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Sample records for second-order reaction kinetics

  1. A Kinetic Study of the Diels-Alder Reaction. An Experiment Illustrating Simple Second-Order Reaction Kinetics.

    ERIC Educational Resources Information Center

    Silvestri, Michael G.; Dills, Charles E.

    1989-01-01

    Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)

  2. Power optimization of chemically driven heat engine based on first and second order reaction kinetic theory and probability theory

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Chen, Lingen; Sun, Fengrui

    2016-03-01

    The finite-time thermodynamic method based on probability analysis can more accurately describe various performance parameters of thermodynamic systems. Based on the relation between optimal efficiency and power output of a generalized Carnot heat engine with a finite high-temperature heat reservoir (heat source) and an infinite low-temperature heat reservoir (heat sink) and with the only irreversibility of heat transfer, this paper studies the problem of power optimization of chemically driven heat engine based on first and second order reaction kinetic theory, puts forward a model of the coupling heat engine which can be run periodically and obtains the effects of the finite-time thermodynamic characteristics of the coupling relation between chemical reaction and heat engine on the power optimization. The results show that the first order reaction kinetics model can use fuel more effectively, and can provide heat engine with higher temperature heat source to increase the power output of the heat engine. Moreover, the power fluctuation bounds of the chemically driven heat engine are obtained by using the probability analysis method. The results may provide some guidelines for the character analysis and power optimization of the chemically driven heat engines.

  3. Application of chemometrics methods with kinetic constraints for estimation of rate constants of second order consecutive reactions.

    PubMed

    Kompany-Zareh, Mohsen; Khoshkam, Maryam

    2008-05-01

    To determine the rate constants for the second order consecutive reactions of the form U + V -(k1)--> W -(k2)--> P, a number of chemometrics and hard modeling-based methods are described. The absorption spectroscopic data from the reaction were utilized for performing the analysis. Concentrations and extinctions of components were comparable, and all of them were absorbing species. The number of steps in the reaction was less than the number of absorbing species, which resulted in a rank-deficient response matrix. This can cause difficulties for some of the methods described in the literature. The standard MATLAB functions were used for determining the solutions of the differential equations as well as for finding the optimal rate constants to describe the kinetic profiles. The available knowledge about the system determines the approaches described in this paper. The knowledge includes the spectra of reactants and products, the initial concentrations, and the exact kinetics. Some of this information is sometimes not available or is hard to estimate. Multiple linear regression for fitting the kinetic parameters to the obtained concentration profiles, rank augmentation using multiple batch runs, a mixed spectral approach which treats the reaction using a pseudo species concept, and principal components regression are the four groups of methods discussed in this study. In one of the simulated datasets the spectra are quite different, and in the other one the spectra of one reactant and of the product share a high degree of overlap. Instrumental noise, sampling error are the sources of error considered. Our aim was the investigation of the relative merits of each method. PMID:18469471

  4. ROTATING BIOLOGICAL CONTACTORS - SECOND ORDER KINETICS

    EPA Science Inventory

    Rotating biological contactors (RBC) have been employed for treating municipal wastewaters within the United States since 1970. The RBC process lends itself to kinetic interpretation because of the sequential stages employed in the operation. This mode of operation enables the su...

  5. Drift kinetic equation exact through second order in gyroradius expansion

    SciTech Connect

    Simakov, Andrei N.; Catto, Peter J.

    2005-01-01

    The drift kinetic equation of Hazeltine [R. D. Hazeltine, Plasma Phys. 15, 77 (1973)] for a magnetized plasma of arbitrary collisionality is widely believed to be exact through the second order in the gyroradius expansion. It is demonstrated that this equation is only exact through the first order. The reason is that when evaluating the second-order gyrophase dependent distribution function, Hazeltine neglected contributions from the first-order gyrophase dependent distribution function, and then used this incomplete expression to derive the equation for the gyrophase independent distribution function. Consequently, the second-order distribution function and the stress tensor derived by this approach are incomplete. By relaxing slightly Hazeltine's orderings one is able to obtain a drift kinetic equation accurate through the second order in the gyroradius expansion. In addition, the gyroviscous stress tensor for plasmas of arbitrary collisionality is obtained.

  6. Modeling Second-Order Chemical Reactions using Cellular Automata

    NASA Astrophysics Data System (ADS)

    Hunter, N. E.; Barton, C. C.; Seybold, P. G.; Rizki, M. M.

    2012-12-01

    Cellular automata (CA) are discrete, agent-based, dynamic, iterated, mathematical computational models used to describe complex physical, biological, and chemical systems. Unlike the more computationally demanding molecular dynamics and Monte Carlo approaches, which use "force fields" to model molecular interactions, CA models employ a set of local rules. The traditional approach for modeling chemical reactions is to solve a set of simultaneous differential rate equations to give deterministic outcomes. CA models yield statistical outcomes for a finite number of ingredients. The deterministic solutions appear as limiting cases for conditions such as a large number of ingredients or a finite number of ingredients and many trials. Here we present a 2-dimensional, probabilistic CA model of a second-order gas phase reaction A + B → C, using a MATLAB basis. Beginning with a random distribution of ingredients A and B, formation of C emerges as the system evolves. The reaction rate can be varied based on the probability of favorable collisions of the reagents A and B. The model permits visualization of the conversion of reagents to products, and allows one to plot concentration vs. time for A, B and C. We test hypothetical reaction conditions such as: limiting reagents, the effects of reaction probabilities, and reagent concentrations on the reaction kinetics. The deterministic solutions of the reactions emerge as statistical averages in the limit of the large number of cells in the array. Modeling results for dynamic processes in the atmosphere will be presented.

  7. Second-order kinetic Kohn-Sham lattice model

    NASA Astrophysics Data System (ADS)

    Solórzano, S.; Mendoza, M.; Herrmann, H. J.

    2016-06-01

    In this work, we introduce a semi-implicit second-order correction scheme to the kinetic Kohn-Sham lattice model. This approach is validated by performing realistic exchange-correlation energy calculations of atoms and dimers of the first two rows of the Periodic Table, finding good agreement with the expected values. Additionally, we simulate the ethane molecule, where we recover the bond lengths and compare the results with standard methods. Finally, we discuss the current applicability of pseudopotentials within the lattice kinetic Kohn-Sham approach.

  8. The role of reduction extent of graphene oxide in the photocatalytic performance of Ag/AgX (X = Cl, Br)/rGO composites and the pseudo-second-order kinetics reaction nature of the Ag/AgBr system.

    PubMed

    Gao, Weiyin; Ran, Chenxin; Wang, Minqiang; Li, Le; Sun, Zhongwang; Yao, Xi

    2016-07-21

    Although reduced graphene oxide (rGO)-based photocatalyst composites have been intensively developed during the past few years, the influence of reduction extent of rGO on the photocatalytic performance of the rGO-based composite has virtually not been investigated due to some technical limitations, such as the poor water dispersibility of rGO and low reduction selectivity of the hydrothermal method, which make it difficult to control the reduction extent of rGO in these composites. Herein, we used a facile room-temperature method to synthesize Ag/AgX (X = Cl, Br)/rGO photocatalyst composites as a model to study the effect of reduction extent of rGO on the photocatalytic performance of the photocatalyst. It was found that the photocatalytic activities of both Ag/AgCl/PrGO and Ag/AgBr/PrGO systems had an optimized threshold of the reduction extent of photoreduced GO (PrGO). More importantly, due to the different conductive band values of AgCl and AgBr, the optimized thresholds in the two systems were at different PrGO reduction extents, based on which we proposed that the favorable energy band matching between AgX and PrGO in the two systems played a crucial role in obtaining high photocatalysis performance. Besides, the photocatalytic reaction of the Ag/AgBr based system was confirmed to be a pseudo-second-order kinetics reaction rather than pseudo-first-order kinetics reaction. The new insights presented in this work provided useful information on the design and development of a more sophisticated photocatalyst, and can also be applied to many other applications. PMID:27332751

  9. 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)

  10. Second-order radio frequency kinetic theory revisited: Resolving inconsistency with conventional fluid theory

    SciTech Connect

    Chen, Jiale; Gao, Zhe

    2013-08-15

    The second-order velocity distribution function was calculated from the second-order rf kinetic theory [Jaeger et al., Phys. Plasmas 7, 641 (2000)]. However, the nonresonant ponderomotive force in the radial direction derived from the theory is inconsistent with that from the fluid theory. The inconsistency arises from that the multiple-timescale-separation assumption fails when the second-order Vlasov equation is directly integrated along unperturbed particle orbits. A slowly ramped wave field including an adiabatic turn-on process is applied in the modified kinetic theory in this paper. Since this modification leads only to additional reactive/nonresonant response relevant with the secular resonant response from the previous kinetic theory, the correct nonresonant ponderomotive force can be obtained while all the resonant moments remain unchanged.

  11. First-Order or Second-Order Kinetics? A Monte Carlo Answer

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2005-01-01

    Monte Carlo computational experiments reveal that the ability to discriminate between first- and second-order kinetics from least-squares analysis of time-dependent concentration data is better than implied in earlier discussions of the problem. The problem is rendered as simple as possible by assuming that the order must be either 1 or 2 and that…

  12. Second-order fluid dynamics for the unitary Fermi gas from kinetic theory

    NASA Astrophysics Data System (ADS)

    Schäfer, Thomas

    2014-10-01

    We compute second-order transport coefficients of the dilute Fermi gas at unitarity. The calculation is based on kinetic theory and the Boltzmann equation at second order in the Knudsen expansion. The second-order transport coefficients describe the shear stress relaxation time, nonlinear terms in the strain-stress relation, and nonlinear couplings between vorticity and strain. An exact calculation in the dilute limit gives τR=η /P , where τR is the shear stress relaxation time, η is the shear viscosity, and P is pressure. This relation is identical to the result obtained using the Bhatnagar-Gross-Krook approximation to the collision term, but other transport coefficients are sensitive to the exact collision integral.

  13. Second-order accurate kinetic schemes for the ultra-relativistic Euler equations

    NASA Astrophysics Data System (ADS)

    Kunik, Matthias; Qamar, Shamsul; Warnecke, Gerald

    2003-12-01

    A second-order accurate kinetic scheme for the numerical solution of the relativistic Euler equations is presented. These equations describe the flow of a perfect fluid in terms of the particle density n, the spatial part of the four-velocity u and the pressure p. The kinetic scheme, is based on the well-known fact that the relativistic Euler equations are the moments of the relativistic Boltzmann equation of the kinetic theory of gases when the distribution function is a relativistic Maxwellian. The kinetic scheme consists of two phases, the convection phase (free-flight) and collision phase. The velocity distribution function at the end of the free-flight is the solution of the collisionless transport equation. The collision phase instantaneously relaxes the distribution to the local Maxwellian distribution. The fluid dynamic variables of density, velocity, and internal energy are obtained as moments of the velocity distribution function at the end of the free-flight phase. The scheme presented here is an explicit method and unconditionally stable. The conservation laws of mass, momentum and energy as well as the entropy inequality are everywhere exactly satisfied by the solution of the kinetic scheme. The scheme also satisfies positivity and L1-stability. The scheme can be easily made into a total variation diminishing method for the distribution function through a suitable choice of the interpolation strategy. In the numerical case studies the results obtained from the first- and second-order kinetic schemes are compared with the first- and second-order upwind and central schemes. We also calculate the experimental order of convergence and numerical L1-stability of the scheme for smooth initial data.

  14. 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…

  15. DECAY OF DISSOLVED SUBSTANCES BY SECOND-ORDER REACTION: PROBLEM DESCRIPTION AND BATCH-REACTOR SOLUTIONS

    EPA Science Inventory

    The mass transport (advection-dispersion) equations allowing coupled second-order reaction (i.e. Omega sub 1, C sub 1) + (omega sub 2, C sub 2) (R sub 12) -> Re) between two constituents are derived and result in a set of coupled nonlinear partial differential equations. Neglecti...

  16. Implementing the Second-Order Fermi Process in a Kinetic Monte-Carlo Simulation

    NASA Astrophysics Data System (ADS)

    Summerlin, E. J.

    2010-12-01

    Kinetic Monte-Carlo test-particle simulations require a way to simulate the effects of turbulence on particles. One way to do this is to prescribe a phenomenological scattering mechanism based on an empirical and/or qualitative description of turbulent scattering. Previous incarnations of the simulation presented here parameterize a scattering mean free path proportional to some power of the particle’s momentum in agreement with observational evidence from many sources. The scattering itself was done by scattering of the particle’s local fluid frame velocity onto a sphere of radius |v| via either large of small angle scattering. However, in real plasmas the scattering centers (turbulent plasma waves) are not stationary in the local fluid frame and particle velocities should, instead, be randomized in the frame of the moving scattering centers (which presumably move with the Alfvén speed) to more accurately represent the effects of turbulence on particles. Allowing scattering centers to move introduces heating as particles now diffuse in momentum as well as space (receiving a random kick of order the Alfvén speed at each scattering event). In 1965, Eugene Parker considered this effect (then called fermi acceleration) for cosmic ray particles and (correctly) concluded that it was negligible for those highly energetic particles because the particle speed was so much larger than the Alfvén speed kick which it received. However, doing the same calculation for thermal particles embedded in the solar wind (for whom a single kick of an Alfvén speed is significant) yields a very different result and it becomes clear that this process, now called second-order Fermi acceleration, must be included to get an accurate picture of particle acceleration in the heliosphere. This presentation will highlight the theoretical argument for the importance of second-order fermi acceleration in both the solar wind and shock environs as well as problems in heliophysics to which it

  17. An Activation Energy Experiment for a Second-Order Reaction in a Single Laboratory Period.

    ERIC Educational Resources Information Center

    Barile, Raymond C.; Michiels, Leo P.

    1983-01-01

    Describes modification of a chemical reaction to a single 4 1/2-hour laboratory period. Reaction kinetics between 2, 4-initrochlorobenzene and piperidine to form 2, 4-dinitrophenyl-piperidine and piperidinium hydrochloride are followed conductometrically at three temperatures to obtain data to calculate activation parameters. (Author/JN)

  18. Radiation-Reaction Force on a Small Charged Body to Second Order

    NASA Astrophysics Data System (ADS)

    Moxon, Jordan; Flanagan, Eanna

    2015-04-01

    In classical electrodynamics, an accelerating charge emits radiation and experiences a corresponding radiation reaction force, or self force. We extend to greater precision (higher order in perturbation theory) a previous rigorous derivation of the electromagnetic self force in flat spacetime by Gralla, Harte, and Wald. The method introduced by Gralla, Harte, and Wald computes the self-force from the Maxwell field equations and conservation of stress-energy, and does not require regularization of a singular point charge, as has been necessary in prior computations. For our higher order compuation, it becomes necessary to adopt an adjusted definition of the mass of the body to avoid including self-energy from the electromagnetic field sourced during the history of the body. We derive the evolution equations for the mass, spin, and center of mass position of an extended body through second order using our adjusted formalism. The final equations give an acceleration dependent evolution of the spin (self-torque), as well as a mixing between the extended body effects and the acceleration dependent effects on the overall body motion.

  19. Applying constraints on model-based methods: estimation of rate constants in a second order consecutive reaction.

    PubMed

    Kompany-Zareh, Mohsen; Khoshkam, Maryam

    2013-02-01

    This paper describes estimation of reaction rate constants and pure ultraviolet/visible (UV-vis) spectra of the component involved in a second order consecutive reaction between Ortho-Amino benzoeic acid (o-ABA) and Diazoniom ions (DIAZO), with one intermediate. In the described system, o-ABA was not absorbing in the visible region of interest and thus, closure rank deficiency problem did not exist. Concentration profiles were determined by solving differential equations of the corresponding kinetic model. In that sense, three types of model-based procedures were applied to estimate the rate constants of the kinetic system, according to Levenberg/Marquardt (NGL/M) algorithm. Original data-based, Score-based and concentration-based objective functions were included in these nonlinear fitting procedures. Results showed that when there is error in initial concentrations, accuracy of estimated rate constants strongly depends on the type of applied objective function in fitting procedure. Moreover, flexibility in application of different constraints and optimization of the initial concentrations estimation during the fitting procedure were investigated. Results showed a considerable decrease in ambiguity of obtained parameters by applying appropriate constraints and adjustable initial concentrations of reagents. PMID:23220674

  20. Structural changes of small amplitude kinetic Alfvén solitary waves due to second-order corrections

    SciTech Connect

    Choi, Cheong R.

    2015-10-15

    The structural changes of kinetic Alfvén solitary waves (KASWs) due to higher-order terms are investigated. While the first-order differential equation for KASWs provides the dispersion relation for kinetic Alfvén waves, the second-order differential equation describes the structural changes of the solitary waves due to higher-order nonlinearity. The reductive perturbation method is used to obtain the second-order and third-order partial differential equations; then, Kodama and Taniuti's technique [J. Phys. Soc. Jpn. 45, 298 (1978)] is applied in order to remove the secularities in the third-order differential equations and derive a linear second-order inhomogeneous differential equation. The solution to this new second-order equation indicates that, as the amplitude increases, the hump-type Korteweg-de Vries solution is concentrated more around the center position of the soliton and that dip-type structures form near the two edges of the soliton. This result has a close relationship with the interpretation of the complex KASW structures observed in space with satellites.

  1. Structural changes of small amplitude kinetic Alfvén solitary waves due to second-order corrections

    NASA Astrophysics Data System (ADS)

    Choi, Cheong R.

    2015-10-01

    The structural changes of kinetic Alfvén solitary waves (KASWs) due to higher-order terms are investigated. While the first-order differential equation for KASWs provides the dispersion relation for kinetic Alfvén waves, the second-order differential equation describes the structural changes of the solitary waves due to higher-order nonlinearity. The reductive perturbation method is used to obtain the second-order and third-order partial differential equations; then, Kodama and Taniuti's technique [J. Phys. Soc. Jpn. 45, 298 (1978)] is applied in order to remove the secularities in the third-order differential equations and derive a linear second-order inhomogeneous differential equation. The solution to this new second-order equation indicates that, as the amplitude increases, the hump-type Korteweg-de Vries solution is concentrated more around the center position of the soliton and that dip-type structures form near the two edges of the soliton. This result has a close relationship with the interpretation of the complex KASW structures observed in space with satellites.

  2. Positronium formation as a three-body reaction. II. The second-order nuclear amplitudes

    SciTech Connect

    Shojaei, F.; Bolorizadeh, M. A.; Ghanbari-Adivi, E.; Brunger, M. J.

    2009-01-15

    We derive an exact analytic form for the second-order nuclear amplitudes, under the Faddeev three-body approach, which is applicable to the nonrelativistic high energy impact interaction where positronium is formed in the collision of a positron with an atom.

  3. 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.

  4. First- and Second-Order Stimuli Reaction Time Measures Are Highly Sensitive to Mild Traumatic Brain Injuries.

    PubMed

    Piponnier, Jean-Claude; Forget, Robert; Gagnon, Isabelle; McKerral, Michelle; Giguère, Jean-François; Faubert, Jocelyn

    2016-01-15

    Mild traumatic brain injury (mTBI) has subtle effects on several brain functions that can be difficult to assess and follow up. We investigated the impact of mTBI on the perception of sine-wave gratings defined by first- and second-order characteristics. Fifteen adults diagnosed with mTBI were assessed at 15 days, 3 months, and 12 months postinjury. Fifteen matched controls followed the same testing schedule. Reaction times (RTs) for flicker detection and motion direction discrimination were measured. Stimulus contrast of first- and second-order patterns was equated to control for visibility, and correct-response RT means, standard deviations (SDs), medians, and interquartile ranges (IQRs) were calculated. The level of symptoms was also evaluated to compare it to RT data. In general in mTBI, RTs were longer, and SDs as well as IQRs larger, than those of controls. In addition, mTBI participants' RTs to first-order stimuli were shorter than those to second-order stimuli, and SDs as well as IQRs larger for first- than for second-order stimuli in the motion condition. All these observations were made over the three sessions. The level of symptoms observed in mTBI was higher than that of control participants, and this difference did also persist up to 1 year after the brain injury, despite an improvement. The combination of RT measures with particular stimulus properties is a highly sensitive method for measuring mTBI-induced visuomotor anomalies and provides a fine probe of the underlying mechanisms when the brain is exposed to mild trauma. PMID:25950948

  5. Impact of magnetohydrodynamics in bidirectional flow of nanofluid subject to second order slip velocity and homogeneous-heterogeneous reactions

    NASA Astrophysics Data System (ADS)

    Hayat, Tasawar; Imtiaz, Maria; Alsaedi, Ahmed

    2015-12-01

    This paper addresses the steady three-dimensional boundary layer flow of viscous nanofluid. The flow is caused by a permeable stretching surface with second order velocity slip and homogeneous-heterogeneous reactions. Water is treated as base fluid and copper as nanoparticle. An incompressible fluid fills the porous space. The fluid is electrically conducting in the presence of an applied magnetic field. A system of ordinary differential equations is obtained by using suitable transformations. Convergent series solutions are derived. Impact of various pertinent parameters on the velocity, concentration and skin friction coefficient is discussed. Analysis of the obtained results shows that the flow field is influenced appreciably by the presence of velocity slip parameters. Also concentration distribution decreases for larger values of strength of homogeneous reaction parameter while it increases for strength of heterogeneous reaction parameter.

  6. Mapping of the relativistic kinetic balance equations onto the Klein Gordon and second-order Dirac equations

    NASA Astrophysics Data System (ADS)

    Pesci, Adriana I.; Goldstein, Raymond E.; Uys, Hermann

    2005-05-01

    In previous work we have shown that the quantum potential can be derived from the classical kinetic equations both for particles with and without spin. Here, we extend these mappings to the relativistic case. The essence of the analysis consists of Fourier transforming the momentum coordinate of the distribution function. This procedure introduces a natural parameter η with units of angular momentum. In the non-relativistic case the ansatz of either separability, or separability and additivity, imposed on the probability distribution function produces mappings onto the Schrödinger equation and the Pauli equation, respectively. The former corresponds to an irrotational flow, the latter to a fluid with non-zero vorticity. In this work we show that the relativistic mappings lead to the Klein-Gordon equation in the irrotational case and to the second-order Dirac equation in the rotational case. These mappings are irreversible; an approximate inverse is the Wigner function. Taken together, these results provide a statistical interpretation of quantum mechanics.

