of zero-order, first-order, and second-order expressions. First-order kinetic model described the removal of COD, TOC, TSS, and color from leachate better than two other kinetic models. In spite of extremely difficulty of leachate treatment, the previous results seem rather encouraging on the application of Fenton's oxidation. PMID:23840229

pyJac: Analytical Jacobian generator for chemical kinetics

NASA Astrophysics Data System (ADS)

Niemeyer, Kyle E.; Curtis, Nicholas J.; Sung, Chih-Jen

2017-06-01

Accurate simulations of combustion phenomena require the use of detailed chemical kinetics in order to capture limit phenomena such as ignition and extinction as well as predict pollutant formation. However, the chemical kinetic models for hydrocarbon fuels of practical interest typically have large numbers of species and reactions and exhibit high levels of mathematical stiffness in the governing differential equations, particularly for larger fuel molecules. In order to integrate the stiff equations governing chemical kinetics, generally reactive-flow simulations rely on implicit algorithms that require frequent Jacobian matrix evaluations. Some in situ and a posteriori computational diagnostics methods also require accurate Jacobian matrices, including computational singular perturbation and chemical explosive mode analysis. Typically, finite differences numerically approximate these, but for larger chemical kinetic models this poses significant computational demands since the number of chemical source term evaluations scales with the square of species count. Furthermore, existing analytical Jacobian tools do not optimize evaluations or support emerging SIMD processors such as GPUs. Here we introduce pyJac, a Python-based open-source program that generates analytical Jacobian matrices for use in chemical kinetics modeling and analysis. In addition to producing the necessary customized source code for evaluating reaction rates (including all modern reaction rate formulations), the chemical source terms, and the Jacobian matrix, pyJac uses an optimized evaluation order to minimize computational and memory operations. As a demonstration, we first establish the correctness of the Jacobian matrices for kinetic models of hydrogen, methane, ethylene, and isopentanol oxidation (number of species ranging 13-360) by showing agreement within 0.001% of matrices obtained via automatic differentiation. We then demonstrate the performance achievable on CPUs and GPUs using py

Synthesis, kinetics and characterizations of polyimide based semi-IPN systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tai, H.J.

1992-01-01

The PMR-15 polyimide is the leading matrix resin for high performance composites for use in high temperature and thermo-oxidative environments. This resin has superior mechanical properties, good processability and a high working temperature at around 300[degrees]C. It has the disadvantages of being brittle and high susceptibility to microcracking from thermal cycling that limit its widespread application. To improve the fracture toughness, a thermoplastic polyimide, LARC-TPI, and a thermoplastic poly (amide imide), Amoco AI-10, were added individually to PMR-15 resin to form sequential semi-interpenetrating polymer networks (semi-2-IPNs). the kinetics of imidization of LARC-TPI were studied using TGA technique. Both the solventmore » and the glass transition temperature were found to greatly affect the imidization kinetics. The kinetics could be well modeled by a two-step reaction: the first step being a second order reaction followed by a first order diffusion controlled reaction as the second step. The curing of PMR-15 and PMR-15/LARC-TPI semi-IPN was investigated by DSC. A first order reaction kinetics could describe the curing process adequately, implying that the reverse Diels-Alder reaction of the Norbornene end group was the rate controlling step. The glass transition temperature played an important role. The higher the fraction LARC-TPI, the higher the glass transition temperature of the semi-IPN prepolymer, and the slower the cure reaction. From a knowledge of kinetics, the molding cycle of PMR-15 and PMR-15/LARC-TPI semi-IPNs were determined. Both PMR-15/LARC-TPI and PMR-15/AI-10 semi-IPN systems exhibited much higher fracture toughness than PMR-15, but at the compromise of a reduction in the glass transition temperature. A single glass transition temperature for each semi-IPN was observed but there was presence of special intermolecular interaction. Tg measurements and IR spectroscopy indicated that both semi-IPN systems were compatible polymer pairs.« less

Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate

PubMed Central

Omedes-Pujol, Marta

2010-01-01

Summary Propylene carbonate can be used as a green solvent for the asymmetric synthesis of cyanohydrin trimethylsilyl ethers from aldehydes and trimethylsilyl cyanide catalysed by VO(salen)NCS, though reactions are slower in this solvent than the corresponding reactions carried out in dichloromethane. A mechanistic study has been undertaken, comparing the catalytic activity of VO(salen)NCS in propylene carbonate and dichloromethane. Reactions in both solvents obey overall second-order kinetics, the rate of reaction being dependent on the concentration of both the aldehyde and trimethylsilyl cyanide. The order with respect to VO(salen)NCS was determined and found to decrease from 1.2 in dichloromethane to 1.0 in propylene carbonate, indicating that in propylene carbonate, VO(salen)NCS is present only as a mononuclear species, whereas in dichloromethane dinuclear species are present which have previously been shown to be responsible for most of the catalytic activity. Evidence from 51V NMR spectroscopy suggested that propylene carbonate coordinates to VO(salen)NCS, blocking the free coordination site, thus inhibiting its Lewis acidity and accounting for the reduction in catalytic activity. This explanation was further supported by a Hammett analysis study, which indicated that Lewis base catalysis made a much greater contribution to the overall catalytic activity of VO(salen)NCS in propylene carbonate than in dichloromethane. PMID:21085513

The kinetics and mechanism of the organo-iridium catalysed racemisation of amines.

PubMed

Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I

2016-08-07

The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

Thermal degradation kinetics of all-trans and cis-carotenoids in a light-induced model system.

PubMed

Xiao, Ya-Dong; Huang, Wu-Yang; Li, Da-Jing; Song, Jiang-Feng; Liu, Chun-Quan; Wei, Qiu-Yu; Zhang, Min; Yang, Qiu-Ming

2018-01-15

Thermal degradation kinetics of lutein, zeaxanthin, β-cryptoxanthin, β-carotene was studied at 25, 35, and 45°C in a model system. Qualitative and quantitative analyses of all-trans- and cis-carotenoids were conducted using HPLC-DAD-MS technologies. Kinetic and thermodynamic parameters were calculated by non-linear regression. A total of 29 geometrical isomers and four oxidation products were detected, including all-trans-, keto compounds, mono-cis- and di-cis-isomers. Degradations of all-trans-lutein, zeaxanthin, β-cryptoxanthin, and β-carotene were described by a first-order kinetic model, with the order of rate constants as k β -carotene >k β -cryptoxanthin >k lutein >k zeaxanthin . Activation energies of zeaxanthin, lutein, β-cryptoxanthin, and β-carotene were 65.6, 38.9, 33.9, and 8.6kJ/moL, respectively. cis-carotenoids also followed with the first-order kinetic model, but they did not show a defined sequence of degradation rate constants and activation energies at different temperatures. A possible degradation pathway of four carotenoids was identified to better understand the mechanism of carotenoid degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetics for the distribution of acrylamide in French fries, fried oil and vapour during frying of potatoes.

PubMed

Hsu, Hui-Tsung; Chen, Ming-Jen; Tseng, Tzu-Ping; Cheng, Li-Hsin; Huang, Li-Jen; Yeh, Tai-Sheng

2016-11-15

Kinetic analysis for the formation of acrylamide in heated foods has been typically performed using only measured data of acrylamide in foods; however, its possible loss caused by release from heated foods into fried oil and air has seldom been considered. The results obtained from the monitoring of acrylamide by frying French fries indicated that acrylamide is distributed in three phases: French fries, frying oil, and air. From the evolved gas analysis of acrylamide and the measured concentration profile of the total acrylamide amount present in these phases, the kinetic behaviour for acrylamide formation does not obey the commonly used model of two-step consecutive reactions during frying, while a lumped kinetic model was proposed for the total acrylamide amount. Moreover, a high acrylamide level in air was observed, implying that, apart from consumers of French fries, fast-food restaurant workers are potentially subject to occupational hazards from acrylamide inhalation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorptive Removal of Cadmium (II) from Aqueous Solution by Multi-Carboxylic-Functionalized Silica Gel: Equilibrium, Kinetics and Thermodynamics

NASA Astrophysics Data System (ADS)

Li, Min; Meng, Xiaojing; Yuan, Jinhai; Deng, Wenwen; Liang, Xiuke

2018-01-01

In the present study, the adsorption behavior of cadmium (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of various experimental parameters such as pH value, contact time and initial concentration on adsorption capacity of cadmium (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. Equilibrium isotherms for the adsorption of cadmium (II) ion were analyzed by Freundlich and Langmuir isotherm models, the results indicate that Langmuir isotherm model was found to be credible to express the data for cadmium (II) ion from aqueous solution onto the SG-MCF. Various thermodynamics parameters of the adsorption process, including free energy of adsorption (ΔG0 ), the enthalpy of adsorption (ΔH0 ) and standard entropy changes (ΔS0 ), were calculated to predict the nature of adsorption. The positive value of the enthalpy change and the negative value of free energy change indicate that the process is endothermic and spontaneous process.

Xenon elimination kinetics following brief exposure.

PubMed

Schaefer, Maximilian S; Piper, Thomas; Geyer, Hans; Schneemann, Julia; Neukirchen, Martin; Thevis, Mario; Kienbaum, Peter

2017-05-01

Xenon is a modern inhalative anaesthetic with a very low solubility in tissues providing rapid elimination and weaning from anaesthesia. Besides its anaesthetic properties, Xenon promotes the endogenous erythropoietin biosynthesis and thus has been enlisted as prohibited substance by the World Anti-Doping Agency (WADA). For effective doping controls, knowledge about the elimination kinetics of Xenon and the duration of traceability are of particular importance. Seventy-seven full blood samples were obtained from 7 normal weight patients undergoing routine Xenon-based general anaesthesia with a targeted inspiratory concentration of 60% Xenon in oxygen. Samples were taken before and during Xenon inhalation as well as one, two, 4, 8, 16, 24, 32, 40, and 48 h after exposure. Xenon concentrations were assessed in full blood by gas chromatography and triple quadrupole tandem mass spectrometry with a detection limit of 0.25 µmol/L. The elimination of Xenon was characterized by linear regression of log-transformed Xenon blood concentrations, as well as non-linear regression. Xenon exposure yielded maximum concentrations in arterial blood of 1.3 [1.1; 1.6] mmol/L. Xenon was traceable for 24 to 48 h. The elimination profile was characterized by a biphasic pattern with a rapid alpha phase, followed by a slower beta phase showing a first order kinetics (c[Xe] = 69.1e -0.26x , R 2  = 0.83, t 1/2  = 2.7 h). Time in hours after exposure could be estimated by 50*ln(1.39/c[Xe] 0.077 ). Xenon's elimination kinetics is biphasic with a delayed beta phase following a first order kinetics. Xenon can reliably be detected for at least 24 h after brief exposure. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Fractal reaction kinetics.

PubMed

Kopelman, R

1988-09-23

Classical reaction kinetics has been found to be unsatisfactory when the reactants are spatially constrained on the microscopic level by either walls, phase boundaries, or force fields. Recently discovered theories of heterogeneous reaction kinetics have dramatic consequences, such as fractal orders for elementary reactions, self-ordering and self-unmixing of reactants, and rate coefficients with temporal "memories." The new theories were needed to explain the results of experiments and supercomputer simulations of reactions that were confined to low dimensions or fractal dimensions or both. Among the practical examples of "fractal-like kinetics" are chemical reactions in pores of membranes, excitation trapping in molecular aggregates, exciton fusion in composite materials, and charge recombination in colloids and clouds.

Kinetic limitation of chemical ordering in Bi2Te3-x Se x layers grown by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Schreyeck, S.; Brunner, K.; Kirchner, A.; Bass, U.; Grauer, S.; Schumacher, C.; Gould, C.; Karczewski, G.; Geurts, J.; Molenkamp, L. W.

2016-04-01

We study the chemical ordering in Bi2Te3-x Se x grown by molecular beam epitaxy on Si substrates. We produce films in the full composition range from x  =  0 to 3, and determine their material properties using energy dispersive x-ray spectroscopy, x-ray diffraction and Raman spectroscopy. By fitting the parameters of a kinetic growth model to these results, we obtain a consistent description of growth at a microscopic level. Our main finding is that despite the incorporation of Se in the central layer being much more probable than that of Te, the formation of a fully ordered Te-Bi-Se-Bi-Te layer is prevented by kinetic of the growth process. Indeed, the Se concentration in the central layer of Bi2Te2Se1 reaches a maximum of only  ≈75% even under ideal growth conditions. A second finding of our work is that the intensity ratio of the 0 0 12 and 0 0 6 x-ray reflections serves as an experimentally accessible quantitative measure of the degree of ordering in these films.

Removal of ibuprofen, naproxen and carbamazepine in aqueous solution onto natural clay: equilibrium, kinetics, and thermodynamic study

NASA Astrophysics Data System (ADS)

Khazri, Hassen; Ghorbel-Abid, Ibtissem; Kalfat, Rafik; Trabelsi-Ayadi, Malika

2017-10-01

This study aimed to describe the adsorption of three pharmaceuticals compounds (ibuprofen, naproxen and carbamazepine) onto natural clay on the basis of equilibrium parameters such as a function of time, effect of pH, varying of the concentration and the temperature. Adsorption kinetic data were modeled using the Lagergren's first-order and the pseudo-second-order kinetic equations. The kinetic results of adsorption are described better using the pseudo-second order model. The isotherm results were tested in the Langmuir, Freundlich and Dubinin-Radushkevich models. The thermodynamic parameters obtained indicate that the adsorption of pharmaceuticals on the clay is a spontaneous and endothermic process.

Domain Decomposition Algorithms for First-Order System Least Squares Methods

NASA Technical Reports Server (NTRS)

Pavarino, Luca F.

1996-01-01

Least squares methods based on first-order systems have been recently proposed and analyzed for second-order elliptic equations and systems. They produce symmetric and positive definite discrete systems by using standard finite element spaces, which are not required to satisfy the inf-sup condition. In this paper, several domain decomposition algorithms for these first-order least squares methods are studied. Some representative overlapping and substructuring algorithms are considered in their additive and multiplicative variants. The theoretical and numerical results obtained show that the classical convergence bounds (on the iteration operator) for standard Galerkin discretizations are also valid for least squares methods.

Un-collided-flux preconditioning for the first order transport equation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rigley, M.; Koebbe, J.; Drumm, C.

2013-07-01

Two codes were tested for the first order neutron transport equation using finite element methods. The un-collided-flux solution is used as a preconditioner for each of these methods. These codes include a least squares finite element method and a discontinuous finite element method. The performance of each code is shown on problems in one and two dimensions. The un-collided-flux preconditioner shows good speedup on each of the given methods. The un-collided-flux preconditioner has been used on the second-order equation, and here we extend those results to the first order equation. (authors)

[Influence of pH on Kinetics of Anilines Oxidation by Permanganate].

PubMed

Wang, Hui; Sun, Bo; Guan, Xiao-hong

2016-02-15

To investigate the effect of pH on the oxidation of anilines by potassium permanganate, aniline and p-Chloroaniline were taken as the target contaminants, and the experiments were conducted under the condition with potassium permanganate in excess over a wide pH range. The reaction displayed remarkable autocatalysis, which was presumably ascribed to the formation of complexes by the in situ generated MnOx and the target contaminants on its surface, and thereby improved the oxidation rate of the target contaminants by permanganate. The reaction kinetics was fitted with the pseudo-first-order kinetics at different pH to obtain the pseudo-first-order reaction constants (k(obs)). The second-order rate constants calculated from permanganate concentration and k,b, increased with the increase of pH and reached the maximum near their respective pKa, after which they decreased gradually. This tendency is called parabola-like shaped pH-rate profile. The second-order rate constants between permanganate and anilines were well fitted by the proton transfer model proposed by us in previous work.

Reflection and transmission characteristics of a layer obeying the two-pressure field poroelastic phenomenological model of Berryman and Wang.

PubMed

Kachkouch, F; Franklin, H; Tinel, A

2018-07-01

The characteristics of the reflection and transmission by a fluid-loaded double porosity layer are studied. The medium obeys the two-pressure field poroelastic phenomenological model of Berryman and Wang. The open pore hydraulic conditions applied at the interfaces yield factorized expressions for the coefficients exhibiting on the one hand a separation allowing to distinguish between symmetrical and antisymmetrical motions and on the other hand the way each of the three dilatational waves associate with the shear wave. The numerical study done for a layer of Berea sandstone saturated by water shows clearly the role of each of the dilatational waves. There are peculiarities such as the absence of the fundamental antisymmetrical mode (zero order) and a singular behaviour of the symmetrical fundamental mode. The low frequency approximation for this latter is derived from the proposed formulas and compared with the numerical results. Copyright © 2018 Elsevier B.V. All rights reserved.

Sorption kinetics and isotherm modelling of imidacloprid on bentonite and organobentonites.

PubMed

Jain, Shailesh K; Shakil, Najam A; Dutta, Anirban; Kumar, Jitendra; Saini, Mukesh K

2017-05-04

Bentonite was modified by quaternary ammonium cations viz. cetytrimethylammonium (CTA), cetylpyridinium (CP), rioctylmethylammonium (TOM) and pcholine (PTC) at 100% cation exchange capacity of bentonite and was characterized by X-ray diffraction, CHNS elemental analyser and Fourier transform infrared spectroscopy. The sorption of imidacloprid on organobentonites/bentonite was studied by batch method. Normal bentonite could adsorb imidacloprid only upto 19.31-22.18% while all organobentonites except PTC bentonite (PTCB), enhanced its adsorption by three to four times. Highest adsorption was observed in case of TOM bentonite (TOMB) (76.94-83.16%). Adsorption kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. For normal bentonite data were best fitted to pseudo-first-order kinetic, while for organobentonites fitted to pseudo-second-order kinetics. Sorption data were analysed using Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherm models. Data were well fitted to Freundlich adsorption isotherm. Product of Freundlich adsorption constant and heterogeneity parameter (K f .1/n) was in following order: TOMB (301.87) > CTA bentonite (CTAB) (152.12) > CP bentonite (CPB) (92.58) > bentonite (27.25). Desorption study confirmed hysteresis and concentration dependence. The present study showed that the organobentonite could be a good sorbent for removal of imidacloprid from natural water sample also. Percentage adsorption and Distribution coefficient (mL g -1 ) value of different adsorbent was in following order: TOMB (74.85% and 297.54) > CTAB (55.78% and 126.15) > CPB (45.81% and 84.55) > bentonite (10.65% and 11.92).

Kinetic study of corn straw pyrolysis: comparison of two different three-pseudocomponent models.

PubMed

Li, Zhengqi; Zhao, Wei; Meng, Baihong; Liu, Chunlong; Zhu, Qunyi; Zhao, Guangbo

2008-11-01

With heating rates of 20, 50 and 100 K min(-1), the thermal decomposition of corn straw samples (corn stalks skins, corn stalks cores, corn bracts and corn leaves) were studied using thermogravimetric analysis. The maximum pyrolysis rates increased with the heating rate increasing and the temperature at the peak pyrolysis rate also increased. Assuming the addition of three independent parallel reactions, corresponding to three pseudocomponents linked to the hemicellulose, cellulose and lignin, two different three-pseudocomponent models were used to simulate the corn straw pyrolysis. Model parameters of pyrolysis were given. It was found that the three-pseudocomponent model with n-order kinetics was more accurate than the model with first-order kinetics at most cases. It showed that the model with n-order kinetics was more accurate to describe the pyrolysis of the hemicellulose.

Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors

PubMed Central

Hassan, Refat M.; Zaafarany, Ishaq A.

2013-01-01

Corrosion inhibition of aluminum (Al) in hydrochloric acid by anionic polyeletrolyte pectates (PEC) as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper. PMID:28809282

Water sorption equilibria and kinetics of henna leaves

NASA Astrophysics Data System (ADS)

Sghaier, Khamsa; Peczalski, Roman; Bagane, Mohamed

2018-05-01

In this work, firstly the sorption isotherms of henna leaves were determined using a dynamic vapor sorption ( DVS) device at 3 temperatures (30, 40, 50 °C). The equilibrium data were well fitted by the GAB model. Secondly, drying kinetics were measured using a pilot convective dryer for 3 air temperatures (same as above), 3 velocities (0.5, 1, 1.42 m/s) and 4 relative humidities (20, 30, 35, 40%). The drying kinetic coefficients were identified by fitting the DVS and pilot dryer data by Lewis semi-empirical model. In order to compare the obtained kinetic parameters with literature, the water diffusivities were also identified by fitting the data by the simplified solution of fickian diffusion equation. The identified kinetic coefficient was mainly dependent on air temperature and velocity what proved that it represented rather the external transfer and not the internal one.

Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate.

PubMed

Forsey, Steven P; Thomson, Neil R; Barker, James F

2010-04-01

The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics. The oxidation of pyrene was initially very rapid and did not follow pseudo first-order kinetics at early times. Fluoranthene was only partially oxidized and the oxidation of anthracene was too fast to be captured. Biphenyl, dibenzofuran, benzene and tert-butylbenzene were non-reactive under the study conditions. The oxidation rate was shown to increase with increasing number of polycyclic rings because less energy is required to overcome the aromatic character of a polycyclic ring than is required for benzene. Thus the rate of oxidation increased in the series naphthalene

Testing First-Order Logic Axioms in AutoCert

NASA Technical Reports Server (NTRS)

Ahn, Ki Yung; Denney, Ewen

2009-01-01

AutoCert [2] is a formal verification tool for machine generated code in safety critical domains, such as aerospace control code generated from MathWorks Real-Time Workshop. AutoCert uses Automated Theorem Provers (ATPs) [5] based on First-Order Logic (FOL) to formally verify safety and functional correctness properties of the code. These ATPs try to build proofs based on user provided domain-specific axioms, which can be arbitrary First-Order Formulas (FOFs). These axioms are the most crucial part of the trusted base, since proofs can be submitted to a proof checker removing the need to trust the prover and AutoCert itself plays the part of checking the code generator. However, formulating axioms correctly (i.e. precisely as the user had really intended) is non-trivial in practice. The challenge of axiomatization arise from several dimensions. First, the domain knowledge has its own complexity. AutoCert has been used to verify mathematical requirements on navigation software that carries out various geometric coordinate transformations involving matrices and quaternions. Axiomatic theories for such constructs are complex enough that mistakes are not uncommon. Second, adjusting axioms for ATPs can add even more complexity. The axioms frequently need to be modified in order to have them in a form suitable for use with ATPs. Such modifications tend to obscure the axioms further. Thirdly, speculating validity of the axioms from the output of existing ATPs is very hard since theorem provers typically do not give any examples or counterexamples.

Sorption isotherm and kinetic modeling of aniline on Cr-bentonite.

PubMed

Zheng, Hong; Liu, Donghong; Zheng, Yan; Liang, Shuping; Liu, Zhe

2009-08-15

In this paper, the sorption characteristics of aniline on Cr-bentonite prepared using synthetic wastewater containing chromium was investigated in a batch system at 30 degrees C. The effects of relevant parameters, such as pH value of solution, adsorbent dosage and initial aniline concentration were examined. The experimental data were analyzed by the Langmuir and Freundlich, and Temkin models of sorption. The sorption isotherm data were fitted well to Langmuir isotherm and the monolayer sorption capacity was found to be 21.60 mg/g at 30 degrees C. Dubinin-Redushkevich (D-R) isotherm was applied to describe the nature of aniline uptake and it was found that it occurred chemically. The kinetic data obtained at different concentrations were analyzed using a pseudo first-order, pseudo second-order kinetic equation and intraparticle diffusion model. The experimental data fitted very well the pseudo second-order kinetic model. Intraparticle diffusion affects aniline uptake. The results indicate that there is significant potential for Cr-bentonite as an adsorbent material for aniline removal from aqueous solutions.

Kinetic modelling for zinc (II) ions biosorption onto Luffa cylindrica

NASA Astrophysics Data System (ADS)

Oboh, I.; Aluyor, E.; Audu, T.

2015-03-01

The biosorption of Zinc (II) ions onto a biomaterial - Luffa cylindrica has been studied. This biomaterial was characterized by elemental analysis, surface area, pore size distribution, scanning electron microscopy, and the biomaterial before and after sorption, was characterized by Fourier Transform Infra Red (FTIR) spectrometer. The kinetic nonlinear models fitted were Pseudo-first order, Pseudo-second order and Intra-particle diffusion. A comparison of non-linear regression method in selecting the kinetic model was made. Four error functions, namely coefficient of determination (R2), hybrid fractional error function (HYBRID), average relative error (ARE), and sum of the errors squared (ERRSQ), were used to predict the parameters of the kinetic models. The strength of this study is that a biomaterial with wide distribution particularly in the tropical world and which occurs as waste material could be put into effective utilization as a biosorbent to address a crucial environmental problem.

First Observation of Switch-Off Slow Shocks in Fully Kinetic Particle in Cell Simulation of Magnetic Reconnection

NASA Astrophysics Data System (ADS)

Lapenta, G.; Sanna, L.; Goldman, M. V.; Newman, D. L.; Markidis, S.

2014-12-01

A perduring challenge in the study of reconnection it has long been the failing attempts to reconcile the large scale MHD view based on the Petschek model with the small scale view based on kinetic theory. The first is based on the existence of standing switch off slow shocks (SSS) that eliminate the horizontal (the x component in the usual GSM coordinates) reconnecting magnetic field component forming vertical magnetic field lines. The second is based on nested diffusion regions where the magnetic field lines become decoupled first from ions and then from electrons. The kinetic picture when observed superficially does seem to have seem resemblance to the Petschek topology, despite the nested boxes being more of a Sweet-Parker concept. Nevertheless, the question has always been: if expanded to sufficiently large scales, does the kinetic description eventually lead tot the formation os SSS? The question remains answered. Recently a first negative answer has been proposed in Ref. [1]. The proposed answer is in essence that SSS are made impossible by the presence of a firehose instability in the reconnection exhaust and by the formation of a plateau in the firehose parameter at a value of 0.25 corresponding to the condition where nonlinear slow and intermediate wave become degenerate. We report a new series of simulations where we demonstrate that this is not the case in general. While for the specific case used in Ref [1], we indeed re-obtain the same conclusions reached by the authors. But our study demonstrates that case to be very peculiar and not representative of the more general kinetic answer. We will report direct evidence of the presence of extended SSS (over regions of hundreds of ion inertial lengths) in fully kinetic simulations for parameters typical of the magntotail and of the solar wind. Our results indicate that SSS are the natural extension of kinetic reconnection to large scales. The simulations required for the study are heroic and were conducted

Neutron diffraction study of the formation kinetics of ordered antiphase domains in titanium carbohydride TiC x H y

NASA Astrophysics Data System (ADS)

Khidirov, I.

2015-09-01

The kinetics of formation and growth of ordered antiphase domains (APDs) in titanium carbohydride TiC0.50H0.21 has been investigated by neutron diffraction. A model of ordered APDs is proposed. It is established that the pronounced ordering of interstitial atoms and APDs begin at 450°C. It is shown that the period of ordered APDs ( Р ≈ 10-12) is independent of the exposure time at a constant temperature. It is found that the temperature of ordered APDs, T OAPD, increases nonlinearly with an increase in the carbon concentration in the range 0.50 ≤ C/Ti ≤ 0.70. The formation temperature of ordered APDs is found to correlate with the concentration dependence of the order-disorder transition temperature and be 0.60 of the order-disorder transition temperature: T APD = 0.60 Т С.

The first experimental confirmation of the fractional kinetics containing the complex-power-law exponents: Dielectric measurements of polymerization reactions

NASA Astrophysics Data System (ADS)

Nigmatullin, R. R.; Arbuzov, A. A.; Salehli, F.; Giz, A.; Bayrak, I.; Catalgil-Giz, H.

2007-01-01

For the first time we achieved incontestable evidence that the real process of dielectric relaxation during the polymerization reaction of polyvinylpyrrolidone (PVP) is described in terms of the fractional kinetic equations containing complex-power-law exponents. The possibility of the existence of the fractional kinetics containing non-integer complex-power-law exponents follows from the general theory of dielectric relaxation that has been suggested recently by one of the authors (R.R.N). Based on the physical/geometrical meaning of the fractional integral with complex exponents there is a possibility to develop a general theory of dielectric relaxation based on the self-similar (fractal) character of the reduced (averaged) microprocesses that take place in the mesoscale region. This theory contains some essential predictions related to existence of the non-integer power-law kinetics and the results of this paper can be considered as the first confirmation of existence of the kinetic phenomena that are described by fractional derivatives with complex-power-law exponents. We want to stress here that with the help of a new complex fitting function for the complex permittivity it becomes possible to describe the whole process for real and imaginary parts simultaneously throughout the admissible frequency range (30 Hz-13 MHz). The fitting parameters obtained for the complex permittivity function for three temperatures (70, 90 and 110 °C) confirm in general the picture of reaction that was known qualitatively before. They also reveal some new features, which improve the interpretation of the whole polymerization process. We hope that these first results obtained in the paper will serve as a good stimulus for other researches to find the traces of the existence of new fractional kinetics in other relaxation processes unrelated to the dielectric relaxation. These results should lead to the reconsideration and generalization of irreversibility and kinetic phenomena that

Modeling transport kinetics in clinoptilolite-phosphate rock systems

NASA Technical Reports Server (NTRS)

Allen, E. R.; Ming, D. W.; Hossner, L. R.; Henninger, D. L.

1995-01-01

Nutrient release in clinoptilolite-phosphate rock (Cp-PR) systems occurs through dissolution and cation-exchange reactions. Investigating the kinetics of these reactions expands our understanding of nutrient release processes. Research was conducted to model transport kinetics of nutrient release in Cp-PR systems. The objectives were to identify empirical models that best describe NH4, K, and P release and define diffusion-controlling processes. Materials included a Texas clinoptilolite (Cp) and North Carolina phosphate rock (PR). A continuous-flow thin-disk technique was used. Models evaluated included zero order, first order, second order, parabolic diffusion, simplified Elovich, Elovich, and power function. The power-function, Elovich, and parabolic-diffusion models adequately described NH4, K, and P release. The power-function model was preferred because of its simplicity. Models indicated nutrient release was diffusion controlled. Primary transport processes controlling nutrient release for the time span observed were probably the result of a combination of several interacting transport mechanisms.

An Introductory Level Kinetics Investigation.

ERIC Educational Resources Information Center

McGarvey, J. E. B.; Knipe, A. C.

1980-01-01

Provides a list of the reactions commonly used for introductory kinetics studies. These reactions illustrate the kinetics concepts of rate law, rate constant, and reaction order. Describes a kinetic study of the hydrolysis of 3-bromo-3-phenylpropanoic acid which offers many educational advantages. (CS)

A Bayesian Interpretation of First-Order Phase Transitions

NASA Astrophysics Data System (ADS)

Davis, Sergio; Peralta, Joaquín; Navarrete, Yasmín; González, Diego; Gutiérrez, Gonzalo

2016-03-01

In this work we review the formalism used in describing the thermodynamics of first-order phase transitions from the point of view of maximum entropy inference. We present the concepts of transition temperature, latent heat and entropy difference between phases as emergent from the more fundamental concept of internal energy, after a statistical inference analysis. We explicitly demonstrate this point of view by making inferences on a simple game, resulting in the same formalism as in thermodynamical phase transitions. We show that analogous quantities will inevitably arise in any problem of inferring the result of a yes/no question, given two different states of knowledge and information in the form of expectation values. This exposition may help to clarify the role of these thermodynamical quantities in the context of different first-order phase transitions such as the case of magnetic Hamiltonians (e.g. the Potts model).

Thermal inactivation kinetics of hepatitis A virus in homogenized clam meat (Mercenaria mercenaria).

PubMed

Bozkurt, H; D'Souza, D H; Davidson, P M

2015-09-01

Epidemiological evidence suggests that hepatitis A virus (HAV) is the most common pathogen transmitted by bivalve molluscs such as clams, cockles, mussels and oysters. This study aimed to generate thermal inactivation kinetics for HAV as a first step to design adequate thermal processes to control clam-associated HAV outbreaks. Survivor curves and thermal death curves were generated for different treatment times (0-6 min) at different temperatures (50-72°C) and Weibull and first-order models were compared. D-values for HAV ranged from 47·37 ± 1·23 to 1·55 ± 0·12 min for the first-order model and 64·43 ± 3·47 to 1·25 ± 0·45 min for the Weibull model at temperatures from 50 to 72°C. z-Values for HAV in clams were 12·97 ± 0·59°C and 14·83 ± 0·0·28°C using the Weibull and first-order model respectively. The calculated activation energies for the first-order and Weibull model were 145 and 170 kJ mole(-1) respectively. The Weibull model described the thermal inactivation behaviour of HAV better than the first-order model. This study provides novel and precise information on thermal inactivation kinetics of HAV in homogenized clams. This will enable reliable thermal process calculations for HAV inactivation in clams and closely related seafood. © 2015 The Society for Applied Microbiology.

Finding higher order Darboux polynomials for a family of rational first order ordinary differential equations

NASA Astrophysics Data System (ADS)

Avellar, J.; Claudino, A. L. G. C.; Duarte, L. G. S.; da Mota, L. A. C. P.

2015-10-01

For the Darbouxian methods we are studying here, in order to solve first order rational ordinary differential equations (1ODEs), the most costly (computationally) step is the finding of the needed Darboux polynomials. This can be so grave that it can render the whole approach unpractical. Hereby we introduce a simple heuristics to speed up this process for a class of 1ODEs.

Kinetic modeling and fitting software for interconnected reaction schemes: VisKin.

PubMed

Zhang, Xuan; Andrews, Jared N; Pedersen, Steen E

2007-02-15

Reaction kinetics for complex, highly interconnected kinetic schemes are modeled using analytical solutions to a system of ordinary differential equations. The algorithm employs standard linear algebra methods that are implemented using MatLab functions in a Visual Basic interface. A graphical user interface for simple entry of reaction schemes facilitates comparison of a variety of reaction schemes. To ensure microscopic balance, graph theory algorithms are used to determine violations of thermodynamic cycle constraints. Analytical solutions based on linear differential equations result in fast comparisons of first order kinetic rates and amplitudes as a function of changing ligand concentrations. For analysis of higher order kinetics, we also implemented a solution using numerical integration. To determine rate constants from experimental data, fitting algorithms that adjust rate constants to fit the model to imported data were implemented using the Levenberg-Marquardt algorithm or using Broyden-Fletcher-Goldfarb-Shanno methods. We have included the ability to carry out global fitting of data sets obtained at varying ligand concentrations. These tools are combined in a single package, which we have dubbed VisKin, to guide and analyze kinetic experiments. The software is available online for use on PCs.

Mean-field dynamo in a turbulence with shear and kinetic helicity fluctuations.

PubMed

Kleeorin, Nathan; Rogachevskii, Igor

2008-03-01

We study the effects of kinetic helicity fluctuations in a turbulence with large-scale shear using two different approaches: the spectral tau approximation and the second-order correlation approximation (or first-order smoothing approximation). These two approaches demonstrate that homogeneous kinetic helicity fluctuations alone with zero mean value in a sheared homogeneous turbulence cannot cause a large-scale dynamo. A mean-field dynamo is possible when the kinetic helicity fluctuations are inhomogeneous, which causes a nonzero mean alpha effect in a sheared turbulence. On the other hand, the shear-current effect can generate a large-scale magnetic field even in a homogeneous nonhelical turbulence with large-scale shear. This effect was investigated previously for large hydrodynamic and magnetic Reynolds numbers. In this study we examine the threshold required for the shear-current dynamo versus Reynolds number. We demonstrate that there is no need for a developed inertial range in order to maintain the shear-current dynamo (e.g., the threshold in the Reynolds number is of the order of 1).

First and second order derivatives for optimizing parallel RF excitation waveforms

NASA Astrophysics Data System (ADS)

Majewski, Kurt; Ritter, Dieter

2015-09-01

For piecewise constant magnetic fields, the Bloch equations (without relaxation terms) can be solved explicitly. This way the magnetization created by an excitation pulse can be written as a concatenation of rotations applied to the initial magnetization. For fixed gradient trajectories, the problem of finding parallel RF waveforms, which minimize the difference between achieved and desired magnetization on a number of voxels, can thus be represented as a finite-dimensional minimization problem. We use quaternion calculus to formulate this optimization problem in the magnitude least squares variant and specify first and second order derivatives of the objective function. We obtain a small tip angle approximation as first order Taylor development from the first order derivatives and also develop algorithms for first and second order derivatives for this small tip angle approximation. All algorithms are accompanied by precise floating point operation counts to assess and compare the computational efforts. We have implemented these algorithms as callback functions of an interior-point solver. We have applied this numerical optimization method to example problems from the literature and report key observations.

Kinetics of natural oxidant demand by permanganate in aquifer solids.

PubMed

Urynowicz, Michael A; Balu, Balamurali; Udayasankar, Umamaheshwari

2008-02-19

During in situ chemical oxidation with permanganate, natural organic matter and other reduced species in the subsurface compete with the target compounds for the available oxidant and can exert a significant natural oxidant demand. This competition between target and nontarget compounds can have a significant impact on the permeation, dispersal, and persistence of permanganate in the subsurface. The kinetics of natural oxidant demand by permanganate was investigated using a composite sample made up of aquifer material collected from three different sites. The study found that although the depletion of organic carbon increased with increased permanganate dosage and increased reaction period, the mass ratio of MnO(4)(-):OC (wt/wt) was relatively constant over time (11.4+/-0.9). The reaction order and rate with respect to permanganate were found to decrease with time suggesting a continuum of reactions with the slower reactions becoming more controlling with time. However, the data also suggests that this continuum of reactions can be simplified into short- and long-term kinetic expressions representing fast and slow reactions. An independent first-order kinetic model with separate fast and slow reaction rate constants was used to successfully describe the complete kinetic expression of natural oxidant demand. The kinetic parameters used in the model are easily determined and can be used to better understand the complex kinetics of natural oxidant demand.

Effect of Proton Radiation on the Kinetics of Phosphorescence Decay in the Ceramic Material ZnS-Cu

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuchakova, T.A.; Vesna, G.V.; Makara, V.A.

2004-11-01

The results of studying the dose dependences of the decay kinetics of phosphorescence excited by X-ray radiation in luminescent ZnS-Cu ceramic material before and after irradiation with 50-MeV protons are considered. An anomalous variation in the exponent of the hyperbolic phosphorescence curves was observed experimentally as the accumulated light sum increased. It is found from an analysis of the data obtained that two processes are involved in the decay: one of these is monomolecular and corresponds to the first-order kinetics; the other is bimolecular and corresponds to the second-order kinetics. Transitions of charge carriers delocalized from traps occur at themore » nonradiative-recombination centers induced by proton radiation. Recombination of these charge carriers at the emission centers in the course of decay is described by the second-order kinetics.« less

Asymptotic symmetries and geometry on the boundary in the first order formalism

NASA Astrophysics Data System (ADS)

Korovin, Yegor

2018-03-01

Proper understanding of the geometry on the boundary of a spacetime is a critical step on the way to extending holography to spaces with non-AdS asymptotics. In general the boundary cannot be described in terms of the Riemannian geometry and the first order formalism is more appropriate as we show. We analyze the asymptotic symmetries in the first order formalism for large classes of theories on AdS, Lifshitz or flat space. In all cases the asymptotic symmetry algebra is realized on the first order variables as a gauged symmetry algebra. First order formalism geometrizes and simplifies the analysis. We apply our framework to the issue of scale versus conformal invariance in AdS/CFT and obtain new perspective on the structure of asymptotic expansions for AdS and flat spaces.

Determination of astaxanthin in Haematococcus pluvialis by first-order derivative spectrophotometry.

PubMed

Liu, Xiao Juan; Juan, Liu Xiao; Wu, Ying Hua; Hua, Wu Ying; Zhao, Li Chao; Chao, Zhao Li; Xiao, Su Yao; Yao, Xiao Su; Zhou, Ai Mei; Mei, Zhou Ai; Liu, Xin; Xin, Liu

2011-01-01

A highly selective, convenient, and precise method, first-order derivative spectrophotometry, was applied for the determination of astaxanthin in Haematococcus pluvialis. Ethyl acetate and ethanol (1:1, v/v) were found to be the best extraction solvent tested due to their high efficiency and low toxicity compared with nine other organic solvents. Astaxanthin coexisting with chlorophyll and beta-carotene was analyzed by first-order derivative spectrophotometry in order to optimize the conditions for the determination of astaxanthin. The results show that when detected at 432 nm, the interfering substances could be eliminated. The dynamic linear range was 2.0-8.0 microg/mL, with a correlation coefficient of 0.9916. The detection threshold was 0.41 microg/mL. The RSD for the determination of astaxanthin was in the range of 0.01-0.06%; the results of recovery test were 98.1-108.0%. The statistical analysis between first-order derivative spectrophotometry and HPLC by T-testing did not exceed their critical values, revealing no significant differences between these two methods. It was proved that first-order derivative spectrophotometry is a rapid and convenient method for the determination of astaxanthin in H. pluvialis that can eliminate the negative effect resulting from the coexistence of astaxanthin with chlorophyll and beta-carotene.

Kinetics of monomer biodegradation in soil.

PubMed

Siotto, Michela; Sezenna, Elena; Saponaro, Sabrina; Innocenti, Francesco Degli; Tosin, Maurizio; Bonomo, Luca; Mezzanotte, Valeria

2012-01-01

In modern intensive agriculture, plastics are used in several applications (i.e. mulch films, drip irrigation tubes, string, clips, pots, etc.). Interest towards applying biodegradable plastics to replace the conventional plastics is promising. Ten monomers, which can be applied in the synthesis of potentially biodegradable polyesters, were tested according to ASTM 5988-96 (standard respirometric test to evaluate aerobic biodegradation in soil by measuring the carbon dioxide evolution): adipic acid, azelaic acid, 1,4-butanediol, 1,2-ethanediol, 1,6-hexanediol, lactic acid, glucose, sebacic acid, succinic acid and terephthalic acid. Eight replicates were carried out for each monomer for 27-45 days. The numerical code AQUASIM was applied to process the CO₂ experimental data in order to estimate values for the parameters describing the different mechanisms occurring to the monomers in soil: i) the first order solubilization kinetic constant, K(sol) (d⁻¹); ii) the first order biodegradation kinetic constant, K(b) (d⁻¹); iii) the lag time in biodegradation, t(lag) (d); and iv) the carbon fraction biodegraded but not transformed into CO₂, Y (-). The following range of values were obtained: [0.006 d⁻¹, 6.9 d⁻¹] for K(sol), [0.1 d⁻¹, 1.2 d⁻¹] for K(b), and [0.32-0.58] for Y; t(lag) was observed for azelaic acid, 1,2-ethanediol, and terephthalic acid, with estimated values between 3.0 e 4.9 d. Copyright © 2011 Elsevier Ltd. All rights reserved.

Kinetic modelling for zinc (II) ions biosorption onto Luffa cylindrica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oboh, I., E-mail: innocentoboh@uniuyo.edu.ng; Aluyor, E.; Audu, T.

The biosorption of Zinc (II) ions onto a biomaterial - Luffa cylindrica has been studied. This biomaterial was characterized by elemental analysis, surface area, pore size distribution, scanning electron microscopy, and the biomaterial before and after sorption, was characterized by Fourier Transform Infra Red (FTIR) spectrometer. The kinetic nonlinear models fitted were Pseudo-first order, Pseudo-second order and Intra-particle diffusion. A comparison of non-linear regression method in selecting the kinetic model was made. Four error functions, namely coefficient of determination (R{sup 2}), hybrid fractional error function (HYBRID), average relative error (ARE), and sum of the errors squared (ERRSQ), were used tomore » predict the parameters of the kinetic models. The strength of this study is that a biomaterial with wide distribution particularly in the tropical world and which occurs as waste material could be put into effective utilization as a biosorbent to address a crucial environmental problem.« less

A Native Threonine Coordinates Ordered Water to Tune Light-Oxygen-Voltage (LOV) Domain Photocycle Kinetics and Osmotic Stress Signaling in Trichoderma reesei ENVOY.

PubMed

Lokhandwala, Jameela; Silverman Y de la Vega, Rafael I; Hopkins, Hilary C; Britton, Collin W; Rodriguez-Iglesias, Aroa; Bogomolni, Roberto; Schmoll, Monika; Zoltowski, Brian D

2016-07-08

Light-oxygen-voltage (LOV) domain-containing proteins function as small light-activated modules capable of imparting blue light control of biological processes. Their small modular nature has made them model proteins for allosteric signal transduction and optogenetic devices. Despite intense research, key aspects of their signal transduction mechanisms and photochemistry remain poorly understood. In particular, ordered water has been identified as a possible key mediator of photocycle kinetics, despite the lack of ordered water in the LOV active site. Herein, we use recent crystal structures of a fungal LOV protein ENVOY to interrogate the role of Thr(101) in recruiting water to the flavin active site where it can function as an intrinsic base to accelerate photocycle kinetics. Kinetic and molecular dynamic simulations confirm a role in solvent recruitment to the active site and identify structural changes that correlate with solvent recruitment. In vivo analysis of T101I indicates a direct role of the Thr(101) position in mediating adaptation to osmotic stress, thereby verifying biological relevance of ordered water in LOV signaling. The combined studies identify position 101 as a mediator of both allostery and photocycle catalysis that can impact organism physiology. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Sensitivity of STIS First-OrderMedium Resolution Modes

NASA Astrophysics Data System (ADS)

Proffitt, Charles R.

2006-07-01

The sensitivities for STIS first-order medium resolution modes were redetermined usingon-orbit observations of the standard DA white dwarfs G 191-B2B, GD 71, and GD 153.We review the procedures and assumptions used to derive the adopted throughputs, and discuss the remaining errors and uncertainties.

Approach to the origin of turbulence on the basis of two-point kinetic theory

NASA Technical Reports Server (NTRS)

Tsuge, S.

1974-01-01

Equations for the fluctuation correlation in an incompressible shear flow are derived on the basis of kinetic theory, utilizing the two-point distribution function which obeys the BBGKY hierarchy equation truncated with the hypothesis of 'ternary' molecular chaos. The step from the molecular to the hydrodynamic description is accomplished by a moment expansion which is a two-point version of the thirteen-moment method, and which leads to a series of correlation equations, viz., the two-point counterparts of the continuity equation, the Navier-Stokes equation, etc. For almost parallel shearing flows the two-point equation is separable and reduces to two Orr-Sommerfeld equations with different physical implications.

First-Order Parametric Model of Reflectance Spectra for Dyed Fabrics

DTIC Science & Technology

2016-02-19

Unclassified Unlimited 31 Daniel Aiken (202) 279-5293 Parametric modeling Inverse /direct analysis This report describes a first-order parametric model of...Appendix: Dielectric Response Functions for Dyes Obtained by Inverse Analysis ……………………………...…………………………………………………….19 1 First-Order Parametric...which provides for both their inverse and direct modeling1. The dyes considered contain spectral features that are of interest to the U.S. Navy for

Montelukast photodegradation: elucidation of Ф-order kinetics, determination of quantum yields and application to actinometry.

PubMed

Maafi, Mounir; Maafi, Wassila

2014-08-25

A recently developed Ф-order semi-emperical integrated rate-law for photoreversible AB(2Ф) reactions has been successfully applied to investigate Montelukast sodium (Monte) photodegradation kinetics in ethanol. The model equations also served to propose a new stepwise kinetic elucidation method valid for any AB(2Ф) system and its application to the determination of Monte's forward (Ф(λ(irr))(A-->B)) and reverse (Ф(λ(irr))(B-->A)) quantum yields at various irradiation wavelengths. It has been found that Ф(λ(irr))(A-->B) undergoes a 15-fold increase with wavelength between 220 and 360 nm, with the spectral section 250-360 nm representing Monte effective photodegradation causative range. The reverse quantum yield values were generally between 12 and 54% lower than those recorded for Ф(λ(irr))(A-->B), with the trans-isomer (Monte) converting almost completely to its cis-counterpart at high irradiation wavelengths. Furthermore, the potential use of Monte as an actinometer has been investigated, and an actinometric method was proposed. This study demonstrated the usefulness of Monte for monochromatic light actinometry for the dynamic range 258-380 nm. Copyright © 2014 Elsevier B.V. All rights reserved.

Adolescents' as Active Agents in the Socialization Process: Legitimacy of Parental Authority and Obligation to Obey as Predictors of Obedience

ERIC Educational Resources Information Center

Darling, Nancy; Cumsille, Patricio; Loreto Martinez, M.

2007-01-01

Adolescents' agreement with parental standards and beliefs about the legitimacy of parental authority and their own obligation to obey were used to predict adolescents' obedience, controlling for parental monitoring, rules, and rule enforcement. Hierarchical linear models were used to predict both between-adolescent and within-adolescent,…

First and second order derivatives for optimizing parallel RF excitation waveforms.

PubMed

Majewski, Kurt; Ritter, Dieter

2015-09-01

For piecewise constant magnetic fields, the Bloch equations (without relaxation terms) can be solved explicitly. This way the magnetization created by an excitation pulse can be written as a concatenation of rotations applied to the initial magnetization. For fixed gradient trajectories, the problem of finding parallel RF waveforms, which minimize the difference between achieved and desired magnetization on a number of voxels, can thus be represented as a finite-dimensional minimization problem. We use quaternion calculus to formulate this optimization problem in the magnitude least squares variant and specify first and second order derivatives of the objective function. We obtain a small tip angle approximation as first order Taylor development from the first order derivatives and also develop algorithms for first and second order derivatives for this small tip angle approximation. All algorithms are accompanied by precise floating point operation counts to assess and compare the computational efforts. We have implemented these algorithms as callback functions of an interior-point solver. We have applied this numerical optimization method to example problems from the literature and report key observations. Copyright © 2015 Elsevier Inc. All rights reserved.

Convergent sum of gradient expansion of the kinetic-energy density functional up to the sixth order term using Padé approximant

NASA Astrophysics Data System (ADS)

Sergeev, A.; Alharbi, F. H.; Jovanovic, R.; Kais, S.

2016-04-01

The gradient expansion of the kinetic energy density functional, when applied to atoms or finite systems, usually grossly overestimates the energy in the fourth order and generally diverges in the sixth order. We avoid the divergence of the integral by replacing the asymptotic series including the sixth order term in the integrand by a rational function. Padé approximants show moderate improvements in accuracy in comparison with partial sums of the series. The results are discussed for atoms and Hooke’s law model for two-electron atoms.

Illustrated structural application of universal first-order reliability method

NASA Technical Reports Server (NTRS)

Verderaime, V.

1994-01-01

The general application of the proposed first-order reliability method was achieved through the universal normalization of engineering probability distribution data. The method superimposes prevailing deterministic techniques and practices on the first-order reliability method to surmount deficiencies of the deterministic method and provide benefits of reliability techniques and predictions. A reliability design factor is derived from the reliability criterion to satisfy a specified reliability and is analogous to the deterministic safety factor. Its application is numerically illustrated on several practical structural design and verification cases with interesting results and insights. Two concepts of reliability selection criteria are suggested. Though the method was developed to support affordable structures for access to space, the method should also be applicable for most high-performance air and surface transportation systems.

The Limits of Military Officers’ Duty to Obey Civilian Orders: A Neo-classical Perspective

DTIC Science & Technology

2015-07-01

subject to a penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. 1. REPORT DATE...Orders: A Neo-classical Perspective 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK...73 19a. NAME OF RESPONSIBLE PERSON a . REPORT unclassified b. ABSTRACT unclassified c. THIS PAGE unclassified Standard Form 298 (Rev. 8-98

A multi-dimensional high-order DG-ALE method based on gas-kinetic theory with application to oscillating bodies

NASA Astrophysics Data System (ADS)

Ren, Xiaodong; Xu, Kun; Shyy, Wei

2016-07-01

This paper presents a multi-dimensional high-order discontinuous Galerkin (DG) method in an arbitrary Lagrangian-Eulerian (ALE) formulation to simulate flows over variable domains with moving and deforming meshes. It is an extension of the gas-kinetic DG method proposed by the authors for static domains (X. Ren et al., 2015 [22]). A moving mesh gas kinetic DG method is proposed for both inviscid and viscous flow computations. A flux integration method across a translating and deforming cell interface has been constructed. Differently from the previous ALE-type gas kinetic method with piecewise constant mesh velocity at each cell interface within each time step, the mesh velocity variation inside a cell and the mesh moving and rotating at a cell interface have been accounted for in the finite element framework. As a result, the current scheme is applicable for any kind of mesh movement, such as translation, rotation, and deformation. The accuracy and robustness of the scheme have been improved significantly in the oscillating airfoil calculations. All computations are conducted in a physical domain rather than in a reference domain, and the basis functions move with the grid movement. Therefore, the numerical scheme can preserve the uniform flow automatically, and satisfy the geometric conservation law (GCL). The numerical accuracy can be maintained even for a largely moving and deforming mesh. Several test cases are presented to demonstrate the performance of the gas-kinetic DG-ALE method.

A Study of the Optimal Model of the Flotation Kinetics of Copper Slag from Copper Mine BOR

NASA Astrophysics Data System (ADS)

Stanojlović, Rodoljub D.; Sokolović, Jovica M.

2014-10-01

In this study the effect of mixtures of copper slag and flotation tailings from copper mine Bor, Serbia on the flotation results of copper recovery and flotation kinetics parameters in a batch flotation cell has been investigated. By simultaneous adding old flotation tailings in the ball mill at the rate of 9%, it is possible to increase copper recovery for about 20%. These results are compared with obtained copper recovery of pure copper slag. The results of batch flotation test were fitted by MatLab software for modeling the first-order flotation kinetics in order to determine kinetics parameters and define an optimal model of the flotation kinetics. Six kinetic models are tested on the batch flotation copper recovery against flotation time. All models showed good correlation, however the modified Kelsall model provided the best fit.

Influence of dynamic compressive loading on the in vitro degradation behavior of pure PLA and Mg/PLA composite.

PubMed

Li, Xuan; Qi, Chenxi; Han, Linyuan; Chu, Chenglin; Bai, Jing; Guo, Chao; Xue, Feng; Shen, Baolong; Chu, Paul K

2017-12-01

The effects of dynamic compressive loading on the in vitro degradation behavior of pure poly-lactic acid (PLA) and PLA-based composite unidirectionally reinforced with micro-arc oxidized magnesium alloy wires (Mg/PLA) are investigated. Dynamic compressive loading is shown to accelerate degradation of pure PLA and Mg/PLA. As the applied stress is increased from 0.1MPa to 0.9MPa or frequency from 0.5Hz to 2.5Hz, the overall degradation rate goes up. After immersion for 21days at 0.9MPa and 2.5Hz, the bending strength retention of the composite and pure PLA is 60.1% and 50%, respectively. Dynamic loading enhances diffusion of small acidic molecules resulting in significant pH decrease in the immersion solution. The synergistic reaction between magnesium alloy wires and PLA in the composite is further clarified by electrochemical tests. The degradation behavior of the pure PLA and PLA matrix in the composite under dynamic conditions obey the first order degradation kinetics and a numerical model is postulated to elucidate the relationship of the bending strength, stress, frequency, and immersion time under dynamic conditions. We systematically study the influence of dynamic loading on the degradation behavior of pure PLA and Mg/PLA. Dynamic compressive loading is shown to accelerate degradation of pure PLA and Mg/PLA. The synergistic reaction between magnesium alloy wires and PLA in the composite is firstly clarified by electrochemical tests. The degradation behavior of the pure PLA and PLA matrix in the composite under dynamic conditions obey the first order degradation kinetics. Then, a numerical model is postulated to elucidate the relationship of the bending strength, stress, frequency, and immersion time under dynamic conditions. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Chlorine decay and bacterial inactivation kinetics in drinking water in the tropics.

PubMed

Thøgersen, J; Dahi, E

1996-09-01

The decay of free chlorine (Cl2) and combined chlorine (mostly monochloramine: NH2Cl) and the inactivation of bacteria was examined in Dar es Salaam, Tanzania. Batch experiments, pilot-scale pipe experiments and full-scale pipe experiments were carried out to establish the kinetics for both decay and inactivation, and to compare the two disinfectants for use under tropical conditions. The decay of both disinfectants closely followed first order kinetics, with respect to the concentration of both disinfectant and disinfectant-consuming substances. Bacterial densities exhibited a kinetic pattern consisting of first order inactivation with respect to the density of the bacteria and the concentration of the disinfectant, and first order growth with respect to the bacterial density. The disinfection kinetic model takes the decaying concentration of the disinfectant into account. The decay rate constant for free chlorine was 114 lg(-1)h(-1), while the decay rate constant for combined chlorine was 1.84 lg(-1)h(-1) (1.6% of the decay rate for free chlorine). The average concentration of disinfectant consuming substances in the water phase was 2.6 mg Cl2/l for free chlorine and 5.6 mg NH2Cl/l for combined chlorine. The decay rate constant and the concentration of disinfectant consuming substances when water was pumped through pipes, depended on whether or not chlorination was continuous. Combined chlorine especially could clean the pipes of disinfectant consuming substances. The inactivation rate constant λ, was estimated at 3.06×10(4) lg(-1)h(-1). Based on the inactivation rate constant, and a growth rate constant determined in a previous study, the critical concentration of free chlorine was found to be 0.08 mg Cl2/l. The critical concentration is a value below which growth rates dominate over inactivation.