  7. Evaluating rates and yields of second-order, photoinitiated reactions under conditons of Gaussian-profile excitation

    SciTech Connect

    Cambron, R.T.; Zhu, X.R.; Harris, J.M.

    1994-09-01

    Under conditions of Gaussian radial profile excitation, a mixed-order kinetic model is used to interpret the rates and yields of photoinitiated reactions. This model is used to determine the triplet-triplet annihilation rate constant for benzophenone in acetonitrile and anthracene at room temperature. 34 refs., 9 figs.

  8. Free [ADP] and aerobic muscle work follow at least second order kinetics in rat gastrocnemius in vivo.

    PubMed

    Cieslar, J H; Dobson, G P

    2000-03-01

    The relationship between free cytosolic [ADP] (and [P(i)]) and steady-state aerobic muscle work in rat gastrocnemius muscle in vivo using (31)P NMR was investigated. Anesthetized rats were ventilated and placed in a custom-built cradle fitted with a force transducer that could be placed into a 7-tesla NMR magnet. Muscle work was induced by supramaximal sciatic nerve stimulation that activated all fibers. Muscles were stimulated at 0.1, 0.2, 0.3, 0.4, 0.5, 0.8, 1.0, and 2.0 Hz until twitch force, phosphocreatine, and P(i) were unchanged between two consecutive spectra acquired in 4-min blocks (8-12 min). Parallel bench experiments were performed to measure total tissue glycogen, lactate, total creatine, and pyruvate in freeze-clamped muscles after 10 min of stimulation at each frequency. Up to 0.5 Hz, there was no significant change in muscle glycogen, lactate, and the lactate/pyruvate ratios between 8-12 min. At 0.8 Hz, there was a 17% fall in glycogen and a 65% rise in the muscle lactate with a concomitant fall in pH. Above this frequency, glycogen fell rapidly, lactate continued to rise, and ATP and pH declined. On the basis of these force and metabolic measurements, we estimated the maximal mitochondrial capacity (V(max)) to be 0.8 Hz. Free [ADP] was then calculated at each submaximal workload from measuring all the reactants of the creatine kinase equilibrium after adjusting the K'(CK) to the muscle temp (30 degrees C), pH, and pMg. We show that ADP (and P(i)) and tension-time integral follow a Hill relationship with at least a second order function. The K(0.5) values for free [ADP] and [P(i)] were 48 microM and 9 mM, respectively. Our data did not fit any form of the Michaelis-Menten equation. We therefore conclude that free cytosolic [ADP] and [P(i)] could potentially control steady-state oxidative phosphorylation in skeletal muscle in vivo. PMID:10692403

  9. Second order kinetic modeling of headspace solid phase microextraction of flavors released from selected food model systems.

    PubMed

    Zhang, Jiyuan; Cheong, Mun-Wai; Yu, Bin; Curran, Philip; Zhou, Weibiao

    2014-01-01

    The application of headspace-solid phase microextraction (HS-SPME) has been widely used in various fields as a simple and versatile method, yet challenging in quantification. In order to improve the reproducibility in quantification, a mathematical model with its root in psychological modeling and chemical reactor modeling was developed, describing the kinetic behavior of aroma active compounds extracted by SPME from two different food model systems, i.e., a semi-solid food and a liquid food. The model accounted for both adsorption and release of the analytes from SPME fiber, which occurred simultaneously but were counter-directed. The model had four parameters and their estimated values were found to be more reproducible than the direct measurement of the compounds themselves by instrumental analysis. With the relative standard deviations (RSD) of each parameter less than 5% and root mean square error (RMSE) less than 0.15, the model was proved to be a robust one in estimating the release of a wide range of low molecular weight acetates at three environmental temperatures i.e., 30, 40 and 60 °C. More insights of SPME behavior regarding the small molecule analytes were also obtained through the kinetic parameters and the model itself. PMID:25255763

  10. Reaction path determination for quantum mechanical/molecular mechanical modeling of enzyme reactions by combining first order and second order ``chain-of-replicas'' methods

    NASA Astrophysics Data System (ADS)

    Cisneros, G. Andrés; Liu, Haiyan; Lu, Zhenyu; Yang, Weitao

    2005-03-01

    A two-step procedure for the determination of reaction paths in enzyme systems is presented. This procedure combines two chain-of-states methods: a quantum mechanical/molecular mechanical (QM/MM) implementation of the nudged elastic band (NEB) method and a second order parallel path optimizer method both recently developed in our laboratory. In the first step, a reaction path determination is performed with the NEB method, along with a restrained minimization procedure for the MM environment to obtain a first approximation to the reaction path. In the second step, the calculated path is refined with the parallel path optimizer method. By combining these two methods the reaction paths are determined accurately, and in addition, the number of path optimization iterations are significantly reduced. This procedure is tested by calculating both steps of the isomerization of 2-oxo-4-hexenedioate by 4-oxalocrotonate tautomerase, which have been previously determined by our group. The calculated paths agree with the previously reported results and we obtain a reduction of 45%-55% in the number of path optimization cycles.

  11. Second order Standard Model

    NASA Astrophysics Data System (ADS)

    Espin, Johnny; Krasnov, Kirill

    2015-06-01

    It is known, though not commonly, that one can describe fermions using a second order in derivatives Lagrangian instead of the first order Dirac one. In this description the propagator is scalar, and the complexity is shifted to the vertex, which contains a derivative operator. In this paper we rewrite the Lagrangian of the fermionic sector of the Standard Model in such second order form. The new Lagrangian is extremely compact, and is obtained from the usual first order Lagrangian by integrating out all primed (or dotted) 2-component spinors. It thus contains just half of the 2-component spinors that appear in the usual Lagrangian, which suggests a new perspective on unification. We sketch a natural in this framework SU (2) × SU (4) ⊂ SO (9) unified theory.

  12. Quantitative fluorescence kinetic analysis of NADH and FAD in human plasma using three- and four-way calibration methods capable of providing the second-order advantage.

    PubMed

    Kang, Chao; Wu, Hai-Long; Zhou, Chang; Xiang, Shou-Xia; Zhang, Xiao-Hua; Yu, Yong-Jie; Yu, Ru-Qin

    2016-03-01

    The metabolic coenzymes reduced nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) are the primary electron donor and acceptor respectively, participate in almost all biological metabolic pathways. This study develops a novel method for the quantitative kinetic analysis of the degradation reaction of NADH and the formation reaction of FAD in human plasma containing an uncalibrated interferent, by using three-way calibration based on multi-way fluorescence technique. In the three-way analysis, by using the calibration set in a static manner, we directly predicted the concentrations of both analytes in the mixture at any time after the start of their reactions, even in the presence of an uncalibrated spectral interferent and a varying background interferent. The satisfactory quantitative results indicate that the proposed method allows one to directly monitor the concentration of each analyte in the mixture as the function of time in real-time and nondestructively, instead of determining the concentration after the analytical separation. Thereafter, we fitted the first-order rate law to their concentration data throughout their reactions. Additionally, a four-way calibration procedure is developed as an alternative for highly collinear systems. The results of the four-way analysis confirmed the results of the three-way analysis and revealed that both the degradation reaction of NADH and the formation reaction of FAD in human plasma fit the first-order rate law. The proposed methods could be expected to provide promising tools for simultaneous kinetic analysis of multiple reactions in complex systems in real-time and nondestructively. PMID:26873466

  13. Local reaction kinetics by imaging

    NASA Astrophysics Data System (ADS)

    Suchorski, Yuri; Rupprechter, Günther

    2016-01-01

    In the present contribution we present an overview of our recent studies using the "kinetics by imaging" approach for CO oxidation on heterogeneous model systems. The method is based on the correlation of the PEEM image intensity with catalytic activity: scaled down to the μm-sized surface regions, such correlation allows simultaneous local kinetic measurements on differently oriented individual domains of a polycrystalline metal-foil, including the construction of local kinetic phase diagrams. This allows spatially- and component-resolved kinetic studies and, e.g., a direct comparison of inherent catalytic properties of Pt(hkl)- and Pd(hkl)-domains or supported μm-sized Pd-powder agglomerates, studies of the local catalytic ignition and the role of defects and grain boundaries in the local reaction kinetics.

  14. Local reaction kinetics by imaging☆

    PubMed Central

    Suchorski, Yuri; Rupprechter, Günther

    2016-01-01

    In the present contribution we present an overview of our recent studies using the “kinetics by imaging” approach for CO oxidation on heterogeneous model systems. The method is based on the correlation of the PEEM image intensity with catalytic activity: scaled down to the μm-sized surface regions, such correlation allows simultaneous local kinetic measurements on differently oriented individual domains of a polycrystalline metal-foil, including the construction of local kinetic phase diagrams. This allows spatially- and component-resolved kinetic studies and, e.g., a direct comparison of inherent catalytic properties of Pt(hkl)- and Pd(hkl)-domains or supported μm-sized Pd-powder agglomerates, studies of the local catalytic ignition and the role of defects and grain boundaries in the local reaction kinetics. PMID:26865736

  15. Relation of Turbojet and Ramjet Combustion Efficiency to Second-Order Reaction Kinetics and Fundamental Flame Speed

    NASA Technical Reports Server (NTRS)

    Childs, J Howard; Reynolds, Thaine W; Graves, Charles C

    1957-01-01

    Theoretical studies of the turbojet and ramjet combustion process are summarized and the resulting equations are applied to experimental data obtained from various combustor tests. The theoretical treatment assumes that one step in the over-all chain of processes which constitute jet-engine combustion is sufficiently slow to be the rate-controlling step that determines combustion efficiency.

  16. Ametryn degradation by aqueous chlorine: kinetics and reaction influences.

    PubMed

    Xu, Bin; Gao, Nai-yun; Cheng, Hefa; Hu, Chen-yan; Xia, Sheng-ji; Sun, Xiao-feng; Wang, Xuejiao; Yang, Shaogui

    2009-09-30

    The chemical oxidation of the herbicide ametryn was investigated by aqueous chlorination between pH 4 and 10 at a temperature of 25 degrees C. Ametryn was found to react very rapidly with aqueous chlorine. The reaction kinetics can be well described by a second-order kinetic model. The apparent second-order rate constants are greater than 5 x 10(2)M(-1)s(-1) under acidic and neutral conditions. The reaction proceeds much more slowly under alkaline conditions. The predominant reactions were found to be the reactions of HOCl with neutral ametryn and the charged ametryn, with rate constants equal to 7.22 x 10(2) and 1.58 x 10(3)M(-1)s(-1), respectively. The ametryn degradation rate increases with addition of bromide and decreases with addition of ammonia during the chlorination process. Based on elementary chemical reactions, a kinetic model of ametryn degradation by chlorination in the presence of bromide or ammonia ion was also developed. By employing this model, we estimate that the rate constants for the reactions of HOBr with neutral ametryn and charged ametryn were 9.07 x 10(3) and 3.54 x 10(6)M(-1)s(-1), respectively. These values are 10- to 10(3)-fold higher than those of HOCl, suggesting that the presence of bromine species during chlorination could significantly accelerate ametryn degradation. PMID:19423216

  17. Second-order modeling of arsenite transport in soils

    NASA Astrophysics Data System (ADS)

    Zhang, Hua; Magdi Selim, H.

    2011-11-01

    Rate limited processes including kinetic adsorption-desorption can greatly impact the fate and behavior of toxic arsenic compounds in heterogeneous soils. In this study, miscible displacement column experiments were carried out to investigate the extent of reactivity during transport of arsenite in soils. Arsenite breakthrough curves (BTCs) of Olivier and Windsor soils exhibited strong retardation with diffusive effluent fronts followed by slow release or tailing during leaching. Such behavior is indicative of the dominance of kinetic retention reactions for arsenite transport in the soil columns. Sharp decrease or increase in arsenite concentration in response to flow interruptions (stop-flow) further verified that non-equilibrium conditions are dominant. After some 40-60 pore volumes of continued leaching, 30-70% of the applied arsenite was retained by the soil in the columns. Furthermore, continued arsenite slow release for months was evident by the high levels of residual arsenite concentrations observed during leaching. In contrast, arsenite transport in a reference sand material exhibited no retention where complete mass recovery in the effluent solution was attained. A second-order model (SOM) which accounts for equilibrium, reversible, and irreversible retention mechanisms was utilized to describe arsenite transport results from the soil columns. Based on inverse and predictive modeling results, the SOM model successfully depicted arsenite BTCs from several soil columns. Based on inverse and predictive modeling results, a second-order model which accounts for kinetic reversible and irreversible reactions is recommended for describing arsenite transport in soils.

  18. Kinetics of actinide complexation reactions

    SciTech Connect

    Nash, K.L.; Sullivan, J.C.

    1997-09-01

    Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions.

  19. Second-Order Footsteps Illusions

    PubMed Central

    Anstis, Stuart

    2015-01-01

    In the “footsteps illusion”, light and dark squares travel at constant speed across black and white stripes. The squares appear to move faster and slower as their contrast against the stripes varies. We now demonstrate some second-order footsteps illusions, in which all edges are defined by colors or textures—even though luminance-based neural motion detectors are blind to such edges. PMID:27551366

  20. Second-Order Footsteps Illusions.

    PubMed

    Kitaoka, Akiyoshi; Anstis, Stuart

    2015-12-01

    In the "footsteps illusion", light and dark squares travel at constant speed across black and white stripes. The squares appear to move faster and slower as their contrast against the stripes varies. We now demonstrate some second-order footsteps illusions, in which all edges are defined by colors or textures-even though luminance-based neural motion detectors are blind to such edges. PMID:27551366

  1. Combustion kinetics and reaction pathways

    SciTech Connect

    Klemm, R.B.; Sutherland, J.W.

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  2. Aqueous-phase chemistry and bactericidal effects from an air discharge plasma in contact with water: evidence for the formation of peroxynitrite through a pseudo-second-order post-discharge reaction of H2O2 and HNO2

    NASA Astrophysics Data System (ADS)

    Lukes, P.; Dolezalova, E.; Sisrova, I.; Clupek, M.

    2014-02-01

    The formation of transient species (OH·, NO2·, NO radicals) and long-lived chemical products (O3, H2O2, NO_{3}^{-} , NO_{2}^{-} ) produced by a gas discharge plasma at the gas-liquid interface and directly in the liquid was measured in dependence on the gas atmosphere (20% oxygen mixtures with nitrogen or with argon) and pH of plasma-treated water (controlled by buffers at pH 3.3, 6.9 or 10.1). The aqueous-phase chemistry and specific contributions of these species to the chemical and biocidal effects of air discharge plasma in water were evaluated using phenol as a chemical probe and bacteria Escherichia coli. The nitrated and nitrosylated products of phenol (4-nitrophenol, 2-nitrophenol, 4-nitrocatechol, 4-nitrosophenol) in addition to the hydroxylated products (catechol, hydroquinone, 1,4-benzoquinone, hydroxy-1,4-benzoquinone) evidenced formation of NO2·, NO· and OH· radicals and NO+ ions directly by the air plasma at the gas-liquid interface and through post-discharge processes in plasma-activated water (PAW) mediated by peroxynitrite (ONOOH). Kinetic study of post-discharge evolution of H2O2 and NO_{2}^{-} in PAW has demonstrated excellent fit with the pseudo-second-order reaction between H2O2 and NO_{2}^{-} . The third-order rate constant k = 1.1 × 103 M-2 s-1 for the reaction NO_{2}^{-} +H_{2}O_{2}+H^{+}\\to ONOOH+H_{2}O was determined in PAW at pH 3.3 with the rate of ONOOH formation in the range 10-8-10-9 M s-1. Peroxynitrite chemistry was shown to significantly participate in the antibacterial properties of PAW. Ozone presence in PAW was proved indirectly by pH-dependent degradation of phenol and detection of cis,cis-muconic acid, but contribution of ozone to the inactivation of bacteria by the air plasma was negligible.

  3. Kinetic and mechanistic investigations of progesterone reaction with ozone.

    PubMed

    Barron, Emmanuelle; Deborde, Marie; Rabouan, Sylvie; Mazellier, Patrick; Legube, Bernard

    2006-06-01

    The removal of progesterone by ozone in aqueous solution was studied in this work. The absolute rate constant was evaluated and first by-products were identified. The reaction was studied in the 2.0-8.0 pH range and was found to be a second-order reaction, first-order relative to each compound concentration. The rate constant, determined by kinetic experiments in presence of an OH radical scavenger (tert-butanol), was independent of pH. The value was evaluated to be equal to 480+/-30 M(-1)s(-1) by two kinetic methods. Mass spectrometry analyses were performed to investigate primary degradation products generated by the reaction of ozone with progesterone. Two by-products were evidenced. According to these results, a degradation pathway of progesterone reacting with ozone was proposed. PMID:16725173

  4. Modelling reaction kinetics inside cells

    PubMed Central

    Grima, Ramon; Schnell, Santiago

    2009-01-01

    In the past decade, advances in molecular biology such as the development of non-invasive single molecule imaging techniques have given us a window into the intricate biochemical activities that occur inside cells. In this article we review four distinct theoretical and simulation frameworks: (1) non-spatial and deterministic, (2) spatial and deterministic, (3) non-spatial and stochastic and (4) spatial and stochastic. Each framework can be suited to modelling and interpreting intracellular reaction kinetics. By estimating the fundamental length scales, one can roughly determine which models are best suited for the particular reaction pathway under study. We discuss differences in prediction between the four modelling methodologies. In particular we show that taking into account noise and space does not simply add quantitative predictive accuracy but may also lead to qualitatively different physiological predictions, unaccounted for by classical deterministic models. PMID:18793122

  5. Complete active space second order perturbation theory (CASPT2) study of N(²D) + H₂O reaction paths on D₁ and D₀ potential energy surfaces: direct and roaming pathways.

    PubMed

    Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji

    2014-10-21

    We report reaction paths starting from N((2)D) + H2O for doublet spin states, D0 and D1. The potential energy surfaces are explored in an automated fashion using the global reaction route mapping strategy. The critical points and reaction paths have been fully optimized at the complete active space second order perturbation theory level taking all valence electrons in the active space. In addition to direct dissociation pathways that would be dominant, three roaming processes, two roaming dissociation, and one roaming isomerization: (1) H2ON → H-O(H)N → H-HON → NO((2)Π) + H2, (2) cis-HNOH → HNO-H → H-HNO → NO + H2, (3) H2NO → H-HNO → HNO-H → trans-HNOH, are confirmed on the D0 surface. PMID:25338892

  6. Complete active space second order perturbation theory (CASPT2) study of N(2D) + H2O reaction paths on D1 and D0 potential energy surfaces: Direct and roaming pathways

    NASA Astrophysics Data System (ADS)

    Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji

    2014-10-01

    We report reaction paths starting from N(2D) + H2O for doublet spin states, D0 and D1. The potential energy surfaces are explored in an automated fashion using the global reaction route mapping strategy. The critical points and reaction paths have been fully optimized at the complete active space second order perturbation theory level taking all valence electrons in the active space. In addition to direct dissociation pathways that would be dominant, three roaming processes, two roaming dissociation, and one roaming isomerization: (1) H2ON → H-O(H)N → H-HON → NO(2Π) + H2, (2) cis-HNOH → HNO-H → H-HNO → NO + H2, (3) H2NO → H-HNO → HNO-H → trans-HNOH, are confirmed on the D0 surface.

  7. Complete active space second order perturbation theory (CASPT2) study of N({sup 2}D) + H{sub 2}O reaction paths on D{sub 1} and D{sub 0} potential energy surfaces: Direct and roaming pathways

    SciTech Connect

    Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji

    2014-10-21

    We report reaction paths starting from N({sup 2}D) + H{sub 2}O for doublet spin states, D{sub 0} and D{sub 1}. The potential energy surfaces are explored in an automated fashion using the global reaction route mapping strategy. The critical points and reaction paths have been fully optimized at the complete active space second order perturbation theory level taking all valence electrons in the active space. In addition to direct dissociation pathways that would be dominant, three roaming processes, two roaming dissociation, and one roaming isomerization: (1) H{sub 2}ON → H–O(H)N → H–HON → NO({sup 2}Π) + H{sub 2}, (2) cis-HNOH → HNO–H → H–HNO → NO + H{sub 2}, (3) H{sub 2}NO → H–HNO → HNO–H → trans-HNOH, are confirmed on the D{sub 0} surface.

  8. Kinetic studies of elementary chemical reactions

    SciTech Connect

    Durant, J.L. Jr.

    1993-12-01

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

  9. Source of second order chromaticity in RHIC

    SciTech Connect

    Luo, Y.; Gu, X.; Fischer, W.; Trbojevic, D.

    2011-01-01

    In this note we will answer the following questions: (1) what is the source of second order chromaticities in RHIC? (2) what is the dependence of second order chromaticity on the on-momentum {beta}-beat? (3) what is the dependence of second order chromaticity on {beta}* at IP6 and IP8? To answer these questions, we use the perturbation theory to numerically calculate the contributions of each quadrupole and sextupole to the first, second, and third order chromaticities.

  10. The Kinetics of Isotopic Exchange Reactions.

    ERIC Educational Resources Information Center

    Logan, S. R.

    1990-01-01

    Discussed are the kinetic interactions of these chemical processes and the determination of the actual order of such reactions. Included are multiple exchange, catalytic exchange with deuterium, and depletion of the original substrate. (CW)

  11. Binocular Combination of Second-Order Stimuli

    PubMed Central

    Zhou, Jiawei; Liu, Rong; Zhou, Yifeng; Hess, Robert F.