Nonlinear isotherm and kinetics of adsorption of copper from aqueous solutions on bentonite

NASA Astrophysics Data System (ADS)

Sadeghalvad, Bahareh; Khosravi, Sara; Azadmehr, Amir Reza

2016-11-01

Bentonite is one of the most significant of clay minerals that has been studied extensively due to its potential applications in removal of various environmental pollutants. This ability is related to its high ionic exchange capacity and high specific surface area. Copper is one of the important elements of non-ferrous metals found in industrial waste waters. In the present work, the removal of copper from aqueous solutions with Iranian bentonite (from Birjand area, southeastern Iran) used without any chemical pretreatment, was studied. The experimental results were fitted by adsorption isotherms equations with two or three parameters, which include Langmuir, Freundlich, Dubinin-Radushkevich (D-R), Redlich-Peterson, Khan, and Toth models. The best correlation coefficient ( r 2) is 0.9879 observed for Langmuir model, maximum adsorption capacity of bentonite was 55.71 mg/g. The first-order and pseudo-second-order kinetic equations were used to describe the kinetics of adsorption. The experimental data were well fitted by the pseudo-second-order kinetics.

Investigating the mechanisms of surface-bound functional groups in overcoming kinetic barriers to the precipitation of ordered dolomite at low temperature (Invited)

NASA Astrophysics Data System (ADS)

Kenward, P. A.; Roberts, J.; Fowle, D.; Goldstein, R.; Moore, D.; Gonzalez, L. A.

2013-12-01

The mineral dolomite, while abundant in the geologic record, is scarce in modern environments and limited to specific environments, due to kinetic barriers at low temperature (< 50°C). The microbial mediation of dolomite has been extensively studied using numerous microorganisms and disordered dolomite has been synthesized under abiotic conditions. However these studies either yielded disordered dolomite or failed to elucidate the specific mechanism(s) necessary to achieve the precipitation ordered phases of dolomite. Our work [1,2] demonstrates laboratory synthesis of dolomite at 25 °C using microcosms composed of either microbial biomass or abiotic carboxylated polystyrene micro-spheres and fluids with a range of marine-type compositions. We identify the density of surface-bound carboxyl-groups of organic matter as a primary control in ordered dolomite formation at low temperatures under the conditions studied. We hypothesize that surface-bound carboxyl-groups, such as those associated with organic matter or microbial biomass, overcome slow reaction kinetics for dolomite precipitation by dehydrating Mg2+ in an energetically favorable reaction. The precipitation of solid carbonate phases remains the most effective means of permanently sequestering CO2 from the atmosphere. As such, an increased understanding of dolomite kinetics at low temperature affords us the opportunity to apply this mechanism to engineered systems designed to enhance carbon sequestration in environments which do not kinetically favor the formation of carbonate mineral phases. [1] Kenward et al. (2013) AAPG, in press. [2] Roberts et al. (2013) PNAS, in press.

Kinetics of Electrocatalytic Reactions from First-Principles: A Critical Comparison with the Ab Initio Thermodynamics Approach.

PubMed

Exner, Kai S; Over, Herbert

2017-05-16

Multielectron processes in electrochemistry require the stabilization of reaction intermediates (RI) at the electrode surface after every elementary reaction step. Accordingly, the bond strengths of these intermediates are important for assessing the catalytic performance of an electrode material. Current understanding of microscopic processes in modern electrocatalysis research is largely driven by theory, mostly based on ab initio thermodynamics considerations, where stable reaction intermediates at the electrode surface are identified, while the actual free energy barriers (or activation barriers) are ignored. This simple approach is popular in electrochemistry in that the researcher has a simple tool at hand in successfully searching for promising electrode materials. The ab initio TD approach allows for a rough but fast screening of the parameter space with low computational cost. However, ab initio thermodynamics is also frequently employed (often, even based on a single binding energy only) to comprehend on the activity and on the mechanism of an electrochemical reaction. The basic idea is that the activation barrier of an endergonic reaction step consists of a thermodynamic part and an additional kinetically determined barrier. Assuming that the activation barrier scales with thermodynamics (so-called Brønsted-Polanyi-Evans (BEP) relation) and the kinetic part of the barrier is small, ab initio thermodynamics may provide molecular insights into the electrochemical reaction kinetics. However, for many electrocatalytic reactions, these tacit assumptions are violated so that ab initio thermodynamics will lead to contradictions with both experimental data and ab initio kinetics. In this Account, we will discuss several electrochemical key reactions, including chlorine evolution (CER), oxygen evolution reaction (OER), and oxygen reduction (ORR), where ab initio kinetics data are available in order to critically compare the results with those derived from a

Adsorption of anionic and cationic dyes on activated carbon from aqueous solutions: equilibrium and kinetics.

PubMed

Rodríguez, Araceli; García, Juan; Ovejero, Gabriel; Mestanza, María

2009-12-30

Activated carbon was utilized as adsorbent to remove anionic dye, Orange II (OII), and cationic dye, Methylene blue (MB), from aqueous solutions by adsorption. Batch experiments were conducted to study the effects of temperature (30-65 degrees C), initial concentration of adsorbate (300-500 mg L(-1)) and pH (3.0-9.0) on dyes adsorption. Equilibrium adsorption isotherms and kinetics were investigated. The equilibrium experimental data were analyzed by the Langmuir, Freundlich, Toth and Redlich-Peterson models. The kinetic data obtained with different carbon mass were analyzed using a pseudo-first order, pseudo-second order, intraparticle diffusion, Bangham and Chien-Clayton equations. The best results were achieved with the Langmuir isotherm equilibrium model and with the pseudo-second order kinetic model. The activated carbon was found to be very effective as adsorbent for MB and OII from aqueous solutions.

Transformation of general binary MRF minimization to the first-order case.

PubMed

Ishikawa, Hiroshi

2011-06-01

We introduce a transformation of general higher-order Markov random field with binary labels into a first-order one that has the same minima as the original. Moreover, we formalize a framework for approximately minimizing higher-order multi-label MRF energies that combines the new reduction with the fusion-move and QPBO algorithms. While many computer vision problems today are formulated as energy minimization problems, they have mostly been limited to using first-order energies, which consist of unary and pairwise clique potentials, with a few exceptions that consider triples. This is because of the lack of efficient algorithms to optimize energies with higher-order interactions. Our algorithm challenges this restriction that limits the representational power of the models so that higher-order energies can be used to capture the rich statistics of natural scenes. We also show that some minimization methods can be considered special cases of the present framework, as well as comparing the new method experimentally with other such techniques.

Decay Kinetics of UV-Sensitive Materials: An Introductory Chemistry Experiment

ERIC Educational Resources Information Center

Via, Garrhett; Williams, Chelsey; Dudek, Raymond; Dudek, John

2015-01-01

First-order kinetic decay rates can be obtained by measuring the time-dependent reflection spectra of ultraviolet-sensitive objects as they returned from their excited, colored state back to the ground, colorless state. In this paper, a procedure is described which provides an innovative and unique twist on standard, undergraduate, kinetics…

Specifying and Verifying Organizational Security Properties in First-Order Logic

NASA Astrophysics Data System (ADS)

Brandt, Christoph; Otten, Jens; Kreitz, Christoph; Bibel, Wolfgang

In certain critical cases the data flow between business departments in banking organizations has to respect security policies known as Chinese Wall or Bell-La Padula. We show that these policies can be represented by formal requirements and constraints in first-order logic. By additionally providing a formal model for the flow of data between business departments we demonstrate how security policies can be applied to a concrete organizational setting and checked with a first-order theorem prover. Our approach can be applied without requiring a deep formal expertise and it therefore promises a high potential of usability in the business.

Kinetics and regulation of the myofibrillar adenosine triphosphatase.

PubMed Central

Goodno, C C; Wall, C M; Perry, S V

1978-01-01

1. The steady-state kinetic behaviour of the ATPase (adenosine triphosphatase) of intact myofibrils was studied in the presence of both high and low concentrations of Ca2+ (0.25 mM and less than 10 nM respectively). 2. Kinetic data were collected over the initial linear phase of the assay, which lasts for 20--60s. To obtain consistent data we found it necessary to use either fresh myofibril preparations or preparations that had been stored in the presence of thiol compounds. 3. When assayed in the presence of 0.25 mM-Ca2+, the myofibrillar ATPase obeyed Michaelis-Menten kinetics over the range 0.03--5.0 mM-MgATP (Km 16 +/- 6 micrometer, V 0.4 +/- 0.1 mumol/min per mg). 4. At low Ca2+ concentrations (less than 10 nM) the myofibrillar ATPase displayed pronounced substrate inhibition, which was not observed at high Ca2+ concentrations. Thus increasing the MgATP concentration had the net effect of decreasing the ATPase activity at low Ca2+ relative to that at high Ca2+. This preferential effect of MgATP on the low-Ca2+ ATPase may be important in Ca2+ control. 5. The substrate inhibition that was observed at low Ca2+ was lost on storage or thiol modification of the myofibrils. 6. Under physiological conditions (2 mM-MgATP, I 0.15, pH 7.0), the ATPase of fresh and thiol-protected myofibrils displayed approx. 100-fold activation by Ca2+. PMID:154323

Equilibrium, kinetic and thermodynamic studies for adsorption of BTEX onto Ordered Mesoporous Carbon (OMC).

PubMed

Konggidinata, Mas Iwan; Chao, Bing; Lian, Qiyu; Subramaniam, Ramalingam; Zappi, Mark; Gang, Daniel Dianchen

2017-08-15

Chemical and petrochemical industries produce substantial amounts of wastewater everyday. This wastewater contains organic pollutants such as benzene, toluene, ethylbenzene and xylenes (BTEX) that are toxic to human and aquatic life. Ordered Mesoporous Carbon (OMC), the adsorbent that possesses the characteristics of an ideal adsorbent was investigated to understand its properties and suitability for BTEX removal. Adsorption isotherms, adsorption kinetics, the effects of initial BTEX concentrations and temperatures on the adsorption process were studied. The OMCs were characterized using surface area and pore size analyzer, transmission electron microscopy (TEM), elemental analysis, thermogravimetric analysis (TGA) and fourier transform infrared spectroscopy (FTIR). The results suggested that the Langmuir Isotherm and Pseudo-Second-Order Models described the experimental data well. The thermodynamic parameters, Gibbs free energy (ΔG°), the enthalpy change (ΔH°) and the entropy change (ΔS°) of adsorption indicated that the adsorption processes were physical, endothermic, and spontaneous. In addition, OMC had 27% higher overall adsorption capacities compared to granular activated carbon (GAC). Copyright © 2017 Elsevier B.V. All rights reserved.

Energy in first order 2 +1 gravity

NASA Astrophysics Data System (ADS)

Corichi, Alejandro; Rubalcava-García, Iraís

2015-08-01

We consider Λ =0 three-dimensional gravity with asymptotically flat boundary conditions. This system was studied by Ashtekar and Varadarajan within the second-order formalism—with metric variables—who showed that the Regge-Teitelboim formalism yields a consistent Hamiltonian description where, surprisingly, the energy is bounded from below and from above. The energy of the spacetime is, however, determined up to an arbitrary constant. The natural choice was to fix that freedom such that Minkowski spacetime has zero energy. More recently, Marolf and Patiño started from the Einstein-Hilbert action supplemented with the Gibbons-Hawking term and showed that, in the (2 +1 ) decomposition of the theory, the energy is shifted from the Ashtekar-Varadarajan analysis in such a way that Minkowski spacetime possesses a negative energy. In this contribution we consider the first-order formalism, where the fundamental variables are a s o (2 ,1 ) connection waIJ and a triad eaI . We consider two actions. A natural extension to 3 dimensions of the consistent action in 4 D Palatini gravity is shown to be finite and differentiable. For this action, the (2 +1 ) decomposition (that we perform using two methods) yields a Hamiltonian boundary term that corresponds to energy. It assigns zero energy to Minkowski spacetime. We then put forward a totally gauge invariant action and show that it is also well defined and differentiable. Interestingly, it turns out to be related, on shell, to the 3D Palatini action by an additive constant in such a way that its associated energy is given by the Marolf-Patiño expression. Thus, we conclude that, from the perspective of the first-order formalism, Minkowski spacetime can consistently have either zero, or a negative energy equal to -1 /4 G , depending on the choice of consistent action employed as starting point.

First-order and higher order sequence learning in specific language impairment.

PubMed

Clark, Gillian M; Lum, Jarrad A G

2017-02-01

A core claim of the procedural deficit hypothesis of specific language impairment (SLI) is that the disorder is associated with poor implicit sequence learning. This study investigated whether implicit sequence learning problems in SLI are present for first-order conditional (FOC) and higher order conditional (HOC) sequences. Twenty-five children with SLI and 27 age-matched, nonlanguage-impaired children completed 2 serial reaction time tasks. On 1 version, the sequence to be implicitly learnt comprised a FOC sequence and on the other a HOC sequence. Results showed that the SLI group learned the HOC sequence (η p ² = .285, p = .005) but not the FOC sequence (η p ² = .099, p = .118). The control group learned both sequences (FOC η p ² = .497, HOC η p 2= .465, ps < .001). The SLI group's difficulty learning the FOC sequence is consistent with the procedural deficit hypothesis. However, the study provides new evidence that multiple mechanisms may underpin the learning of FOC and HOC sequences. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Kinetic Modeling of the Release of Ethylene Oxide from Sterilized Plastic Containers and its Interaction with Monoclonal Antibodies.

PubMed

Yu, Bryan Lei; Han, Jun; Hammond, Matthew; Wang, Xuemei; Zhang, Qingchun; Clausen, Andrew; Forster, Ronald; Eu, Mingda

Ethylene oxide (ETO) is commonly used to sterilize plastic containers, but the effects of residual amounts left after sterilization on protein therapeutics are still not well understood. Here we focus primarily on the factors that influence concentrations of ETO migrating from ETO-treated plastic containers into aqueous solution. A study was designed to investigate the kinetics of this process at various temperatures, and the kinetic data could be fit with a model based on a combination of Fickean diffusion and first-order chemical reaction (to account for observed hydrolysis of ETO). The diffusion and reaction rate constants thus obtained obey Arrhenius-like temperature dependence. These results indicate that for analytical methods involving extraction into water, measurements of residual ETO in a container must account for the effects of ETO hydrolysis. Further, the effects of salt concentration and pH of the fluid in the container on accumulated ETO levels were explored. Finally, interactions of ETO with anti-streptavidin (AntiSA) Immunoglobulin G1 (IgG1) and IgG2 antibodies were studied, with ETO adducts found on all methionine residues when incubated in solutions spiked with ETO at concentrations that could be reached (based on the kinetic studies) in ETO-treated plastic vials. Overall, the likelihood of observable ETO-protein modifications upon storage in ETO-sterilized containers will depend on a complex interplay of protein properties, formulation details, storage conditions, and amount of residual ETO initially in the container. Ethylene oxide (ETO) is commonly used to sterilize plastic containers, but the effects of residual amounts left after sterilization on protein therapeutics are still not well understood. Here we describe experiments exploring the factors that influence concentrations of ETO migrating from ETO-treated plastic containers into aqueous solution over time. Additionally, interactions of ETO with model antibodies were studied, with ETO

Cation ordering/disordering kinetics in Ba3CoNb2O9: An in situ study using synchrotron x-ray powder diffraction

NASA Astrophysics Data System (ADS)

Mallinson, P. M.; Claridge, J. B.; Rosseinsky, M. J.; Ibberson, R. M.; Wright, J. P.; Fitch, A. N.; Price, T.; Iddles, D. M.

2007-11-01

In situ synchrotron x-ray powder diffraction has been used to study the kinetics of cation ordering and disordering in the microwave dielectric electroceramic Ba3CoNb2O9 with a time resolution of 15s. The method enables the order/disorder temperature (To /d) in this material of 1430°C to be directly observed. The changes in the rate and degree of cation ordering and in the growth of ordered domains between samples ordered from standard precursor material and then subsequently reordered following an annealing period above To /d show that small changes in precursor order state and phase assemblage strongly influence the final domain size.

Decay-ratio calculation in the frequency domain with the LAPUR code using 1D-kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Munoz-Cobo, J. L.; Escriva, A.; Garcia, C.

This paper deals with the problem of computing the Decay Ratio in the frequency domain codes as the LAPUR code. First, it is explained how to calculate the feedback reactivity in the frequency domain using slab-geometry i.e. 1D kinetics, also we show how to perform the coupling of the 1D kinetics with the thermal-hydraulic part of the LAPUR code in order to obtain the reactivity feedback coefficients for the different channels. In addition, we show how to obtain the reactivity variation in the complex domain by solving the eigenvalue equation in the frequency domain and we compare this result withmore » the reactivity variation obtained in first order perturbation theory using the 1D neutron fluxes of the base case. Because LAPUR works in the linear regime, it is assumed that in general the perturbations are small. There is also a section devoted to the reactivity weighting factors used to couple the reactivity contribution from the different channels to the reactivity of the entire reactor core in point kinetics and 1D kinetics. Finally we analyze the effects of the different approaches on the DR value. (authors)« less

Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products.

PubMed

Olvera-Vargas, Hugo; Oturan, Nihal; Aravindakumar, C T; Paul, M M Sunil; Sharma, Virender K; Oturan, Mehmet A

2014-01-01

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.

Biodegradation kinetics of BTE-OX and MTBE by a diesel-grown biomass.

PubMed

Acuna-Askar, K; de la Torre-Torres, M A; Guerrero-Munoz, M J; Garza-Gonzalez, M T; Chavez-Gomez, B; Rodriguez-Sanchez, I P; Barrera-Saldana, H A

2006-01-01

The biodegradation kinetics of BTE-oX and MTBE, mixed all together in the presence of diesel-grown bioaugmented bacterial populations as high as 885 mg/L VSS, was evaluated. The effect of soil in aqueous samples and the effect of Tergitol NP-10 on substrate biodegradation rates were also evaluated. Biodegradation kinetics was evaluated for 54 h, every 6 h. All BTE-oX chemicals followed a first-order two-phase biodegradation kinetic model, whereas MTBE followed a zero-order removal kinetic model in all samples. BTE-oX removal rates were much higher than those of MTBE in all samples. The presence of soil in aqueous samples retarded BTE-oX and MTBE removal rates. The addition of Tergitol NP-10 to aqueous samples containing soil had a positive effect on substrate removal rate in all samples. Substrate percent removals ranged between 64.8-98.9% for benzene, toluene and ethylbenzene. O-xylene and MTBE percent removals ranged between 18.7-40.8% and 7.2-10.3%, respectively.

Thermal and high pressure inactivation kinetics of blueberry peroxidase.

PubMed

Terefe, Netsanet Shiferaw; Delon, Antoine; Versteeg, Cornelis

2017-10-01

This study for the first time investigated the stability and inactivation kinetics of blueberry peroxidase in model systems (McIlvaine buffer, pH=3.6, the typical pH of blueberry juice) during thermal (40-80°C) and combined high pressure-thermal processing (0.1-690MPa, 30-90°C). At 70-80°C, the thermal inactivation kinetics was best described by a biphasic model with ∼61% labile and ∼39% stable fractions at temperature between 70 and 75°C. High pressure inhibited the inactivation of the enzyme with no inactivation at pressures as high as 690MPa and temperatures less than 50°C. The inactivation kinetics of the enzyme at 60-70°C, and pressures higher than 500MPa was best described by a first order biphasic model with ∼25% labile fraction and 75% stable fraction. The activation energy values at atmospheric pressure were 548.6kJ/mol and 324.5kJ/mol respectively for the stable and the labile fractions. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Sorption kinetics and isotherm studies of a cationic dye using agricultural waste: broad bean peels.

PubMed

Hameed, B H; El-Khaiary, M I

2008-06-15

In this paper, broad bean peels (BBP), an agricultural waste, was evaluated for its ability to remove cationic dye (methylene blue) from aqueous solutions. Batch mode experiments were conducted at 30 degrees C. Equilibrium sorption isotherms and kinetics were investigated. The kinetic data obtained at different concentrations have been analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equations. The experimental data fitted very well the pseudo-first-order kinetic model. Analysis of the temportal change of q indicates that at the beginning of the process the overall rate of adsorption is controlled by film-diffusion, then at later stage intraparticle-diffusion controls the rate. Diffusion coefficients and times of transition from film to pore-diffusion control were estimated by piecewise linear regression. The experimental data were analyzed by the Langmuir and Freundlich models. The sorption isotherm data fitted well to Langmuir isotherm and the monolayer adsorption capacity was found to be 192.7 mg/g and the equilibrium adsorption constant Ka is 0.07145 l/mg at 30 degrees C. The results revealed that BBP was a promising sorbent for the removal of methylene blue from aqueous solutions.

Finite size effects in phase transformation kinetics in thin films and surface layers

NASA Astrophysics Data System (ADS)

Trofimov, Vladimir I.; Trofimov, Ilya V.; Kim, Jong-Il

2004-02-01

In studies of phase transformation kinetics in thin films, e.g. crystallization of amorphous films, until recent time is widely used familiar Kolmogorov-Johnson-Mehl-Avrami (KJMA) statistical model of crystallization despite it is applicable only to an infinite medium. In this paper a model of transformation kinetics in thin films based on a concept of the survival probability for randomly chosen point during transformation process is presented. Two model versions: volume induced transformation (VIT) when the second-phase grains nucleate over a whole film volume and surface induced transformation (SIT) when they form on an interface with two nucleation mode: instantaneous nucleation at transformation onset and continuous one during all the process are studied. At VIT-process due to the finite film thickness effects the transformation profile has a maximum in a film middle, whereas that of the grains population reaches a minimum inhere, the grains density is always higher than in a volume material, and the thinner film the slower it transforms. The transformation kinetics in a thin film obeys a generalized KJMA equation with parameters depending on a film thickness and in limiting cases of extremely thin and thick film it reduces to classical KJMA equation for 2D- and 3D-system, respectively.

Kinetics studies of d-glucose hydrogenation over activated charcoal supported platinum catalyst

NASA Astrophysics Data System (ADS)

Ahmed, Muthanna J.

2012-02-01

The kinetics of the catalytic hydrogenation of d-glucose to produce d-sorbitol was studied in a three-phase laboratory scale reactor. The hydrogenation reactions were performed on activated charcoal supported platinum catalyst in the temperature range 25-65°C and in a constant pressure of 1 atm. The kinetic data were modeled by zero, first and second-order reaction equations. In the operating regimes studied, the results show that the hydrogenation reaction was of a first order with respect to d-glucose concentration. Also the activation energy of the reaction was determined, and found to be 12.33 kJ mole-1. A set of experiment was carried out to test the deactivation of the catalyst, and the results show that the deactivation is slow with the ability of using the catalyst for several times with a small decrease in product yield.

Toxicokinetics of perfluorooctane sulfonate in birds under environmentally realistic exposure conditions and development of a kinetic predictive model.

PubMed

Tarazona, J V; Rodríguez, C; Alonso, E; Sáez, M; González, F; San Andrés, M D; Jiménez, B; San Andrés, M I

2015-01-22

This article describes the toxicokinetics of perfluorooctane sulfonate (PFOS) in birds under low repeated dosing, equivalent to 0.085 μg/kg per day, representing environmentally realistic exposure conditions. The best fitting was provided by a simple pseudo monocompartmental first-order kinetics model, regulated by two rates, with a pseudo first-order dissipation half-life of 230 days, accounting for real elimination as well as binding of PFOS to non-exchangeable structures. The calculated assimilation efficiency was 0.66 with confidence intervals of 0.64 and 0.68. The model calculations confirmed that the measured maximum concentrations were still far from the steady state situation, which for this dose regime, was estimated at a value of about 65 μg PFOS/L serum achieved after a theoretical 210 weeks continuous exposure. The results confirm a very different kinetics than that observed in single-dose experiments confirming clear dose-related differences in apparent elimination rates in birds, as described for humans and monkeys; suggesting that a capacity-limited saturable process should also be considered in the kinetic behavior of PFOS in birds. Pseudo first-order kinetic models are highly convenient and frequently used for predicting bioaccumulation of chemicals in livestock and wildlife; the study suggests that previous bioaccumulation models using half-lives obtained at high doses are expected to underestimate the biomagnification potential of PFOS. The toxicokinetic parameters presented here can be used for higher-tier bioaccumulation estimations of PFOS in chickens and as surrogate values for modeling PFOS kinetics in wild bird species. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Degradation kinetics of the antioxidant additive ascorbic acid in packed table olives during storage at different temperatures.

PubMed

Montaño, A; Casado, F J; Rejano, L; Sanchez, A H; de Castro, A

2006-03-22

The kinetics of ascorbic acid (AA) loss during storage of packed table olives with two different levels of added AA was investigated. Three selected storage temperatures were assayed: 10 degrees C, ambient (20-24 degrees C), and 40 degrees C. The study was carried out in both pasteurized and unpasteurized product. The effect of pasteurization treatment alone on added AA was not significant. In the pasteurized product, in general AA degraded following a first-order kinetics. The activation energy calculated by using the Arrhenius model averaged 9 kcal/mol. For each storage temperature, the increase in initial AA concentration significantly decreased the AA degradation rate. In the unpasteurized product, AA was not detected after 20 days in samples stored at room temperature and AA degradation followed zero-order kinetics at 10 degrees C, whereas at 40 degrees C a second-order reaction showed the best fit. In both pasteurized and unpasteurized product, the low level of initial dehydroascorbic acid disappeared during storage. Furfural appeared to be formed during storage, mainly at 40 degrees C, following zero-order kinetics.

Kinetic study of Chromium VI adsorption onto palm kernel shell activated carbon

NASA Astrophysics Data System (ADS)

Mohammad, Masita; Sadeghi Louyeh, Shiva; Yaakob, Zahira

2018-04-01

Heavy metal contamination of industrial effluent is one of the significant environmental problems due to their toxicity and its accumulation throughout the food chain. Adsorption is one of the promising methods for removal of heavy metals from aqua solution because of its simple technique, efficient, reliable and low-cost due to the utilization of residue from the agricultural industry. In this study, activated carbon from palm kernel shells has been produced through chemical activation process using zinc chloride as an activating agent and carbonized at 800 °C. Palm kernel shell activated carbon, PAC was assessed for its efficiency to remove Chromium (VI) ions from aqueous solutions through a batch adsorption process. The kinetic mechanisms have been analysed using Lagergren first-order kinetics model, second-order kinetics model and intra-particle diffusion model. The characterizations such as BET surface area, surface morphology, SEM-EDX have been done. The result shows that the activation process by ZnCl2 was successfully improved the porosity and modified the functional group of palm kernel shell. The result shows that the maximum adsorption capacity of Cr is 11.40mg/g at 30ppm initial metal ion concentration and 0.1g/50mL of adsorbent concentration. The adsorption process followed the pseudo second orders kinetic model.

Local divergence and curvature divergence in first order optics

NASA Astrophysics Data System (ADS)

Mafusire, Cosmas; Krüger, Tjaart P. J.

2018-06-01

The far-field divergence of a light beam propagating through a first order optical system is presented as a square root of the sum of the squares of the local divergence and the curvature divergence. The local divergence is defined as the ratio of the beam parameter product to the beam width whilst the curvature divergence is a ratio of the space-angular moment also to the beam width. It is established that the beam’s focusing parameter can be defined as a ratio of the local divergence to the curvature divergence. The relationships between the two divergences and other second moment-based beam parameters are presented. Their various mathematical properties are presented such as their evolution through first order systems. The efficacy of the model in the analysis of high power continuous wave laser-based welding systems is briefly discussed.

First-order dissolution rate law and the role of surface layers in glass performance assessment

NASA Astrophysics Data System (ADS)

Grambow, B.; Müller, R.

2001-09-01

a model based on a surface layer slowing down glass network dissolution, the numerical value of the diffusion coefficient of silica, the layer thickness and the saturation concentration of dissolved silica are interrelated. Often, none of the parameters are measured directly. As a consequence this leads to not-sufficiently constrained models with poor predictive capacity. Recent research has indicated that there might be problems with the applicability of the first-order rate law [C. Jegou, thesis, University of Montpellier II, 1998]. Fresh glass or pre-altered glass samples were put in solutions over-saturated with silica. A decrease in reaction rates by as much as a factor of 10 was observed, but the rates remained much higher than predicted from a first-order rate law. It was argued that none of the kinetic models based on the notions of `chemical affinity' and `deviation from an equilibrium' is adapted to describe the kinetics of glass corrosion. In contrast, the formation of a surface gel and condensation of silanol groups are considered responsible for the decrease in reaction rates. The present communication argues against this view. Based on recent results of Monte Carlo calculations [M. Aertsens, Mater. Res. Soc. Symp. Proc. 556 (1999) 409] it is shown that some time of surface restructuration is necessary before saturation effects become fully effective in controlling long-term release of soluble glass constituents. The formation of a gel layer is not opposed to an affinity based kinetic concept, but it is in contrast a manifestation of this concept. It is the belief of the authors that much of the confusion related to the first-order rate law results from the fact that glass network dissolution is not considered as only one of a series of reaction mechanism and that glass network hydration and alkali ion exchange were ignored as parallel leaching mechanism. Our experimental results show that glass network hydration and ion exchange are important in short

QCD-Electroweak First-Order Phase Transition in a Supercooled Universe.

PubMed

Iso, Satoshi; Serpico, Pasquale D; Shimada, Kengo

2017-10-06

If the electroweak sector of the standard model is described by classically conformal dynamics, the early Universe evolution can be substantially altered. It is already known that-contrarily to the standard model case-a first-order electroweak phase transition may occur. Here we show that, depending on the model parameters, a dramatically different scenario may happen: A first-order, six massless quark QCD phase transition occurs first, which then triggers the electroweak symmetry breaking. We derive the necessary conditions for this dynamics to occur, using the specific example of the classically conformal B-L model. In particular, relatively light weakly coupled particles are predicted, with implications for collider searches. This scenario is also potentially rich in cosmological consequences, such as renewed possibilities for electroweak baryogenesis, altered dark matter production, and gravitational wave production, as we briefly comment upon.

QCD-Electroweak First-Order Phase Transition in a Supercooled Universe

NASA Astrophysics Data System (ADS)

Iso, Satoshi; Serpico, Pasquale D.; Shimada, Kengo

2017-10-01

If the electroweak sector of the standard model is described by classically conformal dynamics, the early Universe evolution can be substantially altered. It is already known that—contrarily to the standard model case—a first-order electroweak phase transition may occur. Here we show that, depending on the model parameters, a dramatically different scenario may happen: A first-order, six massless quark QCD phase transition occurs first, which then triggers the electroweak symmetry breaking. We derive the necessary conditions for this dynamics to occur, using the specific example of the classically conformal B -L model. In particular, relatively light weakly coupled particles are predicted, with implications for collider searches. This scenario is also potentially rich in cosmological consequences, such as renewed possibilities for electroweak baryogenesis, altered dark matter production, and gravitational wave production, as we briefly comment upon.

Quantum correlations with no causal order

PubMed Central

Oreshkov, Ognyan; Costa, Fabio; Brukner, Časlav

2012-01-01

The idea that events obey a definite causal order is deeply rooted in our understanding of the world and at the basis of the very notion of time. But where does causal order come from, and is it a necessary property of nature? Here, we address these questions from the standpoint of quantum mechanics in a new framework for multipartite correlations that does not assume a pre-defined global causal structure but only the validity of quantum mechanics locally. All known situations that respect causal order, including space-like and time-like separated experiments, are captured by this framework in a unified way. Surprisingly, we find correlations that cannot be understood in terms of definite causal order. These correlations violate a 'causal inequality' that is satisfied by all space-like and time-like correlations. We further show that in a classical limit causal order always arises, which suggests that space-time may emerge from a more fundamental structure in a quantum-to-classical transition. PMID:23033068

A kinetic study of the enhancement of solution chemiluminescence of glyoxylic acid oxidation by manganese species.

PubMed

Otamonga, Jean-Paul; Abdel-Mageed, Amal; Agater, Irena B; Jewsbury, Roger A

2015-08-01

In order to study the mechanism of the enhancement of solution chemiluminescence, the kinetics of the decay of the oxidant and the chemiluminescence emission were followed for oxidations by permanganate, manganese dioxide sol and Mn(3+) (aq) of glyoxylic acid, using stopped-flow spectrophotometry. Results are reported for the glyoxylic acid oxidized under pseudo first-order conditions and in an acidic medium at 25 °C. For permanganate under these conditions, the decay is sigmoidal, consistent with autocatalysis, and for manganese dioxide sol and Mn(3+) it is pseudo first order. The effects of the presence of aqueous formaldehyde and Mn(2+) were observed and a fit to a simple mechanism is discussed. It is concluded that chemiluminescent enhancement in these systems is best explained by reaction kinetics. Copyright © 2014 John Wiley & Sons, Ltd.

The First Order Correction to the Exit Distribution for Some Random Walks

NASA Astrophysics Data System (ADS)

Kennedy, Tom

2016-07-01

We study three different random walk models on several two-dimensional lattices by Monte Carlo simulations. One is the usual nearest neighbor random walk. Another is the nearest neighbor random walk which is not allowed to backtrack. The final model is the smart kinetic walk. For all three of these models the distribution of the point where the walk exits a simply connected domain D in the plane converges weakly to harmonic measure on partial D as the lattice spacing δ → 0. Let ω (0,\\cdot ;D) be harmonic measure for D, and let ω _δ (0,\\cdot ;D) be the discrete harmonic measure for one of the random walk models. Our definition of the random walk models is unusual in that we average over the orientation of the lattice with respect to the domain. We are interested in the limit of (ω _δ (0,\\cdot ;D)- ω (0,\\cdot ;D))/δ . Our Monte Carlo simulations of the three models lead to the conjecture that this limit equals c_{M,L} ρ _D(z) times Lebesgue measure with respect to arc length along the boundary, where the function ρ _D(z) depends on the domain, but not on the model or lattice, and the constant c_{M,L} depends on the model and on the lattice, but not on the domain. So there is a form of universality for this first order correction. We also give an explicit formula for the conjectured density ρ _D.

Harmonic Chain with Velocity Flips: Thermalization and Kinetic Theory

NASA Astrophysics Data System (ADS)

Lukkarinen, Jani; Marcozzi, Matteo; Nota, Alessia

2016-12-01

We consider the detailed structure of correlations in harmonic chains with pinning and a bulk velocity flip noise during the heat relaxation phase which occurs on diffusive time scales, for t=O(L^2) where L is the chain length. It has been shown earlier that for non-degenerate harmonic interactions these systems thermalize, and the dominant part of the correlations is given by local thermal equilibrium determined by a temperature profile which satisfies a linear heat equation. Here we are concerned with two new aspects about the thermalization process: the first order corrections in 1 / L to the local equilibrium correlations and the applicability of kinetic theory to study the relaxation process. Employing previously derived explicit uniform estimates for the temperature profile, we first derive an explicit form for the first order corrections to the particle position-momentum correlations. By suitably revising the definition of the Wigner transform and the kinetic scaling limit we derive a phonon Boltzmann equation whose predictions agree with the explicit computation. Comparing the two results, the corrections can be understood as arising from two different sources: a current-related term and a correction to the position-position correlations related to spatial changes in the phonon eigenbasis.

Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

NASA Technical Reports Server (NTRS)

May, C. E.; Philipp, W. H.; Marsik, S. J.

1974-01-01

The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism.

Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules

DOE PAGES

Malila, Jussi; McGraw, Robert; Laaksonen, Ari; ...

2015-01-07

Despite recent advances in monitoring nucleation from a vapor at close-to-molecular resolution, the identity of the critical cluster, forming the bottleneck for the nucleation process, remains elusive. During past twenty years, the first nucleation theorem has been often used to extract the size of the critical cluster from nucleation rate measurements. However, derivations of the first nucleation theorem invoke certain questionable assumptions that may fail, e.g., in the case of atmospheric new particle formation, including absence of subcritical cluster losses and heterogeneous nucleation on pre-existing nanoparticles. Here we extend the kinetic derivation of the first nucleation theorem to give amore » general framework to include such processes, yielding sum rules connecting the size dependent particle formation and loss rates to the corresponding loss-free nucleation rate and the apparent critical size from a naïve application of the first nucleation theorem that neglects them.« less

Approach to first-order exact solutions of the Ablowitz-Ladik equation.

PubMed

Ankiewicz, Adrian; Akhmediev, Nail; Lederer, Falk

2011-05-01

We derive exact solutions of the Ablowitz-Ladik (A-L) equation using a special ansatz that linearly relates the real and imaginary parts of the complex function. This ansatz allows us to derive a family of first-order solutions of the A-L equation with two independent parameters. This novel technique shows that every exact solution of the A-L equation has a direct analog among first-order solutions of the nonlinear Schrödinger equation (NLSE). © 2011 American Physical Society

Kinetics of formation of nanoparticles from first group metal carboxylates

NASA Astrophysics Data System (ADS)

Solov'ev, M. E.; Irzhak, T. F.; Irzhak, V. I.

2015-09-01

A kinetic model of the formation of metal nanoparticles via reduction of their carboxylates under conditions of clustering is proposed. It is found that the kinetics of the process is characterized by an induction period in carboxylate consumption and by almost linear growth of the average size of nanoparticles with conversion. It is shown that the maximum rate of nanoparticle formation grows along with the rate of ternary associate formation, the induction period becomes longer, and the particle size decreases. At the same time, it is characterized by a narrow size distribution.

Kinetic rate laws of Cd, Pb, and Zn vaporization during municipal solid waste incineration.

PubMed

Falcoz, Quentin; Gauthier, Daniel; Abanades, Stéphane; Flamant, Gilles; Patisson, Fabrice

2009-03-15

The kinetic rate laws of heavy metal (HM) vaporization from municipal solid waste during its incineration were studied. Realistic artificial waste (RAW) samples spiked with Pb, Zn, and Cd were injected into a fluidized bed reactor. Metal vaporization wastracked by continuous measure ofthe above metals in exhaust gases. An inverse model of the reactor was used to calculate the metal vaporization rates from the concentration vs time profiles in the outlet gas. For each metal, experiments were carried out at several temperatures in order to determine the kinetic parameters and to obtain specific rate laws as functions of temperature. Temperature has a strong influence on the HM vaporization dynamics, especially on the vaporization kinetics profile. This phenomenon was attributed to internal diffusion control of the HM release. Two types of kinetic rate laws were established based on temperature: a fourth- or fifth-order polynomial rate law (r(x) = k0e(-E(A)/RT)p(x)) for temperatures lower than 740 degrees C and a first-order polynomial (r(x) = k0e(-E(A)/ RT(q-q(f) for temperatures higher than 740 degrees C.

First-order shock acceleration in solar flares

NASA Technical Reports Server (NTRS)

Ellison, D. C.; Ramaty, R.

1985-01-01

The first order Fermi shock acceleration model is compared with specific observations where electron, proton, and alpha particle spectra are available. In all events, it is found that a single shock with a compression ratio as inferred from the low energy proton spectra can reasonably produce the full proton, electron, and alpha particle spectra. The model predicts that the acceleration time to a given energy will be approximately equal for electrons and protons and, for reasonable solar parameters, can be less than 1 sec to 100 MeV.

Biosorption of Food Green 3 by a novel green generation composite biosorbent from aqueous environment.

PubMed

Deniz, Fatih; Kepekci, Remziye Aysun

2017-06-03

A green type composite biosorbent composed of pine, oak, hornbeam, and fir sawdust biomasses modified with cetyltrimethylammonium bromide (CTAB) was first used for biosorption of an unsafe synthetic food dye, Food Green 3 from liquid medium in this study. Batch studies were carried by observing the effects of pH, dye concentration, biosorbent amount, and contact time. The equilibrium data were analyzed using Freundlich, Langmuir, and Dubinin-Radushkevich equations. Freundlich model gave a better conformity than other equations. The maximum dye removal potential of biosorbent was found to be 36.6 mg/g based on Langmuir isotherm. The pseudo-first-order, pseudo-second-order, Elovich, and intra-particle diffusion models were applied to clarify the process kinetics of biosorption. The mechanism studies suggested the biosorption process obeying Elovich kinetics and involving pore diffusion. The estimated values of biosorption free energy from Dubinin-Radushkevich isotherm (E value <8 kJ/mol) and thermodynamic studies (0 < ΔG° < -20 kJ/mol) implied a spontaneous, feasible, and physical process. Hence, this investigation suggested that the CTAB modified mix sawdust biomass could be a promising biosorbent for biosorption of such problematic dyes from impacted media.

Kinetic Landscape of a Peptide Bond-Forming Prolyl Oligopeptidase

PubMed Central

2017-01-01

Prolyl oligopeptidase B from Galerina marginata (GmPOPB) has recently been discovered as a peptidase capable of breaking and forming peptide bonds to yield a cyclic peptide. Despite the relevance of prolyl oligopeptidases in human biology and disease, a kinetic analysis pinpointing rate-limiting steps for a member of this enzyme family is not available. Macrocyclase enzymes are currently exploited to produce cyclic peptides with potential therapeutic applications. Cyclic peptides are promising druglike molecules because of their stability and conformational rigidity. Here we describe an in-depth kinetic characterization of a prolyl oligopeptidase acting as a macrocyclase enzyme. By combining steady-state and pre-steady-state kinetics, we propose a kinetic sequence in which a step after macrocyclization limits steady-state turnover. Additionally, product release is ordered, where the cyclic peptide departs first followed by the peptide tail. Dissociation of the peptide tail is slow and significantly contributes to the turnover rate. Furthermore, trapping of the enzyme by the peptide tail becomes significant beyond initial rate conditions. The presence of a burst of product formation and a large viscosity effect further support the rate-limiting nature of a physical step occurring after macrocyclization. This is the first detailed description of the kinetic sequence of a macrocyclase enzyme from this class. GmPOPB is among the fastest macrocyclases described to date, and this work is a necessary step toward designing broad-specificity efficient macrocyclases. PMID:28332820

An investigation of the kinetic processes influencing mercury emissions from sand and soil samples of varying thickness.

PubMed

Quinones, Jason L; Carpi, Anthony

2011-01-01

Mercury flux from HgCl2-treated sand and untreated soil samples of varying thickness (0.5-15 mm) were measured in dark and light under a Teflon dynamic flux chamber. Mean emissions over a 5.5-d sampling period showed an increase with depth for sand samples between 0.5 and 2 mm, but increasing depth above 2 mm had no effect. First-order kinetic models showed strong goodness of fit to the data and explained a high degree ofvariability in the emissions profile of all sand samples (R = 0.70-0.98). Soil samples showed an initial emissions peak that was not correlated with depth, suggesting a very shallow process at work. However, longer-term "baseline" emissions, measured as mean emissions between days 4.5 and 5.5, did show a relationship with depth. First-order kinetic models showed good fit for soil samples up to 4 mm thick (R2 = 0.66-0.91); however, thicker samples did not show a consistent fit to first- or second-order kinetic models (1 degree R2 = 0.00-0.46; 2 degree R2 = 0.00-0.54). The data suggest that mercury emissions from soil samples may follow a multicomponent model for which more

An Analogy Using Pennies and Dimes to Explain Chemical Kinetics Concepts

ERIC Educational Resources Information Center

Cortes-Figueroa, Jose E.; Perez, Wanda I.; Lopez, Jose R.; Moore-Russo, Deborah A.

2011-01-01

In this article, the authors present an analogy that uses coins and graphical analysis to teach kinetics concepts and resolve pseudo-first-order rate constants related to transition-metal complexes ligand-solvent exchange reactions. They describe an activity that is directed to upper-division undergraduate and graduate students. The activity…

First-order symmetry-adapted perturbation theory for multiplet splittings.

PubMed

Patkowski, Konrad; Żuchowski, Piotr S; Smith, Daniel G A

2018-04-28

We present a symmetry-adapted perturbation theory (SAPT) for the interaction of two high-spin open-shell molecules (described by their restricted open-shell Hartree-Fock determinants) resulting in low-spin states of the complex. The previously available SAPT formalisms, except for some system-specific studies for few-electron complexes, were restricted to the high-spin state of the interacting system. Thus, the new approach provides, for the first time, a SAPT-based estimate of the splittings between different spin states of the complex. We have derived and implemented the lowest-order SAPT term responsible for these splittings, that is, the first-order exchange energy. We show that within the so-called S 2 approximation commonly used in SAPT (neglecting effects that vanish as fourth or higher powers of intermolecular overlap integrals), the first-order exchange energies for all multiplets are linear combinations of two matrix elements: a diagonal exchange term that determines the spin-averaged effect and a spin-flip term responsible for the splittings between the states. The numerical factors in this linear combination are determined solely by the Clebsch-Gordan coefficients: accordingly, the S 2 approximation implies a Heisenberg Hamiltonian picture with a single coupling strength parameter determining all the splittings. The new approach is cast into both molecular-orbital and atomic-orbital expressions: the latter enable an efficient density-fitted implementation. We test the newly developed formalism on several open-shell complexes ranging from diatomic systems (Li⋯H, Mn⋯Mn, …) to the phenalenyl dimer.

First-order symmetry-adapted perturbation theory for multiplet splittings

NASA Astrophysics Data System (ADS)

Patkowski, Konrad; Żuchowski, Piotr S.; Smith, Daniel G. A.

2018-04-01

We present a symmetry-adapted perturbation theory (SAPT) for the interaction of two high-spin open-shell molecules (described by their restricted open-shell Hartree-Fock determinants) resulting in low-spin states of the complex. The previously available SAPT formalisms, except for some system-specific studies for few-electron complexes, were restricted to the high-spin state of the interacting system. Thus, the new approach provides, for the first time, a SAPT-based estimate of the splittings between different spin states of the complex. We have derived and implemented the lowest-order SAPT term responsible for these splittings, that is, the first-order exchange energy. We show that within the so-called S2 approximation commonly used in SAPT (neglecting effects that vanish as fourth or higher powers of intermolecular overlap integrals), the first-order exchange energies for all multiplets are linear combinations of two matrix elements: a diagonal exchange term that determines the spin-averaged effect and a spin-flip term responsible for the splittings between the states. The numerical factors in this linear combination are determined solely by the Clebsch-Gordan coefficients: accordingly, the S2 approximation implies a Heisenberg Hamiltonian picture with a single coupling strength parameter determining all the splittings. The new approach is cast into both molecular-orbital and atomic-orbital expressions: the latter enable an efficient density-fitted implementation. We test the newly developed formalism on several open-shell complexes ranging from diatomic systems (Li⋯H, Mn⋯Mn, …) to the phenalenyl dimer.

"To Obey or Disobey? This Is the Question" NDE: Nonviolent Disobedience Education in Israeli and US Civics Textbooks (1980-2012)

ERIC Educational Resources Information Center

Firer, Ruth

2013-01-01

"To Obey or Disobey" should be a life question for all free people, but for the Israelis, who are in intractable war with their neighbors while facing constant rifts among themselves, it is a concrete problem they have to face every day. Therefore, the research question posed by this article is: How is obedience of laws or military…

Understanding the kinetic mechanism of RNA single base pair formation

PubMed Central

Xu, Xiaojun; Yu, Tao; Chen, Shi-Jie

2016-01-01

RNA functions are intrinsically tied to folding kinetics. The most elementary step in RNA folding is the closing and opening of a base pair. Understanding this elementary rate process is the basis for RNA folding kinetics studies. Previous studies mostly focused on the unfolding of base pairs. Here, based on a hybrid approach, we investigate the folding process at level of single base pairing/stacking. The study, which integrates molecular dynamics simulation, kinetic Monte Carlo simulation, and master equation methods, uncovers two alternative dominant pathways: Starting from the unfolded state, the nucleotide backbone first folds to the native conformation, followed by subsequent adjustment of the base conformation. During the base conformational rearrangement, the backbone either retains the native conformation or switches to nonnative conformations in order to lower the kinetic barrier for base rearrangement. The method enables quantification of kinetic partitioning among the different pathways. Moreover, the simulation reveals several intriguing ion binding/dissociation signatures for the conformational changes. Our approach may be useful for developing a base pair opening/closing rate model. PMID:26699466

Self-Organized Bistability Associated with First-Order Phase Transitions

NASA Astrophysics Data System (ADS)

di Santo, Serena; Burioni, Raffaella; Vezzani, Alessandro; Muñoz, Miguel A.

2016-06-01

Self-organized criticality elucidates the conditions under which physical and biological systems tune themselves to the edge of a second-order phase transition, with scale invariance. Motivated by the empirical observation of bimodal distributions of activity in neuroscience and other fields, we propose and analyze a theory for the self-organization to the point of phase coexistence in systems exhibiting a first-order phase transition. It explains the emergence of regular avalanches with attributes of scale invariance that coexist with huge anomalous ones, with realizations in many fields.

Kinetics of adsorption of dyes from aqueous solution using activated carbon prepared from waste apricot.

PubMed

Onal, Yunus

2006-10-11

Adsorbent (WA11Zn5) has been prepared from waste apricot by chemical activation with ZnCl(2). Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption and DFT plus software. Adsorption of three dyes, namely, Methylene Blue (MB), Malachite Green (MG), Crystal Violet (CV), onto activated carbon in aqueous solution was studied in a batch system with respect to contact time, temperature. The kinetics of adsorption of MB, MG and CV have been discussed using six kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model, the Elovich equation, the intraparticle diffusion model, the Bangham equation, the modified Freundlich equation. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the adsorption kinetics for three dyes. The dyes uptake process was found to be controlled by external mass transfer at earlier stages (before 5 min) and by intraparticle diffusion at later stages (after 5 min). Thermodynamic parameters, such as DeltaG, DeltaH and DeltaS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures and concentrations. The thermodynamics of dyes-WA11Zn5 system indicates endothermic process.

FORCinel Version 3.0: An Integrated Environment for Processing, Analysis and Simulation of First-Order Reversal Curve Diagrams

NASA Astrophysics Data System (ADS)

Lascu, I.; Harrison, R. J.

2016-12-01

First-order reversal curve (FORC) diagrams are a powerful method to characterise the hysteresis properties of magnetic grain ensembles. Methods of processing, analysis and simulation of FORC diagrams have developed rapidly over the past few years, dramatically expanding their utility within rock magnetic research. Here we announce the latest release of FORCinel (Version 3.0), which integrates many of these developments into a unified, user-friendly package running within Igor Pro (www.wavemetrics.com). FORCinel v. 3.0 can be downloaded from https://wserv4.esc.cam.ac.uk/nanopaleomag/. The release will be accompanied by a series of video tutorials outlining each of the new features, including: i) improved work flow, with unified smoothing approach; ii) increased processing speed using multiple processors; iii) control of output resolution, enabling large datasets (> 500 FORCs) to be smoothed in a matter of seconds; iv) load, process, analyse and average multiple FORC diagrams; v) load and process non-gridded data and data acquired on non-PMC systems; vi) improved method for exploring optimal smoothing parameters; vii) interactive and un-doable data-pretreatments; viii) automated detection and removal of measurement outliers; ix) improved interactive method for the generation and optimisation of colour scales; x) full integration with FORCem1 - supervised quantitative unmixing of FORC diagrams using principle component analysis (PCA); xi) full integration with FORCulator2 - micromagnetic simulation of FORC diagrams; xiii) simulate TRM acquisition using the kinetic Monte Carlo simulation algorithm of Shcherbakov3. 1. Lascu, I., Harrison, R.J., Li, Y., Muraszko, J.R., Channell, J.E.T., Piotrowski, A.M., Hodell, D.A., 2015. Magnetic unmixing of first-order reversal curve diagrams using principal component analysis. Geochemistry, Geophys. Geosystems 16, 2900-2915. 2. Harrison, R.J., Lascu, I., 2014. FORCulator: A micromagnetic tool for simulating first-order reversal

First and second order approximations to stage numbers in multicomponent enrichment cascades

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scopatz, A.

2013-07-01

This paper describes closed form, Taylor series approximations to the number product stages in a multicomponent enrichment cascade. Such closed form approximations are required when a symbolic, rather than a numeric, algorithm is used to compute the optimal cascade state. Both first and second order approximations were implemented. The first order solution was found to be grossly incorrect, having the wrong functional form over the entire domain. On the other hand, the second order solution shows excellent agreement with the 'true' solution over the domain of interest. An implementation of the symbolic, second order solver is available in the freemore » and open source PyNE library. (authors)« less

Removal Rate of Organic Matter Using Natural Cellulose via Adsorption Isotherm and Kinetic Studies.

PubMed

Din, Mohd Fadhil Md; Ponraj, Mohanadoss; Low, Wen-Pei; Fulazzaky, Mohamad Ali; Iwao, Kenzo; Songip, Ahmad Rahman; Chelliapan, Shreeshivadasan; Ismail, Zulhilmi; Jamal, Mohamad Hidayat

2016-02-01

In this study, the removal of natural organic matter (NOM) using coconut fiber (CF) and palm oil fiber (POF) was investigated. Preliminary analysis was performed using a jar test for the selection of optimal medium before the fabricated column model experiment. The equilibrium studies on isotherms and kinetic models for NOM adsorption were analyzed using linearized correlation coefficient. Results showed that the equilibrium data were fitted to Langmuir isotherm model for both CF and POF. The most suitable adsorption model was the pseudo-first-order kinetic model for POF and pseudo-second-order kinetic model for CF. The adsorption capacities achieved by the CF and POF were 15.67 and 30.8 mg/g respectively. Based on this investigation, it can be concluded that the POF is the most suitable material for the removal of NOM in semi polluted river water.

Kinetics of biosorption of hazardous metals by green soil supplement

NASA Astrophysics Data System (ADS)

Bagla, Hemlata; Khilnani, Roshan

2016-04-01

of the biosorption in terms of the order of the rate constant were studied applying different kinetic models such as First order, Second order, Pseudo-first order, Pseudo-second order and the intra particle diffusion model. But among these models best fitting model was Lagergren pseudo second order model. The correlation coefficients of all the elements have R2 values close to 1 indicating the applicability of pseudo second order model to the present system. The applicability of this model suggested that biosorption of elements under study, on DCP was based on chemical interactions between metals and active sites of biosorbent. References 1. E. Tipping, Cation Binding by Humic Substances. Cambridge University Press, 2002. 2. S. Lagergren, Zur theorie der sogenannten adsorption geloster stoffe. Kungliga Svenska Vetenskapsakademiens, Handlingar vol. 24, no.4, pp. 1-39, 1898. 3. Y. S. Ho and G. McKay, "Pseudo-second order model for sorption processes," Process Biochem., vol. 34, no. 5, pp. 451-465, Jul. 1999. 4. N. S. Barot and H. K. Bagla, "Extraction of humic acid from biological matrix - dry cow dung powder," Green Chem. Lett. Rev., vol. 2, no. 4, pp. 217-221, 2009.

First-order wetting transition at a liquid-vapor interface

NASA Technical Reports Server (NTRS)

Schmidt, J. W.; Moldover, M. R.

1983-01-01

Evidence from reflectance and contact angle measurements is presented that three-phase mixtures of i-C3H7OH-C7F14 exhibit a first-order wetting phase transition at the liquid-vapor interface at 38 C. Equilibration phenomena support this interpretation. Ellipsometry was used to measure the apparent thickness of the intruding layer in the three-phase mixture. At temperatures slightly above the wetting temperature T(w), the intruding layer's thickness is several hundred angstroms and its variation with temperature is extremely weak. Below T(w), three-phase contact can occur between the vapor and both the upper and lower liquid phases; one of the angles which characterizes this contact has a very simple temperature dependence. The thickness of the intruding layer, monitored as the solutions approached equilibrium, is found to depend quite weakly on the height spanned by the upper liquid phase in the vicinity of a first-order wetting transition.

TTVFaster: First order eccentricity transit timing variations (TTVs)

NASA Astrophysics Data System (ADS)

Agol, Eric; Deck, Katherine

2016-04-01

TTVFaster implements analytic formulae for transit time variations (TTVs) that are accurate to first order in the planet-star mass ratios and in the orbital eccentricities; the implementations are available in several languages, including IDL, Julia, Python and C. These formulae compare well with more computationally expensive N-body integrations in the low-eccentricity, low mass-ratio regime when applied to simulated and to actual multi-transiting Kepler planet systems.

Modification of drug release from acetaminophen granules by melt granulation technique - consideration of release kinetics.

PubMed

Uhumwangho, M U; Okor, R S

2006-01-01

Acetaminophen granules have been formed by a melt granulation process with the objective of retarding drug release for prolonged action formulations. The waxes used were goat wax, carnuba wax and glyceryl monostearate. In the melt granulation procedure, acetaminophen powder was triturated with the melted waxes and passed through a sieve of mesh 10 (aperture size 710 microm). The content of wax in resulting granules ranged from 10 to 40%w/w. Acetaminophen granules were also formed by the convectional method of wet granulation with starch mucilage (20%w/w). The granules were subjected to in-vitro drug release tests. The release data were subjected to analysis by three different well-established mathematical models (release kinetics) namely, - zero order flux, first order, and the Higuchi square root of time relationship. The convectional granules exhibited an initial zero order flux (first 55%) followed by a first order release profile (the remaining 45%). The pattern of drug release from the melt granulations was consistent with the first order kinetic and the Higuchi square root of time relationship, indicating a diffusion-controlled release mechanism. The first order release rate constant of the convectional granules was 1.95 +/- 0.02 h(-1). After melt granulation (wax content, 20%w/w) the rate constants dropped drastically to 0.130+/-0.001 h(-1) (goat wax), 0.120+/-0.003 h(-1) (carnuba wax), and 0.130+/-0.002 h(-1) (glyceryl monosterate) indicating that all three waxes were equivalent in retarding drug release from the melt granulations.