    2014-01-01

    Phase information is a fundamental aspect of visual stimuli. However, the nature of the binocular combination of stimuli defined by modulations in contrast, so-called second-order stimuli, is presently not clear. To address this issue, we measured binocular combination for first- (luminance modulated) and second-order (contrast modulated) stimuli using a binocular phase combination paradigm in seven normal adults. We found that the binocular perceived phase of second-order gratings depends on the interocular signal ratio as has been previously shown for their first order counterparts; the interocular signal ratios when the two eyes were balanced was close to 1 in both first- and second-order phase combinations. However, second-order combination is more linear than previously found for first-order combination. Furthermore, binocular combination of second-order stimuli was similar regardless of whether the carriers in the two eyes were correlated, anti-correlated, or uncorrelated. This suggests that, in normal adults, the binocular phase combination of second-order stimuli occurs after the monocular extracting of the second-order modulations. The sensory balance associated with this second-order combination can be obtained from binocular phase combination measurements. PMID:24404180

  12. Binocular combination of second-order stimuli.

    PubMed

    Zhou, Jiawei; Liu, Rong; Zhou, Yifeng; Hess, Robert F

    2014-01-01

    Phase information is a fundamental aspect of visual stimuli. However, the nature of the binocular combination of stimuli defined by modulations in contrast, so-called second-order stimuli, is presently not clear. To address this issue, we measured binocular combination for first- (luminance modulated) and second-order (contrast modulated) stimuli using a binocular phase combination paradigm in seven normal adults. We found that the binocular perceived phase of second-order gratings depends on the interocular signal ratio as has been previously shown for their first order counterparts; the interocular signal ratios when the two eyes were balanced was close to 1 in both first- and second-order phase combinations. However, second-order combination is more linear than previously found for first-order combination. Furthermore, binocular combination of second-order stimuli was similar regardless of whether the carriers in the two eyes were correlated, anti-correlated, or uncorrelated. This suggests that, in normal adults, the binocular phase combination of second-order stimuli occurs after the monocular extracting of the second-order modulations. The sensory balance associated with this second-order combination can be obtained from binocular phase combination measurements. PMID:24404180

  13. The second-order gravitational red shift

    NASA Technical Reports Server (NTRS)

    Jaffe, J.

    1973-01-01

    The direct measurement of the nonlinear term of the gravitational field equations by using very stable clocks is discussed along with measuring the perhelion advance of a planet or satellite. These are considered measurements of the second-order gravitational red shift. The exact expression for the frequency shift of light in a gravitational field is derived. Other topics discussed include: The Doppler-cancelling technique; the second-order red shift in a spherically symmetric gravitational field; finite signal transit time; and the reality and interpretation of coordinates in the second-order red shift experiment.

  14. Unraveling reaction pathways and specifying reaction kinetics for complex systems.

    PubMed

    Vinu, R; Broadbelt, Linda J

    2012-01-01

    Many natural and industrial processes involve a complex set of competing reactions that include several different species. Detailed kinetic modeling of such systems can shed light on the important pathways involved in various transformations and therefore can be used to optimize the process conditions for the desired product composition and properties. This review focuses on elucidating the various components involved in modeling the kinetics of pyrolysis and oxidation of polymers. The elementary free radical steps that constitute the chain reaction mechanism of gas-phase/nonpolar liquid-phase processes are outlined. Specification of the rate coefficients of the various reaction families, which is central to the theme of kinetics, is described. Construction of the reaction network on the basis of the types of end groups and reactive moieties in a polymer chain is discussed. Modeling frameworks based on the method of moments and kinetic Monte Carlo are evaluated using illustrations. Finally, the prospects and challenges in modeling biomass conversion are addressed. PMID:22468596

  15. Nine Practices of Second Order Schools

    ERIC Educational Resources Information Center

    Brown, Bill; Tucker, Patrick; Williams, Thomas L.

    2012-01-01

    Many schools are in some stage of implementing differentiated instruction, with some already in what Carol Tomlinson describes in "The Differentiated School" as "second order change," where the entire school practices differentiation. In high-performing schools, differentiation has proved to be an effective instructional strategy; in classroom…

  16. Second-Order Conditioning in "Drosophila"

    ERIC Educational Resources Information Center

    Tabone, Christopher J.; de Belle, J. Steven

    2011-01-01

    Associative conditioning in "Drosophila melanogaster" has been well documented for several decades. However, most studies report only simple associations of conditioned stimuli (CS, e.g., odor) with unconditioned stimuli (US, e.g., electric shock) to measure learning or establish memory. Here we describe a straightforward second-order conditioning…

  17. Correction of second order chromaticity at Tevatron

    SciTech Connect

    Valishev, A.; Annala, G.; Lebedev, V.; Moore, R.S.; /Fermilab

    2007-06-01

    Correction of the second order betatron tune chromaticity is essential for operation at the working point near half integer resonance which is proposed as one of the ways to improve performance of the Tevatron. In this report the new chromaticity correction scheme with split sextupole families is described. Details of implementation and commissioning at the present working point are discussed.

  18. Second-Order Invariants and Holography

    NASA Astrophysics Data System (ADS)

    Luongo, Orlando; Bonanno, Luca; Iannone, Gerardo

    2012-12-01

    Motivated by recent works on the role of the holographic principle in cosmology, we relate a class of second-order Ricci invariants to the IR cutoff characterizing the holographic dark energy density. The choice of second-order invariants provides an invariant way to account the problem of causality for the correct cosmological cutoff, since the presence of event horizons is not an a priori assumption. We find that these models work fairly well, by fitting the observational data, through a combined cosmological test with the use of SNeIa, BAO and CMB. This class of models is also able to overcome the fine-tuning and coincidence problems. Finally, to make a comparison with other recent models, we adopt the statistical tests AIC and BIC.

  19. Calculating Second-Order Effects in MOSFET's

    NASA Technical Reports Server (NTRS)

    Benumof, Reuben; Zoutendyk, John A.; Coss, James R.

    1990-01-01

    Collection of mathematical models includes second-order effects in n-channel, enhancement-mode, metal-oxide-semiconductor field-effect transistors (MOSFET's). When dimensions of circuit elements relatively large, effects neglected safely. However, as very-large-scale integration of microelectronic circuits leads to MOSFET's shorter or narrower than 2 micrometer, effects become significant in design and operation. Such computer programs as widely-used "Simulation Program With Integrated Circuit Emphasis, Version 2" (SPICE 2) include many of these effects. In second-order models of n-channel, enhancement-mode MOSFET, first-order gate-depletion region diminished by triangular-cross-section deletions on end and augmented by circular-wedge-cross-section bulges on sides.

  20. Properties of second-order geometrical aberrations

    NASA Astrophysics Data System (ADS)

    Grammatin, A. P.

    1994-08-01

    This paper analyzes the properties of second-order aberrations that arise in centered optical systems that contain an aspherical surface whose sagittal equation contains a term proportional to the cube of the distance from a surface point to the optical axis. It is shown that the second-order spherical aberration decreases from the center of the field to its edge. No astigmatism appears in wide, oblique beams in the central part of the field. Coma increases linearly from zero at the center of the field to a value equal to the spherical aberration, and then remains constant over the field. A proof is given of the possibility of correcting the image curvature by using an aspherical surface of the type described above.

  1. Visualizing second order tensor fields with hyperstreamlines

    NASA Technical Reports Server (NTRS)

    Delmarcelle, Thierry; Hesselink, Lambertus

    1993-01-01

    Hyperstreamlines are a generalization to second order tensor fields of the conventional streamlines used in vector field visualization. As opposed to point icons commonly used in visualizing tensor fields, hyperstreamlines form a continuous representation of the complete tensor information along a three-dimensional path. This technique is useful in visulaizing both symmetric and unsymmetric three-dimensional tensor data. Several examples of tensor field visualization in solid materials and fluid flows are provided.

  2. Spacetime encodings. III. Second order Killing tensors

    SciTech Connect

    Brink, Jeandrew

    2010-01-15

    This paper explores the Petrov type D, stationary axisymmetric vacuum (SAV) spacetimes that were found by Carter to have separable Hamilton-Jacobi equations, and thus admit a second-order Killing tensor. The derivation of the spacetimes presented in this paper borrows from ideas about dynamical systems, and illustrates concepts that can be generalized to higher-order Killing tensors. The relationship between the components of the Killing equations and metric functions are given explicitly. The origin of the four separable coordinate systems found by Carter is explained and classified in terms of the analytic structure associated with the Killing equations. A geometric picture of what the orbital invariants may represent is built. Requiring that a SAV spacetime admits a second-order Killing tensor is very restrictive, selecting very few candidates from the group of all possible SAV spacetimes. This restriction arises due to the fact that the consistency conditions associated with the Killing equations require that the field variables obey a second-order differential equation, as opposed to a fourth-order differential equation that imposes the weaker condition that the spacetime be SAV. This paper introduces ideas that could lead to the explicit computation of more general orbital invariants in the form of higher-order Killing tensors.

  3. Manganese peroxidase from the lignin-degrading basidiomycete Phanerochaete chrysosporium: Transient state kinetics and reaction mechanism

    SciTech Connect

    Wariishi, Hiroyuki; Gold, M.H. ); Dunford, H.B.; MacDonald, I.D. )

    1989-02-25

    Stopped-flow techniques were used to investigate the kinetics of the formation of manganese peroxidase compound I (MnPI) and of the reactions of MnPI and manganese peroxidase compound II (MnPII) with p-cresol and Mn{sup II}. All of the rate data were obtained from single turnover experiments under pseudo-first order conditions. In the presence of H{sub 2}O{sub 2} the formation of MnPI is independent of pH over the range 3.12-8.29 with a second-order rate constant of (2.0{+-}0.1) {times} 10{sup 6} M{sup {minus}1} s{sup {minus}1}. The activation energy for MnPI formation is 20 kJ mol{sup {minus}1}. MnPI formation also occurs with organic peroxides such as peracetic acid, m-chloroperoxybenzoic acid, and p-nitroperoxybenzoic acid with second-order rate constants of 9.7 x 10{sup 5}, 9.5 {times} 10{sup 4}, and 5.9 {times} 10{sup 4} M{sup {minus}1} s{sup {minus}1}, respectively. The reactions of MnPI and MnPII with p-cresol strictly obeyed second-order kinetics. The second-order rate constant for the reaction of MnPII with p-cresol is extremely low, (9.5{+-}0.5) m{sup {minus}1} s{sup {minus}1}. Kinetic analysis of the reaction of Mn{sup II} with MnPI and MnPII showed a binding interaction with the oxidized enzymes which led to saturation kinetics. The first-order dissociation rate constants for the reaction of Mn{sup II} with MnPI and MnPII are (0.7{+-}0.1) and (0.14{+-}0.01) s{sup {minus}1}, respectively, when the reaction is conducted in lactate buffer. Rate constants are considerably lower when the reactions are conducted in succinate buffer. Single turnover experiments confirmed that Mn{sup II} serves as an obligatory substrate for MnPII and that both oxidized forms of the enzyme form productive complexes with Mn{sup II}. Finally, these results suggest the {alpha}-hydroxy acids such as lactate facilitate the dissociation of Mn{sup II} from the enzyme.

  4. Kinetic analysis of complex reactions using FEMLAB

    SciTech Connect

    Cao, Chunshe; Wang, Yong

    2005-06-07

    A finite element method software FEMALB has been implemented to the kinetic analysis of complex reaction systems. The established protocol provides fast solutions to the coupled differential-algebraic equations. It shows significant advantages over the conventional coding process with the standard implicit Runge-Kutta (IRK) method. The accuracy and high efficiency have been demonstrated in the simulation of the reaction processes such as glucose/fructose hydrogenation and catalytic cracking of gasoil. As model validation, the numerical results showed satisfactory agreement with the exact solutions. With the powerful capability of solving large matrixes of differential equations (both ODE and PDE) with nonlinear algebraic constrains, such an algorithm has greatly reduced the coding labor in reaction mechanistic studies and provided a unique tool in reactor design and optimization.

  5. Spectroscopy and reaction kinetics of HCO

    SciTech Connect

    Guo, Yili

    1989-01-01

    The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ..nu../sub 1/ band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ..nu../sub 1/ data with previous microwave and FIR LMR measurements. A new set of spectroscopic constants for the (1, 0, 0) state, the equilibrium rotational constants, and the orientation of the transition dipole moment are also reported. The kinetics and product branching ratios of the HCO + NO/sub 2/ reaction have been studied using visible and infrared laser flash kinetic spectroscopy. The rate constant for the disappearance of HCO radical at 296 K is (5.7 +- 0.9) /times/ 10/sup /minus/11/ cm/sup 3/ molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF/sub 6/ buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO/sub 2/. The product channel, H + CO/sub 2/ + NO, is responsible for 52% of the reaction. HONO has been observed, though not quantitatively, as a reaction product corresponding to the HONO + CO channel. 51 refs., 21 figs., 8 tabs.

  6. Kinetic features of an intraresin reaction

    SciTech Connect

    Kim, B.; Kirszensztejn, P.; Bolikal, D.; Regen, S.L.

    1983-03-23

    The kinetic features of the intraresin displacement by pendant ammonium acetate groups on chloromethylated polystrene have been investigated as a function of temperature, swelling solvent, and cross-link density. In all cases, intraresin displacement proceeds with a rapid initial rate followed by a very slow stage; the latter represents that fraction of reactants which become ''kinetically isolated''. The free energy of activation for the first stage, under the various swelling conditions used, lies in the range 24.4-26.8 kcal mol/sup -1/, which is similar to that found for analogous homogeneous reactions. The absolute rates measured for the homogeneous and the initial intraresin displacement in dioxane were similar; with n-hexane and toluene as solvents, polymeric rates were considerably slower than those of their homogeneous counterparts. Intraresin displacement was rapid even when a poor swelling solvent (n-hexane) was used. As the rate of intrapolymeric reaction decreased (through a decrease in temperature, increase in cross-link density, or change in solvent), the percent of ''kinetical isolated'' sites increased.

  7. Understanding Arsenate Reaction Kinetics with Ferric Hydroxides

    PubMed Central

    Farrell, James; Chaudhary, Binod K.

    2015-01-01

    Understanding arsenic reactions with ferric hydroxides is important in understanding arsenic transport in the environment and in designing systems for removing arsenic from potable water. Many experimental studies have shown that the kinetics of arsenic adsorption on ferric hydroxides is biphasic, where a fraction of the arsenic adsorption occurs on a time scale of seconds while full equilibrium may require weeks to attain. This research employed density functional theory modeling in order to understand the mechanisms contributing to biphasic arsenic adsorption kinetics. The reaction energies and activation barriers for three modes of arsenate adsorption to ferric hydroxides were calculated. Gibbs free energies of reaction depended on the net charge of the complexes, which is a function of the system pH value. Physical adsorption of arsenate to ferric hydroxide proceeded with no activation barrier, with Gibbs free energies of reaction ranging from −21 to −58 kJ/mol. The highest Gibbs free energies of reaction for physical adsorption resulted from negative charge assisted hydrogen bonding between H atoms on the ferric hydroxide and O atoms in arsenate. The conversion of physically adsorbed arsenate into monodentate surface complexes had Gibbs free energies of activation ranging from 62 to 73 kJ/mol, and Gibbs free energies of reaction ranging from −23 to −38 kJ/mol. The conversion of monodentate surface complexes to bidentate, binuclear complexes had Gibbs free energies of activation ranging from 79 to 112 kJ/mol, and Gibbs free energies of reaction ranging from −11 to −55 kJ/mol. For release of arsenate from uncharged bidentate complexes, energies of activation as high as 167 kJ/mol were encountered. Increasingly negative charges on the complexes lowered the activation barriers for desorption of arsenate, and in complexes with −2 charges, the highest activation barrier was 65 kJ/mol. This study shows that the slow kinetics associated with arsenic

  8. Second order Kerr-Newman time delay

    NASA Astrophysics Data System (ADS)

    He, G.; Lin, W.

    2016-01-01

    The explicit form for the post-Newtonian gravitational time delay of light signals propagating on the equatorial plane of a Kerr-Newman black hole is derived. Based on the null geodesic in Kerr-Newman spacetime, we adopt the iterative method to calculate the time delay. Our result reduces to the previous formulation for the Kerr black hole if we drop the contribution from the electrical charge. Our time-delay formula for the Reissner-Nordström geometry is different from the previous publication [Phys. Rev. D 69, 023002 (2004)], in which the largest second order contribution to the time delay is missing.

  9. Analysis of second-order gratings

    SciTech Connect

    Hardy, A.; Welch, D.F.; Streifer, W. )

    1989-10-01

    The authors report the results of a second-order grating analysis. The gratings are used as distributed Bragg reflectors in surface-emitting lasers, which are currently being fabricated in several laboratories. The gratings provide reflection, output coupling, and power transmission to other gain segments for purposes of injection locking. The analysis determines these quantities for arbitrary-shaped grating teeth and includes the presence of a substrate reflector to reduce the radiated power in that direction. The reflector is shown to be effective, but only if it can be precisely positioned. Examples illustrating variations in dimensions, tooth shapes and heights, waveguide loss, and detuning are included.

  10. Second-order coherence of supercontinuum light.

    PubMed

    Genty, Goëry; Surakka, Minna; Turunen, Jari; Friberg, Ari T

    2010-09-15

    We analyze the coherence properties of supercontinuum generated in photonic crystal fibers by applying the second-order coherence theory of nonstationary light. Using an ensemble of simulated realizations, we construct two-frequency cross-spectral density and two-time mutual coherence functions. This allows us to introduce measures of temporal and spectral coherence. We show that, in the long-pulse regime, supercontinuum light can be decomposed into a sum of coherent and quasi-stationary contributions. Our approach and findings are also applicable in the short-pulse regime. PMID:20847777

  11. Robust stability of second-order systems

    NASA Technical Reports Server (NTRS)

    Chuang, C.-H.

    1995-01-01

    It has been shown recently how virtual passive controllers can be designed for second-order dynamic systems to achieve robust stability. The virtual controllers were visualized as systems made up of spring, mass and damping elements. In this paper, a new approach emphasizing on the notion of positive realness to the same second-order dynamic systems is used. Necessary and sufficient conditions for positive realness are presented for scalar spring-mass-dashpot systems. For multi-input multi-output systems, we show how a mass-spring-dashpot system can be made positive real by properly choosing its output variables. In particular, sufficient conditions are shown for the system without output velocity. Furthermore, if velocity cannot be measured then the system parameters must be precise to keep the system positive real. In practice, system parameters are not always constant and cannot be measured precisely. Therefore, in order to be useful positive real systems must be robust to some degrees. This can be achieved with the design presented in this paper.

  12. First- and second-order Poisson spots

    NASA Astrophysics Data System (ADS)

    Kelly, William R.; Shirley, Eric L.; Migdall, Alan L.; Polyakov, Sergey V.; Hendrix, Kurt

    2009-08-01

    Although Thomas Young is generally given credit for being the first to provide evidence against Newton's corpuscular theory of light, it was Augustin Fresnel who first stated the modern theory of diffraction. We review the history surrounding Fresnel's 1818 paper and the role of the Poisson spot in the associated controversy. We next discuss the boundary-diffraction-wave approach to calculating diffraction effects and show how it can reduce the complexity of calculating diffraction patterns. We briefly discuss a generalization of this approach that reduces the dimensionality of integrals needed to calculate the complete diffraction pattern of any order diffraction effect. We repeat earlier demonstrations of the conventional Poisson spot and discuss an experimental setup for demonstrating an analogous phenomenon that we call a "second-order Poisson spot." Several features of the diffraction pattern can be explained simply by considering the path lengths of singly and doubly bent paths and distinguishing between first- and second-order diffraction effects related to such paths, respectively.

  13. Synchronization from Second Order Network Connectivity Statistics

    PubMed Central

    Zhao, Liqiong; Beverlin, Bryce; Netoff, Theoden; Nykamp, Duane Q.

    2011-01-01

    We investigate how network structure can influence the tendency for a neuronal network to synchronize, or its synchronizability, independent of the dynamical model for each neuron. The synchrony analysis takes advantage of the framework of second order networks, which defines four second order connectivity statistics based on the relative frequency of two-connection network motifs. The analysis identifies two of these statistics, convergent connections, and chain connections, as highly influencing the synchrony. Simulations verify that synchrony decreases with the frequency of convergent connections and increases with the frequency of chain connections. These trends persist with simulations of multiple models for the neuron dynamics and for different types of networks. Surprisingly, divergent connections, which determine the fraction of shared inputs, do not strongly influence the synchrony. The critical role of chains, rather than divergent connections, in influencing synchrony can be explained by their increasing the effective coupling strength. The decrease of synchrony with convergent connections is primarily due to the resulting heterogeneity in firing rates. PMID:21779239

  14. Slowly rotating scalar field wormholes: The second order approximation

    SciTech Connect

    Kashargin, P. E.; Sushkov, S. V.

    2008-09-15

    We discuss rotating wormholes in general relativity with a scalar field with negative kinetic energy. To solve the problem, we use the assumption about slow rotation. The role of a small dimensionless parameter plays the ratio of the linear velocity of rotation of the wormhole's throat and the velocity of light. We construct the rotating wormhole solution in the second-order approximation with respect to the small parameter. The analysis shows that the asymptotical mass of the rotating wormhole is greater than that of the nonrotating one, and the null energy condition violation in the rotating wormhole spacetime is weaker than that in the nonrotating one.

  15. Second-order (2 +1 ) -dimensional anisotropic hydrodynamics

    NASA Astrophysics Data System (ADS)

    Bazow, Dennis; Heinz, Ulrich; Strickland, Michael

    2014-11-01

    We present a complete formulation of second-order (2 +1 ) -dimensional anisotropic hydrodynamics. The resulting framework generalizes leading-order anisotropic hydrodynamics by allowing for deviations of the one-particle distribution function from the spheroidal form assumed at leading order. We derive complete second-order equations of motion for the additional terms in the macroscopic currents generated by these deviations from their kinetic definition using a Grad-Israel-Stewart 14-moment ansatz. The result is a set of coupled partial differential equations for the momentum-space anisotropy parameter, effective temperature, the transverse components of the fluid four-velocity, and the viscous tensor components generated by deviations of the distribution from spheroidal form. We then perform a quantitative test of our approach by applying it to the case of one-dimensional boost-invariant expansion in the relaxation time approximation (RTA) in which case it is possible to numerically solve the Boltzmann equation exactly. We demonstrate that the second-order anisotropic hydrodynamics approach provides an excellent approximation to the exact (0+1)-dimensional RTA solution for both small and large values of the shear viscosity.

  16. Theory of Neutron Chain Reactions: Extracts from Volume I, Diffusion and Slowing Down of Neutrons: Chapter I. Elementary Theory of Neutron Diffusion. Chapter II. Second Order Diffusion Theory. Chapter III. Slowing Down of Neutrons

    DOE R&D Accomplishments Database

    Weinberg, Alvin M.; Noderer, L. C.

    1951-05-15

    The large scale release of nuclear energy in a uranium fission chain reaction involves two essentially distinct physical phenomena. On the one hand there are the individual nuclear processes such as fission, neutron capture, and neutron scattering. These are essentially quantum mechanical in character, and their theory is non-classical. On the other hand, there is the process of diffusion -- in particular, diffusion of neutrons, which is of fundamental importance in a nuclear chain reaction. This process is classical; insofar as the theory of the nuclear chain reaction depends on the theory of neutron diffusion, the mathematical study of chain reactions is an application of classical, not quantum mechanical, techniques.

  17. Kinetic Roughening and Bifurcations in Reaction - Systems

    NASA Astrophysics Data System (ADS)

    Provatas, Nikolas

    1995-01-01

    We study the dynamics of two reaction-diffusion phenomena driven by chemical activation and thermal dissipation and evolving, respectively, on a randomly distributed or continuous medium. The first system describes the process of slow combustion of a randomly distributed reactant. It is studied by a phase-field model built up from first principles and describes the evolution of thermal and reactant concentration fields. Our combustion model incorporates thermal diffusion, activation and dissipation. We examine it in a manner which makes a connection between the propagation of combustion fronts, their kinetic roughening and the percolation transition. In so doing, we examine slow combustion in the context phase transitions. The second system describes propagation of reaction fronts arising in transformations obeying the Arrhenius law of chemical reactions. It too is modelled by a set of phase-field equations describing the dynamics of both thermal and concentration fields. A typical example of this transformation is the crystallization of an amorphous material. In addition to the features of our combustion model, this model also incorporated a realistic treatment of mass diffusion. Front propagation of our model is shown to undergo period doubling bifurcations as one varies the background temperature at which the system is maintained. The signature of these bifurcations is the same as those of the logistics map. We study how the bifurcation structure changes as a function mass diffusion, focusing on changes of the background temperature for which period doubling first emerges. This temperature is the most easily obtained experimentally.

  18. Kinetics investigations of atmospheric chemical reactions

    SciTech Connect

    Hills, A.J.

    1987-01-01

    Two separate gas-phase kinetics investigations were performed using a low-pressure fast-flow system with mass spectrometer detection. The first part of this research was a study of the atmospheric reactivity of diatomic sulfur, S/sub 2/. Rates of the reactions of sulfur with O, O/sub 2/, O/sub 3/, N/sub 2/O, NO, and NO/sub 2/ were investigated at 409 K and low pressure (0.89-3.0 Torr) in a discharge-flow system with mass spectrometric detection. The second investigation involves a study of the synergistic coupling of atmospheric bromine and chlorine chemistry. Recent measurements of ozone in the stratosphere over Antarctica have shown that the springtime ozone column decreased by 40% from 1960 to 1985. Both dynamical and chemical theories have been advanced to explain the formation of the Antarctic ozone hole. Prominent among these theories is that a synergistic interaction between gas-phase BrO and ClO radicals may be responsible for springtime ozone loss. The overall rate constant for the reaction, BrO + ClO ..-->.. Br + OClO ..-->.. Br + Cl + O/sub 2/ ..-->.. BrCl + O/sub 2/, has been measured over the temperature range 241-408 K. The rate constant for the overall reaction equals (8.2 +/- 1.0) 10/sup -12/ cm/sup 3//molecule s, independent of temperature.

  19. Reaction rate kinetics for in situ combustion retorting of Michigan Antrim oil shale

    USGS Publications Warehouse

    Rostam-Abadi, M.; Mickelson, R.W.

    1984-01-01

    The intrinsic reaction rate kinetics for the pyrolysis of Michigan Antrim oil shale and the oxidation of the carbonaceous residue of this shale have been determined using a thermogravimetric analysis method. The kinetics of the pyrolysis reaction were evaluated from both isothermal and nonisothermal rate data. The reaction was found to be second-order with an activation energy of 252.2 kJ/mole, and with a frequency factor of 9.25 ?? 1015 sec-1. Pyrolysis kinetics were not affected by heating rates between 0.01 to 0.67??K/s. No evidence of any reactions among the oil shale mineral constituents was observed at temperatures below 1173??K. However, it was found that the presence of pyrite in oil shale reduces the primary devolatilization rate of kerogen and increases the amount of residual char in the spent shale. Carbonaceous residues which were prepared by heating the oil shale at a rate of 0.166??K/s to temperatures between 923??K and 1073??K, had the highest reactivities when oxidized at 0.166??K/s in a gas having 21 volume percent oxygen. Oxygen chemisorption was found to be the initial precursor to the oxidation process. The kinetics governing oxygen chemisorption is (Equation Presented) where X is the fractional coverage. The oxidation of the carbonaceous residue was found also to be second-order. The activation energy and the frequency factor determined from isothermal experiments were 147 kJ/mole and 9.18??107 sec-1 respectively, while the values of these parameters obtained from a nonisothermal experiment were 212 kJ/mole and 1.5??1013 sec-1. The variation in the rate constants is attributed to the fact that isothermal and nonisothermal analyses represent two different aspects of the combustion process.

  20. A second order parameter for 3SAT

    SciTech Connect

    Sandholm, T.W.

    1996-12-31

    The 3-satisfiability problem (3SAT) has had a central role in the study of complexity. It was recently found that 3SAT instances transition sharply from satisfiable to nonsatisfiable as the ratio of clauses to variables increases. Because this phase transition is so sharp, the ratio - an order parameter - can be used to predict satisfiability. This paper describes a second order parameter for 3SAT. Like the classical order parameter, it can be computed in linear time, but it analyzes the structure of the problem instance more deeply. We present an analytical method for using this new order parameter in conjunction with the classical one to enhance satisfiability prediction accuracy. The assumptions of the method are verified by rigorous statistical testing. The method significantly increases the satisfiability prediction accuracy over using the classical order parameter alone. Hardness - i.e. how long it takes to determine satisfiability - results for one complete and one incomplete algorithm from the literature are also presented as a function of the two order parameters. The importance of new order parameters lies in the fact that they refine the locating of satisfiable vs. nonsatisfiable and hard vs. easy formulas in the space of all problem instances by adding a new dimension in the analysis.

  1. Reaction kinetic analysis of reactor surveillance data

    NASA Astrophysics Data System (ADS)

    Yoshiie, T.; Sato, K.; Xu, Q.; Nagai, Y.

    2015-06-01

    In reactor pressure vessel surveillance data, it was found that the concentration of matrix defects was very low even after nearly 40 years of operation, though a large number of precipitates existed. In this paper, defect structures obtained from surveillance data of A533B (high Cu concentration) were simulated using reaction kinetic analysis with 11 rate equations. The coefficients used in the equations were quite different from those obtained by fitting a Fe-0.6 wt%Cu alloy irradiated by the Kyoto University Reactor. The difference was mainly caused by alloying elements in A533B, and the effect of alloying elements was extracted. The same code was applied to low-Cu A533B irradiated with high irradiation damage rate, and the formation of voids was correctly simulated.

  2. Reactions of lignin peroxidase compounds I and II with veratryl alcohol. Transient-state kinetic characterization.

    PubMed

    Wariishi, H; Huang, J; Dunford, H B; Gold, M H

    1991-11-01

    Stopped-flow techniques were utilized to investigate the kinetics of the reaction of lignin peroxidase compounds I and II (LiPI and LiPII) with veratryl alcohol (VA). All rate data were collected from single turnover experiments under pseudo first-order conditions. The reaction of LiPI with VA strictly obeys second-order kinetics over the pH range 2.72-5.25 as demonstrated by linear plots of the pseudo first-order rate constants versus concentrations of VA. The second-order rate constants are strongly dependent on pH and range from 2.62 x 10(6) M-1 s-1 (pH 2.72) to 1.45 x 10(4) M-1 s-1 (pH 5.25). The reaction of LiPII and VA exhibits saturation behavior when the observed pseudo first-order rate constants are plotted against VA concentrations. The saturation phenomenon is quantitatively explained by the formation of a 1:1 LiPII-substrate complex. Results of kinetic and rapid scan spectral analyses exclude the formation of a LiPII-VA cation radical complex. The first-order dissociation rate constant and the equilibrium dissociation constant for the LiPII reaction are also pH dependent. Binding of VA to LiPII is controlled by a heme-linked ionizable group of pKa approximately 4.2. The pH profiles of the second-order rate constants for the LiPI reaction and of the first-order dissociation constants for the LiPII reaction both demonstrate two pKa values at approximately 3.0 and approximately 4.2. Protonated oxidized enzyme intermediates are most active, suggesting that only electron transfer, not proton uptake from the reducing substrate, occurs at the enzyme active site. These results are consistent with the one-electron oxidation of VA to an aryl cation radical by LiPI and LiPII. PMID:1939119

  3. Second-order splitting schemes for a class of reactive systems

    NASA Astrophysics Data System (ADS)

    Ren, Zhuyin; Pope, Stephen B.

    2008-09-01

    We consider the numerical time integration of a class of reaction-transport systems that are described by a set of ordinary differential equations for primary variables. In the governing equations, the terms involved may require the knowledge of secondary variables, which are functions of the primary variables. Specifically, we consider the case where, given the primary variables, the evaluation of the secondary variables is computationally expensive. To solve this class of reaction-transport equations, we develop and demonstrate several computationally efficient splitting schemes, wherein the portions of the governing equations containing chemical reaction terms are separated from those parts containing the transport terms. A computationally efficient solution to the transport sub-step is achieved through the use of linearization or predictor-corrector methods. The splitting schemes are applied to the reactive flow in a continuously stirred tank reactor (CSTR) with the Davis-Skodjie reaction model, to the CO+H oxidation in a CSTR with detailed chemical kinetics, and to a reaction-diffusion system with an extension of the Oregonator model of the Belousov-Zhabotinsky reaction. As demonstrated in the test problems, the proposed splitting schemes, which yield efficient solutions to the transport sub-step, achieve second-order accuracy in time.

  4. Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

    ERIC Educational Resources Information Center

    Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

  5. Kinetic analysis of free-radical reactions in the low-temperature autoxidation of triglycerides

    SciTech Connect

    Zhu, Jingmin; Sevilla, M.D. )

    1990-02-22

    The kinetics of the low-temperature autoxidation of triglycerides has been investigated by electron spin resonance spectroscopy. After initial radical production, four reaction stages are found in the overall autoxidation of unsaturated lipids: (1) formation of peroxyl radicals by addition of molecular oxygen to the initial carbon radicals, (2) consumption of oxygen in the autoxidation cycle, (3) decay of the lipid peroxyl radical into allylic and pentadienyl radicals, and (4) recombination of the carbon-centered radicals. Peroxyl radical decay in saturated lipids follows second-order kinetics with an apparent activation energy of ca. 50 kJ/mol. The authors find that, for polyunsaturated lipids, even at quite low temperatures (120 K), the autoxidation process occurs readily and must be considered in the storage of biological samples.

  6. Second-Order Nonlinear Optical Imaging of Chiral Crystals

    PubMed Central

    Kissick, David J.; Wanapun, Debbie; Simpson, Garth J.

    2012-01-01

    Second-order nonlinear optical imaging of chiral crystals (SONICC) is an emerging technique for crystal imaging and characterization. We provide a brief overview of the origin of second harmonic generation signals in SONICC and discuss recent studies using SONICC for biological applications. Given that they provide near-complete suppression of any background, SONICC images can be used to determine the presence or absence of protein crystals through both manual inspection and automated analysis. Because SONICC creates high-resolution images, nucleation and growth kinetics can also be observed. SONICC can detect metastable, homochiral crystalline forms of amino acids crystallizing from racemic solutions, which confirms Ostwald’s rule of stages for crystal growth. SONICC’s selectivity, based on order, and sensitivity, based on background suppression, make it a promising technique for numerous fields concerned with chiral crystal formation. PMID:21469954

  7. A Case Study in Chemical Kinetics: The OH + CO Reaction.

    ERIC Educational Resources Information Center

    Weston, Ralph E., Jr.

    1988-01-01

    Reviews some important properties of the bimolecular reaction between the hydroxyl radical and carbon monoxide. Investigates the kinetics of the reaction, the temperature and pressure dependence of the rate constant, the state-to-state dynamics of the reaction, and the reverse reaction. (MVL)

  8. A generalized kinetic model for heterogeneous gas-solid reactions.

    PubMed

    Xu, Zhijie; Sun, Xin; Khaleel, Mohammad A

    2012-08-21

    We present a generalized kinetic model for gas-solid heterogeneous reactions taking place at the interface between two phases. The model studies the reaction kinetics by taking into account the reactions at the interface, as well as the transport process within the product layer. The standard unreacted shrinking core model relies on the assumption of quasi-static diffusion that results in a steady-state concentration profile of gas reactant in the product layer. By relaxing this assumption and resolving the entire problem, general solutions can be obtained for reaction kinetics, including the reaction front velocity and the conversion (volume fraction of reacted solid). The unreacted shrinking core model is shown to be accurate and in agreement with the generalized model for slow reaction (or fast diffusion), low concentration of gas reactant, and small solid size. Otherwise, a generalized kinetic model should be used. PMID:22920132

  9. A generalized kinetic model for heterogeneous gas-solid reactions

    NASA Astrophysics Data System (ADS)

    Xu, Zhijie; Sun, Xin; Khaleel, Mohammad A.

    2012-08-01

    We present a generalized kinetic model for gas-solid heterogeneous reactions taking place at the interface between two phases. The model studies the reaction kinetics by taking into account the reactions at the interface, as well as the transport process within the product layer. The standard unreacted shrinking core model relies on the assumption of quasi-static diffusion that results in a steady-state concentration profile of gas reactant in the product layer. By relaxing this assumption and resolving the entire problem, general solutions can be obtained for reaction kinetics, including the reaction front velocity and the conversion (volume fraction of reacted solid). The unreacted shrinking core model is shown to be accurate and in agreement with the generalized model for slow reaction (or fast diffusion), low concentration of gas reactant, and small solid size. Otherwise, a generalized kinetic model should be used.

  10. Kinetics of the reaction between carbon dioxide and tertiary amines

    SciTech Connect

    Crooks, J.E.; Donnellan, J.P. )

    1990-02-16

    The reaction between carbon dioxide and amines is of great technical importance and has been the subject of many investigations. The authors have shown that the reaction for secondary amines in anhydrous ethanol and in aqueous solution is exclusively second-order in amine and that the zwitterion intermediate postulated by Danckwerts is probably of negligible significance in the mechanism. The reaction with tertiary amines has also been studied, but the data are less controversial. In order to complete their studies of the reactions of carbon dioxide with amines, using their conductimetric stopped-flow apparatus, they have studied this reaction for MDEA (methyldiethanolamine, IUPAC name N-methyl-2,2{prime}-iminodiethanol) and TEA (triethanolamine, IUPAC name 2,2{prime},2{double prime}-nitrilotris(ethanol)).

  11. Assessment of closure schemes in second-order conditional moment closure against DNS with extinction and ignition

    SciTech Connect

    Sreedhara, S.; Huh, Kang Y.

    2005-12-01

    The performance of second-order conditional moment closure (CMC) depends on models to evaluate conditional variances and covariances of temperature and species mass fractions. In this paper the closure schemes based on the steady laminar flamelet model (SLFM) are validated against direct numerical simulation (DNS) involving extinction and ignition. Scaling is performed to reproduce proper absolute magnitudes, irrespective of the origin of mismatch between local flamelet structures and scalar dissipation rates. DNS based on the pseudospectral method is carried out to study hydrogen-air combustion with a detailed kinetic mechanism, in homogeneous, isotropic, and decaying turbulent media. Lewis numbers are set equal to unity to avoid complication of differential diffusion. The SLFM-based closures for correlations among fluctuations of reaction rate, scalar dissipation rate, and species mass fractions show good comparison with DNS. The variance parameter in lognormal PDF and the constants in the dissipation term have been estimated from DNS results. Comparison is made for the resulting conditional profiles from DNS, first-order CMC, and second-order CMC with correction to the most critical reaction step according to sensitivity analysis. Overall good agreement ensures validity of the SLFM-based closures for modeling conditional variances and covariances in second-order CMC.

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

    ERIC Educational Resources Information Center

    Gozzi, Christel; Bouzidi, Naoual

    2008-01-01

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

  13. The surface reaction kinetics of salicylate on alumina

    SciTech Connect

    Wang, Z.; Ainsworth, C.C.; Friedrich, D.M.; Joly, A.G.; Gassman, P.L.

    1997-12-31

    The kinetics of reaction of salicylate with colloidal alumina in aqueous suspension and with Al(III) in homogeneous aqueous solution were studied by stopped-flow laser fluorescence spectroscopy. The emission spectra confirmed the formation of both monodentate complexes and more stable bidentate chelates. Temporal evolution of the spectra indicated that the reaction was fast (within first few minutes) for both the homogeneous and heterogeneous reactions but slowed down afterwards for the latter. Reactions completed within 10 minutes in homogeneous phase at pH 3.3 but took more than 12 hours in alumina suspension. Analysis of the fluorescence intensity within first four minutes showed that in homogeneous phase the reaction followed a single pseudo-first-order kinetics. In alumina suspension log plots were nonlinear and characteristic of multiple heterogeneous reaction paths. The kinetics are interpreted in terms of the simultaneous formation of multiple species as well as subsequent conversion between species.

  14. Moment equations for chromatography based on Langmuir type reaction kinetics.

    PubMed

    Miyabe, Kanji

    2014-08-22

    Moment equations were derived for chromatography, in which the reaction kinetics between solute molecules and functional ligands on the stationary phase was represented by the Langmuir type rate equation. A set of basic equations of the general rate model of chromatography representing the mass balance, mass transfer rate, and reaction kinetics in the column were analytically solved in the Laplace domain. The moment equations for the first absolute moment and the second central moment in the real time domain were derived from the analytical solution in the Laplace domain. The moment equations were used for predicting the chromatographic behavior under hypothetical HPLC conditions. The influence of the parameters relating to the adsorption equilibrium and to the reaction kinetics on the chromatographic behavior was quantitatively evaluated. It is expected that the moment equations are effective for a detailed analysis of the influence of the mass transfer rates and of the Langmuir type reaction kinetics on the column efficiency. PMID:24999066

  15. Reaction Kinetics: An Experiment for Biochemistry and Organic Chemistry Laboratories.

    ERIC Educational Resources Information Center

    Ewing, Sheila

    1982-01-01

    Describes an experiment to examine the kinetics of carbamate decomposition and the effect of buffer catalysis on the reaction. Includes background information, laboratory procedures, evaluation of data, and teaching suggestions. (Author/JN)

  16. Kinetics of Acid Reactions: Making Sense of Associated Concepts

    ERIC Educational Resources Information Center

    Tan, Kim Chwee Daniel; Treagust, David F.; Chandrasegaran, A. L.; Mocerino, Mauro

    2010-01-01

    In chemical kinetics, in addition to the concepts related to kinetics, stoichiometry, chemical equilibrium and the characteristics of the reactants are often involved when comparing the rates of different reactions, making such comparisons very challenging for students at all levels, as well as for pre-service science teachers. Consequently, four…

  17. A joint experimental and theoretical investigation of kinetics and mechanistic study in a synthesis reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of benzhydrazide.

    PubMed

    Kazemian, Mohammad Amin; Habibi-Khorassani, Sayyed Mostafa; Ebrahimi, Ali; Maghsoodlou, Malek Taher; Jahani, Peyman Mohammadzadeh; Ghahramaninezhad, Mahbobeh

    2012-12-01

    Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine (TPP) and dialkyl acetylenedicarboxylates, in the presence of NH-acids, such as benzhydrazide. To determine the kinetic parameters of the reactions, they were monitored by UV spectrophotometery. The second order fits were automatically drawn and the values of the second order rate constant (k(2)) were calculated using standard equations within the program. At the temperature range studied the dependence of the second order rate constant (Ln k(2)) on reciprocal temperature was compatible with Arrhenius equation. This provided the relevant plots to calculate the activation energy of all reactions. Furthermore, useful information were obtained from studies of the effect of solvent, structure of reactants (different alkyl groups within the dialkyl acetylenedicarboxylates) and also concentration of reactants on the rate of reactions. On the basis of experimental data the proposed mechanism was confirmed according to the obtained results and a steady state approximation and the first step (k(2)) and third (k(3)) steps of the reactions were recognized as the rate determining steps, respectively. In addition, three speculative proposed mechanisms were theoretically investigated using quantum mechanical calculation. The results, arising from the second and third speculative mechanisms, were far from the experimental data. Nevertheless, there was a good agreement between the theoretical kinetic data, emerge from the first speculative mechanism, and experimental kinetic data of proposed mechanism. PMID:22752542

  18. Bose-Einstein or HBT Correlation Signals of a Second Order QCD Phase Transition

    SciTech Connect

    Csoergo, T.; Hegyi, S.; Novak, T.; Zajc, W. A.

    2006-04-11

    For particles emerging from a second order QCD phase transition, we show that a recently introduced shape parameter of the Bose-Einstein correlation function, the Levy index of stability equals to the correlation exponent -- one of the critical exponents that characterize the behaviour of the matter in the vicinity of the second order phase transition point. Hence the shape of the Bose-Einstein / HBT correlation functions, when measured as a function of bombarding energy and centrality in various heavy ion reactions, can be utilized to locate experimentally the second order phase transition and the critical end point of the first order phase transition line in QCD.

  19. Implementation of high throughput experimentation techniques for kinetic reaction testing.

    PubMed

    Nagy, Anton J

    2012-02-01

    Successful implementation of High throughput Experimentation (EE) tools has resulted in their increased acceptance as essential tools in chemical, petrochemical and polymer R&D laboratories. This article provides a number of concrete examples of EE systems, which have been designed and successfully implemented in studies, which focus on deriving reaction kinetic data. The implementation of high throughput EE tools for performing kinetic studies of both catalytic and non-catalytic systems results in a significantly faster acquisition of high-quality kinetic modeling data, required to quantitatively predict the behavior of complex, multistep reactions. PMID:21902639

  20. Reaction kinetics of hydrothermal carbonization of loblolly pine.

    PubMed

    Reza, M Toufiq; Yan, Wei; Uddin, M Helal; Lynam, Joan G; Hoekman, S Kent; Coronella, Charles J; Vásquez, Victor R

    2013-07-01

    Hydrothermal carbonization (HTC) is a pretreatment process to convert diverse feedstocks to homogeneous energy-dense solid fuels. Understanding of reaction kinetics is necessary for reactor design and optimization. In this study, the reaction kinetics and effects of particle size on HTC were investigated. Experiments were conducted in a novel two-chamber reactor maintaining isothermal conditions for 15s to 30 min reaction times. Loblolly pine was treated at 200, 230, and 260°C. During the first few minutes of reaction, the solid-product mass yield decreases rapidly while the calorific value increases rapidly. A simple reaction mechanism is proposed and validated, in which both hemicellulose and cellulose degrade in parallel first-order reactions. Activation energy of hemicellulose and cellulose degradation were determined to be 30 and 73 kJ/mol, respectively. For short HTC times, both reaction and diffusion effects were observed. PMID:23651600

  1. A study of the Sabatier-methanation reaction kinetics

    NASA Technical Reports Server (NTRS)

    Verostko, C. E.; Forsythe, R. K.