Novel structures for Discrete Hartley Transform based on first-order moments

NASA Astrophysics Data System (ADS)

Xiong, Jun; Zheng, Wenjuan; Wang, Hao; Liu, Jianguo

2018-03-01

Discrete Hartley Transform (DHT) is an important tool in digital signal processing. In the present paper, the DHT is firstly transformed into the first-order moments-based form, then a new fast algorithm is proposed to calculate the first-order moments without multiplication. Based on the algorithm theory, the corresponding hardware architecture for DHT is proposed, which only contains shift operations and additions with no need for multipliers and large memory. To verify the availability and effectiveness, the proposed design is implemented with hardware description language and synthesized by Synopsys Design Compiler with 0.18-μm SMIC library. A series of experiments have proved that the proposed architecture has better performance in terms of the product of the hardware consumption and computation time.

Holographic equipartition from first order action

NASA Astrophysics Data System (ADS)

Wang, Jingbo

2017-12-01

Recently, the idea that gravity is emergent has attract many people's attention. The "Emergent Gravity Paradigm" is a program that develop this idea from the thermodynamical point of view. It expresses the Einstein equation in the language of thermodynamics. A key equation in this paradigm is the holographic equipartition which says that, in all static spacetimes, the degrees of freedom on the boundary equal those in the bulk. And the time evolution of spacetime is drove by the departure from the holographic equipartition. In this paper, we get the holographic equipartition and its generalization from the first order formalism, that is, the connection and its conjugate momentum are considered to be the canonical variables. The final results have similar structure as those from the metric formalism. It gives another proof of holographic equipartition.

Critical ignition conditions in exothermically reacting systems: first-order reactions

NASA Astrophysics Data System (ADS)

Filimonov, Valeriy Yu.

2017-10-01

In this paper, the comparative analysis of the thermal explosion (TE) critical conditions on the planes temperature-conversion degree and temperature-time was conducted. It was established that the ignition criteria are almost identical only at relatively small values of Todes parameter. Otherwise, the results of critical conditions analysis on the plane temperature-conversion degree may be wrong. The asymptotic method of critical conditions calculation for the first-order reactions was proposed (taking into account the reactant consumption). The degeneration conditions of TE were determined. The calculation of critical conditions for specific first-order reaction was made. The comparison of the analytical results obtained with the results of numerical calculations and experimental data showed that they are in good agreement.

Critical ignition conditions in exothermically reacting systems: first-order reactions.

PubMed

Filimonov, Valeriy Yu

2017-10-01

In this paper, the comparative analysis of the thermal explosion (TE) critical conditions on the planes temperature-conversion degree and temperature-time was conducted. It was established that the ignition criteria are almost identical only at relatively small values of Todes parameter. Otherwise, the results of critical conditions analysis on the plane temperature-conversion degree may be wrong. The asymptotic method of critical conditions calculation for the first-order reactions was proposed (taking into account the reactant consumption). The degeneration conditions of TE were determined. The calculation of critical conditions for specific first-order reaction was made. The comparison of the analytical results obtained with the results of numerical calculations and experimental data showed that they are in good agreement.

A higher-order Skyrme model

NASA Astrophysics Data System (ADS)

Gudnason, Sven Bjarke; Nitta, Muneto

2017-09-01

We propose a higher-order Skyrme model with derivative terms of eighth, tenth and twelfth order. Our construction yields simple and easy-to-interpret higher-order Lagrangians. We first show that a Skyrmion with higher-order terms proposed by Marleau has an instability in the form of a baby-Skyrmion string, while the static energies of our construction are positive definite, implying stability against time-independent perturbations. However, we also find that the Hamiltonians of our construction possess two kinds of dynamical instabilities, which may indicate the instability with respect to time-dependent perturbations. Different from the well-known Ostrogradsky instability, the instabilities that we find are intrinsically of nonlinear nature and also due to the fact that even powers of the inverse metric gives a ghost-like higher-order kinetic-like term. The vacuum state is, however, stable. Finally, we show that at sufficiently low energies, our Hamiltonians in the simplest cases, are stable against time-dependent perturbations.

From differential to difference equations for first order ODEs

NASA Technical Reports Server (NTRS)

Freed, Alan D.; Walker, Kevin P.

1991-01-01

When constructing an algorithm for the numerical integration of a differential equation, one should first convert the known ordinary differential equation (ODE) into an ordinary difference equation. Given this difference equation, one can develop an appropriate numerical algorithm. This technical note describes the derivation of two such ordinary difference equations applicable to a first order ODE. The implicit ordinary difference equation has the same asymptotic expansion as the ODE itself, whereas the explicit ordinary difference equation has an asymptotic that is similar in structure but different in value when compared with that of the ODE.

Revisiting kinetic boundary conditions at the surface of fuel droplet hydrocarbons: An atomistic computational fluid dynamics simulation

PubMed Central

Nasiri, Rasoul

2016-01-01

The role of boundary conditions at the interface for both Boltzmann equation and the set of Navier-Stokes equations have been suggested to be important for studying of multiphase flows such as evaporation/condensation process which doesn’t always obey the equilibrium conditions. Here we present aspects of transition-state theory (TST) alongside with kinetic gas theory (KGT) relevant to the study of quasi-equilibrium interfacial phenomena and the equilibrium gas phase processes, respectively. A two-state mathematical model for long-chain hydrocarbons which have multi-structural specifications is introduced to clarify how kinetics and thermodynamics affect evaporation/condensation process at the surface of fuel droplet, liquid and gas phases and then show how experimental observations for a number of n-alkane may be reproduced using a hybrid framework TST and KGT with physically reasonable parameters controlling the interface, gas and liquid phases. The importance of internal activation dynamics at the surface of n-alkane droplets is established during the evaporation/condensation process. PMID:27215897

Using a CBL Unit, a Temperature Sensor, and a Graphing Calculator to Model the Kinetics of Consecutive First-Order Reactions as Safe In-Class Demonstrations

ERIC Educational Resources Information Center

Moore-Russo, Deborah A.; Cortes-Figueroa, Jose E.; Schuman, Michael J.

2006-01-01

The use of Calculator-Based Laboratory (CBL) technology, the graphing calculator, and the cooling and heating of water to model the behavior of consecutive first-order reactions is presented, where B is the reactant, I is the intermediate, and P is the product for an in-class demonstration. The activity demonstrates the spontaneous and consecutive…

In Situ μGISAXS: II. Thaumatin Crystal Growth Kinetic

PubMed Central

Gebhardt, Ronald; Pechkova, Eugenia; Riekel, Christian; Nicolini, Claudio

2010-01-01

The formation of thaumatin crystals by Langmuir-Blodgett (LB) film nanotemplates was studied by the hanging-drop technique in a flow-through cell by synchrotron radiation micrograzing-incidence small-angle x-ray scattering. The kinetics of crystallization was measured directly on the interface of the LB film crystallization nanotemplate. The evolution of the micrograzing-incidence small-angle x-ray scattering patterns suggests that the increase in intensity in the Yoneda region is due to protein incorporation into the LB film. The intensity variation suggests several steps, which were modeled by system dynamics based on first-order differential equations. The kinetic data can be described by two processes that take place on the LB film, a first, fast, process, attributed to the crystal growth and its detachment from the LB film, and a second, slower process, attributed to an unordered association and conversion of protein on the LB film. PMID:20713011

Assessment of kinetic models on Fe adsorption in groundwater using high-quality limestone

NASA Astrophysics Data System (ADS)

Akbar, N. A.; Kamil, N. A. F. Mohd; Zin, N. S. Md; Adlan, M. N.; Aziz, H. A.

2018-04-01

During the groundwater pumping process, dissolved Fe2+ is oxidized into Fe3+ and produce rust-coloured iron mineral. Adsorption kinetic models are used to evaluate the performance of limestone adsorbent and describe the mechanism of adsorption and the diffusion processes of Fe adsorption in groundwater. This work presents the best kinetic model of Fe adsorption, which was chosen based on a higher value of coefficient correlation, R2. A batch adsorption experiment was conducted for various contact times ranging from 0 to 135 minutes. From the results of the batch study, three kinetic models were analyzed for Fe removal onto limestone sorbent, including the pseudo-first order (PFO), pseudo-second order (PSO) and intra-particle diffusion (IPD) models. Results show that the adsorption kinetic models follow the sequence: PSO > PFO > IPD, where the values of R2 are 0.997 > 0.919 > 0.918. A high value of R2 (0.997) reveals better fitted experimental data. Furthermore, the value of qe cal in the PSO kinetic model is very near to qe exp rather than that in other models. This finding therefore suggests that the PSO kinetic model has the good fitted with the experimental data which involved chemisorption process of divalent Fe removal in groundwater solution. Thus, limestone adsorbent media found to be an alternative and effective treatment of Fe removal from groundwater.

Kinetic characteristic of phenanthrene sorption in aged soil amended with biochar

NASA Astrophysics Data System (ADS)

Kim, Chanyang; Kim, Yong-Seong; Hyun, Seunghun

2015-04-01

Biochar has been recently highlighted as an amendment that affects yield of the crops by increasing pH, cation exchange capacity and water retention, and reduces the lability of contaminants by increasing sorption capacity in the soil system. Biochar's physico-chemical properties, high CEC, surfaces containing abundant micropores and macropores, and various types of functional groups, play important roles in enhancing sorption capacity of contaminants. Aging through a natural weathering process might change physico-chemical properties of biochar amended in soils, which can affect the sorption behavior of contaminants. Thus, in this study, the sorption characteristics of phenanthrene (PHE) on biochar-amended soils were studied with various types of chars depending on aging time. To do this, 1) soil was amended with sludge waste char (SWC), wood char (WC), and municipal waste char (MWC) during 0, 6, and 12 month. Chars were applied to soil at 1% and 2.5% (w/w) ratio. 2) Several batch kinetic and equilibrium studies were conducted. One-compartment first order and two-compartment first order model apportioning the fraction of fast and slow sorbing were selected for kinetic models. Where, qt is PHE concentration in biochar-amended soils at each time t, qeis PHE concentration in biochar-amended soils at equilibrium. ff is fastly sorbing fraction and (1-ff) is slowly sorbing fraction. k is sorption rate constant from one-compartment first order model, k1 and k2 are sorption rate constant from two-compartment first order model, t is time (hr). The equilibrium sorption data were fitted with Fruendlich and Langmuir equation. 3) Change in physico-chemical properties of biochar-amended soils was investigated with aging time. Batch equilibrium sorption results suggested that sorbed amount of PHE on WC was greater than SWC and MWC. The more char contents added to soil, the greater sorption capacity of PHE. Sorption equilibrium was reached after 4 hours and equilibrium pH ranged

Strong first order EWPT & strong gravitational waves in Z 3-symmetric singlet scalar extension

NASA Astrophysics Data System (ADS)

Kang, Zhaofeng; Ko, P.; Matsui, Toshinori

2018-02-01

The nature of electroweak (EW) phase transition (PT) is of great importance. It may give a clue to the origin of baryon asymmetry if EWPT is strong first order. Although it is a cross over within the standard model (SM), a great many extensions of the SM are capable of altering the nature. Thus, gravitational wave (GW), which is supposed to be relics of strong first order PT, is a good complementary probe to new physics beyond SM (BSM). We in this paper elaborate the patterns of strong first order EWPT in the next to simplest extension to the SM Higgs sector, by introducing a Z 3-symmetric singlet scalar. We find that, in the Z 3-symmetric limit, the tree level barrier could lead to strong first order EWPT either via three or two-step PT. Moreover, they could produce two sources of GW, despite of the undetectability from the first-step strong first order PT for the near future GW experiments. But the other source with significant supercooling which then gives rise to α ˜ O(0.1) almost can be wholly covered by future space-based GW interferometers such as eLISA, DECIGO and BBO.

The weaker effects of First-order mean motion resonances in intermediate inclinations

NASA Astrophysics Data System (ADS)

Chen, YuanYuan; Quillen, Alice C.; Ma, Yuehua; Chinese Scholar Council, the National Natural Science Foundation of China, the Natural Science Foundation of Jiangsu Province, the Minor Planet Foundation of the Purple Mountain Observatory

2017-10-01

During planetary migration, a planet or planetesimal can be captured into a low-order mean motion resonance with another planet. Using a second-order expansion of the disturbing function in eccentricity and inclination, we explore the sensitivity of the capture probability of first-order mean motion resonances to orbital inclination. We find that second-order inclination contributions affect the resonance strengths, reducing them at intermediate inclinations of around 10-40° for major first-order resonances. We also integrated the Hamilton's equations with arbitrary initial arguments, and provided the varying tendencies of resonance capture probabilities versus orbital inclinations for different resonances and different particle or planetary eccentricities. Resonance-weaker ranges in inclinations generally appear at the places where resonance strengths are low, around 10-40° in general. The weaker ranges disappear with a higher particle eccentricity (≳0.05) or planetary eccentricity (≳0.05). These resonance-weaker ranges in inclinations implies that intermediate-inclination objects are less likely to be disturbed or captured into the first-order resonances, which would make them entering into the chaotic area around Neptune with a larger fraction than those with low inclinations, during the epoch of Neptune's outward migration. The privilege of high-inclination particles leave them to be more likely captured into Neptune Trojans, which might be responsible for the unexpected high fraction of high-inclination Neptune Trojans.

Strongly first-order electroweak phase transition and classical scale invariance

NASA Astrophysics Data System (ADS)

Farzinnia, Arsham; Ren, Jing

2014-10-01

In this work, we examine the possibility of realizing a strongly first-order electroweak phase transition within the minimal classically scale-invariant extension of the standard model (SM), previously proposed and analyzed as a potential solution to the hierarchy problem. By introducing one complex gauge-singlet scalar and three (weak scale) right-handed Majorana neutrinos, the scenario was successfully rendered capable of achieving a radiative breaking of the electroweak symmetry (by means of the Coleman-Weinberg mechanism), inducing nonzero masses for the SM neutrinos (via the seesaw mechanism), presenting a pseudoscalar dark matter candidate (protected by the CP symmetry of the potential), and predicting the existence of a second CP-even boson (with suppressed couplings to the SM content) in addition to the 125 GeV scalar. In the present treatment, we construct the full finite-temperature one-loop effective potential of the model, including the resummed thermal daisy loops, and demonstrate that finite-temperature effects induce a first-order electroweak phase transition. Requiring the thermally driven first-order phase transition to be sufficiently strong at the onset of the bubble nucleation (corresponding to nucleation temperatures TN˜100-200 GeV) further constrains the model's parameter space; in particular, an O(0.01) fraction of the dark matter in the Universe may be simultaneously accommodated with a strongly first-order electroweak phase transition. Moreover, such a phase transition disfavors right-handed Majorana neutrino masses above several hundreds of GeV, confines the pseudoscalar dark matter masses to ˜1-2 TeV, predicts the mass of the second CP-even scalar to be ˜100-300 GeV, and requires the mixing angle between the CP-even components of the SM doublet and the complex singlet to lie within the range 0.2≲sinω ≲0.4. The obtained results are displayed in comprehensive exclusion plots, identifying the viable regions of the parameter space

Degradation kinetics and mechanism of RDX and HMX in TiO2 photocatalysis.

PubMed

Choi, J K; Son, H S; Kim, T S; Stenstrom, M K; Zoh, K D

2006-02-01

This study was undertaken to examine the photocatalytic degradation of explosives hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) with a circular photocatalytic reactor, using a UV lamp as a light source and TiO2 as a photocatalyst. The effects of various parameters, such as the RDX or HMX concentration, the amount of TiO, and the initial pH, on the photocatalytic degradation rates of explosives were examined. In the presence of both UV light and TiO2 RDX and HMX were more effectively degraded than with either UV or TiO2 alone. The degradation rates were found to obey pseudo-first-order kinetics represented by the Langmuir-Hinshelwood model. Increases in the RDX and HMX degradation rates were obtained with decreasing initial concentrations of the explosives. The RDX and HMX degradation rates were higher at pH 7 than at either pH 3 or pH 11. A dose of approximately 0.7 g l(-1) of TiO2 degraded HMX more rapidly than did higher or lower TiO2 doses. RDX (20 mg l(-1)) photocatalysis resulted in an approximately 20% decrease in TOC, and HMX (5 mg l(-1)) photocatalysis resulted in a 60%, decrease in TOC within 150 minutes. A trace amount of formate was produced as an intermediate that was further mineralized by RDX or HMX photocatalysis. The nitrogen byproducts from the photocatalysis of RDX and HMX were mainly NO3- with NO2-, and NH4+. The total nitrogen recovery was about 60% from RDX (20 mg l(-1)), and 70% from HMX (5 mg l(-1)), respectively. Finally, a mechanism for RDX/HMX photocatalysis was proposed, along with supporting qualitative and quantitative evidence.

Rhodopsin kinetics in the cat retina.

PubMed

Ripps, H; Mehaffey, L; Siegel, I M

1981-03-01

The bleaching and regeneration of rhodopsin in the living cat retina was studied by means of fundus reflectometry. Bleaching was effected by continuous light exposures of 1 min or 20 min, and the changes in retinal absorbance were measured at 29 wavelengths. For all of the conditions studied (fractional bleaches of from 65 to 100%), the regeneration of rhodopsin to its prebleach levels required greater than 60 min in darkness. After the 1-min exposures, the difference spectra recorded during the first 10 min of dark adaptation were dominated by photoproduct absorption, and rhodopsin regeneration kinetics were obscured by these intermediate processes. Extending the bleaching duration to 20 min gave the products of photolysis an opportunity to dissipate, and it was possible to follow the regenerative process over its full time-course. It was not possible, however, to fit these data with the simple exponential function predicted by first-order reaction kinetics. Other possible mechanisms were considered and are presented in the text. Nevertheless, the kinetics of regeneration compared favorably with the temporal changes in log sensitivity determined electrophysiologically by other investigators. Based on the bleaching curve for cat rhodopsin, the photosensitivity was determined and found to approximate closely the value obtained for human rhodopsin; i.e., the energy Ec required to bleach 1-e-1 of the available rhodopsin was 7.09 log scotopic troland-seconds (corrected for the optics of the cat eye), as compared with approximately 7.0 in man.

First-principles thermodynamics and defect kinetics guidelines for engineering a tailored RRAM device

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clima, Sergiu, E-mail: clima@imec.be; Chen, Yang Yin; Goux, Ludovic

Resistive Random Access Memories are among the most promising candidates for the next generation of non-volatile memory. Transition metal oxides such as HfOx and TaOx attracted a lot of attention due to their CMOS compatibility. Furthermore, these materials do not require the inclusion of extrinsic conducting defects since their operation is based on intrinsic ones (oxygen vacancies). Using Density Functional Theory, we evaluated the thermodynamics of the defects formation and the kinetics of diffusion of the conducting species active in transition metal oxide RRAM materials. The gained insights based on the thermodynamics in the Top Electrode, Insulating Matrix and Bottommore » Electrode and at the interfaces are used to design a proper defect reservoir, which is needed for a low-energy reliable switching device. The defect reservoir has also a direct impact on the retention of the Low Resistance State due to the resulting thermodynamic driving forces. The kinetics of the diffusing conducting defects in the Insulating Matrix determine the switching dynamics and resistance retention. The interface at the Bottom Electrode has a significant impact on the low-current operation and long endurance of the memory cell. Our first-principles findings are confirmed by experimental measurements on fabricated RRAM devices.« less

Removal of copper by oxygenated pyrolytic tire char: kinetics and mechanistic insights.

PubMed

Quek, Augustine; Balasubramanian, Rajashekhar

2011-04-01

The kinetics of copper ion (Cu(II)) removal from aqueous solution by pyrolytic tire char was modeled using five different conventional models. A modification to these models was also developed through a modified equation that accounts for precipitation. Conventional first- and second-order reaction models did not fit the copper sorption kinetics well, indicating a lack of simple rate-order dependency on solute concentration. Instead, a reversible first-order rate reaction showed the best fit to the data, indicating a dependence on surface functional groups. Due to the varying solution pH during the sorption process, modified external and internal mass transfer models were employed. Results showed that the sorption of copper onto oxygenated chars was limited by external mass transfer and internal resistance with and without the modification. However, the modification of the sorption process produced very different results for unoxygenated chars, which showed neither internal nor external limitation to sorption. Instead, its slow sorption rate indicates a lack of surface functional groups. The sorption of Cu(II) by oxygenated and unoxygenated chars was also found to occur via three and two distinct stages, respectively. Copyright © 2010 Elsevier Inc. All rights reserved.

Chemiomics: network reconstruction and kinetics of port wine aging.

PubMed

Monforte, Ana Rita; Jacobson, Dan; Silva Ferreira, A C

2015-03-11

Network reconstruction (NR) has proven to be useful in the detection and visualization of relationships among the compounds present in a Port wine aging data set. This view of the data provides a considerable amount of information with which to understand the kinetic contexts of the molecules represented by peaks in each chromatogram. The aim of this study was to use NR together with the determination of kinetic parameters to extract more information about the mechanisms involved in Port wine aging. The volatile compounds present in samples of Port wines spanning 128 years in age were measured with the use of GC-MS. After chromatogram alignment, a peak matrix was created, and all peak vectors were compared to one another to determine their Pearson correlations over time. A correlation network was created and filtered on the basis of the resulting correlation values. Some nodes in the network were further studied in experiments on Port wines stored under different conditions of oxygen and temperature in order to determine their kinetic parameters. The resulting network can be divided into three main branches. The first branch is related to compounds that do not directly correlate to age, the second branch contains compounds affected by temperature, and the third branch contains compounds associated with oxygen. Compounds clustered in the same branch of the network have similar expression patterns over time as well as the same kinetic order, thus are likely to be dependent on the same technological parameters. Network construction and visualization provides more information with which to understand the probable kinetic contexts of the molecules represented by peaks in each chromatogram. The approach described here is a powerful tool for the study of mechanisms and kinetics in complex systems and should aid in the understanding and monitoring of wine quality.

Chemiomics: Network Reconstruction and Kinetics of Port Wine Aging

DOE PAGES

Monforte, Ana Rita; Jacobson, Dan; Silva Ferreira, A. C.

2015-02-11

Network reconstruction (NR) has proven to be useful in the detection and visualization of relationships among the compounds present in a Port wine aging data set. This view of the data provides a considerable amount of information with which to understand the kinetic contexts of the molecules represented by peaks in each chromatogram. The aim of this paper was to use NR together with the determination of kinetic parameters to extract more information about the mechanisms involved in Port wine aging. The volatile compounds present in samples of Port wines spanning 128 years in age were measured with the usemore » of GC-MS. After chromatogram alignment, a peak matrix was created, and all peak vectors were compared to one another to determine their Pearson correlations over time. A correlation network was created and filtered on the basis of the resulting correlation values. Some nodes in the network were further studied in experiments on Port wines stored under different conditions of oxygen and temperature in order to determine their kinetic parameters. The resulting network can be divided into three main branches. The first branch is related to compounds that do not directly correlate to age, the second branch contains compounds affected by temperature, and the third branch contains compounds associated with oxygen. Compounds clustered in the same branch of the network have similar expression patterns over time as well as the same kinetic order, thus are likely to be dependent on the same technological parameters. Network construction and visualization provides more information with which to understand the probable kinetic contexts of the molecules represented by peaks in each chromatogram. Finally, the approach described here is a powerful tool for the study of mechanisms and kinetics in complex systems and should aid in the understanding and monitoring of wine quality.« less

Free radical kinetics on irradiated fennel

NASA Astrophysics Data System (ADS)

Yamaoki, Rumi; Kimura, Shojiro; Ohta, Masatoshi

2008-09-01

Herein, an electron spin resonance study on the behavior of organic radicals in fennel before and after irradiation is reported. The spectrum of irradiated fennel composed of the spectrum component derived from the un-irradiated sample (near g=2.005) and the spectra components derived from carbohydrates. The time decay of intensity spectral components was well explained by first-order kinetics with a variety of rate constants. Especially, the signal at near g=2.02 ascribed to stable cellulose-derivative components is expected to be a good indicator in the identification of irradiated plant samples.

Magnetostructural Transition Kinetics in Shocked Iron

DOE PAGES

Surh, Michael P.; Benedict, Lorin X.; Sadigh, Babak

2016-08-15

Here, a generalized Heisenberg model is implemented to study the effect of thermal magnetic disorder on kinetics of the Fe α–ε transition. The barrier to bulk martensitic displacement remains large in α-Fe shocked well past the phase line but is much reduced in the [001] α–ε boundary. The first result is consistent with observed overdriving to metastable α, while the second suggests structural instability, as implied by observation of a [001] shock transformation front without plastic relaxation. Reconciling both behaviors may require concurrent treatment of magnetic and structural order.

AMD-stability in the presence of first-order mean motion resonances

NASA Astrophysics Data System (ADS)

Petit, A. C.; Laskar, J.; Boué, G.

2017-11-01

The angular momentum deficit (AMD)-stability criterion allows to discriminate between a priori stable planetary systems and systems for which the stability is not granted and needs further investigations. AMD-stability is based on the conservation of the AMD in the averaged system at all orders of averaging. While the AMD criterion is rigorous, the conservation of the AMD is only granted in absence of mean-motion resonances (MMR). Here we extend the AMD-stability criterion to take into account mean-motion resonances, and more specifically the overlap of first-order MMR. If the MMR islands overlap, the system will experience generalized chaos leading to instability. The Hamiltonian of two massive planets on coplanar quasi-circular orbits can be reduced to an integrable one degree of freedom problem for period ratios close to a first-order MMR. We use the reduced Hamiltonian to derive a new overlap criterion for first-order MMR. This stability criterion unifies the previous criteria proposed in the literature and admits the criteria obtained for initially circular and eccentric orbits as limit cases. We then improve the definition of AMD-stability to take into account the short term chaos generated by MMR overlap. We analyze the outcome of this improved definition of AMD-stability on selected multi-planet systems from the Extrasolar Planets Encyclopædia.

Enzyme catalysis in microgravity: steady-state kinetic analysis of the isocitrate lyase reaction.

PubMed

Ranaldi, Francesco; Vanni, Paolo; Giachetti, Eugenio

2003-01-21

Two decades of research in microgravity have shown that certain biochemical processes can be altered by weightlessness. Approximately 10 years ago, our team, supported by the European Space Agency (ESA) and the Agenzia Spaziale Italiana, started the Effect of Microgravity on Enzyme Catalysis project to test the possibility that the microgravity effect observed at cellular level could be mediated by enzyme reactions. An experiment to study the cleavage reaction catalyzed by isocitrate lyase was flown on the sounding rocket MASER 7, and we found that the kinetic parameters were not altered by microgravity. During the 28th ESA parabolic flight campaign, we had the opportunity to replicate the MASER 7 experiment and to perform a complete steady-state analysis of the isocitrate lyase reaction. This study showed that both in microgravity and in standard g controls the enzyme reaction obeyed the same kinetic mechanism and none of the kinetic parameters, nor the equilibrium constant of the overall reaction were altered. Our results contrast with those of a similar experiment, which was performed during the same parabolic flight campaign, and showed that microgravity increased the affinity of lipoxygenase-1 for linoleic acid. The hypotheses suggested to explain this change effect of the latter were here tested by computer simulation, and appeared to be inconsistent with the experimental outcome.

Kinetics and thermodynamics studies of silver ions adsorption onto coconut shell activated carbon.

PubMed

Silva-Medeiros, Flávia V; Consolin-Filho, Nelson; Xavier de Lima, Mateus; Bazzo, Fernando Previato; Barros, Maria Angélica S D; Bergamasco, Rosângela; Tavares, Célia R G

2016-12-01

The presence of silver in the natural water environment has been of great concern because of its toxicity, especially when it is in the free ion form (Ag(+)). This paper aims to study the adsorption kinetics of silver ions from an aqueous solution onto coconut shell activated carbon using batch methods. Batch kinetic data were fitted to the first-order model and the pseudo-second-order model, and this last equation fits correctly the experimental data. Equilibrium experiments were carried out at 30°C, 40°C, and 50°C. The adsorption isotherms were reasonably fit using Langmuir model, and the adsorption process was slightly influenced by changes in temperature. Thermodynamic parameters (ΔH°, ΔG°, and ΔS°) were determined. The adsorption process seems to be non-favorable, exothermic, and have an increase in the orderness.

Kinetics of carotenoids degradation and furosine formation in dried apricots (Prunus armeniaca L.).

PubMed

Fratianni, A; Niro, S; Messia, M C; Cinquanta, L; Panfili, G; Albanese, D; Di Matteo, M

2017-09-01

The kinetics of carotenoid and color degradation, as well as furosine formation, were investigated in apricot fruits during convective heating at 50, 60 and 70°C. Degradation of carotenoids and color, expressed as total color difference (TCD), followed a first and zero order kinetic, respectively. The activation energy (Ea) for carotenoids degradation ranged from 73.7kJ/mol for 13-cis-β-carotene to 120.7kJ/mol for lutein, being about 91kJ/mol for all-trans-β-carotene. Violaxanthin and anteraxanthin were the most susceptible to thermal treatment. The furosine evolution was fitted at zero order kinetic model. The Ea for furosine formation was found to be 83.3kJ/mol and the Q 10 (temperature coefficient) varied from 1.59 to 4.14 at the temperature ranges 50-60°C and 60-70°C, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

First-Order Open-Universe POMDPs: Formulation and Algorithms

DTIC Science & Technology

2013-12-25

A full DTBLOG model for the airport domain example is presented in the appendix. Let M ( S , A ) be a DTBLOG model defined using the sets S and A of...respectively. IfM satisfies BLOG’s requirements for well-defined probabilistic models then it constitutes a well-defined OUPOMDP model wrt S and A . Actions on... a first-order, open-universe language to describe POMDPs and identify non-trivial representational issues in describing an agent? s

FIRST-ORDER COSMOLOGICAL PERTURBATIONS ENGENDERED BY POINT-LIKE MASSES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eingorn, Maxim, E-mail: maxim.eingorn@gmail.com

2016-07-10

In the framework of the concordance cosmological model, the first-order scalar and vector perturbations of the homogeneous background are derived in the weak gravitational field limit without any supplementary approximations. The sources of these perturbations (inhomogeneities) are presented in the discrete form of a system of separate point-like gravitating masses. The expressions found for the metric corrections are valid at all (sub-horizon and super-horizon) scales and converge at all points except at the locations of the sources. The average values of these metric corrections are zero (thus, first-order backreaction effects are absent). Both the Minkowski background limit and the Newtonianmore » cosmological approximation are reached under certain well-defined conditions. An important feature of the velocity-independent part of the scalar perturbation is revealed: up to an additive constant, this part represents a sum of Yukawa potentials produced by inhomogeneities with the same finite time-dependent Yukawa interaction range. The suggested connection between this range and the homogeneity scale is briefly discussed along with other possible physical implications.« less

Kinetics of DCE and VC mineralization under methanogenic and Fe(III)- reducing conditions

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.

1997-01-01

The kinetics of anaerobic mineralization of DCE and VC under mathanogenic and Fe(III)-reducing conditions as a function of dissolved contaminant concentration were evaluated. Microorganisms indigenous to creek bed sediments, where groundwater contaminated with chlorinated ethenes continuously discharges, demonstrated significant mineralization of DCE and VC under methanogenic and Fe(III)- reducing conditions. Over 37 days, the recovery of [1,214C]VC radioactivity as 14CO2 ranged from 5% to 44% and from 8% to 100% under methanogenic and Fe(III)-reducing conditions, respectively. The recovery of [1,2-14C]DCE radioactivity as 14CO2 ranged from 4% to 14% and did not vary significantly between methanogenic and Fe(III)reducing conditions. VC mineralization was described by Michaelis- Menten kinetics. Under methanogenic conditions, V(max) was 0.19 ?? 0.01 ??mol L-1 d-1 and the half-saturation constant, k(m), was 7.6 ?? 1.7 ??M. Under Fe(III)-reducing conditions, V(max) was 0.76 ?? 0.07 ??mol L-1 d-1 and k(m) was 1.3 ?? 0.5 ??M. In contrast, DCE mineralization could be described by first-order kinetics. The first-order degradation rate constant for DCE mineralization was 0.6 ?? 0.2% d-1 under methanogenic and Fe(III)-reducing conditions. The results indicate that the kinetics of chlorinated ethane mineralization can vary significantly with the specific contaminant and the predominant redox conditions under which mineralization occurs.

Coherency strain and precipitation kinetics: crystalline and amorphous nitride formation in ternary Fe-Ti/Cr/V-Si alloys

NASA Astrophysics Data System (ADS)

Schwarz, B.; Rossi, P. J.; Straßberger, L.; Jörg, F.; Meka, S. R.; Bischoff, E.; Schacherl, R. E.; Mittemeijer, E. J.

2014-09-01

Specimens of iron-based binary Fe-Si alloy and ternary Fe-Me-Si alloys (with Me = Ti, Cr and V) were nitrided at 580 °C in a NH3/H2-gas mixture applying a nitriding potential of 0.1 atm-1/2 until nitrogen saturation in the specimens was attained. In contrast with recent observations in other Fe-Me1-Me2 alloys, no "mixed" (Me1, Me2) nitrides developed in Fe-Me-Si alloys upon nitriding: first, all Me precipitates as MeN; and thereafter, all Si precipitates as Si3N4. The MeN precipitates as crystalline, finely dispersed, nanosized platelets, obeying a Baker-Nutting orientation relationship (OR) with respect to the ferrite matrix. The Si3N4 precipitates as cubically, amorphous particles; the incoherent (part of the) MeN/α-Fe interface acts as heterogeneous nucleation site for Si3N4. The Si3N4-precipitation rate was found to be strongly dependent on the degree of coherency of the first precipitating MeN. The different, even opposite, kinetic effects observed for the various Fe-Me-Si alloys could be ascribed to the different time dependences of the coherent → incoherent transitions of the MeN particles in the different Fe-Me-Si alloys.

Desorption Kinetics of Benzene and Cyclohexane from a Graphene Surface.

PubMed

Smith, R Scott; Kay, Bruce D

2018-01-18

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature-programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer and submonolayer TPD spectra for coverages greater than ∼0.1 ML have nearly the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An "inversion" procedure in which the prefactor is varied to find the value that best reproduces the entire set of experimental desorption spectra was used to analyze the benzene data. The inversion analysis of the benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 10 17±1 s -1 . The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 10 16±1 ML s -1 .

A second-order accurate kinetic-theory-based method for inviscid compressible flows

NASA Technical Reports Server (NTRS)

Deshpande, Suresh M.

1986-01-01

An upwind method for the numerical solution of the Euler equations is presented. This method, called the kinetic numerical method (KNM), is based on the fact that the Euler equations are moments of the Boltzmann equation of the kinetic theory of gases when the distribution function is Maxwellian. The KNM consists of two phases, the convection phase and the collision phase. The method is unconditionally stable and explicit. It is highly vectorizable and can be easily made total variation diminishing for the distribution function by a suitable choice of the interpolation strategy. The method is applied to a one-dimensional shock-propagation problem and to a two-dimensional shock-reflection problem.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sabari Arul, N.; Department of Nanoscience and Technology, Bharathiar University, Coimbatore-641 046; Mangalaraj, D.

Hierarchical rose-flower-like CeO{sub 2} nanostructures were formed by using solvothermal and thermal annealing processes. The CeCO{sub 3}OH thin film was transformed into CeO{sub 2} roses due to thermal annealing. CeO{sub 2} nanostructured roses exhibited excellent photocatalytic activity with a degradation rate of 65% for the azo dye acid orange 7 (AO7) under ultraviolet illumination. The fitting of the absorbance maximum versus time showed that the degradation of AO7 obeyed pseudo-first-order reaction kinetics. The enhancement of the photocatalytic activity for the CeO{sub 2} roses was attributed to the high adsorptivity resulting from the surface active sites and special 4f electron configuration.

Ruthenium(III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid—A kinetic study

NASA Astrophysics Data System (ADS)

Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

2016-02-01

Kinetics of ruthenium(III) catalyzed oxidation of biologically important sugar alcohols (myo-inositol, D-sorbitol, and D-mannitol) by dichloroisocyanuric acid was carried out in aqueous acetic acid—perchloric medium. The reactions were found to be first order in case of oxidant and ruthenium(III). Zero order was observed with the concentrations of sorbitol and mannitol whereas, a positive fractional order was found in the case of inositol concentration. An inverse fractional order was observed with perchloric acid in oxidation of three substrates. Arrhenius parameters were calculated and a plausible mechanism was proposed.

Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron.

PubMed

Agrawal, Abinash; Ferguson, William J; Gardner, Bruce O; Christ, John A; Bandstra, Joel Z; Tratnyek, Paul G

2002-10-15

The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.

Kinetics of hydrophobic organic contaminant extraction from sediment by granular activated carbon.

PubMed

Rakowska, M I; Kupryianchyk, D; Smit, M P J; Koelmans, A A; Grotenhuis, J T C; Rijnaarts, H H M

2014-03-15

Ex situ solid phase extraction with granular activated carbon (GAC) is a promising technique to remediate contaminated sediments. The methods' efficiency depends on the rate by which contaminants are transferred from the sediment to the surface of GAC. Here, we derive kinetic parameters for extraction of polycyclic aromatic hydrocarbons (PAH) from sediment by GAC, using a first-order multi-compartment kinetic model. The parameters were obtained by modeling sediment-GAC exchange kinetic data following a tiered model calibration approach. First, parameters for PAH desorption from sediment were calibrated using data from systems with 50% (by weight) GAC acting as an infinite sink. Second, the estimated parameters were used as fixed input to obtain GAC uptake kinetic parameters in sediment slurries with 4% GAC, representing the ex situ remediation scenario. PAH uptake rate constants (kGAC) by GAC ranged from 0.44 to 0.0005 d(-1), whereas GAC sorption coefficients (KGAC) ranged from 10(5.57) to 10(8.57) L kg(-1). These values are the first provided for GAC in the presence of sediment and show that ex situ extraction with GAC is sufficiently fast and effective to reduce the risks of the most available PAHs among those studied, such as fluorene, phenanthrene and anthracene. Copyright © 2013 Elsevier Ltd. All rights reserved.

Kinetics of pack aluminization of nickel

NASA Technical Reports Server (NTRS)

Seigle, L. L.; Gupta, B. K.; Shankar, R.; Sarkhel, A. K.

1978-01-01

The kinetics of pack aluminization of unalloyed nickel in packs of varying aluminum activity with various halide activators were studied. Surface compositions of the coatings as functions of time, temperature, and pack composition were obtained in order to establish the boundary conditions for diffusion in the system. The structure of the packs was also examined in order to clarify the mechanism of aluminum transport. The results indicate that the kinetics of pack aluminization are controlled jointly by gas diffusion in the pack and solid diffusion in the coating. Levine and Caves' model for gas diffusion was combined with calculations of rates of diffusion in the solid to formulate a more complete theory for the kinetics of pack aluminization.

Kinetic model for astaxanthin aggregation in water-methanol mixtures

NASA Astrophysics Data System (ADS)

Giovannetti, Rita; Alibabaei, Leila; Pucciarelli, Filippo

2009-07-01

The aggregation of astaxanthin in hydrated methanol was kinetically studied in the temperature range from 10 °C to 50 °C, at different astaxanthin concentrations and solvent composition. A kinetic model for the formation and transformation of astaxanthin aggregated has been proposed. Spectrophotometric studies showed that monomeric astaxanthin decayed to H-aggregates that after-wards formed J-aggregates when water content was 50% and the temperature lower than 20 °C; at higher temperatures, very stable J-aggregates were formed directly. Monomer formed very stable H-aggregates when the water content was greater than 60%; in these conditions H-aggregates decayed into J-aggregates only when the temperature was at least 50 °C. Through these findings it was possible to establish that the aggregation reactions took place through a two steps consecutive reaction with first order kinetic constants and that the values of these depended on the solvent composition and temperature.

Reproducing Phenomenology of Peroxidation Kinetics via Model Optimization

NASA Astrophysics Data System (ADS)

Ruslanov, Anatole D.; Bashylau, Anton V.

2010-06-01

We studied mathematical modeling of lipid peroxidation using a biochemical model system of iron (II)-ascorbate-dependent lipid peroxidation of rat hepatocyte mitochondrial fractions. We found that antioxidants extracted from plants demonstrate a high intensity of peroxidation inhibition. We simplified the system of differential equations that describes the kinetics of the mathematical model to a first order equation, which can be solved analytically. Moreover, we endeavor to algorithmically and heuristically recreate the processes and construct an environment that closely resembles the corresponding natural system. Our results demonstrate that it is possible to theoretically predict both the kinetics of oxidation and the intensity of inhibition without resorting to analytical and biochemical research, which is important for cost-effective discovery and development of medical agents with antioxidant action from the medicinal plants.

Pediatric zolpidem ingestion demonstrating zero-order kinetics treated with flumazenil.

PubMed

Thornton, Stephen L; Negus, Elezer; Carstairs, Shaun D

2013-11-01

Zolpidem is a widely prescribed anti-insomnia agent. Although most pediatric zolpidem ingestions are benign, large ingestions can cause significant central nervous system (CNS) depression. Flumazenil has been reported to reverse the CNS effects of zolpidem. We describe a case of a large pediatric zolpidem ingestion resulting in profound CNS depression that responded to flumazenil administration. Serial zolpidem serum levels confirmed the ingestion. A 10-year-old boy with trisomy 21 presented to the emergency department 1 hour after he was found sedate with several zolpidem 5-mg tablets in his mouth. Seventeen tables (85 mg) were unaccounted for from a prescription bottle. He became unarousable approximately 2 hours after his ingestion. Flumazenil 0.2 mg intravenously was given with rapid return to his baseline mental status. He became resedate 1 hour later but was arousable. Sixteen hours after his presentation, he was asymptomatic. Serial zolpidem serum levels were obtained, showed an initial level of 310 ng/mL, and demonstrated zero-order kinetics. Zolpidem is an imidazopyridine, which binds to the benzodiazepine receptor. It is rapidly absorbed and has a short-half life. Unintentional pediatric ingestions of zolpidem are typically well tolerated. However, this case demonstrates that large ingestions may cause significant and prolonged CNS depression. Flumazenil, a benzodiazepine receptor antagonist, has been described to reverse the effects of zolpidem in adult ingestions. There are few published reports describing flumazenil use in pediatric ingestion patients. This case suggests that flumazenil may be an effective treatment for zolpidem-induced CNS depression in the pediatric patient.

Compensation for first-order polarization-mode dispersion by using a novel tunable compensator

NASA Astrophysics Data System (ADS)

Qiu, Feng; Ning, Tigang; Pei, Shanshan; Xing, Yujun; Jian, Shuisheng

2005-01-01

Polarization-related impairments have become a critical issue for high-data-rate optical systems, particularly when considering polarization-mode dispersion (PMD). Consequently, compensation of PMD, especially for the first-order PMD is necessary to maintain adequate performance in long-haul systems at a high bit rate of 10 Gb/s or beyond. In this paper, we successfully demonstrated automatic and tunable compensation for first-order polarization-mode dispersion. Furthermore, we reported the statistical assessment of this tunable compensator at 10 Gbit/s. Experimental results, including bit error rate measurements, are successfully compared with theory, therefore demonstrating the compensator efficiency at 10 Gbit/s. The first-order PMD was max 274 ps before PMD compensation, and it was lower than 7ps after PMD compensation.

Kinetics of Chronic Oxidation of NBG-17 Nuclear Graphite by Water Vapor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Contescu, Cristian I; Burchell, Timothy D; Mee, Robert

2015-05-01

This report presents the results of kinetic measurements during accelerated oxidation tests of NBG-17 nuclear graphite by low concentration of water vapor and hydrogen in ultra-high purity helium. The objective is to determine the parameters in the Langmuir-Hinshelwood (L-H) equation describing the oxidation kinetics of nuclear graphite in the helium coolant of high temperature gas-cooled reactors (HTGR). Although the helium coolant chemistry is strictly controlled during normal operating conditions, trace amounts of moisture (predictably < 0.2 ppm) cannot be avoided. Prolonged exposure of graphite components to water vapor at high temperature will cause very slow (chronic) oxidation over the lifetimemore » of graphite components. This behavior must be understood and predicted for the design and safe operation of gas-cooled nuclear reactors. The results reported here show that, in general, oxidation by water of graphite NBG-17 obeys the L-H mechanism, previously documented for other graphite grades. However, the characteristic kinetic parameters that best describe oxidation rates measured for graphite NBG-17 are different than those reported previously for grades H-451 (General Atomics, 1978) and PCEA (ORNL, 2013). In some specific conditions, certain deviations from the generally accepted L-H model were observed for graphite NBG-17. This graphite is manufactured in Germany by SGL Carbon Group and is a possible candidate for the fuel elements and reflector blocks of HTGR.« less

Combined TGA-MS kinetic analysis of multistep processes. Thermal decomposition and ceramification of polysilazane and polysiloxane preceramic polymers.

PubMed

García-Garrido, C; Sánchez-Jiménez, P E; Pérez-Maqueda, L A; Perejón, A; Criado, José M

2016-10-26

The polymer-to-ceramic transformation kinetics of two widely employed ceramic precursors, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (TTCS) and polyureamethylvinylsilazane (CERASET), have been investigated using coupled thermogravimetry and mass spectrometry (TG-MS), Raman, XRD and FTIR. The thermally induced decomposition of the pre-ceramic polymer is the critical step in the synthesis of polymer derived ceramics (PDCs) and accurate kinetic modeling is key to attaining a complete understanding of the underlying process and to attempt any behavior predictions. However, obtaining a precise kinetic description of processes of such complexity, consisting of several largely overlapping physico-chemical processes comprising the cleavage of the starting polymeric network and the release of organic moieties, is extremely difficult. Here, by using the evolved gases detected by MS as a guide it has been possible to determine the number of steps that compose the overall process, which was subsequently resolved using a semiempirical deconvolution method based on the Frasier-Suzuki function. Such a function is more appropriate that the more usual Gaussian or Lorentzian functions since it takes into account the intrinsic asymmetry of kinetic curves. Then, the kinetic parameters of each constituent step were independently determined using both model-free and model-fitting procedures, and it was found that the processes obey mostly diffusion models which can be attributed to the diffusion of the released gases through the solid matrix. The validity of the obtained kinetic parameters was tested not only by the successful reconstruction of the original experimental curves, but also by predicting the kinetic curves of the overall processes yielded by different thermal schedules and by a mixed TTCS-CERASET precursor.

Investigation of kinetics and absorption isotherm models for hydroponic phytoremediation of waters contaminated with sulfate.

PubMed

Saber, Ali; Tafazzoli, Milad; Mortazavian, Soroosh; James, David E

2018-02-01

Two common wetland plants, Pampas Grass (Cortaderia selloana) and Lucky Bamboo (Dracaena sanderiana), were used in hydroponic cultivation systems for the treatment of simulated high-sulfate wastewaters. Plants in initial experiments at pH 7.0 removed sulfate more efficiently compared to the same experimental conditions at pH 6.0. Results at sulfate concentrations of 50, 200, 300, 600, 900, 1200, 1500 and 3000 mg/L during three consecutive 7-day treatment periods with 1-day rest intervals, showed decreasing trends of both removal efficiencies and uptake rates with increasing sulfate concentrations from the first to the second to the third 7-day treatment periods. Removed sulfate masses per unit dry plant mass, calculated after 23 days, showed highest removal capacity at 600 mg/L sulfate for both plants. A Langmuir-type isotherm best described sulfate uptake capacity of both plants. Kinetic studies showed that compared to pseudo first-order kinetics, pseudo-second order kinetic models slightly better described sulfate uptake rates by both plants. The Elovich kinetic model showed faster rates of attaining equilibrium at low sulfate concentrations for both plants. The dimensionless Elovich model showed that about 80% of sulfate uptake occurred during the first four days' contact time. Application of three 4-day contact times with 2-day rest intervals at high sulfate concentrations resulted in slightly higher uptakes compared to three 7-day contact times with 1-day rest intervals, indicating that pilot-plant scale treatment systems could be sized with shorter contact times and longer rest-intervals. Copyright © 2017 Elsevier Ltd. All rights reserved.

An investigation on the modelling of kinetics of thermal decomposition of hazardous mercury wastes.

PubMed

Busto, Yailen; M G Tack, Filip; Peralta, Luis M; Cabrera, Xiomara; Arteaga-Pérez, Luis E

2013-09-15

The kinetics of mercury removal from solid wastes generated by chlor-alkali plants were studied. The reaction order and model-free method with an isoconversional approach were used to estimate the kinetic parameters and reaction mechanism that apply to the thermal decomposition of hazardous mercury wastes. As a first approach to the understanding of thermal decomposition for this type of systems (poly-disperse and multi-component), a novel scheme of six reactions was proposed to represent the behaviour of mercury compounds in the solid matrix during the treatment. An integration-optimization algorithm was used in the screening of nine mechanistic models to develop kinetic expressions that best describe the process. The kinetic parameters were calculated by fitting each of these models to the experimental data. It was demonstrated that the D₁-diffusion mechanism appeared to govern the process at 250°C and high residence times, whereas at 450°C a combination of the diffusion mechanism (D₁) and the third order reaction mechanism (F3) fitted the kinetics of the conversions. The developed models can be applied in engineering calculations to dimension the installations and determine the optimal conditions to treat a mercury containing sludge. Copyright © 2013 Elsevier B.V. All rights reserved.

Toward efficiency in heterogeneous multispecies reactive transport modeling: A particle-tracking solution for first-order network reactions

NASA Astrophysics Data System (ADS)

Henri, Christopher; Fernàndez-Garcia, Daniel

2015-04-01

Modeling multi-species reactive transport in natural systems with strong heterogeneities and complex biochemical reactions is a major challenge for assessing groundwater polluted sites with organic and inorganic contaminants. A large variety of these contaminants react according to serial-parallel reaction networks commonly simplified by a combination of first-order kinetic reactions. In this context, a random-walk particle tracking method is presented. This method is capable of efficiently simulating the motion of particles affected by first-order network reactions in three-dimensional systems, which are represented by spatially variable physical and biochemical coefficients described at high resolution. The approach is based on the development of transition probabilities that describe the likelihood that particles belonging to a given species and location at a given time will be transformed into and moved to another species and location afterwards. These probabilities are derived from the solution matrix of the spatial moments governing equations. The method is fully coupled with reactions, free of numerical dispersion and overcomes the inherent numerical problems stemming from the incorporation of heterogeneities to reactive transport codes. In doing this, we demonstrate that the motion of particles follows a standard random walk with time-dependent effective retardation and dispersion parameters that depend on the initial and final chemical state of the particle. The behavior of effective parameters develops as a result of differential retardation effects among species. Moreover, explicit analytic solutions of the transition probability matrix and related particle motions are provided for serial reactions. An example of the effect of heterogeneity on the dechlorination of organic solvents in a three-dimensional random porous media shows that the power-law behavior typically observed in conservative tracers breakthrough curves can be largely compromised by the

Toward efficiency in heterogeneous multispecies reactive transport modeling: A particle-tracking solution for first-order network reactions

NASA Astrophysics Data System (ADS)

Henri, Christopher V.; Fernàndez-Garcia, Daniel

2014-09-01

Modeling multispecies reactive transport in natural systems with strong heterogeneities and complex biochemical reactions is a major challenge for assessing groundwater polluted sites with organic and inorganic contaminants. A large variety of these contaminants react according to serial-parallel reaction networks commonly simplified by a combination of first-order kinetic reactions. In this context, a random-walk particle tracking method is presented. This method is capable of efficiently simulating the motion of particles affected by first-order network reactions in three-dimensional systems, which are represented by spatially variable physical and biochemical coefficients described at high resolution. The approach is based on the development of transition probabilities that describe the likelihood that particles belonging to a given species and location at a given time will be transformed into and moved to another species and location afterward. These probabilities are derived from the solution matrix of the spatial moments governing equations. The method is fully coupled with reactions, free of numerical dispersion and overcomes the inherent numerical problems stemming from the incorporation of heterogeneities to reactive transport codes. In doing this, we demonstrate that the motion of particles follows a standard random walk with time-dependent effective retardation and dispersion parameters that depend on the initial and final chemical state of the particle. The behavior of effective parameters develops as a result of differential retardation effects among species. Moreover, explicit analytic solutions of the transition probability matrix and related particle motions are provided for serial reactions. An example of the effect of heterogeneity on the dechlorination of organic solvents in a three-dimensional random porous media shows that the power-law behavior typically observed in conservative tracers breakthrough curves can be largely compromised by the

Kinetics of anaerobic degradation of screened dairy manure by upflow fixed bed digesters: effect of natural zeolite addition.

PubMed

Nikolaeva, S; Sánchez, E; Borja, R; Raposo, F; Colmenarejo, M F; Montalvo, S; Jiménez-Rodríguez, A M

2009-02-01

The effect of the hydraulic retention time (HRT) on the performance of two up-flow anaerobic fixed bed digesters (UFAFBDs) packed with waste tire rubber (D1) and waste tire rubber and zeolite (D2) as micro-organism immobilization supports was studied. It was found that a first-order kinetic model described well the experimental results obtained. The kinetic constants for COD, BOD5, total solids (TS) and volatile solids (VS) removal were determined to be higher in digester D2 than in digester D1 or control. Specifically, they were 0.28 +/- 0.01, 0.32 +/- 0.02, 0.16 +/- 0.01 and 0.24 +/- 0.01 d(- 1) respectively for D1 and 0.33 +/- 0.02, 0.40 +/- 0.02, 0.21 +/- 0.01 and 0.28 +/- 0.01 d(- 1) respectively for D2. This was significant at the 95% confidence level. In addition, the first-order model was also adequate for assessing the effect of the HRT on the removal efficiency and methane production. Maximum methane yield and the first-order constant for methane production were determined and the results obtained were comparable with those obtained by other authors but operating at higher HRTs. Maximum methane yields and the kinetic constant for methane production were 11.1% and 29.4% higher in digester D2 than in D1.

Thermoluminescence kinetic features of Lithium Iodide (LiI) single crystal grown by vertical Bridgman technique

NASA Astrophysics Data System (ADS)

Daniel, D. Joseph; Kim, H. J.; Kim, Sunghwan; Khan, Sajid

2017-08-01

Single crystal of pure Lithium Iodide (LiI) has been grown from melt by using the vertical Bridgman technique. Thermoluminescence (TL) Measurements were carried out at 1 K/s following X-ray irradiation. The TL glow curve consists of a dominant peak at (peak-maximum Tm) 393 K and one low temperature peak of weaker intensity at 343 K. The order of kinetics (b), activation energy (E), and the frequency factor (S) for a prominent TL glow peak observed around 393 K for LiI crystals are reported for the first time. The peak shape analysis of the glow peak indicates the kinetics to be of the first order. The value of E is calculated using various standard methods such as initial rise (IR), whole glow peak (WGP), peak shape (PS), computerized glow curve deconvolution (CGCD) and Variable Heating rate (VHR) methods. An average value of 1.06 eV is obtained in this case. In order to validate the obtained parameters, numerically integrated TL glow curve has been generated using experimentally determined kinetic parameters. The effective atomic number (Zeff) for this material was determined and found to be 52. X-ray induced emission spectra of pure LiI single crystal are studied at room temperature and it is found that the sample exhibit sharp emission at 457 nm and broad emission at 650 nm.

A first-order model for impact crater degradation on Venus

NASA Technical Reports Server (NTRS)

Izenberg, Noam R.; Arvidson, Raymond E.; Phillips, Roger J.

1993-01-01

A first-order impact crater aging model is presented based on observations of the global crater population of Venus. The total population consists of 879 craters found over the approximately 98 percent of the planet that has been mapped by the Magellan spacecraft during the first three cycles of its mission. The model is based upon three primary aspects of venusian impact craters: (1) extended ejecta deposits (EED's); (2) crater rims and continuous ejecta deposits; and (3) crater interiors and floors.

On entropy change measurements around first order phase transitions in caloric materials.

PubMed

Caron, Luana; Ba Doan, Nguyen; Ranno, Laurent

2017-02-22

In this work we discuss the measurement protocols for indirect determination of the isothermal entropy change associated with first order phase transitions in caloric materials. The magneto-structural phase transitions giving rise to giant magnetocaloric effects in Cu-doped MnAs and FeRh are used as case studies to exemplify how badly designed protocols may affect isothermal measurements and lead to incorrect entropy change estimations. Isothermal measurement protocols which allow correct assessment of the entropy change around first order phase transitions in both direct and inverse cases are presented.

First order coupled dynamic model of flexible space structures with time-varying configurations

NASA Astrophysics Data System (ADS)

Wang, Jie; Li, Dongxu; Jiang, Jianping

2017-03-01

This paper proposes a first order coupled dynamic modeling method for flexible space structures with time-varying configurations for the purpose of deriving the characteristics of the system. The model considers the first time derivative of the coordinate transformation matrix between the platform's body frame and the appendage's floating frame. As a result it can accurately predict characteristics of the system even if flexible appendages rotate with complex trajectory relative to the rigid part. In general, flexible appendages are fixed on the rigid platform or forced to rotate with a slow angular velocity. So only the zero order of the transformation matrix is considered in conventional models. However, due to neglecting of time-varying terms of the transformation matrix, these models introduce severe error when appendages, like antennas, for example, rotate with a fast speed relative to the platform. The first order coupled dynamic model for flexible space structures proposed in this paper resolve this problem by introducing the first time derivative of the transformation matrix. As a numerical example, a central core with a rotating solar panel is considered and the results are compared with those given by the conventional model. It has been shown that the first order terms are of great importance on the attitude of the rigid body and dynamic response of the flexible appendage.