    1974-01-01

    The kinetics of the Sabatier methanation reaction, the reduction of carbon dioxide with hydrogen to methane and water, was investigated for 58 percent nickel on kieselguhr catalyst and 20 percent ruthenium on alumina catalyst. Differential rate data from an experimental program were correlated with a power function rate equation both for forward and reverse reactions. The kinetic parameters of activation energy, frequency rate constant and reaction order were determined for the rate equation. The values of these parameters were obtained from an Arrhenius plot of the experimental differential rate data. Also the carbon monoxide side reaction effect was measured and included in the correlation of parameters. The reaction was found to fit the rate equation experimentally within the temperature range 421 K, where the reaction effectively begins, the 800 K where the reaction rate drops and departs from the rate equation form.

  2. Design of optimal second-order state estimators

    NASA Technical Reports Server (NTRS)

    Joshi, Suresh M.

    1991-01-01

    The present consideration of the design of online computation-saving second-order state estimators for second-order vector-matrix differential systems proposes a class of such estimators which is proven to possess guaranteed convergence. A class of optimal second-order estimators is then obtained, and the conditions required for optimality are identified. The estimator proposed offers high performance in conjunction with online computation reductions sufficiently great to allow the estimation of the large number of state variables associated with control of large, flexible space structures represented by high-dimensional second-order systems.

  3. Reaction kinetics of selected micropollutants in ozonation and advanced oxidation processes.

    PubMed

    Jin, Xiaohui; Peldszus, Sigrid; Huck, Peter M

    2012-12-01

    Second-order reaction rate constants of micropollutants with ozone (k(O3)) and hydroxyl radicals (k(OH)) are essential for evaluating their removal efficiencies from water during ozonation and advanced oxidation processes. Kinetic data are unavailable for many of the emerging micropollutants. Twenty-four micropollutants with very diverse structures and applications including endocrine disrupting compounds, pharmaceuticals, and personal care products were selected, and their k(O3) and k(OH) values were determined using bench-scale reactors (at pH 7 and T = 20 °C). Reactions with molecular ozone are highly selective as indicated by their k(O3) values ranging from 10(-2)-10(7) M(-1) s(-1). The general trend of ozone reactivity can be explained by micropollutant structures in conjunction with the electrophilic nature of ozone reactions. All of the studied compounds are highly reactive with hydroxyl radicals as shown by their high k(OH) values (10(8)-10(10) M(-1) s(-1)) even though they are structurally very diverse. For compounds with a low reactivity toward ozone, hydroxyl radical based treatment such as O(3)/H(2)O(2) or UV/H(2)O(2) is a viable alternative. This study contributed to filling the data gap pertaining kinetic data of organic micropollutants while confirming results reported in the literature where available. PMID:23079129

  4. Kinetic and theoretical study of the reaction of Cl atoms with a series of linear thiols

    SciTech Connect

    Garzon, Andres; Albaladejo, Jose

    2008-11-21

    The reactions of Cl with a series of linear thiols: 1-propanethiol (k{sub 1}), 1-butanethiol (k{sub 2}), and 1-pentanethiol (k{sub 3}) were investigated as a function of temperature (in the range of 268-379 K) and pressure (in the range of 50-200 Torr) by laser photolysis-resonance fluorescence. Only 1-propanethiol has previously been studied, but at 1 Torr of total pressure. The derived Arrhenius expressions obtained using our kinetic data were as follows: k{sub 1}=(3.97{+-}0.44)x10{sup -11} exp[(410{+-}36)/T], k{sub 2}=(1.01{+-}0.16)x10{sup -10} exp[(146{+-}23)/T], and k{sub 3}=(1.28{+-}0.10)x10{sup -10} exp[(129{+-}25)/T] (in units of cm{sup 3} molecule{sup -1} s{sup -1}). Moreover, a theoretical insight into mechanisms of these reactions has also been pursued through ab initio Moeller-Plesset second-order perturbation treatment calculations with 6-311G** basis set. Optimized geometries have been obtained for transition states and molecular complexes appearing along the different reaction pathways. Furthermore, molecular energies have been calculated at QCISD(T) level in order to get an estimation of the activation energies. Finally, the nature of the molecular complexes and transitions states is analyzed by using kinetic-potential and natural bond orbital total energy decomposition schemes.

  5. Kinetics of enzymatic reactions in lipid membranes containing domains

    NASA Astrophysics Data System (ADS)

    Zhdanov, Vladimir P.; Höök, Fredrik

    2015-04-01

    An appreciable part of enzymes operating in vivo is associated with lipid membranes. The function of such enzymes can be influenced by the presence of domains containing proteins and/or composed of different lipids. The corresponding experimental model-system studies can be performed under well controlled conditions, e.g., on a planar supported lipid bilayer or surface-immobilized vesicles. To clarify what may happen in such systems, we propose general kinetic equations describing the enzyme-catalyzed substrate conversion occurring via the Michaelis-Menten (MM) mechanism on a membrane with domains which do not directly participate in reaction. For two generic situations when a relatively slow reaction takes place primarily in or outside domains, we take substrate saturation and lateral substrate-substrate interactions at domains into account and scrutinize the dependence of the reaction rate on the average substrate coverage. With increasing coverage, depending on the details, the reaction rate reaches saturation via an inflection point or monotonously as in the conventional MM case. In addition, we show analytically the types of reaction kinetics occurring primarily at domain boundaries. In the physically interesting situation when the domain growth is fast on the reaction time scale, the latter kinetics are far from conventional. The opposite situation when the reaction is fast and controlled by diffusion has been studied by using the Monte Carlo technique. The corresponding results indicate that the dependence of the reaction kinetics on the domain size may be weak.

  6. Chemical kinetics computer program for static and flow reactions

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Scullin, V. J.

    1972-01-01

    General chemical kinetics computer program for complex gas mixtures has been developed. Program can be used for any homogeneous reaction in either one dimensional flow or static system. It is flexible, accurate, and easy to use. It can be used for any chemical system for which species thermodynamic data and reaction rate constant data are known.

  7. The Kinetic Rate Law for Autocatalytic Reactions.

    ERIC Educational Resources Information Center

    Mata-Perez, Fernando; Perez-Benito, Joaquin F.

    1987-01-01

    Presented is a method of obtaining accurate rate constants for autocatalytic reactions. The autocatalytic oxidation of dimethylamine by permanganate ion in aqueous solution is used as an example. (RH)

  8. Adsorption Isotherms and Surface Reaction Kinetics

    ERIC Educational Resources Information Center

    Lobo, L. S.; Bernardo, C. A.

    1974-01-01

    Explains an error that occurs in calculating the conditions for a maximum value of a rate expression for a bimolecular reaction. The rate expression is derived using the Langmuir adsorption isotherm to relate gas pressures and corresponding surface coverages. (GS)

  9. Kinetics of Chemical Reactions in Flames

    NASA Technical Reports Server (NTRS)

    Zeldovich, Y.; Semenov, N.

    1946-01-01

    In part I of the paper the theory of flame propagation is developed along the lines followed by Frank-Kamenetsky and one of the writers. The development of chain processes in flames is considered. A basis is given for the application of the method of stationary concentrations to reactions in flames; reactions with branching chains are analyzed. The case of a diffusion coefficient different from the coefficient of temperature conductivity is considered.

  10. Fluid flow and chemical reaction kinetics in metamorphic systems

    SciTech Connect

    Lasaga, A.C.; Rye, D.M. )

    1993-05-01

    The treatment and effects of chemical reaction kinetics during metamorphism are developed along with the incorporation of fluid flow, diffusion, and thermal evolution. The interplay of fluid flow and surface reaction rates, the distinction between steady state and equilibrium, and the possible overstepping of metamorphic reactions are discussed using a simple analytic model. This model serves as an introduction to the second part of the paper, which develops a reaction model that solves the coupled temperature-fluid flow-chemical composition differential equations relevant to metamorphic processes. Consideration of stable isotopic evidence requires that such a kinetic model be considered for the chemical evolution of a metamorphic aureole. A general numerical scheme is discussed to handle the solution of the model. The results of this kinetic model allow us to reach several important conclusions regarding the factors controlling the chemical evolution of mineral assemblages during a metamorphic event. 41 refs., 19 figs., 5 tabs.

  11. The Morse Oscillator and Second-Order Perturbation Theory

    NASA Astrophysics Data System (ADS)

    Pettitt, B. A.

    1998-09-01

    This article shows how the energies of the Morse oscillator are obtained exactly from a second-order perturbation expansion in a harmonic oscillator basis. This exercise is recommended for its instructional value in intermediate quantum chemistry, in that the second-order term is entirely tractable, it arises within an important context (anharmonicity of vibrations), and it gives the right answer.

  12. Kinetics and mechanisms of some atomic oxygen reactions

    NASA Technical Reports Server (NTRS)

    Cvetanovic, R. J.

    1987-01-01

    Mechanisms and kinetics of some reactions of the ground state of oxygen atoms, O(3P), are briefly summarized. Attention is given to reactions of oxygen atoms with several different types of organic and inorganic compounds such as alkanes, alkenes, alkynes, aromatics, and some oxygen, nitrogen, halogen and sulfur derivatives of these compounds. References to some recent compilations and critical evaluations of reaction rate constants are given.

  13. Modelling couplings between reaction, fluid flow and deformation: Kinetics

    NASA Astrophysics Data System (ADS)

    Malvoisin, Benjamin; Podladchikov, Yury Y.; Connolly, James A. D.

    2016-04-01

    Mineral assemblages out of equilibrium are commonly found in metamorphic rocks testifying of the critical role of kinetics for metamorphic reactions. As experimentally determined reaction rates in fluid-saturated systems generally indicate complete reaction in less than several years, i.e. several orders of magnitude faster than field-based estimates, metamorphic reaction kinetics are generally thought to be controlled by transport rather than by processes at the mineral surface. However, some geological processes like earthquakes or slow-slip events have shorter characteristic timescales, and transport processes can be intimately related to mineral surface processes. Therefore, it is important to take into account the kinetics of mineral surface processes for modelling fluid/rock interactions. Here, a model coupling reaction, fluid flow and deformation was improved by introducing a delay in the achievement of equilibrium. The classical formalism for dissolution/precipitation reactions was used to consider the influence of the distance from equilibrium and of temperature on the reaction rate, and a dependence on porosity was introduced to model evolution of reacting surface area during reaction. The fitting of experimental data for three reactions typically occurring in metamorphic systems (serpentine dehydration, muscovite dehydration and calcite decarbonation) indicates a systematic faster kinetics close from equilibrium on the dehydration side than on the hydration side. This effect is amplified through the porosity term in the reaction rate since porosity is formed during dehydration. Numerical modelling indicates that this difference in reaction rate close from equilibrium plays a key role in microtextures formation. The developed model can be used in a wide variety of geological systems where couplings between reaction, deformation and fluid flow have to be considered.

  14. Reaction kinetics between fiber and matrix

    NASA Technical Reports Server (NTRS)

    Kopp, M. W.; Tien, J. K.; Petrasek, D. W.

    1988-01-01

    Interdiffusion and interdiffusion controlled intermediate phase formation in metal matrix composites can be of interest for the prolonged application of these systems at high temperatures. Methods are discussed that address the kinetics of interdiffusion in systems that exhibit solid solution intermixing or the formation of a third intermediate phase at the fiber/matrix interface, or both. The tungsten fiber reinforced niobium and tungsten fiber reinforced superalloy systems are employed as model systems for experimentation and discussion. In an effort to impede interdiffusion, the concept of ion implanted diffusion barriers have been examined. Preliminary results on the feasibility and effectiveness of ion implanted diffusion barriers are presented.

  15. Visualization of second order tensor fields and matrix data

    NASA Technical Reports Server (NTRS)

    Delmarcelle, Thierry; Hesselink, Lambertus

    1992-01-01

    We present a study of the visualization of 3-D second order tensor fields and matrix data. The general problem of visualizing unsymmetric real or complex Hermitian second order tensor fields can be reduced to the simultaneous visualization of a real and symmetric second order tensor field and a real vector field. As opposed to the discrete iconic techniques commonly used in multivariate data visualization, the emphasis is on exploiting the mathematical properties of tensor fields in order to facilitate their visualization and to produce a continuous representation of the data. We focus on interactively sensing and exploring real and symmetric second order tensor data by generalizing the vector notion of streamline to the tensor concept of hyperstreamline. We stress the importance of a structural analysis of the data field analogous to the techniques of vector field topology extraction in order to obtain a unique and objective representation of second order tensor fields.

  16. Reversibly Switching Silver Hierarchical Structures via Reaction Kinetics

    PubMed Central

    Liu, Jianmei; Yang, Tao; Li, Chengxiang; Dai, Jinhui; Han, Yongsheng

    2015-01-01

    Here we report a study on controllable synthesis of hierarchical silver structures via regulating reaction kinetics. Silver particles with various morphologies are synthesized by a solution-based reduction approach at the addition of amino acids. The amino acid is used to coordinate with silver ions to slow down the reduction of silver ions. With the increase of glycine concentration, the morphologies of silver particles switch from dendrites, to flowers and to compacted spheres, which is attributed to the decrease of reaction rate as a result of the coordination. Three more amino acids are examined and confirms the role of reaction kinetic in shaping silver particles. Furthermore, by increasing the concentration of the reductant, the silver morphologies change from compact spheres to loose flowers as a result of the increase of reaction rate. Therefore the silver hierarchical structure can be reversibly switched by reaction kinetics. The silver particles synthesized are tested for surface enhanced Raman scattering (SERS) property and the dendritic particles present a remarkable SERS activity. This study shows that reaction kinetics is a powerful tool to tune hierarchical structures of silver particles, which is expected to be transferable to other material systems. PMID:26442867

  17. Periodic perturbation of the kinetics of heterogeneous catalytic reactions

    NASA Astrophysics Data System (ADS)

    Zhdanov, Vladimir P.

    2004-09-01

    Periodic forcing of reaction kinetics via, e.g., variation of reactant pressure(s), temperature or flow reversal is one of the useful tools employed in basic and applied studies of heterogeneous catalytic processes. In the case of conventional (stable) kinetics, this strategy is used to clarify the mechanisms of reactions and obtain data on reaction rate constants or to improve the reaction performance, e.g., to increase reaction rate and/or selectivity with respect to desired products. In experiments, that are focused on oscillatory catalytic reactions, periodic perturbations are employed to stabilize period-1 oscillations. This is easily achieved if the external and internal frequencies are equal. In a more general context, periodic perturbation of chemical reactions, that exhibit period-1 oscillations, may result in complex reaction behaviour, including period doubling and irregular kinetics provided that the external and internal frequencies do not coincide. We consider in this review both the relevant data available in the literature and the results of systematic calculations for a few generic models.

  18. A TGA study on the chlorination reaction kinetics of Zircaloy-4 cladding hulls

    NASA Astrophysics Data System (ADS)

    Jeon, Min Ku; Choi, Yong Taek; Kang, Kweon Ho; Park, Geun Il

    2015-04-01

    The chlorination reaction kinetics of Zircaloy-4 cladding hulls were investigated using a home-made thermogravimetric analysis for a hull chlorination (TGA-HC) system. The reproducibility of the TGA-HC system was verified by repeated measurements at an identical condition, which showed only 6.6% of maximum difference. The effect of total flow rate (Q) was investigated for Q of 120 and 240 mL/min, and it was revealed that the reaction rate is not influenced in this condition. Using the Sharp-Hancock plot, the volumetric contraction model was identified as the most suitable model for the Zircaloy-4 chlorination reaction. The influence of chlorine partial pressure was studied at 9.21, 16.9, and 23.4 kPa of Cl2 partial pressure conditions, and it was identified that the reaction rate is proportional to the chlorine partial pressure on the order of (0.669). The effect of reaction temperature was investigated for 300-450 °C, and it was revealed that the chlorination reaction exhibits an activation energy of 26.2 kJ/mol. Using the experimental and fitting results, the reaction rate equation for the Zircaloy-4 chlorination reaction was achieved, but the equation was valid only until the conversion fraction (α) reaches up to (0.60). When α is higher than 0.60, the volumetric contraction model was not applicable. A second-order reaction rate equation was suggested for the 0.6 < α region, although it needs further investigation.

  19. Insights into the "free state" enzyme reaction kinetics in nanoconfinement.

    PubMed

    Wang, Chen; Ye, De-Kai; Wang, Yun-Yi; Lu, Tao; Xia, Xing-Hua

    2013-04-21

    The investigation of enzyme reaction kinetics in nanoconfined spaces mimicking the conditions in living systems is of great significance. Here, a nanofluidics chip integrated with an electrochemical detector has been designed for studying "free state" enzyme reaction kinetics in nanoconfinement. The nanofluidics chip is fabricated using the UV-ablation technique developed in our group. The enzyme and substrate solutions are simultaneously supplied from two single streams into a nanochannel through a Y-shaped junction. The laminar flow forms in the front of the nanochannel, then the two liquids fully mix at their downstream where a homogeneous enzyme reaction occurs. The "free state" enzyme reaction kinetics in nanoconfinement can thus be investigated in this laminar flow based nanofluidics device. For demonstration, glucose oxidase (GOx) is chosen as the model enzyme, which catalyzes the oxidation of beta-d-glucose. The reaction product hydrogen peroxide (H2O2) can be electrochemically detected by a microelectrode aligning to the end of nanochannel. The steady-state electrochemical current responding to various glucose concentrations is used to evaluate the activity of the "free state" GOx under nanoconfinement conditions. The effect of liquid flow rate, enzyme concentration, and nanoconfinement on reaction kinetics has been studied in detail. Results show that the "free state" GOx activity increases significantly compared to the immobilized enzyme and bath system, and the GOx reaction rate in the nanochannel is two-fold faster than that in bulk solution, demonstrating the importance of "free state" and spatial confinement for the enzyme reaction kinetics. The present approach provides an effective method for exploiting the "free state" enzyme activity in nanospatial confinement. PMID:23429726

  20. Reaction kinetics of free fatty acids esterification in palm fatty acid distillate using coconut shell biochar sulfonated catalyst

    NASA Astrophysics Data System (ADS)

    Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief

    2015-12-01

    Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

  1. The Reaction of a Food Colorant with Sodium Hypochlorite: A Student-Designed Kinetics Experiment

    NASA Astrophysics Data System (ADS)

    Arce, Josefina; Betancourt, Rosa; Rivera, Yamil; Pijem, Joan

    1998-09-01

    The kinetics of the reaction of the food colorant FD&C Blue #1 with sodium hypochlorite (Clorox) is described in a student-designed experimental format. In this format, students are guided- by means of questions- to make decisions regarding concentration of reagents, choice of equipment, and actual laboratory procedures to be followed. This format provides an opportunity for students to apply the concepts and skills learned in class and in previous laboratory sessions to a new problem. We have found that this experience helps students gain depth of understanding of all concepts involved. The reaction (with a large excess of NaOCl) is followed with a Spectronic 20 at the Blue #1 colorant lmax of 630 nm. The %T is measured over time and three graphs: A vs time, ln A vs time and 1/A vs time are plotted to find that the second one is linear and thus first order with respect to the Blue #1. When the concentration of NaOCl is reduced to one-half the original value, it is found that the rate is reduced by one-half, indicating that the reaction is first order with respect to NaOCl and second order overall. The rate constant of the reaction is determined from the slope of the curve and the mean obtained by our students is 17 M-1 min-1 at room temperature (about 28° C).

  2. Study of second order upwind differencing in a recirculating flow

    NASA Technical Reports Server (NTRS)

    Vanka, S. P.

    1985-01-01

    The accuracy and stability of the second order upwind differencing scheme was investigated. The solution algorithm employed is based on a coupled solution of the nonlinear finite difference equations by the multigrid technique. Calculations have been made of the driven cavity flow for several Reynolds numbers and finite difference grids. In comparison with the hybrid differencing, the second order upwind differencing is somewhat more accurate but it is not monotonically accurate with mesh refinement. Also, the convergence of the solution algorithm deteriorates with the use of the second order upwind differencing.

  3. A study of second-order supersonic flow theory

    NASA Technical Reports Server (NTRS)

    Van Dyke, Milton D

    1952-01-01

    Second-order solutions of supersonic-flow problems are sought by iteration, using the linearized solution as the first step. For plane and axially symmetric flows, particular solutions of the iteration equation are discovered which reduce the second-order problem to an equivalent linearized problem. Comparison of second-order solutions with exact and numerical results shows great improvement over linearized theory. For full three-dimensional flow, only a partial particular solution is found. The inclined cone is solved, and the possibility of treating more general problems is considered.

  4. Method to render second order beam optics programs symplectic

    SciTech Connect

    Douglas, D.; Servranckx, R.V.

    1984-10-01

    We present evidence that second order matrix-based beam optics programs violate the symplectic condition. A simple method to avoid this difficulty, based on a generating function approach to evaluating transfer maps, is described. A simple example illustrating the non-symplectricity of second order matrix methods, and the effectiveness of our solution to the problem, is provided. We conclude that it is in fact possible to bring second order matrix optics methods to a canonical form. The procedure for doing so has been implemented in the program DIMAT, and could be implemented in programs such as TRANSPORT and TURTLE, making them useful in multiturn applications. 15 refs.

  5. Second-order state estimation experiments using acceleration measurements

    NASA Technical Reports Server (NTRS)

    Belvin, W. K.

    1992-01-01

    The estimation of dynamic states for feedback control of structural systems using second-order differential equations and acceleration measurements is described. The formulation of the observer model, and the design of the observer gains is discussed in detail. It is shown the second-order observer is highly stable because the stability constraints on the observer gains are model independent. The limitation of the proposed observer is the need for 'nearly' collocated actuators and accelerometers. Experimental results using a control-structure interaction testbed are presented that show the second-order observer provided more stability than a Kalman filter estimator without decreasing closed-loop performance.

  6. Reaction kinetics of nanostructured silicon carbide

    NASA Astrophysics Data System (ADS)

    Wallis, K. L.; Patyk, J. K.; Zerda, T. W.