The kinetics of the 2π+2π photodimerisation reactions of single-crystalline derivatives of trans-cinnamic acid: A study by infrared microspectroscopy

NASA Astrophysics Data System (ADS)

Jenkins, Samantha L.; Almond, Matthew J.; Atkinson, Samantha D. M.; Drew, Michael G. B.; Hollins, Peter; Mortimore, Joanne L.; Tobin, Mark J.

2006-04-01

The kinetics of the photodimerisation reactions of the 2- and 4-β-halogeno-derivatives of trans-cinnamic acid (where the halogen is fluorine, chlorine or bromine) have been investigated by infrared microspectroscopy. It is found that none of the reactions proceed to 100% yield. This is in line with a reaction mechanism developed by Wernick and his co-workers that postulates the formation of isolated monomers within the solid, which cannot react. β-4-Bromo and β-4-chloro- trans-cinnamic acids show approximately first order kinetics, although in both cases the reaction accelerates somewhat as it proceeds. First order kinetics is explained in terms of a reaction between one excited- and one ground-state monomer molecule, while the acceleration of the reaction implies that it is promoted as defects are formed within the crystal. By contrast β-2-chloro- trans-cinnamic acid shows a strongly accelerating reaction which models closely to the contracting cube equation. β-2-Fluoro- and β-4-fluoro- trans-cinnamic acids show a close match to first order kinetics. The 4-fluoro-derivative, however, shows a reaction that proceeds via a structural intermediate. The difference in behaviour between the 2-fluoro- and 4-fluoro-derivative may be due to different C-H⋯F hydrogen bonds observed within these single-crystalline starting materials.

First and second order semi-Markov chains for wind speed modeling

NASA Astrophysics Data System (ADS)

Prattico, F.; Petroni, F.; D'Amico, G.

2012-04-01

The increasing interest in renewable energy leads scientific research to find a better way to recover most of the available energy. Particularly, the maximum energy recoverable from wind is equal to 59.3% of that available (Betz law) at a specific pitch angle and when the ratio between the wind speed in output and in input is equal to 1/3. The pitch angle is the angle formed between the airfoil of the blade of the wind turbine and the wind direction. Old turbine and a lot of that actually marketed, in fact, have always the same invariant geometry of the airfoil. This causes that wind turbines will work with an efficiency that is lower than 59.3%. New generation wind turbines, instead, have a system to variate the pitch angle by rotating the blades. This system able the wind turbines to recover, at different wind speed, always the maximum energy, working in Betz limit at different speed ratios. A powerful system control of the pitch angle allows the wind turbine to recover better the energy in transient regime. A good stochastic model for wind speed is then needed to help both the optimization of turbine design and to assist the system control to predict the value of the wind speed to positioning the blades quickly and correctly. The possibility to have synthetic data of wind speed is a powerful instrument to assist designer to verify the structures of the wind turbines or to estimate the energy recoverable from a specific site. To generate synthetic data, Markov chains of first or higher order are often used [1,2,3]. In particular in [3] is presented a comparison between a first-order Markov chain and a second-order Markov chain. A similar work, but only for the first-order Markov chain, is conduced by [2], presenting the probability transition matrix and comparing the energy spectral density and autocorrelation of real and synthetic wind speed data. A tentative to modeling and to join speed and direction of wind is presented in [1], by using two models, first-order

Kinetically controlled transition from disordered aggregates to ordered lattices of a computationally designed peptide sequence.

NASA Astrophysics Data System (ADS)

Tian, Yu; Zhang, Huixi; Kiick, Kristi; Saven, Jeffrey; Pochan, Darrin

Peptides with well-defined secondary-structures have the ability to exhibit specific, local shapes, which enables the design of complex nanostructures through intermolecular assembly. Our computationally designed coiled-coil homotetrameric peptide building block can self-assemble into 2-D nanomaterial lattices with predetermined symmetries by control of the coiled-coil bundle exterior amino acid residues. And the assemblies can be controlled kinetically. Firstly, the solution pH influences the assembly by affecting the external charged state of peptide bundles which can lead the bundles to be either repulsive or attractive to each other. At room temperature when peptides are under the least charged pH conditions, disordered aggregates are formed that slowly transformed into the desired 2-D lattice structures over long periods of time (weeks). Around neutral pH, even subtle charge differences that come from small pH changes can have an influence on the thickness of afterwards formed plates. Secondly, the solution temperature can largely eliminate the formation of disordered aggregates and accelerate the assembling of matured, desired nanomaterial plates by providing extra energy for the organization process of assembly building blocks. The ability to control the assembly process kinetically makes our peptide plate assemblies very promising templates for further applications to develop inorganic-organic hybrid materials. Funding acknowledged from NSF DMREF program under awards DMR-1234161 and DMR-1235084.

Kinetics and mechanism of imazosulfuron hydrolysis.

PubMed

Morrica, P; Barbato, F; Della Iacovo, R; Seccia, S; Ungaro, F

2001-08-01

Knowledge of the kinetics and pathways of hydrolytic degradation is crucial to the prediction of the fate and transport mechanism of chemicals. This work first describes the kinetics of the chemical hydrolysis of imazosulfuron, a new sulfonylurea herbicide, and evaluates the results to propose a degradation pathway. The hydrolysis of imazosulfuron has been studied in aqueous buffers both within the pH range 1.9-12.3 at ambient temperature (thermostated at 25 +/- 2 degrees C) and at pH 3.6 within the temperature range of 15-55 degrees C. The hydrolysis rate of imazosulfuron was characterized by a first-order kinetics, pH- and temperature-dependent, and accelerated by acidic conditions and higher temperatures. The calculated half-lives at pH 4.5 and 5.9 were 36.5 and 578 days, respectively. At pH 6.6, 7.4, 9.2, and 12.3 no significant change in imazosulfuron concentration was observed after 150 days. Half-lives were much lower at pH <4 (= imazosulfuron pK(a)), at which they ranged from 3.3 to 6.3 days. Moreover, a change in temperature from 15 to 25 degrees C in acidic conditions (pH 3.6) decreased the half-life of imazosulfuron by a factor of approximately 4.0; in any case, a 3-5-fold increase in the rate of hydrolysis was found for each 10 degrees C increase in temperature. In acidic conditions the only hydrolysis products were the two molecules resulting from the cleavage of the sulfonylurea bridge.

Kinetics of silicide formation over a wide range of heating rates spanning six orders of magnitude

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molina-Ruiz, Manel; Lopeandía, Aitor F.; Gonzalez-Silveira, Marta

Kinetic processes involving intermediate phase formation are often assumed to follow an Arrhenius temperature dependence. This behavior is usually inferred from limited data over narrow temperature intervals, where the exponential dependence is generally fully satisfied. However, direct evidence over wide temperature intervals is experimentally challenging and data are scarce. Here, we report a study of silicide formation between a 12 nm film of palladium and 15 nm of amorphous silicon in a wide range of heating rates, spanning six orders of magnitude, from 0.1 to 10{sup 5 }K/s, or equivalently more than 300 K of variation in reaction temperature. The calorimetric traces exhibit severalmore » distinct exothermic events related to interdiffusion, nucleation of Pd{sub 2}Si, crystallization of amorphous silicon, and vertical growth of Pd{sub 2}Si. Interestingly, the thickness of the initial nucleation layer depends on the heating rate revealing enhanced mass diffusion at the fastest heating rates during the initial stages of the reaction. In spite of this, the formation of the silicide strictly follows an Arrhenius temperature dependence over the whole temperature interval explored. A kinetic model is used to fit the calorimetric data over the complete heating rate range. Calorimetry is complemented by structural analysis through transmission electron microscopy and both standard and in-situ synchrotron X-ray diffraction.« less

Tunneling effects in the kinetics of helium and hydrogen isotopes desorption from single-walled carbon nanotube bundles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danilchenko, B. A., E-mail: danil@iop.kiev.ua; Yaskovets, I. I.; Uvarova, I. Y.

2014-04-28

The kinetics of desorption both helium isotopes and molecules of hydrogen and deuterium from open-ended or γ-irradiated single-walled carbon nanotube bundles was investigated in temperature range of 10–300 K. The gases desorption rates obey the Arrhenius law at high temperatures, deviate from it with temperature reduction and become constant at low temperatures. These results indicate the quantum nature of gas outflow from carbon nanotube bundles. We had deduced the crossover temperature below which the quantum corrections to the effective activation energy of desorption become significant. This temperature follows linear dependence against the inverse mass of gas molecule and is consistent withmore » theoretical prediction.« less

First things first: similar list length and output order effects for verbal and nonverbal stimuli.

PubMed

Cortis, Cathleen; Dent, Kevin; Kennett, Steffan; Ward, Geoff

2015-07-01

When participants are presented with a short list of unrelated words and they are instructed that they may recall in any order, they nevertheless show a very strong tendency to recall in forward serial order. Thus, if asked to recall in any order: "hat, mouse, tea, stairs," participants often respond "hat, mouse, tea, stairs" even though there was no forward order requirement of the task. In 4 experiments, we examined whether this tendency is language-specific, reflecting mechanisms involved with speech perception, speech production, and/or verbal short-term memory. Specifically, we examined whether we would observe similar findings when participants were asked to recall, in any order, lists of between 1 and 15 nonverbal stimuli, such as visuospatial locations (Experiment 1, Experiment 3, Experiment 4), or touched facial locations (Experiment 2). Contrary to a language-specific explanation, we found corresponding tendencies (albeit somewhat reduced) in the immediate free recall of these nonverbal stimuli. We conclude that the tendency to initiate recall of a short sequence of items with the first item is a general property of memory, which may be augmented by verbal coding. (c) 2015 APA, all rights reserved.

Asymptotic integration algorithms for first-order ODEs with application to viscoplasticity

NASA Technical Reports Server (NTRS)

Freed, Alan D.; Yao, Minwu; Walker, Kevin P.

1992-01-01

When constructing an algorithm for the numerical integration of a differential equation, one must first convert the known ordinary differential equation (ODE), which is defined at a point, into an ordinary difference equation (O(delta)E), which is defined over an interval. Asymptotic, generalized, midpoint, and trapezoidal, O(delta)E algorithms are derived for a nonlinear first order ODE written in the form of a linear ODE. The asymptotic forward (typically underdamped) and backward (typically overdamped) integrators bound these midpoint and trapezoidal integrators, which tend to cancel out unwanted numerical damping by averaging, in some sense, the forward and backward integrations. Viscoplasticity presents itself as a system of nonlinear, coupled first-ordered ODE's that are mathematically stiff, and therefore, difficult to numerically integrate. They are an excellent application for the asymptotic integrators. Considering a general viscoplastic structure, it is demonstrated that one can either integrate the viscoplastic stresses or their associated eigenstrains.

Vertical flow constructed wetlands: kinetics of nutrient and organic matter removal.

PubMed

Pérez, M M; Hernández, J M; Bossens, J; Jiménez, T; Rosa, E; Tack, F

2014-01-01

The kinetics of organic matter and nutrient removal in a pilot vertical subsurface wetland with red ferralitic soil as substrate were evaluated. The wetland (20 m(2)) was planted with Cyperus alternifolius. The domestic wastewater that was treated in the wetland had undergone a primary treatment consisting of a septic moat and a buffer tank. From the sixth week of operation, the performance of the wetland stabilized, and a significant reduction in pollutant concentration of the effluent wastewater was obtained. Also a significant increase of dissolved oxygen (5 mg/l) was obtained. The organic matter removal efficiency was greater than 85% and the nutrient removal efficiency was greater than 75% in the vertical subsurface wetland. Nitrogen and biochemical oxygen demand (BOD) removal could be described by a first-order model. The kinetic constants were 3.64 and 3.27 d(-1) for BOD and for total nitrogen, respectively. Data on the removal of phosphorus were adapted to a second-order model. The kinetic constant was 0.96 (mg/l)(-1) d(-1). The results demonstrated the potential of vertical flow constructed wetlands to clean treated domestic wastewater before discharge into the environment.

Kinetics of Bacterial Growth on Chlorinated Aliphatic Compounds

PubMed Central

van den Wijngaard, Arjan J.; Wind, Richèle D.; Janssen, Dick B.

1993-01-01

With the pure bacterial cultures Ancylobacter aquaticus AD20 and AD25, Xanthobacter autotrophicus GJ10, and Pseudomonas sp. strain AD1, Monod kinetics was observed during growth in chemostat cultures on 1,2-dichloroethane (AD20, AD25, and GJ10), 2-chloroethanol (AD20 and GJ10), and 1,3-dichloro-2-propanol (AD1). Both the Michaelis-Menten constants (Km) of the first catabolic (dehalogenating) enzyme and the Monod half-saturation constants (Ks) followed the order 2-chloroethanol, 1,3-dichloro-2-propanol, epichlorohydrin, and 1,2-dichloroethane. The Ks values of strains GJ10, AD20, and AD25 for 1,2-dichloroethane were 260, 222, and 24 μM, respectively. The low Ks value of strain AD25 was correlated with a higher haloalkane dehalogenase content of this bacterium. The growth rates of strains AD20 and GJ10 in continuous cultures on 1,2-dichloroethane were higher than the rates predicted from the kinetics of the haloalkane dehalogenase and the concentration of the enzyme in the cells. The results indicate that the efficiency of chlorinated compound removal is indeed influenced by the kinetic properties and cellular content of the first catabolic enzyme. The cell envelope did not seem to act as a barrier for permeation of 1,2-dichloroethane. PMID:16348981

Online kinetic studies on intermediates of laccase-catalyzed reaction in reversed micelle.

PubMed

Liu, Zhi-Hong; Shao, Mei; Cai, Ru-Xiu; Shen, Ping

2006-02-01

Using water/AOT/n-octane reversed micelle as the medium, the optical signal of the reactive intermediate of laccase-catalyzed oxidation of o-phenylenediamine, which was indetectable in aqueous solutions, was successfully captured. Thus online kinetic studies of the intermediate were accomplished. Two-way kinetic spectral data were acquired with stopped-flow technique. By resolving the data with global analysis software, both the kinetic curves and the absorption spectra of the components involved in the reaction process were simultaneously obtained. The whole reaction in the reversed micelle was proved to be composed of two successive steps, an enzymatic generation of the intermediate and a following nonenzymatic decay of the intermediate. A consecutive first-order kinetic model of the whole reaction was confirmed. The influences of microenvironmental factors of the medium (such as the pH value of the water pool and the water/AOT ratio) on the detection of the intermediate were also investigated.

Quantitative production of compound I from a cytochrome P450 enzyme at low temperatures. Kinetics, activation parameters, and kinetic isotope effects for oxidation of benzyl alcohol.

PubMed

Wang, Qin; Sheng, Xin; Horner, John H; Newcomb, Martin

2009-08-05

Cytochrome P450 enzymes are commonly thought to oxidize substrates via an iron(IV)-oxo porphyrin radical cation transient termed Compound I, but kinetic studies of P450 Compounds I are essentially nonexistent. We report production of Compound I from cytochrome P450 119 (CYP119) in high conversion from the corresponding Compound II species at low temperatures in buffer mixtures containing 50% glycerol by photolysis with 365 nm light from a pulsed lamp. Compound I was studied as a reagent in oxidations of benzyl alcohol and its benzylic mono- and dideuterio isotopomers. Pseudo-first-order rate constants obtained at -50 degrees C with concentrations of substrates between 1.0 and 6.0 mM displayed saturation kinetics that gave binding constants for the substrate in the Compound I species (K(bind)) and first-order rate constants for the oxidation reactions (k(ox)). Representative results are K(bind) = 214 M(-1) and k(ox) = 0.48 s(-1) for oxidation of benzyl alcohol. For the dideuterated substrate C(6)H(5)CD(2)OH, kinetics were studied between -50 and -25 degrees C, and a van't Hoff plot for complexation and an Arrhenius plot for the oxidation reaction were constructed. The H/D kinetic isotope effects (KIEs) at -50 degrees C were resolved into a large primary KIE (P = 11.9) and a small, inverse secondary KIE (S = 0.96). Comparison of values extrapolated to 22 degrees C of both the rate constant for oxidation of C(6)H(5)CD(2)OH and the KIE for the nondeuterated and dideuterated substrates to values obtained previously in laser flash photolysis experiments suggested that tunneling could be a significant component of the total rate constant at -50 degrees C.

The gravitational waves from the first-order phase transition with a dimension-six operator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Rong-Gen; Wang, Shao-Jiang; Sasaki, Misao, E-mail: cairg@itp.ac.cn, E-mail: misao@yukawa.kyoto-u.ac.jp, E-mail: schwang@itp.ac.cn

We investigate in details the gravitational wave (GW) from the first-order phase transition (PT) in the extended standard model of particle physics with a dimension-six operator, which is capable of exhibiting the recently discovered slow first-order PT in addition to the usually studied fast first-order PT. To simplify the discussion, it is sufficient to work with an example of a toy model with the sextic term, and we propose an unified description for both slow and fast first-order PTs. We next study the full one-loop effective potential of the model with fixed/running renormalization-group (RG) scales. Compared to the prediction ofmore » GW energy density spectrum from the fixed RG scale, we find that the presence of running RG scale could amplify the peak amplitude by amount of one order of magnitude while shift the peak frequency to the lower frequency regime, and the promising regime of detection within the sensitivity ranges of various space-based GW detectors shrinks down to a lower cut-off value of the sextic term rather than the previous expectation.« less

Exploring the interaction of silver nanoparticles with pepsin and its adsorption isotherms and kinetics.

PubMed

Li, Xiangrong; Wang, Kaiwei; Peng, Yanru

2018-04-25

The interaction of nanoparticles (NPs) with proteins is a topic of high relevance for the medical application of nanomaterials. In the study, a comprehensive investigation was performed for the binding properties of silver nanoparticles (AgNPs) to pepsin. The results indicate that the binding of AgNPs to pepsin may be a static quenching mechanism. Thermodynamic analysis reveals that AgNPs binds to pepsin is synergistically driven by enthalpy and entropy, and the major driving forces are hydrophobic and electrostatic interactions. Synchronous fluorescence spectroscopy shows that AgNPs may induce microenvironmental changes of pepsin. The hydrophobicity of Trp is increased while the hydrophility of Tyr is increased. The adsorption of pepsin on AgNPs was analyzed by Langmuir and Freundlich models, suggesting that the equilibrium adsorption data fit well with Freundlich model. The equilibrium adsorption data were modeled using the pseudo-first-order and pseudo-second-order kinetic equations. The results indicate that pseudo-second-order kinetic equation better describes the adsorption kinetics. The study provides an accurate and full basic data for clarifying the binding mechanism, adsorption isotherms and kinetic behaviors of AgNPs with pepsin. These fundamental works will provide some new insights into the safe and effective application of AgNPs in biological and medical areas. Copyright © 2018 Elsevier B.V. All rights reserved.

Effects of specific surface area of metallic nickel particles on carbon deposition kinetics

NASA Astrophysics Data System (ADS)

Chen, Zhi-yuan; Bian, Liu-zhen; Yu, Zi-you; Wang, Li-jun; Li, Fu-shen; Chou, Kuo-Chih

2018-02-01

Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and ordered carbon structures at high deposition temperatures. The values of I(D)/ I(G) of the deposited carbon reached 1.86, 1.30, and 1.22 in the first, second, and third stages, respectively. The structure of carbon in the second stage was similar to that in the third stage. Carbon deposited in the first stage rarely contained homogeneous pyrolytic deposit layers. A kinetic model was developed to analyze the carbon deposition behavior in the first stage. The rate-determining step of the first stage is supposed to be interfacial reaction. Based on the investigation of carbon deposition kinetics on nickel powders from different resources, carbon deposition rate is suggested to have a linear relation with the square of specific surface area of nickel particles.

Oxidation of isoniazid by quinolinium dichromate in an aqueous acid medium and kinetic determination of isoniazid in pure and pharmaceutical formulations.

PubMed

Kulkarni, Raviraj M; Bilehal, Dinesh C; Nandibewoor, Sharanappa T

2004-04-01

The kinetics of oxidation of isoniazid in acidic medium was studied spectrophotometrically. The reaction between QDC and isoniazid in acid medium exhibits (4:1) stoichiometry (QDC:isoniazid). The reaction showed first order kinetics in quinolinium dichromate (QDC) concentration and an order of less than unity in isoniazid (INH) and acid concentrations. The oxidation reaction proceeds via a protonated QDC species, which forms a complex with isoniazid. The latter decomposes in a slow step to give a free radical derived from isoniazid and an intermediate chromium(V), which is followed, by subsequent fast steps to give the products. The reaction constants involved in the mechanism are evaluated. Isoniazid was analyzed by kinetic methods in pure and pharmaceutical formulations.

Neutron diffraction study of the formation kinetics of ordered antiphase domains in titanium carbohydride TiC{sub x}H{sub y}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khidirov, I., E-mail: khidirov@inp.uz

2015-09-15

The kinetics of formation and growth of ordered antiphase domains (APDs) in titanium carbohydride TiC{sub 0.50}H{sub 0.21} has been investigated by neutron diffraction. A model of ordered APDs is proposed. It is established that the pronounced ordering of interstitial atoms and APDs begin at 450°C. It is shown that the period of ordered APDs (P ≈ 10–12) is independent of the exposure time at a constant temperature. It is found that the temperature of ordered APDs, T{sub OAPD}, increases nonlinearly with an increase in the carbon concentration in the range 0.50 ≤ C/Ti ≤ 0.70. The formation temperature of orderedmore » APDs is found to correlate with the concentration dependence of the order–disorder transition temperature and be 0.60 of the order–disorder transition temperature: T{sub APD} = 0.60Τ{sub C}.« less

Impacts of amount of impregnated iron in granular activated carbon on arsenate adsorption capacities and kinetics.

PubMed

Chang, Qigang; Lin, Wei; Ying, Wei-Chi

2012-06-01

Iron-impregnated granular activated carbons (Fe-GAC) can remove arsenic effectively from water. In this study, Fe-GACs with iron content of 1.64 to 28.90% were synthesized using a new multi-step procedure for the investigation of effects of iron amount on arsenic adsorption capacities and kinetics. Langmuir model satisfactorily fit arsenic adsorption on Fe-GACs. The maximum arsenic adsorption capacity (q(m)) increased significantly with iron impregnation and reached 1,867 to 1,912 microg/g with iron content of 9.96 to 13.59%. Further increase of iron content (> 13.59%) caused gradual decrease of q(m). It was found that the amount of impregnated iron showed little impact on the affinity for arsenate. Kinetic study showed that the amount of impregnated iron affected the arsenic intraparticle diffusion rate greatly. The pseudo-second-order kinetic model fit arsenic adsorption kinetics on Fe-GACs better than the pseudo-first-order model. The arsenic adsorption rate increased with increasing of iron content from 1.64% to 13.59%, and then decreased with more impregnated iron (13.59 to 28.90%).

Removal of Congo Red from Aqueous Solution by Anion Exchange Membrane (EBTAC): Adsorption Kinetics and Themodynamics.

PubMed

Khan, Muhammad Imran; Akhtar, Shahbaz; Zafar, Shagufta; Shaheen, Aqeela; Khan, Muhammad Ali; Luque, Rafael; Rehman, Aziz Ur

2015-07-08

The adsorption behavior of anionic dye congo red (CR) from aqueous solutions using an anion exchange membrane (EBTAC) has been investigated at room temperature. The effect of several factors including contact time, membrane dosage, ionic strength and temperature were studied. Kinetic models, namely pseudo-first-order and pseudo-second-order, liquid film diffusion and Elovich models as well as Bangham and modified freundlich Equations, were employed to evaluate the experimental results. Parameters such as adsorption capacities, rate constant and related correlation coefficients for every model were calculated and discussed. The adsorption of CR on anion exchange membranes followed pseudo-second-order Kinetics. Thermodynamic parameters, namely changes in Gibbs free energy ( ∆G° ), enthalpy ( ∆H° ) and entropy ( ∆S° ) were calculated for the adsorption of congo red, indicating an exothermic process.

Removal of Congo Red from Aqueous Solution by Anion Exchange Membrane (EBTAC): Adsorption Kinetics and Themodynamics

PubMed Central

Khan, Muhammad Imran; Akhtar, Shahbaz; Zafar, Shagufta; Shaheen, Aqeela; Khan, Muhammad Ali; Luque, Rafael; ur Rehman, Aziz

2015-01-01

The adsorption behavior of anionic dye congo red (CR) from aqueous solutions using an anion exchange membrane (EBTAC) has been investigated at room temperature. The effect of several factors including contact time, membrane dosage, ionic strength and temperature were studied. Kinetic models, namely pseudo-first-order and pseudo-second-order, liquid film diffusion and Elovich models as well as Bangham and modified freundlich Equations, were employed to evaluate the experimental results. Parameters such as adsorption capacities, rate constant and related correlation coefficients for every model were calculated and discussed. The adsorption of CR on anion exchange membranes followed pseudo-second-order Kinetics. Thermodynamic parameters, namely changes in Gibbs free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) were calculated for the adsorption of congo red, indicating an exothermic process. PMID:28793430

Theoretical evidence for a first-order liquid-liquid phase transition in gallium.

PubMed

Carvajal Jara, Diego Alejandro; Fontana Michelon, Mateus; Antonelli, Alex; de Koning, Maurice

2009-06-14

We report on theoretical results that lend support to recent experimental observations suggesting the existence of a first-order liquid-liquid phase transformation (LLPT) in gallium. Using molecular dynamics simulation based on a modified embedded-atom model, we observe a transition from a high-density to a low-density liquid in the supercooled regime. The first-order character of the transition is established through the detection of the release of latent heat and our findings suggest that the LLPT terminates in a critical point that is located in the tensile-strained domain of the metastable phase diagram.

Cross-Course Collaboration in the Undergraduate Chemistry Curriculum: Primary Kinetic Isotope Effect in the Hypochlorite Oxidation of 1-Phenylethanol in the Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Noll, Robert J.; Fitch, Richard W.; Kjonaas, Richard A.; Wyatt, Richard A.

2017-01-01

A kinetic isotope effect (KIE) experiment is described for the physical chemistry laboratory. Students conduct a hypochlorite (household bleach) oxidation of an equimolar mixture of 1-phenylethanol and 1-deuterio-1-phenylethanol to acetophenone. The reaction occurs in a biphasic reaction mixture and follows first-order kinetics with respect to…

Promoting Graphical Thinking: Using Temperature and a Graphing Calculator to Teach Kinetics Concepts

ERIC Educational Resources Information Center

Cortes-Figueroa, Jose E.; Moore-Russo, Deborah A.

2004-01-01

A combination of graphical thinking with chemical and physical theories in the classroom is encouraged by using the Calculator-Based Laboratory System (CBL) with a temperature sensor and graphing calculator. The theory of first-order kinetics is logically explained with the aid of the cooling or heating of the metal bead of the CBL's temperature…

Estimation of periodic solutions number of first-order differential equations

NASA Astrophysics Data System (ADS)

Ivanov, Gennady; Alferov, Gennady; Gorovenko, Polina; Sharlay, Artem

2018-05-01

The paper deals with first-order differential equations under the assumption that the right-hand side is a periodic function of time and continuous in the set of arguments. Pliss V.A. obtained the first results for a particular class of equations and showed that a number of theorems can not be continued. In this paper, it was possible to reduce the restrictions on the degree of smoothness of the right-hand side of the equation and obtain upper and lower bounds on the number of possible periodic solutions.

The kinetics and mechanism of the ferrate(VI) oxidation of hydroxylamines.

PubMed

Johnson, Michael D; Hornstein, Brooks J

2003-10-20

Aqueous solutions of potassium ferrate(VI) cleanly and rapidly oxidize hydroxylamine to nitrous oxide, N-methylhydroxylamine to nitrosomethane, N-phenylhydroxylamine to nitrosobenzene, and O-methylhydroxylamine to methanol and nitrogen. The kinetics show first-order behavior with respect to each reactant and a two term component representing acid dependent and independent pathways. A general mechanism involving intermediate formation coupled with a two-electron oxidation is proposed.

Einstein’s quadrupole formula from the kinetic-conformal Hořava theory

NASA Astrophysics Data System (ADS)

Bellorín, Jorge; Restuccia, Alvaro

We analyze the radiative and nonradiative linearized variables in a gravity theory within the family of the nonprojectable Hořava theories, the Hořava theory at the kinetic-conformal point. There is no extra mode in this formulation, the theory shares the same number of degrees of freedom with general relativity. The large-distance effective action, which is the one we consider, can be given in a generally-covariant form under asymptotically flat boundary conditions, the Einstein-aether theory under the condition of hypersurface orthogonality on the aether vector. In the linearized theory, we find that only the transverse-traceless tensorial modes obey a sourced wave equation, as in general relativity. The rest of variables are nonradiative. The result is gauge-independent at the level of the linearized theory. For the case of a weak source, we find that the leading mode in the far zone is exactly Einstein’s quadrupole formula of general relativity, if some coupling constants are properly identified. There are no monopoles nor dipoles in this formulation, in distinction to the nonprojectable Horava theory outside the kinetic-conformal point. We also discuss some constraints on the theory arising from the observational bounds on Lorentz-violating theories.

First-Order Hyperbolic System Method for Time-Dependent Advection-Diffusion Problems

NASA Technical Reports Server (NTRS)

Mazaheri, Alireza; Nishikawa, Hiroaki

2014-01-01

A time-dependent extension of the first-order hyperbolic system method for advection-diffusion problems is introduced. Diffusive/viscous terms are written and discretized as a hyperbolic system, which recovers the original equation in the steady state. The resulting scheme offers advantages over traditional schemes: a dramatic simplification in the discretization, high-order accuracy in the solution gradients, and orders-of-magnitude convergence acceleration. The hyperbolic advection-diffusion system is discretized by the second-order upwind residual-distribution scheme in a unified manner, and the system of implicit-residual-equations is solved by Newton's method over every physical time step. The numerical results are presented for linear and nonlinear advection-diffusion problems, demonstrating solutions and gradients produced to the same order of accuracy, with rapid convergence over each physical time step, typically less than five Newton iterations.

First-order discrete Faddeev gravity at strongly varying fields

NASA Astrophysics Data System (ADS)

Khatsymovsky, V. M.

2017-11-01

We consider the Faddeev formulation of general relativity (GR), which can be characterized by a kind of d-dimensional tetrad (typically d = 10) and a non-Riemannian connection. This theory is invariant w.r.t. the global, but not local, rotations in the d-dimensional space. There can be configurations with a smooth or flat metric, but with the tetrad that changes abruptly at small distances, a kind of “antiferromagnetic” structure. Previously, we discussed a first-order representation for the Faddeev gravity, which uses the orthogonal connection in the d-dimensional space as an independent variable. Using the discrete form of this formulation, we considered the spectrum of (elementary) area. This spectrum turns out to be physically reasonable just on a classical background with large connection like rotations by π, that is, with such an “antiferromagnetic” structure. In the discrete first-order Faddeev gravity, we consider such a structure with periodic cells and large connection and strongly changing tetrad field inside the cell. We show that this system in the continuum limit reduces to a generalization of the Faddeev system. The action is a sum of related actions of the Faddeev type and is still reduced to the GR action.

Invariant Functions, Symmetries and Primary Branch Solutions of First Order Autonomous Systems

NASA Astrophysics Data System (ADS)

Lou, Sen-Yue; Yao, Ruo-Xia

2017-07-01

An invariant function (IF) is defined as a multiplier of a symmetry that means a symmetry multiplied by an IF is still a symmetry. Primary branch solutions of arbitrary first order scalar systems can be obtained by means of the IF and its related symmetry approach. Especially, one recursion operator and some sets of infinitely many high order symmetries are also explicitly given for arbitrary (1+1)-dimensional first order autonomous systems. Because of the intrusion of the arbitrary function, various implicit special exact solutions can be found by fixing the arbitrary functions and selecting different seed solutions. Supported by the National Natural Science Foundations of China under Grant Nos. 11435005, 11471004, 11175092, and 11205092, Shanghai Knowledge Service Platform for Trustworthy Internet of Things No. ZF1213 and K. C. Wong Magna Fund in Ningbo University

Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

PubMed

Li, Kai; Zhang, Peng; Ge, Linke; Ren, Honglei; Yu, Chunyan; Chen, Xiaoyang; Zhao, Yuanfeng

2014-09-01

Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

First-order intervalley scattering in low-dimensional systems

NASA Astrophysics Data System (ADS)

Monsef, Florian; Dollfus, Philippe; Galdin, Sylvie; Bournel, Arnaud

2002-06-01

The intervalley phonon scattering rate in one- and two-dimensional electron gases is calculated for the case in which the transition matrix element is of first order in the phonon wave vector. This type of interaction is important in silicon at low temperature. The interaction between electrons and bulk phonons is considered in the standard golden rule approach by including the contribution of the components of phonon wave vector in the confinement direction(s). This process makes possible the transition between different subbands, and the resulting total scattering rate differs significantly from the rate commonly used in Si quantum wells.

Liquid-phase separation of reactive dye by wood-rotting fungus: a biotechnological approach.

PubMed

Binupriya, Arthur R; Sathishkumar, Muthuswamy; Dhamodaran, Kavitha; Jayabalan, Rasu; Swaminathan, Krishnaswamy; Yun, Sei Eok

2007-08-01

The live and pretreated mycelial pellets/biomass of Trametes versicolor was used for the biosorption of a textile dye, reactive blue MR (RBMR) from aqueous solution. The parameters that affect the biosorption of RBMR, such as contact time, concentration of dye and pH, on the extent of RBMR adsorption were investigated. To develop an effective and accurate design model for removal of dye, adsorption kinetics and equilibrium data are essential basic requirements. Lagergren first-order, second-order and Bangham's model were used to fit the experimental data. Results of the kinetic studies showed that the second order kinetic model fitted well for the present experimental data. The Langmuir, Freundlich and Temkin adsorption models were used for the mathematical description of the biosorption equilibrium. The biosorption equilibrium data obeyed well for Langmuir isotherm and the maximum adsorption capacities were found to be 49.8, 51.6, 47.4 and 46.7 mg/g for live, autoclaved, acid- and alkali-pretreated biomass. The dye uptake capacity order of the fungal biomass was found as autoclaved > live > acid-treated > alkali-pretreated. The Freundlich and Temkin models were also able to describe the biosorption equilibrium on RBMR on live and pretreated fungal biomass. Acidic pH was favorable for the adsorption of dye. Studies on pH effect and desorption show that chemisorption seems to play a major role in the adsorption process. On comparison with fixed bed adsorption, batch mode adsorption was more efficient in adsorption of RBMR.

FIRST ORDER KINETIC GAS GENERATION MODEL PARAMETERS FOR WET LANDFILLS

EPA Science Inventory

Landfill gas is produced as a result of a sequence of physical, chemical, and biological processes occurring within an anaerobic landfill. Landfill operators, energy recovery project owners, regulators, and energy users need to be able to project the volume of gas produced and re...

An electronically tunable, first-order Fabry-Perot infrared filter

NASA Astrophysics Data System (ADS)

Knudtson, J. T.; Levy, D. S.; Herr, K. C.

1995-04-01

A tunable infrared filter capable of scanning from 8.2 to 12.8 micrometers has been designed, constructed and tested. It is a first order Fabry Perot interferometer with piezoelectrically driven cavity spacing. Multilayer dielectric coatings for the partially transmitting mirrors were designed to minimize the wavelength dependent phase change produced by reflection. The transmission bandwidth ranged from 2.8 to 4.0% across the tuning range. Continuous scanning at 20 Hz rates was demonstrated.

Kinetic Damage from Meteorites

NASA Technical Reports Server (NTRS)

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 Damage from Meteorites

NASA Technical Reports Server (NTRS)

Cooke, W.; Matney, M.; Brown, P.

2017-01-01

Comparing the natural meteorite flux at the Earth's surface to that of space debris, reentering debris is approx. 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.

Independence of First- and Second-Order Memories in Newborn Rabbits

ERIC Educational Resources Information Center

Coureaud, Gerard; Languille, Solene; Joly, Virginie; Schaal, Benoist; Hars, Bernard

2011-01-01

The mammary pheromone promotes the acquisition of novel odorants (CS1) in newborn rabbits. Here, experiments pinpoint that CS1 becomes able to support neonatal learning of other odorants (CS2). We therefore evaluated whether these first- and second-order memories remained dependent after reactivation. Amnesia induced after CS2 recall selectively…

The puzzling first-order phase transition in water–glycerol mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Popov, Ivan; Greenbaum; Sokolov, Alexei P.

2015-06-05

Over the last decade, discussions on a possible liquid-liquid transition (LLT) have strongly intensified. The LLT proposed by several authors focused mostly on explaining the anomalous properties of water in a deeply supercooled state. However, there have been no direct experimental observations yet of LLT in bulk water in the so-called 'no man's land', where water exists only in the crystalline states. Recently, a novel experimental strategy to detect LLT in water has been employed using water-glycerol (W-G) mixtures, because glycerol can generate a strong hindrance for water crystallization. As a result, the observed first-order phase transition at a concentrationmore » of glycerol around c(g) approximate to 20 mol% was ascribed to the LLT. Here we show unambiguously that the first order phase transition in W-G mixtures is caused by the ice formation. We provide additional dielectric measurements, applying specific annealing temperature protocols in order to reinforce this conclusion. We also provide an explanation, why such a phase transition occurs only in the narrow glycerol concentration range. These results clearly demonstrate the danger of analysis of phase-separating liquids to gain better insights into water dynamics. These liquids have complex phase behavior that is affected by temperature, phase stability and segregation, viscosity and nucleation, and finally by crystallization, that might lead to significant misinterpretations.« less

The Universal Statistical Distributions of the Affinity, Equilibrium Constants, Kinetics and Specificity in Biomolecular Recognition

PubMed Central

Zheng, Xiliang; Wang, Jin

2015-01-01

We uncovered the universal statistical laws for the biomolecular recognition/binding process. We quantified the statistical energy landscapes for binding, from which we can characterize the distributions of the binding free energy (affinity), the equilibrium constants, the kinetics and the specificity by exploring the different ligands binding with a particular receptor. The results of the analytical studies are confirmed by the microscopic flexible docking simulations. The distribution of binding affinity is Gaussian around the mean and becomes exponential near the tail. The equilibrium constants of the binding follow a log-normal distribution around the mean and a power law distribution in the tail. The intrinsic specificity for biomolecular recognition measures the degree of discrimination of native versus non-native binding and the optimization of which becomes the maximization of the ratio of the free energy gap between the native state and the average of non-native states versus the roughness measured by the variance of the free energy landscape around its mean. The intrinsic specificity obeys a Gaussian distribution near the mean and an exponential distribution near the tail. Furthermore, the kinetics of binding follows a log-normal distribution near the mean and a power law distribution at the tail. Our study provides new insights into the statistical nature of thermodynamics, kinetics and function from different ligands binding with a specific receptor or equivalently specific ligand binding with different receptors. The elucidation of distributions of the kinetics and free energy has guiding roles in studying biomolecular recognition and function through small-molecule evolution and chemical genetics. PMID:25885453

Assessment of First- and Second-Order Wave-Excitation Load Models for Cylindrical Substructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pereyra, Brandon; Wendt, Fabian; Robertson, Amy

2016-07-01

The hydrodynamic loads on an offshore wind turbine's support structure present unique engineering challenges for offshore wind. Two typical approaches used for modeling these hydrodynamic loads are potential flow (PF) and strip theory (ST), the latter via Morison's equation. This study examines the first- and second-order wave-excitation surge forces on a fixed cylinder in regular waves computed by the PF and ST approaches to (1) verify their numerical implementations in HydroDyn and (2) understand when the ST approach breaks down. The numerical implementation of PF and ST in HydroDyn, a hydrodynamic time-domain solver implemented as a module in the FASTmore » wind turbine engineering tool, was verified by showing the consistency in the first- and second-order force output between the two methods across a range of wave frequencies. ST is known to be invalid at high frequencies, and this study investigates where the ST solution diverges from the PF solution. Regular waves across a range of frequencies were run in HydroDyn for a monopile substructure. As expected, the solutions for the first-order (linear) wave-excitation loads resulting from these regular waves are similar for PF and ST when the diameter of the cylinder is small compared to the length of the waves (generally when the diameter-to-wavelength ratio is less than 0.2). The same finding applies to the solutions for second-order wave-excitation loads, but for much smaller diameter-to-wavelength ratios (based on wavelengths of first-order waves).« less

Inflation Rates, Car Devaluation, and Chemical Kinetics.

ERIC Educational Resources Information Center

Pogliani, Lionello; Berberan-Santos, Mario N.

1996-01-01

Describes the inflation rate problem and offers an interesting analogy with chemical kinetics. Presents and solves the car devaluation problem as a normal chemical kinetic problem where the order of the rate law and the value of the rate constant are derived. (JRH)

Enzymatic synthesis of farnesyl laurate in organic solvent: initial water activity, kinetics mechanism, optimization of continuous operation using packed bed reactor and mass transfer studies.

PubMed

Rahman, N K; Kamaruddin, A H; Uzir, M H

2011-08-01

The influence of water activity and water content was investigated with farnesyl laurate synthesis catalyzed by Lipozyme RM IM. Lipozyme RM IM activity depended strongly on initial water activity value. The best results were achieved for a reaction medium with an initial water activity of 0.11 since it gives the best conversion value of 96.80%. The rate constants obtained in the kinetics study using Ping-Pong-Bi-Bi and Ordered-Bi-Bi mechanisms with dead-end complex inhibition of lauric acid were compared. The corresponding parameters were found to obey the Ordered-Bi-Bi mechanism with dead-end complex inhibition of lauric acid. Kinetic parameters were calculated based on this model as follows: V (max) = 5.80 mmol l(-1) min(-1) g enzyme(-1), K (m,A) = 0.70 mmol l(-1) g enzyme(-1), K (m,B) = 115.48 mmol l(-1) g enzyme(-1), K (i) = 11.25 mmol l(-1) g enzyme(-1). The optimum conditions for the esterification of farnesol with lauric acid in a continuous packed bed reactor were found as the following: 18.18 cm packed bed height and 0.9 ml/min substrate flow rate. The optimum molar conversion of lauric acid to farnesyl laurate was 98.07 ± 0.82%. The effect of mass transfer in the packed bed reactor has also been studied using two models for cases of reaction limited and mass transfer limited. A very good agreement between the mass transfer limited model and the experimental data obtained indicating that the esterification in a packed bed reactor was mass transfer limited.

Experimental and theoretical investigation of the first-order hyperpolarizability of a class of triarylamine derivatives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silva, Daniel L., E-mail: dlsilva.physics@gmail.com, E-mail: deboni@ifsc.usp.br; Instituto de Física, Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP; Fonseca, Ruben D.

2015-02-14

This paper reports on the static and dynamic first-order hyperpolarizabilities of a class of push-pull octupolar triarylamine derivatives dissolved in toluene. We have combined hyper-Rayleigh scattering experiment and the coupled perturbed Hartree-Fock method implemented at the Density Functional Theory (DFT) level of theory to determine the static and dynamic (at 1064 nm) first-order hyperpolarizability (β{sub HRS}) of nine triarylamine derivatives with distinct electron-withdrawing groups. In four of these derivatives, an azoaromatic unit is inserted and a pronounceable increase of the first-order hyperpolarizability is reported. Based on the theoretical results, the dipolar/octupolar character of the derivatives is determined. By using amore » polarizable continuum model in combination with the DFT calculations, it was found that although solvated in an aprotic and low dielectric constant solvent, due to solvent-induced polarization and the frequency dispersion effect, the environment substantially affects the first-order hyperpolarizability of all derivatives investigated. This statement is supported due to the solvent effects to be essential for the better agreement between theoretical results and experimental data concerning the dynamic first-order hyperpolarizability of the derivatives. The first-order hyperpolarizability of the derivatives was also modeled using the two- and three-level models, where the relationship between static and dynamic first hyperpolarizabilities is given by a frequency dispersion model. Using this approach, it was verified that the dynamic first hyperpolarizability of the derivatives is satisfactorily reproduced by the two-level model and that, in the case of the derivatives with an azoaromatic unit, the use of a damped few-level model is essential for, considering also the molecular size of such derivatives, a good quantitative agreement between theoretical results and experimental data to be observed.« less

Antiferromagnetic order and the structural order-disorder transition in the Cd6Ho quasicrystal approximant

NASA Astrophysics Data System (ADS)

Kreyssig, Andreas; Beutier, Guillaume; Hiroto, Takanobu; Kim, Min Gyu; Tucker, Gregory S.; de Boissieu, Marc; Tamura, Ryuji; Goldman, Alan I.

2013-09-01

It has generally been accepted that the orientational ordering of the Cd4 tetrahedron within the Cd6 R quasicrystal approximants is kinetically inhibited for R = Ho, Er, Tm and Lu by steric constraints. Our high-resolution X-ray scattering measurements of the Cd6Ho quasicrystal approximant, however, reveal an abrupt (first-order) transition to a monoclinic structure below T S = 178 K for samples that have 'aged' at room temperature for approximately one year, reopening this question. Using X-ray resonant magnetic scattering at the Ho L 3-edge we have elucidated the nature of the antiferromagnetic ordering below T N = 8.5 K in Cd6Ho. The magnetic Bragg peaks are found at the charge forbidden H + K + L = 2n + 1 positions, referenced to the high-temperature body-centred cubic structure. In general terms, this corresponds to antiferromagnetic arrangements of the Ho moments on adjacent clusters in the unit cell as previously found for Cd6Tb.

Pyrolysis and kinetic analyses of Camel grass (Cymbopogon schoenanthus) for bioenergy.

PubMed

Mehmood, Muhammad Aamer; Ye, Guangbin; Luo, Huibo; Liu, Chenguang; Malik, Sana; Afzal, Ifrah; Xu, Jianren; Ahmad, Muhammad Sajjad

2017-03-01

The aim of this work was to study the thermal degradation of grass (Cymbopogon schoenanthus) under an inert environment at three heating rates, including 10, 30, and 50°Cmin -1 in order to evaluate its bioenergy potential. Pyrolysis experiments were performed in a simultaneous Thermogravimetry-Differential Scanning Calorimetry analyzer. Thermal data were used to analyze kinetic parameters through isoconversional models of Flynn-Wall-Ozawa (FWO) and Kissenger-Akahira-Sunose (KSA) methods. The pre-exponential factors values have shown the reaction to follow first order kinetics. Activation energy values were shown to be 84-193 and 96-192kJmol -1 as calculated by KSA and FWO methods, respectively. Differences between activation energy and enthalpy of reaction values (∼5 to 6kJmol -1 ) showed product formation is favorable. The Gibb's free energy (173-177kJmol -1 ) and High Heating Value (15.00MJkg -1 ) have shown the considerable bioenergy potential of this low-cost biomass. Copyright © 2016 Elsevier Ltd. All rights reserved.

NIMROD modeling of poloidal flow damping in tokamaks using kinetic closures

NASA Astrophysics Data System (ADS)

Jepson, J. R.; Hegna, C. C.; Held, E. D.

2017-10-01

Calculations of poloidal flow damping in a tokamak are undertaken using two different implementations of the ion drift kinetic equation (DKE) in the extended MHD code NIMROD. The first approach is hybrid fluid/kinetic and uses a Chapman Enskog-like (CEL) Ansatz. Closure of the evolving lower-order fluid moment equations for n, V , and T is provided by solutions to the ion CEL-DKE written in the macroscopic flow reference frame. The second implementation solves the DKE using a delta-f approach. Here, the delta-f distribution describes all of the information beyond a static, lowest-order Maxwellian. We compare the efficiency and accuracy of these two approaches for a simple initial value problem that monitors the relaxation of the poloidal flow profile in high- and low-aspect-ratio tokamak geometry. The computation results are compared against analytic predictions of time dependent closures for the parallel viscous force. Supported by DoE Grants DE-FG02-86ER53218 and DE-FG02-04ER54746.

[Kinetics of alkylphenols degradation in aqueous phase with excilamp irradiation].

PubMed

Liu, Yu-Hai; Ye, Zhao-Lian; Wen, Ying-Pin; Bi, Cheng-Lu

2014-06-01

The 206 nm irradiation from excilamp was able to directly photo-degrade 4-nonylphenol (4-NP) and 4-octylphenol (4-OP), but it could not oxidize them completely into CO2. Under the same irradiation condition, the removal efficiency of 4-OP was higher than that of 4-NP. Pseudo-first order kinetic model and modified kinetic model were used to fit the kinetics of photo-degradation process, and the direct photolysis rate constants under 206 nm UV irradiation were obtained. The experimental results demonstrated that the photolysis rate constant was higher at lower initial concentration of alkylphenols. Two kinetic models were appropriate for the direct photolysis of alkylphenols at low concentration, but the modified model did not fit for high concentrations. Degradation rate can be obviously enhanced when adding H2O2 into the reaction, but the TOC removal was distinct only when the dosage of H2O2 was high. At last, we concluded that the direct photolysis rate constant k(d) was 0.032 8 min(-1) and the reaction rate constant k(pH) between 4-OP and H2O2 was 17.4520 L x (mol x min)(-1).

Effects of thermal treatment on high solid anaerobic digestion of swine manure: Enhancement assessment and kinetic analysis.

PubMed

Wu, Jing; Hu, Yu-Ying; Wang, Shi-Feng; Cao, Zhi-Ping; Li, Huai-Zhi; Fu, Xin-Mei; Wang, Kai-Jun; Zuo, Jian-E

2017-04-01

Anaerobic digestion (AD), which is a process for generating biogas, can be applied to the treatment of organic wastes. Owing to its smaller footprint, lower energy consumption, and less digestate, high solid anaerobic digestion (HSAD) has attracted increasing attention. However, its biogas production is poor. In order to improve biogas production and decrease energy consumption, an improved thermal treatment process was proposed. Raw swine manure (>20% solid content) without any dilution was thermally treated at 70±1°C for different retention times, and then its effect on HSAD was investigated via batch AD experiments at 8.9% solid content. Results showed that the main organic components of swine manure hydrolyzed significantly during the thermal treatment, and HSAD's methane production rate was improved by up to 39.5%. Analysis using two kinetic models confirmed that the treatment could increase biodegradable organics (especially the readily biodegradable organics) in swine manure rather than upgrading its hydrolysis rate. It is worth noting that the superimposed first-order kinetics model was firstly applied in AD, and was a good tool to reveal the AD kinetics mechanism of substrates with complex components. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic Study on the Esterification of Palm Fatty Acid Distillate (PFAD) Using Heterogeneous Catalyst

NASA Astrophysics Data System (ADS)

Rofiqah, U.; Djalal, R. A.; Sutrisno, B.; Hidayat, A.

2018-05-01

Esterification with heterogeneous catalysts is believed to have advantages compared to homogeneous catalysts. Palm Fatty Acid Distillate (PFAD) was esterified by ZrO2 -SO4 2-/natural zeolite at temperature variation of 55°C, 60°C, and 65°C to produce biodiesel. Determination of reaction kinetics was done by experiment and modeling. Kinetic study was approached using pseudo-homogeneous model of first order. For experiment, reaction kinetics were 0.0031 s-1, 0.0054 s-1, and 0.00937 s-1 for a temperature of 55 °C, 60 °C and 65 °C, respectively. For modelling, reaction kinetics were 0.0030 s-1, 0.0055 s-1, and 0.0090 s-1 for a temperature of 55°C, 60°C and 65°C, respectively. Rate and conversion of reaction are getting increased by increasing temperature.

High order ADER schemes for a unified first order hyperbolic formulation of Newtonian continuum mechanics coupled with electro-dynamics

NASA Astrophysics Data System (ADS)

Dumbser, Michael; Peshkov, Ilya; Romenski, Evgeniy; Zanotti, Olindo

2017-11-01

In this paper, we propose a new unified first order hyperbolic model of Newtonian continuum mechanics coupled with electro-dynamics. The model is able to describe the behavior of moving elasto-plastic dielectric solids as well as viscous and inviscid fluids in the presence of electro-magnetic fields. It is actually a very peculiar feature of the proposed PDE system that viscous fluids are treated just as a special case of elasto-plastic solids. This is achieved by introducing a strain relaxation mechanism in the evolution equations of the distortion matrix A, which in the case of purely elastic solids maps the current configuration to the reference configuration. The model also contains a hyperbolic formulation of heat conduction as well as a dissipative source term in the evolution equations for the electric field given by Ohm's law. Via formal asymptotic analysis we show that in the stiff limit, the governing first order hyperbolic PDE system with relaxation source terms tends asymptotically to the well-known viscous and resistive magnetohydrodynamics (MHD) equations. Furthermore, a rigorous derivation of the model from variational principles is presented, together with the transformation of the Euler-Lagrange differential equations associated with the underlying variational problem from Lagrangian coordinates to Eulerian coordinates in a fixed laboratory frame. The present paper hence extends the unified first order hyperbolic model of Newtonian continuum mechanics recently proposed in [110,42] to the more general case where the continuum is coupled with electro-magnetic fields. The governing PDE system is symmetric hyperbolic and satisfies the first and second principle of thermodynamics, hence it belongs to the so-called class of symmetric hyperbolic thermodynamically compatible systems (SHTC), which have been studied for the first time by Godunov in 1961 [61] and later in a series of papers by Godunov and Romenski [67,69,119]. An important feature of the

A new unequal-weighted triple-frequency first order ionosphere correction algorithm and its application in COMPASS

NASA Astrophysics Data System (ADS)

Liu, WenXiang; Mou, WeiHua; Wang, FeiXue

2012-03-01

As the introduction of triple-frequency signals in GNSS, the multi-frequency ionosphere correction technology has been fast developing. References indicate that the triple-frequency second order ionosphere correction is worse than the dual-frequency first order ionosphere correction because of the larger noise amplification factor. On the assumption that the variances of three frequency pseudoranges were equal, other references presented the triple-frequency first order ionosphere correction, which proved worse or better than the dual-frequency first order correction in different situations. In practice, the PN code rate, carrier-to-noise ratio, parameters of DLL and multipath effect of each frequency are not the same, so three frequency pseudorange variances are unequal. Under this consideration, a new unequal-weighted triple-frequency first order ionosphere correction algorithm, which minimizes the variance of the pseudorange ionosphere-free combination, is proposed in this paper. It is found that conventional dual-frequency first-order correction algorithms and the equal-weighted triple-frequency first order correction algorithm are special cases of the new algorithm. A new pseudorange variance estimation method based on the three carrier combination is also introduced. Theoretical analysis shows that the new algorithm is optimal. The experiment with COMPASS G3 satellite observations demonstrates that the ionosphere-free pseudorange combination variance of the new algorithm is smaller than traditional multi-frequency correction algorithms.

First Order Fire Effects Model: FOFEM 4.0, user's guide

Treesearch

Elizabeth D. Reinhardt; Robert E. Keane; James K. Brown

1997-01-01

A First Order Fire Effects Model (FOFEM) was developed to predict the direct consequences of prescribed fire and wildfire. FOFEM computes duff and woody fuel consumption, smoke production, and fire-caused tree mortality for most forest and rangeland types in the United States. The model is available as a computer program for PC or Data General computer.

Fractal kinetics of radiation-induced point-defect formation and decay in amorphous insulators: Application to color centers in silica-based optical fibers

NASA Astrophysics Data System (ADS)

Griscom, David L.

2001-11-01

Formalisms have been developed to express the time evolution of bimolecular processes taking place in fractal spaces. These ``stretched-second-order'' solutions are specifically applicable to radiation-induced electron-hole pairs and/or vacancy-interstitial pairs in insulating glasses. Like the analogous Kohlrausch-type (stretched-first-order) expressions, the present solutions are functions of (kt)β, where 0<β<1, k is an effective rate coefficient, and t is time. Both the new second-order formalism and the familiar Kohlrausch approach have been used to fit experimental data (induced optical absorptions in silica-based glasses monitored at selected wavelengths) that serve as proxies for the numbers of color centers created by γ irradiation and/or destroyed by processes involving thermal, optical, or γ-ray activation. Two material systems were investigated: (1) optical fibers with Ge-doped-silica cores and (2) fibers with low-OH/low-chloride pure-silica cores. Successful fits of the growth curves for the Ge-doped-silica-core fibers at four widely separated dose rates were accomplished using solutions for color-center concentrations, N[(kt)β], which approach steady-state values, Nsat, as t-->∞. The parametrization of these fits reveals some unexpected, and potentially useful, empirical rules regarding the dose-rate dependences of β, k, and Nsat in the fractal regime (0<β<1). Similar, though possibly not identical, rules evidently apply to color centers in the pure-silica-core fibers as well. In both material systems, there appear to be fractal<==> classical phase transitions at certain threshold values of dose rate, below which the dose-rate dependencies of k and Nsat revert to those specified by classical (β=1) first- or second-order kinetics. For kt<<1, both the first- and second-order fractal kinetic growth curves become identical, i.e., N((kt)β)~Atβ, where the coefficient A depends on dose rate but not kinetic order. It is found empirically that A