    2008-08-01

    SiC nanowires were produced from carbon nanotubes and silicon by two different methods at high temperature. X-ray powder diffraction was used to determine SiC concentration. The reaction rate using the Avrami-Erofeev method was determined for samples sintered at temperatures ranging from 1313 to 1823 K. The activation energy was found to be (254 ± 36) kJ mol-1. The limiting factor in SiC formation is diffusion of silicon and carbon atoms through the produced layer of SiC.

  7. Fluctuation Dominated Kinetics in Diffusion-Controlled Reactions.

    NASA Astrophysics Data System (ADS)

    Kang, Kiho

    The kinetics of a number of prototypical diffusion -controlled reactions are studied. Our goal is to investigate the effects of spatial inhomogeneities in the particle densities on the reaction kinetics. In general, we find that there exists an upper critical dimension below which the kinetics cannot be described by a rate equation analysis, an approach which gives the kinetic laws of a mean-field approximation. Below the upper critical dimension, spatial inhomogeneities in the particle densities give rise to new fluctuation-dominated kinetics. For "trapping" reaction, A + B (--->) (1-(epsilon))A + B (0 < (epsilon) (LESSTHEQ) 1), we find a quasi-exponential decay law (rho)(,A)(t)(TURN)t('1/2)exp(-kt('1/3)) for the density of A particle in one dimension. The introduction of drift velocity superimposed on the diffusive motion of the A particles results in a novel crossover to an exponential decay law. For an arbitrary fixed configurations of traps and values of (epsilon) in the case of static B's and mobile A's, an exact formal expression for the kinetics of the reaction is derived by using generating functions. For irreversible multi-particle reactions, with bimolecular decay A + B (--->) inert being a simple generic example, universal kinetic laws are obtained, which are founded to be a function only of the spatial dimension, the number of particles needed to intiate a reaction, and the nature of the particle conservation laws for the system. These results are obtained primarily through the application of scaling approaches. We also introduce a simple and new model of coagulation. In contrast to the often-used cluster-cluster aggregation model, the reaction kernel in our model can be adjusted exactly. For the special case of a constant reaction kernel, we find that the upper critical dimension is two and fluctuations give rise to dimension dependent kinetic exponents and a novel non-monotonic cluster size distribution below two dimensions. Many of our new

  8. A second-order theory for transverse ion heating and momentum coupling due to electrostatic ion cyclotron waves

    NASA Technical Reports Server (NTRS)

    Miller, Ronald H.; Winske, Dan; Gary, S. P.

    1992-01-01

    A second-order theory for electrostatic instabilities driven by counterstreaming ion beams is developed which describes momentum coupling and heating of the plasma via wave-particle interactions. Exchange rates between the waves and particles are derived, which are suitable for the fluid equations simulating microscopic effects on macroscopic scales. Using a fully kinetic simulation, the electrostatic ion cyclotron instability due to counterstreaming H(+) beams has been simulated. A power spectrum from the kinetic simulation is used to evaluate second-order exchange rates. The calculated heating and momentum loss from second-order theory is compared to the numerical simulation.

  9. Orthogonal canonical forms for second-order systems

    NASA Technical Reports Server (NTRS)

    Williams, Trevor; Laub, Alan

    1989-01-01

    The authors prove that a linear second-order system with arbitrary damping cannot be reduced to Hessenberg-triangular form by means of orthogonal transformations, while this reduction is always possible for the modal damping commonly assumed for models of flexible structures. The type of canonical form obtainable by means of orthogonal transformations acting on a second-order system is heavily dependent on the type of damping considered. If the damping matrix is merely positive semi-definite symmetric, it is generally not possible to obtain a reduction to Hessenberg-triangular form, while this reduction is trivial for zero or Rayleigh damping. If damping is modal, however, as is commonly assumed in structural models, the reduction exists and is nontrivial. Furthermore, reduction to triangular second-order Schur form is always possible for such damping: this canonical form appears likely to have applications to second-order system theory.

  10. Oscillation theorems for second order nonlinear forced differential equations.

    PubMed

    Salhin, Ambarka A; Din, Ummul Khair Salma; Ahmad, Rokiah Rozita; Noorani, Mohd Salmi Md

    2014-01-01

    In this paper, a class of second order forced nonlinear differential equation is considered and several new oscillation theorems are obtained. Our results generalize and improve those known ones in the literature. PMID:25077054

  11. Fast second-order consensus via predictive mechanisms

    NASA Astrophysics Data System (ADS)

    Wu, Jie; Zhang, Li-Yi; Bai, Yu

    2015-01-01

    In this paper, we discuss second-order consensus problems for multi-agent systems with dynamic agents and fixed topologies. A new second-order consensus protocol incorporating the predictive mechanism is proposed and a convergence analysis related to the real and imaginary parts of the eigenvalues of the Laplacian matrix of the corresponding network is provided. We establish a direct connection between the eigenvalues of the Laplacian matrix and parameters of the proposed second-order consensus model, and we compute a lower bound for the sum of parameters. It is proved under general conditions related to the second-order consensus protocol and the network topology that the asymptotic consensus is achieved and the convergence speed is increased via designing a state predictor. Finally, simulation results are provided to verify the effectiveness of the proposed protocol and the analytical claims.

  12. Chemical kinetic reaction mechanism for the combustion of propane

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1984-01-01

    A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

  13. Orthogonal canonical forms for second-order systems

    NASA Technical Reports Server (NTRS)

    Williams, Trevor; Laub, Alan J.

    1992-01-01

    It is shown that a linear second-order system with arbitrary damping cannot be reduced to Hessenberg-triangular form by means of orthogonal transformations. However, it is also shown that such an orthogonal reduction is always possible for the modal damping commonly assumed for models of flexible structures. It is shown that modally damped models can be orthogonally reduced to a new triangular second-order Schur form.

  14. [Second-order retrospective revaluation in human contingency learning].

    PubMed

    Numata, Keitaro; Shimazaki, Tsuneo

    2009-04-01

    We demonstrated second-order retrospective revaluation with three cues (T1, T2, and C) and an outcome, in human contingency learning. Experimental task, PC-controlled video game in which participants were required to observe about the relations between firing missiles and the tank destruction, consisted of three training phases and two rating phases. Groups C+ and C- consisted of same first two training phases, CT+ (cues C and T with an outcome) and T1T2+ followed by C+, or C- training for Groups C+, C-, respectively. In rating phases, it is clearly demonstrated that the judgment of predictive value for the outcome of the T2 were higher by C+ training (second-order unovershadowing) and lowered by C- training (second-order backward blocking). The results for Groups RC+ and RC-, in which the orders of the first two training phase for Groups C+ and C- were interchanged, also showed second-order unovershadowing and second-order backward blocking. These results, the robustness of second-order retrospective revaluation against the order of the first training phases, can be explained by the extended comparator hypothesis and probabilistic contrast model. However, these results cannot be explained by traditional associative learning models. PMID:19489431

  15. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Chapman, Piers; *Morse, John W.

    2010-11-15

    1. Objective The general objective of this research was to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, carbon dioxide partial pressure (pCO2), and modest ranges of T and P. This would be done by studying both reaction rates and solubility from changes in solution chemistry. Also, nanoscale observations of calcite surface morphology and composition would be made to provide an understanding of rate controlling mechanisms.

  16. Prediction of Kinetic Isotope Effects for Various Hydride Transfer Reactions Using a New Kinetic Model.

    PubMed

    Shen, Guang-Bin; Xia, Ke; Li, Xiu-Tao; Li, Jun-Ling; Fu, Yan-Hua; Yuan, Lin; Zhu, Xiao-Qing

    2016-03-24

    In this work, kinetic isotope effect (KIEself) values of 68 hydride self-exchange reactions, XH(D) + X(+) → X(+) + XH(D), in acetonitrile at 298 K were determined using a new experimental method. KIE values of 4556 hydride cross transfer reactions, XH(D) + Y(+) → X(+) + YH(D), in acetonitrile were estimated from the 68 determined KIEself values of hydride self-exchange reactions using a new KIE relation formula derived from Zhu's kinetic equation and the reliability of the estimations was verified using different experimental methods. A new KIE kinetic model to explain and predict KIE values was developed according to Zhu's kinetic model using two different Morse free energy curves instead of one Morse free energy curve in the traditional KIE theories to describe the free energy changes of X-H bond and X-D bond dissociation in chemical reactions. The most significant contribution of this paper to KIE theory is to build a new KIE kinetic model, which can be used to not only uniformly explain the various (normal, enormous and inverse) KIE values but also safely prodict KIE values of various chemical reactions. PMID:26938149

  17. The equilibrium assumption is valid for the kinetic treatment of most time-dependent protein-modification reactions.

    PubMed Central

    Brocklehurst, K

    1979-01-01

    To facilitate mechanistic interpretation of the kinetics of time-dependent inhibition of enzymes and of similar protein modification reactions, it is important to know when the equilibrium assumption may be applied to the model: formula: (see text). The conventional criterion of quasi-equilibrium, k + 2 less than k-1, is not always easy to assess, particularly when k + 2 cannot be separately determined. It is demonstrated that the condition k + 2 less than k-1 is necessarily true, however, when the value of the apparent second-order rate constant for the modification reaction is much smaller than the value of k + 1. Since k + 1 is commonly at least 10(7)M-1.S-1 for substrates, it is probable that the equilibrium assumption may be properly applied to most irreversible inhibitions and modification reactions. PMID:518556

  18. REACTION KINETICS OF CA-BASED SORBENTS WITH HC1

    EPA Science Inventory

    The paper gives results of an investigation of the kinetics of the reaction between CaO and HC1 under conditions that minimize bulk mass transfer and pore diffusion limitations. eactivity data from 0.2 to 1 s exposure to 5000 ppm HC1 in a fixed-bed reactor were analyzed by a shri...

  19. REACTION KINETICS OF CA-BASED SORBENTS WITH HC1

    EPA Science Inventory

    The kinetics of the reaction between CaO and HCl were investigated under conditions that minimize bulk mass transfer and pore diffusion limitations. Reactivity data from 0.2- to 1-s exposure to 5000 ppm HCl in a fixed bed reactor were analyzed by a shrinking core model of diffusi...

  20. Penicillin Hydrolysis: A Kinetic Study of a Multistep, Multiproduct Reaction.

    ERIC Educational Resources Information Center

    McCarrick, Thomas A.; McLafferty, Fred W.

    1984-01-01

    Background, procedures used, and typical results are provided for an experiment in which students carry out the necessary measurements on the acid-catalysis of penicillin in two hours. By applying kinetic theory to the data obtained, the reaction pathways for the hydrolysis of potassium benzyl penicillin are elucidated. (JN)

  1. Laccase-catalyzed removal of the antimicrobials chlorophene and dichlorophen from water: Reaction kinetics, pathway and toxicity evaluation.

    PubMed

    Shi, Huanhuan; Peng, Jianbiao; Li, Jianhua; Mao, Liang; Wang, Zunyao; Gao, Shixiang

    2016-11-01

    As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes. PMID:27262275

  2. Palm fatty acid biodiesel: process optimization and study of reaction kinetics.

    PubMed

    Yadav, Praveen K S; Singh, Onkar; Singh, R P

    2010-01-01

    The relatively high cost of refined oils render the resulting fuels unable to compete with petroleum derived fuel. In this study, biodiesel is prepared from palm fatty acid (PFA) which is a by-product of palm oil refinery. The process conditions were optimized for production of palm fatty acid methyl esters. A maximum conversion of 94.4% was obtained using two step trans-esterification with 1:10 molar ratio of oil to methanol at 65°C. Sulfuric acid and Sodium hydroxide were used as acid and base catalyst respectively. The composition of fatty acid methyl esters (FAME) obtained was similar to that of palm oil. The biodiesel produced met the established specifications of biodiesel of American Society for Testing and Materials (ASTM). The kinetics of the trans-esterification reaction was also studied and the data reveals that the reaction is of first order in fatty acid and methanol (MeOH) and over all the reaction is of second order. PMID:20972357

  3. Kinetics and Thermochemistry of the Cl((sup 2)P(sub J)) + C2Cl4 Association Reaction

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Wang, S.; Mckee, M. L.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Cl(sup 2)P(sub j) + C2Cl4 association reaction as a function of temperature (231-390 K) and pressure (3-700 Torr) in nitrogen buffer gas. The reaction is found to be in the falloff regime between third and second order over the range of conditions investigated, although the second-order limit is approached at the highest pressures and lowest temperatures. At temperatures below 300 K, the association reaction is found to be irreversible on the experimental time scale of approximately 20 m-s. The kinetic data at T is less than 300 K have been employed to obtain falloff parameters in a convenient format for atmospheric modeling. At temperatures above 330 K, reversible addition is observed, thus allowing equilibrium constants for C2Cl5 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data lead to the following thermochemical parameters for the association reaction: Delta-H(298) = -18.1 +/- 1.3 kcal/mol, Delta-H(0) = -17.6 +/- 1.3 kcal/mol, and Delta-S(298) = -27.7 +/- 3.0 cal/mol.K. In conjunction with the well-known heats of formation of Cl((sup 2)P(sub j)) and C2Cl4 the above Delta-H values lead to the following heats of formation for C2Cl5, at 298 and 0 K: Delta-H(f,298) = 8.0 +/- 1.3 kcal/mol and Delta-H(f,0) = 8.1 +/- 1.5 kcal/mol. The kinetic and thermochemical parameters reported above are compared with other reported values, and the significance of reported association rate coefficients for understanding tropospheric chlorine chemistry is discussed.

  4. Spatial Variances of Wind Fields and Their Relation to Second-Order Structure Functions and Spectra

    NASA Astrophysics Data System (ADS)

    King, G. P.; Vogelzang, J.; Stoffelen, A.; Portabella, M.

    2014-12-01

    Kinetic energy variance as a function of spatial scale for wind fields is commonly estimated either using second-order structure functions (in the spatial domain) or by spectral analysis (in the frequency domain). It will be demonstrated that neither spectra nor second-order structure functions offer a good representation of the variance as a function of scale. These difficulties can be circumvented by using a statistical quantity called spatial variance. It combines the advantages of spectral analysis and spatial statistics. In particular, when applied to observations, spatial variances have a clear interpretation and are tolerant for missing data. They can be related to second-order structure functions, both for discrete and continuous data. For data sets without missing points the relation is statistically exact. Spatial variances can also be Fourier transformed to yield a relation with spectra. The flexibility of spatial variances is used to study various sampling strategies, and to compare them with second-order structure functions and spectral variances. It is shown that the spectral sampling strategy is not seriously biased to calm conditions for scatterometer ocean surface vector winds, and that one-fifth of the second-order structure function value is a good proxy for the cumulative variance.

  5. Pulsed ion beam investigation of the kinetics of surface reactions

    NASA Technical Reports Server (NTRS)

    Horton, C. C.; Eck, T. G.; Hoffman, R. W.

    1989-01-01

    Pulsed ion beam measurements of the kinetics of surface reactions are discussed for the case where the width of the ion pulse is comparable to the measured reaction time, but short compared to the time between successive pulses. Theoretical expressions are derived for the time dependence of the ion-induced signals for linear surface reactions. Results are presented for CO emission from surface carbon and CF emission from Teflon induced by oxygen ion bombardment. The strengths and limitations of this technique are described.

  6. Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

    NASA Astrophysics Data System (ADS)

    Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

    2016-06-01

    Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

  7. Second-order quasinormal mode of the Schwarzschild black hole

    SciTech Connect

    Nakano, Hiroyuki; Ioka, Kunihito

    2007-10-15

    We formulate and calculate the second-order quasinormal modes (QNMs) of a Schwarzschild black hole (BH). Gravitational waves (GW) from a distorted BH, the so-called ringdowns, are well understood as QNMs in general relativity. Since QNMs from binary BH mergers will be detected with a high signal-to-noise ratio by GW detectors, it is also possible to detect the second perturbative order of QNMs, generated by nonlinear gravitational interaction near the BH. In the BH perturbation approach, we derive the master Zerilli equation for the metric perturbation to second order and explicitly regularize it at the horizon and spatial infinity. We numerically solve the second-order Zerilli equation by implementing the modified Leaver continued fraction method. The second-order QNM frequencies are found to be twice the first-order ones, and the GW amplitude is up to {approx}10% that of the first order for the binary BH mergers. Since the second-order QNMs always exist, we can use their detections (i) to test the nonlinearity of general relativity, in particular, the no-hair theorem, (ii) to remove fake events in the data analysis of QNM GWs, and (iii) to measure the distance to the BH.

  8. Second-Order Olfactory-Mediated Fear-Potentiated Startle

    PubMed Central

    Paschall, Gayla Y.; Davis, Michael

    2002-01-01

    Recently, we reported that discrete (4-sec) olfactory cues paired with footshock serve as effective conditioned stimuli (CSs) for potentiating the acoustic startle response in rats using the fear-potentiated startle paradigm. Because odors are such salient cues for the rat, and because of the robust olfactory conditioning observed previously, the current studies investigated second-order fear conditioning using olfactory and visual cues. In Experiments 1 and 2, we used a small number of first-order and second-order training trials on separate days to investigate second-order fear-potentiated startle. Significant potentiated startle was observed in animals receiving Paired/Paired training in both studies, but surprisingly, control animals in the Unpaired/Paired group (Exp. 1) also showed significant potentiated startle to a light S2 at testing. These findings are addressed in the Discussion. Overall, the results of both experiments suggest that olfactory cues serve as efficient S1 and S2 stimuli in second-order fear-potentiated startle paradigms when only a small number of first and second-order training trials are presented. PMID:12464699

  9. A kinetics investigation of several reactions involving chlorine containing compounds

    NASA Technical Reports Server (NTRS)

    Davis, D. D.

    1978-01-01

    The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

  10. Weak value amplification via second-order correlated technique

    NASA Astrophysics Data System (ADS)

    Ting, Cui; Jing-Zheng, Huang; Xiang, Liu; Gui-Hua, Zeng

    2016-02-01

    We propose a new framework combining weak measurement and second-order correlated technique. The theoretical analysis shows that weak value amplification (WVA) experiment can also be implemented by a second-order correlated system. We then build two-dimensional second-order correlated function patterns for achieving higher amplification factor and discuss the signal-to-noise ratio influence. Several advantages can be obtained by our proposal. For instance, detectors with high resolution are not necessary. Moreover, detectors with low saturation intensity are available in WVA setup. Finally, type-one technical noise can be effectively suppressed. Project supported by the Union Research Centre of Advanced Spaceflight Technology (Grant No. USCAST2013-05), the National Natural Science Foundation of China (Grant Nos. 61170228, 61332019, and 61471239), and the High-Tech Research and Development Program of China (Grant No. 2013AA122901).

  11. Some restrictions on the existence of second order limit language

    NASA Astrophysics Data System (ADS)

    Ahmad, Muhammad Azrin; Sarmin, Nor Haniza; Yusof, Yuhani; Fong, Wan Heng

    2015-10-01

    The cut and paste phenomenon on DNA molecules with the presence of restriction enzyme and appropriate ligase has led to the formalism of mathematical modelling of splicing system. A type of splicing system named Yusof-Goode splicing system is used to present the transparent behaviour of the DNA splicing process. The limit language that is defined as the leftover molecules after the system reaches its equilibrium point has been extended to a second order limit language. The non-existence of the second order limit language biologically has lead to this study by using mathematical approach. In this paper, the factors that restrict the formation of the second order limit language are discussed and are presented as lemmas and theorem using Y-G approach. In addition, the discussion focuses on Yusof- Goode splicing system with at most two initial strings and two rules with one cutting site and palindromic crossing site and recognition sites.

  12. Second order perturbations during inflation beyond slow-roll

    SciTech Connect

    Huston, Ian; Malik, Karim A. E-mail: k.malik@qmul.ac.uk

    2011-10-01

    We numerically calculate the evolution of second order cosmological perturbations for an inflationary scalar field without resorting to the slow-roll approximation or assuming large scales. In contrast to previous approaches we therefore use the full non-slow-roll source term for the second order Klein-Gordon equation which is valid on all scales. The numerical results are consistent with the ones obtained previously where slow-roll is a good approximation. We investigate the effect of localised features in the scalar field potential which break slow-roll for some portion of the evolution. The numerical package solving the second order Klein-Gordon equation has been released under an open source license and is available for download.

  13. Textural segmentation, second-order statistics, and textural elements.

    PubMed

    Beck, J

    1983-01-01

    Beck (1972, 1973) hypothesized that textural segmentation occurs strongly on the basis of simple properties such as brightness, color, size, and the slopes of contours and lines of the elemental descriptors of a texture or textural elements. The experiment reported supports the hypothesis that specific stimulus features, rather than second-order statistics, account for textural segmentation. The results agree with Julesz (1981a,b) who has reported evidence disproving his original conjecture of the importance of second-order statistics. Julesz (1981a,b) now hypothesizes textural segmentation to be a function of local features which he called textons. Textons are features that give textural segmentation when textures have identical second-order statistics. The two hypotheses are to date in complete agreement on the stimulus features producing textural segmentation, and the experiment reported is consistent with both. PMID:6626590

  14. Deflection of light to second order in conformal Weyl gravity

    NASA Astrophysics Data System (ADS)

    Sultana, Joseph

    2013-04-01

    We reexamine the deflection of light in conformal Weyl gravity obtained in Sultana and Kazanas (2010), by extending the calculation based on the procedure by Rindler and Ishak, for the bending angle by a centrally concentrated spherically symmetric matter distribution, to second order in M/R, where M is the mass of the source and R is the impact parameter. It has recently been reported in Bhattacharya et al. (JCAP 09 (2010) 004; JCAP 02 (2011) 028), that when this calculation is done to second order, the term γr in the Mannheim-Kazanas metric, yields again the paradoxical contribution γR (where the bending angle is proportional to the impact parameter) obtained by standard formalisms appropriate to asymptotically flat spacetimes. We show that no such contribution is obtained for a second order calculation and the effects of the term γr in the metric are again insignificant as reported in our earlier work.

  15. Second-order wave effects on TLP tendon tension responses

    SciTech Connect

    Xue, H.; Mercier, R.S.

    1996-12-31

    This paper presents a general procedure for analyzing the second-order wave effects on the tendon tension responses of a TLP. The approach solves both first- and second-order equation of motions for a TLP system in frequency domain. Viscous effects are included in the form of statistically linearized damping coefficients. An efficient algorithm has been devised for reducing the burden of second-order wave diffraction analysis, which selects the interacting frequency pairs according to springing frequency of interest to minimize the cost of computing quadratic transfer functions (QTFs) and allow accurate interpolation of QTFs. Moment statistics of the tension process are computed through an eigenvalue analysis. The developed method is applied to analyze the tendon tension responses of a TLP design in water depth of 3,000 ft.

  16. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    NASA Astrophysics Data System (ADS)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  17. Second-order subsonic airfoil theory including edge effects

    NASA Technical Reports Server (NTRS)

    Van Dyke, Milton D

    1956-01-01

    Several recent advances in plane subsonic flow theory are combined into a unified second-order theory for airfoil sections of arbitrary shape. The solution is reached in three steps: the incompressible result is found by integration, it is converted into the corresponding subsonic compressible result by means of the second-order compressibility rule, and it is rendered uniformly valid near stagnation points by further rules. Solutions for a number of airfoils are given and are compared with the results of other theories and of experiment. A straight-forward computing scheme is outlined for calculating the surface velocities and pressures on any airfoil at any angle of attack

  18. Solution of second order supersymmetrical intertwining relations in Minkowski plane

    NASA Astrophysics Data System (ADS)

    Ioffe, M. V.; Kolevatova, E. V.; Nishnianidze, D. N.

    2016-08-01

    Supersymmetrical (SUSY) intertwining relations are generalized to the case of quantum Hamiltonians in Minkowski space. For intertwining operators (supercharges) of second order in derivatives, the intertwined Hamiltonians correspond to completely integrable systems with the symmetry operators of fourth order in momenta. In terms of components, the intertwining relations correspond to the system of nonlinear differential equations which are solvable with the simplest—constant—ansatzes for the "metric" matrix in second order part of the supercharges. The corresponding potentials are built explicitly both for diagonalizable and nondiagonalizable form of "metric" matrices, and their properties are discussed.

  19. Static second-order polarizabilities of aminobenzophenones and nitrobenzophenones

    NASA Technical Reports Server (NTRS)

    Moore, Craig E.; Cardelino, Beatriz H.

    1991-01-01

    Static-field theoretical studies on molecular second-order polarizabilities (beta) of benzophenone derivatives were performed. Calculations were based on the use of shaped electric fields and semiempirical Hamiltonians. Either an electron-donating (amine) or an electron-withdrawing (nitro) substituent was incorporated into a phenyl ring of benzophenone; the phenyl rings of benzophenone were oriented either coplanar or perpendicular to the carbonyl. The change in charge transfer with respect to the electrophilic character of the carbonyl group was monitored to determine its effect on the molecular second-order polarizability. Calculations were performed for all constitutional isomers of the two benzophenone derivatives.

  20. Kubo Formulas for Second-Order Hydrodynamic Coefficients

    SciTech Connect

    Moore, Guy D.; Sohrabi, Kiyoumars A.

    2011-03-25

    At second order in gradients, conformal relativistic hydrodynamics depends on the viscosity {eta} and on five additional ''second-order'' hydrodynamical coefficients {tau}{sub {Pi}}, {kappa}, {lambda}{sub 1}, {lambda}{sub 2}, and {lambda}{sub 3}. We derive Kubo relations for these coefficients, relating them to equilibrium, fully retarded three-point correlation functions of the stress tensor. We show that the coefficient {lambda}{sub 3} can be evaluated directly by Euclidean means and does not in general vanish.

  1. Elasto-plastic model with second order defect density tensor

    NASA Astrophysics Data System (ADS)

    Cleja-Ţigoiu, Sanda

    2011-05-01

    The paper deals with a second order finite elasto-plastic model, which involves the defect density tensor, as a measure of the extra material defects existing in the damaged microstructure. The material behaviour is described with respect to an anholonomic configuration, which is introduced through the second order plastic deformation, consisting in plastic distortion and plastic connection. The defect density tensor enters the expression of the plastic connection through its gradient and represents a measure of non-metricity. The constitutive and evolution equations are derived to be compatible with the free energy imbalance. The evolution equation for the defect density tensor is non-local and coupled with the plastic distortion.

  2. Controlling flexible structures with second order actuator dynamics

    NASA Technical Reports Server (NTRS)

    Inman, Daniel J.; Umland, Jeffrey W.; Bellos, John

    1989-01-01

    The control of flexible structures for those systems with actuators that are modeled by second order dynamics is examined. Two modeling approaches are investigated. First a stability and performance analysis is performed using a low order finite dimensional model of the structure. Secondly, a continuum model of the flexible structure to be controlled, coupled with lumped parameter second order dynamic models of the actuators performing the control is used. This model is appropriate in the modeling of the control of a flexible panel by proof-mass actuators as well as other beam, plate and shell like structural numbers. The model is verified with experimental measurements.

  3. The Poisson equation at second order in relativistic cosmology

    SciTech Connect

    Hidalgo, J.C.; Christopherson, Adam J.; Malik, Karim A. E-mail: Adam.Christopherson@nottingham.ac.uk

    2013-08-01

    We calculate the relativistic constraint equation which relates the curvature perturbation to the matter density contrast at second order in cosmological perturbation theory. This relativistic ''second order Poisson equation'' is presented in a gauge where the hydrodynamical inhomogeneities coincide with their Newtonian counterparts exactly for a perfect fluid with constant equation of state. We use this constraint to introduce primordial non-Gaussianity in the density contrast in the framework of General Relativity. We then derive expressions that can be used as the initial conditions of N-body codes for structure formation which probe the observable signature of primordial non-Gaussianity in the statistics of the evolved matter density field.

  4. Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

    PubMed

    Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

    2015-12-01

    Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. PMID:26291914

  5. Kinetics of the BrO + NO2 Association Reaction. Temperature and Pressure Dependence in the Falloff Regime

    NASA Technical Reports Server (NTRS)

    Thron, R. P.; Daykin, E. P.; Wine, P.H.

    1997-01-01

    A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reaction BrO + NO2 + M yields (k1) products as a function of temperature (248-346 K), pressure (16-800 torr), and buffer gas identity (N2,CF4) The reaction is found to be in the falloff regime between third and second-order over the entire range of conditions investigated This is the first study where temperature-dependent measurements of k1(P,T) have been reported at pressures greater than 12 torr; hence, our results help constrain choices of k1(P,T) for use in models of lower stratospheric BrO(x) chemistry. Approximate falloff parameters in a convenient form for atmospheric modeling are derived.

  6. Oxidation of triclosan by ferrate: reaction kinetics, products identification and toxicity evaluation.

    PubMed

    Yang, Bin; Ying, Guang-Guo; Zhao, Jian-Liang; Zhang, Li-Juan; Fang, Yi-Xiang; Nghiem, Long Duc

    2011-02-15

    The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0-10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC-MS and RRLC-MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k(app), being 754.7 M(-1) s(-1) at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7(±1.9)×10(2) M(-1) s(-1), while that measured for anionic triclosan was 7.6(±0.6)×10(3) M(-1) s(-1). The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth. PMID:21093982

  7. Second-order accurate nonoscillatory schemes for scalar conservation laws

    NASA Technical Reports Server (NTRS)

    Huynh, Hung T.

    1989-01-01

    Explicit finite difference schemes for the computation of weak solutions of nonlinear scalar conservation laws is presented and analyzed. These schemes are uniformly second-order accurate and nonoscillatory in the sense that the number of extrema of the discrete solution is not increasing in time.

  8. Remarks on the second-order Seiberg-Witten maps

    SciTech Connect

    Trampetic, Josip; Wohlgenannt, Michael

    2007-12-15

    In this brief report, we discuss the Seiberg-Witten maps up to the second order in the noncommutative parameter {theta}. They add to the recently published solutions in [A. Alboteanu, T. Ohl, and R. Rueckl, Phys. Rev. D 76, 105018 (2007).]. Expressions for the vector, fermion, and Higgs fields are given explicitly.

  9. Second-order sliding mode control with experimental application.

    PubMed

    Eker, Ilyas

    2010-07-01

    In this article, a second-order sliding mode control (2-SMC) is proposed for second-order uncertain plants using equivalent control approach to improve the performance of control systems. A Proportional + Integral + Derivative (PID) sliding surface is used for the sliding mode. The sliding mode control law is derived using direct Lyapunov stability approach and asymptotic stability is proved theoretically. The performance of the closed-loop system is analysed through an experimental application to an electromechanical plant to show the feasibility and effectiveness of the proposed second-order sliding mode control and factors involved in the design. The second-order plant parameters are experimentally determined using input-output measured data. The results of the experimental application are presented to make a quantitative comparison with the traditional (first-order) sliding mode control (SMC) and PID control. It is demonstrated that the proposed 2-SMC system improves the performance of the closed-loop system with better tracking specifications in the case of external disturbances, better behavior of the output and faster convergence of the sliding surface while maintaining the stability. PMID:20413118

  10. Second-order nonlinear optical metamaterials: ABC-type nanolaminates

    SciTech Connect

    Alloatti, L. Kieninger, C.; Lauermann, M.; Köhnle, K.; Froelich, A.; Wegener, M.; Frenzel, T.; Freude, W.; Leuthold, J.; Koos, C.

    2015-09-21

    We demonstrate a concept for second-order nonlinear metamaterials that can be obtained from non-metallic centrosymmetric constituents with inherently low optical absorption. The concept is based on iterative atomic-layer deposition of three different materials, A = Al{sub 2}O{sub 3}, B = TiO{sub 2}, and C = HfO{sub 2}. The centrosymmetry of the resulting ABC stack is broken since the ABC and the inverted CBA sequences are not equivalent—a necessary condition for non-zero second-order nonlinearity. In our experiments, we find that the bulk second-order nonlinear susceptibility depends on the density of interfaces, leading to a nonlinear susceptibility of 0.26 pm/V at a wavelength of 800 nm. ABC-type nanolaminates can be deposited on virtually any substrate and offer a promising route towards engineering of second-order optical nonlinearities at both infrared and visible wavelengths.

  11. Children's Understanding of Second-Order Mental States

    ERIC Educational Resources Information Center

    Miller, Scott A.

    2009-01-01

    The most popular topic in theory-of-mind research has been first-order false belief: the realization that it is possible to hold false beliefs about events in the world. A more advanced development is second-order false belief: the realization that it is possible to hold a false belief about someone else's belief. This article reviews research…

  12. Second-order variational equations for N-body simulations

    NASA Astrophysics Data System (ADS)

    Rein, Hanno; Tamayo, Daniel

    2016-07-01

    First-order variational equations are widely used in N-body simulations to study how nearby trajectories diverge from one another. These allow for efficient and reliable determinations of chaos indicators such as the Maximal Lyapunov characteristic Exponent (MLE) and the Mean Exponential Growth factor of Nearby Orbits (MEGNO). In this paper we lay out the theoretical framework to extend the idea of variational equations to higher order. We explicitly derive the differential equations that govern the evolution of second-order variations in the N-body problem. Going to second order opens the door to new applications, including optimization algorithms that require the first and second derivatives of the solution, like the classical Newton's method. Typically, these methods have faster convergence rates than derivative-free methods. Derivatives are also required for Riemann manifold Langevin and Hamiltonian Monte Carlo methods which provide significantly shorter correlation times than standard methods. Such improved optimization methods can be applied to anything from radial-velocity/transit-timing-variation fitting to spacecraft trajectory optimization to asteroid deflection. We provide an implementation of first- and second-order variational equations for the publicly available REBOUND integrator package. Our implementation allows the simultaneous integration of any number of first- and second-order variational equations with the high-accuracy IAS15 integrator. We also provide routines to generate consistent and accurate initial conditions without the need for finite differencing.

  13. Second-Order Conditioning during a Compound Extinction Treatment

    ERIC Educational Resources Information Center

    Pineno, Oskar; Zilski, Jessica M.; Schachtman, Todd R.

    2007-01-01

    Two conditioned taste aversion experiments with rats were conducted to establish if a target taste that had received a prior pairing with illness could be subject to second-order conditioning during extinction treatment in compound with a flavor that also received prior conditioning. In these experiments, the occurrence of second-order…

  14. Green's function of the second order differential operator with involution

    NASA Astrophysics Data System (ADS)

    Ashyralyev, Allaberen; Sarsenbi, Abdisalam A.

    2016-08-01

    In the present paper, the Green's function of the second order differential operator L defined by formula L u =α u″ (x ) -u″ (-x ) =λ u (x ) ,-1

  15. PREDICTIONS OF HIGHWAY EMISSIONS BY A SECOND ORDER CLOSURE MODEL

    EPA Science Inventory

    The dispersion of sulfur hexafluoride tracer and sulfate from automobile emissions in the immediate vicinity of a highway were estimated for conditions similar to those existing during the General Motors sulfate dispersion experiment conducted at a GM test track. A second-order c...

  16. Second-Order Conditioning of Human Causal Learning

    ERIC Educational Resources Information Center

    Jara, Elvia; Vila, Javier; Maldonado, Antonio

    2006-01-01

    This article provides the first demonstration of a reliable second-order conditioning (SOC) effect in human causal learning tasks. It demonstrates the human ability to infer relationships between a cause and an effect that were never paired together during training. Experiments 1a and 1b showed a clear and reliable SOC effect, while Experiments 2a…

  17. Modeling Ability Differentiation in the Second-Order Factor Model

    ERIC Educational Resources Information Center

    Molenaar, Dylan; Dolan, Conor V.; van der Maas, Han L. J.

    2011-01-01

    In this article we present factor models to test for ability differentiation. Ability differentiation predicts that the size of IQ subtest correlations decreases as a function of the general intelligence factor. In the Schmid-Leiman decomposition of the second-order factor model, we model differentiation by introducing heteroscedastic residuals,…

  18. Pecuniary Effects, Second-Order Conditions, and the LRAC Curve.

    ERIC Educational Resources Information Center

    Comolli, Paul M.

    2000-01-01

    Explores the importance of second-order conditions in the cost-minimization problem confronting the monopsonistic employer of factor inputs. Describes an alternative approach to the presence of pecuniary effects that does not depend on the assumption that firms are monopsonistic in factor markets. (CMK)

  19. A New Factorisation of a General Second Order Differential Equation

    ERIC Educational Resources Information Center

    Clegg, Janet

    2006-01-01

    A factorisation of a general second order ordinary differential equation is introduced from which the full solution to the equation can be obtained by performing two integrations. The method is compared with traditional methods for solving these type of equations. It is shown how the Green's function can be derived directly from the factorisation…

  20. Forward and Backward Second-Order Pavlovian Conditioning in Honeybees

    ERIC Educational Resources Information Center

    Hussaini, Syed Abid; Komischke, Bernhard; Menzel, Randolf; Lachnit, Harald

    2007-01-01

    Second-order conditioning (SOC) is the association of a neutral stimulus with another stimulus that had previously been combined with an unconditioned stimulus (US). We used classical conditioning of the proboscis extension response (PER) in honeybees ("Apis mellifera") with odors (CS) and sugar (US). Previous SOC experiments in bees were…

  1. Generalized Second-Order Partial Derivatives of 1/r

    ERIC Educational Resources Information Center

    Hnizdo, V.

    2011-01-01

    The generalized second-order partial derivatives of 1/r, where r is the radial distance in three dimensions (3D), are obtained using a result of the potential theory of classical analysis. Some non-spherical-regularization alternatives to the standard spherical-regularization expression for the derivatives are derived. The utility of a…

  2. Solving Second-Order Differential Equations with Variable Coefficients

    ERIC Educational Resources Information Center

    Wilmer, A., III; Costa, G. B.

    2008-01-01

    A method is developed in which an analytical solution is obtained for certain classes of second-order differential equations with variable coefficients. By the use of transformations and by repeated iterated integration, a desired solution is obtained. This alternative method represents a different way to acquire a solution from classic power…

  3. Kinetic measurements of hydrocarbon conversion reactions on model metal surfaces.

    PubMed

    Wilson, Jarod; Guo, Hansheng; Morales, Ricardo; Podgornov, Egor; Lee, Ilkeun; Zaera, Francisco

    2007-08-01

    Examples from recent studies in our laboratory are presented to illustrate the main tools available to surface scientists for the determination of the kinetics of surface reactions. Emphasis is given here to hydrocarbon conversions and studies that rely on the use of model systems, typically single crystals and controlled (ultrahigh vacuum) environments. A detailed discussion is provided on the use of temperature-programmed desorption for the determination of activation energies as well as for product identification and yield estimations. Isothermal kinetic measurements are addressed next by focusing on studies under vacuum using molecular beams and surface-sensitive spectroscopies. That is followed by a review of the usefulness of high-pressure cells and other reactor designs for the emulation of realistic catalytic conditions. Finally, an analysis of the power of isotope labeling and chemical substitutions in mechanistic research on surface reactions is presented. PMID:17637975

  4. Maximum Probability Reaction Sequences in Stochastic Chemical Kinetic Systems

    PubMed Central

    Salehi, Maryam; Perkins, Theodore J.

    2010-01-01

    The detailed behavior of many molecular processes in the cell, such as protein folding, protein complex assembly, and gene regulation, transcription and translation, can often be accurately captured by stochastic chemical kinetic models. We investigate a novel computational problem involving these models – that of finding the most-probable sequence of reactions that connects two or more states of the system observed at different times. We describe an efficient method for computing the probability of a given reaction sequence, but argue that computing most-probable reaction sequences is EXPSPACE-hard. We develop exact (exhaustive) and approximate algorithms for finding most-probable reaction sequences. We evaluate these methods on test problems relating to a recently-proposed stochastic model of folding of the Trp-cage peptide. Our results provide new computational tools for analyzing stochastic chemical models, and demonstrate their utility in illuminating the behavior of real-world systems. PMID:21629860

  5. High temperature heterogeneous reaction kinetics and mechanisms of tungsten oxidation

    NASA Astrophysics Data System (ADS)

    Sabourin, Justin L.

    Tungsten, which is a material used in many high temperature applications, is limited by its susceptibility to oxidation at elevated temperatures. Although tungsten has the highest melting temperature of any metal, at much lower temperatures volatile oxides are formed during oxidation with oxygen containing species. This differs from many heterogeneous oxidation reactions involving metals since most reactions form very stable oxides that have higher melting or boiling points than the pure metal (e.g., aluminum, iron). Understanding heterogeneous oxidation and vaporization processes may allow for the expansion and improvement of high temperature tungsten applications. In order to increase understanding of the oxidation processes of tungsten, there is a need to develop reaction mechanisms and kinetics for oxidation processes involving oxidizers and environmental conditions of interest. Tungsten oxidation was thoroughly studied in the past, and today there is a good phenomenological understanding of these processes. However, as the design of large scale systems increasingly relies on computer modeling there becomes a need for improved descriptions of chemical reactions. With the increase in computing power over the last several decades, and the development of quantum chemistry and physics theories, heterogeneous systems can be modeled in detail at the molecular level. Thermochemical parameters that may not be measured experimentally may now be determined theoretically, a tool that was previously unavailable to scientists and engineers. Additionally, chemical kinetic modeling software is now available for both homogeneous and heterogeneous reactions. This study takes advantage of these new theoretical tools, as well as a thermogravimetric (TG) flow reactor developed as part of this study to learn about mechanisms and kinetics of tungsten oxidation. Oxidizers of interest are oxygen (O2), carbon dioxide (CO 2), water (H2O), and other oxidizers present in combustion and

  6. Characterization of hot hydrogen-atom reactions by kinetic spectrography.

    NASA Technical Reports Server (NTRS)

    Tomalesky, R. E.; Sturm, J. E.

    1971-01-01

    The flash photolysis of hydrogen iodide in the presence of nitrous oxide, carbon dioxide, and water has been investigated by kinetic spectroscopy. Although the fraction of hydrogen iodide dissociated was very large, the only observable intermediate was imidogen. It was demonstrated that the rapid removal of imidogen and the apparent absence of hydroxyl radicals in each case is a result of the following two reactions, respectively: (1) NH + HI yields NH2 + I; and (2) OH + HI yields H2O + I.

  7. Nanoconfinement effects: glucose oxidase reaction kinetics in nanofluidics.

    PubMed

    Wang, Chen; Sheng, Zhen-Huan; Ouyang, Jun; Xu, Jing-Juan; Chen, Hong-Yuan; Xia, Xing-Hua

    2012-02-01

    Size-tunable nanofluidic devices coupled to an electrochemical detector have been designed and then used to study glucose oxidase (GOx) reaction kinetics confined in nanospaces. The devices are fabricated via a photochemical decomposition reaction, which forms nanochannels covered with carboxyl groups. The generated carboxyl groups enable us to chemically pattern biological molecules on the polymer surfaces via covalent bonding. With this approach, the activity of the immobilized biological molecules confined in nanospaces with different sizes has been investigated. GOx species are chemically immobilized on the surface of the nanochannels, catalyzing the oxidation of substrate glucose as it flows through the channels. The enzyme reaction product, hydrogen peroxide, passing through the nanochannels, reaches an electrochemical detector, giving rise to an increase in anodic current. This steady-state electrochemical current, which responds to various glucose concentrations, can be used to evaluate the GOx activity under confinement conditions. The results show significant nanoconfinement effects that are dependent on the channel size where the reaction occurs, demonstrating the importance of spatial confinement on the GOx reaction kinetics. The present approach provides an effective method for the study of enzyme activity and other bioassay systems, such as cell assays, drug discovery, and clinical diagnosis. PMID:22311832

  8. Second order optical nonlinearity in silicon by symmetry breaking

    NASA Astrophysics Data System (ADS)

    Cazzanelli, Massimo; Schilling, Joerg

    2016-03-01

    Although silicon does not possess a dipolar bulk second order nonlinear susceptibility due to its centro-symmetric crystal structure, in recent years several attempts were undertaken to create such a property in silicon. This review presents the different sources of a second order susceptibility (χ(2)) in silicon and the connected second order nonlinear effects which were investigated up to now. After an introduction, a theoretical overview discusses the second order nonlinearity in general and distinguishes between the dipolar contribution—which is usually dominating in non-centrosymmetric structures—and the quadrupolar contribution, which even exists in centro-symmetric materials. Afterwards, the classic work on second harmonic generation from silicon surfaces in reflection measurements is reviewed. Due to the abrupt symmetry breaking at surfaces and interfaces locally a dipolar second order susceptibility appears, resulting in, e.g., second harmonic generation. Since the bulk contribution is usually small, the study of this second harmonic signal allows a sensitive observation of the surface/interface conditions. The impact of covering films, strain, electric fields, and defect states at the interfaces was already investigated in this way. With the advent of silicon photonics and the search for ever faster electrooptic modulators, the interest turned to the creation of a dipolar bulk χ(2) in silicon. These efforts have been focussing on several experiments applying an inhomogeneous strain to the silicon lattice to break its centro-symmetry. Recent results suggesting the impact of electric fields which are exerted from fixed charges in adjacent covering layers are also included. After a subsequent summary on "competing" concepts using not Si but Si-related materials, the paper will end with some final conclusions, suggesting possible future research direction in this dynamically developing field.

  9. Kinetics of the reversible reaction of struvite crystallisation.

    PubMed

    Crutchik, D; Garrido, J M

    2016-07-01

    The crystallisation of struvite could be a sustainable and economical alternative for recovering phosphorus from wastewater streams with high phosphate concentrations. Knowledge regarding the kinetics and thermodynamics that are involved in the crystallisation of struvite is the key to determine the optimal conditions for obtaining an efficient process. This study was conducted in a continuous stirred batch reactor. Different sets of experiments were performed in which struvite was either dissolved (undersaturated) or precipitated (oversaturated). These experiments were conducted at different temperatures (25, 30 and 35 °C) and pH values (8.2, 8.5 and 8.8) to determine the kinetics of struvite precipitation and dissolution. Struvite crystallisation was modelled as a reversible reaction. The kinetic rate parameters of struvite precipitation were 1.03·10(-4), 1.25·10(-4) and 1.54·10(-4) mol m(-2) min(-1) at 25, 30 and 35 °C, respectively. Similar kinetic rate parameters were determined for struvite dissolution. Struvite heterogeneous crystallisation can be represented by a first-order kinetic model that fitted well the experimental data. PMID:27085317

  10. Permanganate oxidation of diclofenac: The pH-dependent reaction kinetics and a ring-opening mechanism.

    PubMed

    Cheng, Hanyang; Song, Dean; Liu, Huijuan; Qu, Jiuhui

    2015-10-01

    In this work, the fate of diclofenac (DCF) during permanganate (Mn(VII)) oxidation was investigated at environmentally relevant pH conditions (from 5 to 9). The batch experiments showed that the kinetics of the Mn(VII)/DCF reaction follows a second-order rate law with an apparent rate constant of 1.57±0.02 M(-1) s(-1) at pH 7 and 20 °C. The half-value of DCF was calculated to be 37.5 min, when the concentration of Mn(VII) (0.4 mM) was 20-fold excess of DCF. The pH-dependence of the reaction kinetics was investigated, and the DCF reactivity with Mn(VII) was found to decrease with increasing pH. The second-order rate constants were then quantitatively described by incorporating the species distribution of DCF. A lower reactivity of the anionic DCF (DCF(-)) in comparison with its neutral counterpart (DCF(0)) was most likely attributable to the interaction between the ionized carboxylate group and amine nitrogen position, which can reduce the nucleophilicity of amine nitrogen by inductive and resonance effects. Moreover, a range of degradation products and the corresponding structures were proposed on the basis of the LC-Q-TOF-MS analysis. A detailed ring-opening reaction mechanism was proposed as follows: Mn(VII) acts as an electrophile to attack the amine moiety, leading to the formation of the primary intermediate products 2,6-dichloroaniline and 5-hydroxy-diclofenac, which can be further transformed. The further degradation proceeded through a multistep process including ring-opening, decarboxylation, hydroxylation, and cyclation reactions. PMID:25522850

  11. Microdroplet fusion mass spectrometry for fast reaction kinetics

    PubMed Central

    Lee, Jae Kyoo; Kim, Samuel; Nam, Hong Gil; Zare, Richard N.

    2015-01-01

    We investigated the fusion of high-speed liquid droplets as a way to record the kinetics of liquid-phase chemical reactions on the order of microseconds. Two streams of micrometer-size droplets collide with one another. The droplets that fused (13 μm in diameter) at the intersection of the two streams entered the heated capillary inlet of a mass spectrometer. The mass spectrum was recorded as a function of the distance x between the mass spectrometer inlet and the droplet fusion center. Fused droplet trajectories were imaged with a high-speed camera, revealing that the droplet fusion occurred approximately within a 500-μm radius from the droplet fusion center and both the size and the speed of the fused droplets remained relatively constant as they traveled from the droplet fusion center to the mass spectrometer inlet. Evidence is presented that the reaction effectively stops upon entering the heated inlet of the mass spectrometer. Thus, the reaction time was proportional to x and could be measured and manipulated by controlling the distance x. Kinetic studies were carried out in fused water droplets for acid-induced unfolding of cytochrome c and hydrogen–deuterium exchange in bradykinin. The kinetics of the former revealed the slowing of the unfolding rates at the early stage of the reaction within 50 μs. The hydrogen–deuterium exchange revealed the existence of two distinct populations with fast and slow exchange rates. These studies demonstrated the power of this technique to detect reaction intermediates in fused liquid droplets with microsecond temporal resolution. PMID:25775573

  12. Carborane tuning on iridium complexes: redox-switchable second-order NLO responses.

    PubMed

    Wang, Jiao; Wang, Wen-Yong; Fang, Xin-Yan; Qiu, Yong-Qing

    2015-04-01

    Much effort has been devoted to investigating the molecular geometries, electronic structures, redox properties and nonlinear optical (NLO) properties of Ir complexes involving o-, m- or p-carborane groups by density functional theory (DFT) methods. Switchable second-order NLO properties were induced by redox processes involving these complexes, and it was found that mainly the coordination bonds of Ir complexes changed during the oxidation process. Our calculations revealed that oxidation reactions have a significant influence on the second-order NLO response owing to the change in charge transfer pattern. The β tot values of oxidized species are at least ∼9 times larger for set I and ∼5 times larger for set II than those of the corresponding parent complexes. Introduction of carborane groups into ppy (phenylpyridine) ligands can enhance the second-order NLO response by 1.2- 1.6 times by a metal-to-ligand charge transfer (MLCT) transition between the Ir atom and carborane. The β tot of complex 2 [(ppy)2Ir(phen)](+) (phen = phenanthroline) is 3.3 times larger than that of complex 1 (ppy)2Ir(acce) (acce = acetylacetonate), which is caused by ligand-to-ligand charge transfer (LLCT) between ppy ligands and the ancillary ligand. Therefore, it can be concluded that the second-order NLO response can be effectively enhanced by oxidation reactions. PMID:25791353

  13. Kinetic Studies on the Reaction between Dicyanocobinamide and Hypochlorous Acid

    PubMed Central

    Maitra, Dhiman; Ali, Iyad; Abdulridha, Rasha M.; Shaeib, Faten; Khan, Sana N.; Saed, Ghassan M.; Pennathur, Subramaniam; Abu-Soud, Husam M.

    2014-01-01

    Hypochlorous acid (HOCl) is a potent oxidant generated by myeloperoxidase (MPO), which is an abundant enzyme used for defense against microbes. We examined the potential role of HOCl in corrin ring destruction and subsequent formation of cyanogen chloride (CNCl) from dicyanocobinamide ((CN)2-Cbi). Stopped-flow analysis revealed that the reaction consists of at least three observable steps, including at least two sequential transient intermediates prior to corrin ring destruction. The first two steps were attributed to sequential replacement of the two cyanide ligands with hypochlorite, while the third step was the destruction of the corrin ring. The formation of (OCl)(CN)-Cbi and its conversion to (OCl)2-Cbi was fitted to a first order rate equation with second order rate constants of 0.002 and 0.0002 µM−1s−1, respectively. The significantly lower rate of the second step compared to the first suggests that the replacement of the first cyanide molecule by hypochlorite causes an alteration in the ligand trans effects changing the affinity and/or accessibility of Co toward hypochlorite. Plots of the apparent rate constants as a function of HOCl concentration for all the three steps were linear with Y-intercepts close to zero, indicating that HOCl binds in an irreversible one-step mechanism. Collectively, these results illustrate functional differences in the corrin ring environments toward binding of diatomic ligands. PMID:25375773

  14. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Gorman, Brian P

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  15. First- and second-order charged particle optics

    SciTech Connect

    Brown, K.L.; Servranckx, R.V.

    1984-07-01

    Since the invention of the alternating gradient principle there has been a rapid evolution of the mathematics and physics techniques applicable to charged particle optics. In this publication we derive a differential equation and a matrix algebra formalism valid to second-order to present the basic principles governing the design of charged particle beam transport systems. A notation first introduced by John Streib is used to convey the essential principles dictating the design of such beam transport systems. For example the momentum dispersion, the momentum resolution, and all second-order aberrations are expressed as simple integrals of the first-order trajectories (matrix elements) and of the magnetic field parameters (multipole components) characterizing the system. 16 references, 30 figures.

  16. An application of integral inequality to second order nonlinear oscillation

    NASA Astrophysics Data System (ADS)

    Kwong, Man Kam; Wong, James S. W.

    A simple result concerning integral inequalities enables us to give an alternative proof of Waltman's theorem: lim t → ∞ ∝ t0a( s) ds = ∞ implies oscillation of the second order nonlinear equation y″( t) + a( t) f( y( t)) = 0; to prove an analog of Wintner's theorem that relates the nonoscillation of the second order nonlinear equations to the existence of solutions of some integral equations, assuming that lim t → ∞ ∝ t0a( s) ds exists; and to give an alternative proof and to extend a result of Butler. An often used condition on the coefficient a( t) is given a more familiar equivalent form and an oscillation criterion involving this condition is established.

  17. Symmetries of second-order PDEs and conformal Killing vectors

    NASA Astrophysics Data System (ADS)

    Tsamparlis, Michael; Paliathanasis, Andronikos

    2015-06-01

    We study the Lie point symmetries of a general class of partial differential equations (PDE) of second order. An equation from this class naturally defines a second-order symmetric tensor (metric). In the case the PDE is linear on the first derivatives we show that the Lie point symmetries are given by the conformal algebra of the metric modulo a constraint involving the linear part of the PDE. Important elements in this class are the Klein-Gordon equation and the Laplace equation. We apply the general results and determine the Lie point symmetries of these equations in various general classes of Riemannian spaces. Finally we study the type II hidden symmetries of the wave equation in a Riemannian space with a Lorenzian metric.

  18. Robust eigensystem assignment for second-order estimators

    NASA Technical Reports Server (NTRS)

    Juang, Jer-Nan; Maghami, Peiman G.

    1990-01-01

    An approach for the robust eigensystem assignment of flexible structures using full state or output feedback is developed. Using the second-order dynamic equations, the approach can assign the eigenvalues of the system via velocity and displacement feedbacks, or acceleration and velocity feedbacks. The eigenvalues and eigenvectors of the system are assigned, via the second-order eigenvalue problem for the structural system, in two steps. First, an orthonormal basis spanning the attainable closed-loop eigenvector space corresponding to each desired closed-loop eigenvalue is generated using the Singular Value or QR decompositions. Second, a sequential procedure is used to choose a set of closed-loop eigenvectors that are as close as possible to the column space of a well-conditioned target matrix. Among the possible choices of the target matrix, the closest unitary matrix to the open-loop eigenvector matrix appears to be a suitable choice. A numerical example is given to illustrate the proposed algorithm.

  19. On the second order spatiochromatic structure of natural images.

    PubMed

    Provenzi, Edoardo; Delon, Julie; Gousseau, Yann; Mazin, Baptiste

    2016-03-01

    We provide a theoretical analysis of some empirical facts about the second order spatiochromatic structure of natural images in color. In particular, we show that two simple assumptions on the covariance matrices of color images yield eigenvectors made by the Kronecker product of Fourier features times the triad given by luminance plus color opponent channels. The first of these assumptions is second order stationarity while the second one is commutativity between color correlation matrices. The validity of these assumptions and the predicted shape of the PCA components of color images are experimentally observed on two large image databases. As a by-product of this experimental study, we also provide novel data to support an exponential decay law of the spatiochromatic covariance between pairs of pixels as a function of their spatial distance. PMID:26024561

  20. A Second-Order Achromat Design Based on FODO Cell

    SciTech Connect

    Sun, Yipeng; /SLAC

    2011-08-19

    Two dipole doglegs are widely used to translate the beam axis horizontally or vertically. Quadrupoles are placed between the two consecutive dipoles to match first order dispersion and provide betatron focusing. Similarly a four dipole chicane is usually employed to form a bypass region, where the beam axis is transversely shifted first, then translated back to the original axis. In order to generate an isochronous section, quadrupoles are again needed to tune the first order transfer matrix element R{sub 56} equaling zero. Usually sextupoles are needed to correct second order dispersion in the bending plane, for both the dogleg optics and the chicane (with quad) optics. In this paper, an alternative optics design is introduced, which is based on a simple FODO cell and does not need sextupoles assistance to form a second-order achromat. It may provide a similar function of either a dogleg or a bypass, by using 2 or 4 of such combined supercells.

  1. Second order upwind Lagrangian particle method for Euler equations

    DOE PAGESBeta

    Samulyak, Roman; Chen, Hsin -Chiang; Yu, Kwangmin

    2016-06-01

    A new second order upwind Lagrangian particle method for solving Euler equations for compressible inviscid fluid or gas flows is proposed. Similar to smoothed particle hydrodynamics (SPH), the method represents fluid cells with Lagrangian particles and is suitable for the simulation of complex free surface / multiphase flows. The main contributions of our method, which is different from SPH in all other aspects, are (a) significant improvement of approximation of differential operators based on a polynomial fit via weighted least squares approximation and the convergence of prescribed order, (b) an upwind second-order particle-based algorithm with limiter, providing accuracy and longmore » term stability, and (c) accurate resolution of states at free interfaces. In conclusion, numerical verification tests demonstrating the convergence order for fixed domain and free surface problems are presented.« less

  2. Second-order closure models for supersonic turbulent flows

    NASA Technical Reports Server (NTRS)

    Speziale, Charles G.; Sarkar, Sutanu

    1991-01-01

    Recent work on the development of a second-order closure model for high-speed compressible flows is reviewed. This turbulent closure is based on the solution of modeled transport equations for the Favre-averaged Reynolds stress tensor and the solenoidal part of the turbulent dissipation rate. A new model for the compressible dissipation is used along with traditional gradient transport models for the Reynolds heat flux and mass flux terms. Consistent with simple asymptotic analyses, the deviatoric part of the remaining higher-order correlations in the Reynolds stress transport equations are modeled by a variable density extension of the newest incompressible models. The resulting second-order closure model is tested in a variety of compressible turbulent flows which include the decay of isotropic turbulence, homogeneous shear flow, the supersonic mixing layer, and the supersonic flat-plate turbulent boundary layer. Comparisons between the model predictions and the results of physical and numerical experiments are quite encouraging.

  3. Analysis of the blazing effect in second-order gratings

    SciTech Connect

    Matsumoto, Masauki )

    1992-10-01

    The validity of the blazing effect for improving the output-coupling efficiency of second-order gratings for use in grating-coupled surface-emitting lasers is examined. The Floquet-Bloch expansion method is used for the analysis of finite-length gratings with asymmetric tooth shapes operated in resonance condition. It is shown that for saw-tooth gratings the blazing effect is almost lost around the second-order Bragg wavelength because the reflected guide mode generated in the distributed Bragg reflector radiates preferentially into the substrate. By using a parallelogram grating with equal tooth and groove lengths, however, a high efficiency of radiation into the air is attainable even at the Bragg wavelength while the reflectivity is reduced. 32 refs.

  4. Experimental Measurement of the Second-Order Coherence of Supercontinuum.

    PubMed

    Närhi, Mikko; Turunen, Jari; Friberg, Ari T; Genty, Goëry

    2016-06-17

    We measure experimentally the second-order coherence properties of supercontinuum generated in a photonic crystal fiber. Our approach is based on measuring separately the quasicoherent and quasistationary contributions to the cross-spectral density and mutual coherence functions using a combination of interferometric and nonlinear gating techniques. This allows us to introduce two-dimensional coherence spectrograms which provide a direct characterization and convenient visualization of the spectrotemporal coherence properties. The measured second-order coherence functions are in very good agreement with numerical simulations based on the generalized nonlinear Schrödinger equation. Our results pave the way towards the full experimental characterization of supercontinuum coherence properties. More generally, they provide a generic approach for the complete experimental measurement of the coherence of broadband sources. PMID:27367389

  5. Experimental Measurement of the Second-Order Coherence of Supercontinuum

    NASA Astrophysics Data System (ADS)

    Närhi, Mikko; Turunen, Jari; Friberg, Ari T.; Genty, Goëry

    2016-06-01

    We measure experimentally the second-order coherence properties of supercontinuum generated in a photonic crystal fiber. Our approach is based on measuring separately the quasicoherent and quasistationary contributions to the cross-spectral density and mutual coherence functions using a combination of interferometric and nonlinear gating techniques. This allows us to introduce two-dimensional coherence spectrograms which provide a direct characterization and convenient visualization of the spectrotemporal coherence properties. The measured second-order coherence functions are in very good agreement with numerical simulations based on the generalized nonlinear Schrödinger equation. Our results pave the way towards the full experimental characterization of supercontinuum coherence properties. More generally, they provide a generic approach for the complete experimental measurement of the coherence of broadband sources.

  6. Relativistic second-order dissipative hydrodynamics at finite chemical potential

    NASA Astrophysics Data System (ADS)

    Jaiswal, Amaresh; Friman, Bengt; Redlich, Krzysztof

    2015-12-01

    Starting from the Boltzmann equation in the relaxation time approximation and employing a Chapman-Enskog like expansion for the distribution function close to equilibrium, we derive second-order evolution equations for the shear stress tensor and the dissipative charge current for a system of massless quarks and gluons. The transport coefficients are obtained exactly using quantum statistics for the phase space distribution functions at non-zero chemical potential. We show that, within the relaxation time approximation, the second-order evolution equations for the shear stress tensor and the dissipative charge current can be decoupled. We find that, for large values of the ratio of chemical potential to temperature, the charge conductivity is small compared to the coefficient of shear viscosity. Moreover, we show that in the relaxation-time approximation, the limiting behaviour of the ratio of heat conductivity to shear viscosity is qualitatively similar to that obtained for a strongly coupled conformal plasma.

  7. Correction for instrument time constant in determination of reaction kinetics.

    SciTech Connect

    Chilton, Marie; Clark, Jared; Thomas, Nathan; Nicholson, Allen; Hansen, Lee D.; Hansen, Clifford W.; Hansen, Jaron

    2010-02-01

    Rates of reactions can be expressed as dn/dt = kcf(n) where n is moles of reaction, k is a rate constant, c is a proportionality constant, and f(n) is a function of the properties of the sample. When the instrument time constant, ?, and k are sufficiently comparable that measured rates are significantly affected by instrument response, correction for instrument response must be done to obtain accurate reaction kinetics. Correction for instrument response has previously been done by truncating early data or by use of the Tian equation. Both methods can lead to significant errors. We describe a method for simultaneous determination of ?, k, and c by fitting equations describing the combined instrument response and rate law to rates observed as a function of time. The method was tested with data on the heat rate from acid-catalyzed hydrolysis of sucrose.

  8. Reaction kinetics of the CN radical with methyl bromide

    NASA Astrophysics Data System (ADS)

    Hodny, Michael; Hershberger, John F.

    2016-02-01

    The kinetics of the CN + CH3Br reaction were studied using transient infrared laser absorption spectroscopy to detect CN reactants and HCN products. This reaction has a rate constant of k = (2.20 ± 0.6) × 10-12 exp (453 ± 98/T) cm3 molecule-1 s-1 over the range 298-523 K. Hydrogen abstraction to produce HCN + CH2Br is only a minor reaction product, with a branching fraction of 0.12 ± 0.02. Other product channels, including BrCN + CH3, CH2CN + HBr, CH3CN + Br are likely. An upper limit of 0.01 was established for the HBr yield. These results are in qualitative agreement with recent ab initio calculations.

  9. Kinetics of the reaction of nitric oxide with hydrogen

    NASA Technical Reports Server (NTRS)

    Flower, W. L.; Hanson, R. K.; Kruger, C. H.

    1974-01-01

    Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

  10. Extensions and applications of a second-order landsurface parameterization

    NASA Technical Reports Server (NTRS)

    Andreou, S. A.; Eagleson, P. S.

    1983-01-01

    Extensions and applications of a second order land surface parameterization, proposed by Andreou and Eagleson are developed. Procedures for evaluating the near surface storage depth used in one cell land surface parameterizations are suggested and tested by using the model. Sensitivity analysis to the key soil parameters is performed. A case study involving comparison with an "exact" numerical model and another simplified parameterization, under very dry climatic conditions and for two different soil types, is also incorporated.

  11. Gravitational waves from global second order phase transitions

    SciTech Connect

    Jr, John T. Giblin; Price, Larry R.; Siemens, Xavier; Vlcek, Brian E-mail: larryp@caltech.edu E-mail: bvlcek@uwm.edu

    2012-11-01

    Global second-order phase transitions are expected to produce scale-invariant gravitational wave spectra. In this manuscript we explore the dynamics of a symmetry-breaking phase transition using lattice simulations. We explicitly calculate the stochastic gravitational wave background produced during the transition and subsequent self-ordering phase. We comment on this signal as it compares to the scale-invariant spectrum produced during inflation.

  12. Second order filter response with series coupled silica microresonators

    NASA Technical Reports Server (NTRS)

    Savchenkov, A.; Iitchenko, V. S.; Handley, T.; Maleki, L.

    2002-01-01

    We have demonstrated an approach for fabricating a photonic filter with second order response function. The filter consists of two germania-doped silica microtoroidal or microspherical resonators cascaded in series. We use UV irradiation to tune the mode of one microcavity to bring it close to the mode of the second microcavity. This approach produces a filter function with much sharper rolloff than can be obtained with the individual microresonators.

  13. athena: Tree code for second-order correlation functions

    NASA Astrophysics Data System (ADS)

    Kilbinger, Martin; Bonnett, Christopher; Coupon, Jean

    2014-02-01

    athena is a 2d-tree code that estimates second-order correlation functions from input galaxy catalogues. These include shear-shear correlations (cosmic shear), position-shear (galaxy-galaxy lensing) and position-position (spatial angular correlation). Written in C, it includes a power-spectrum estimator implemented in Python; this script also calculates the aperture-mass dispersion. A test data set is available.

  14. Second order parametric processes in nonlinear silica microspheres.

    PubMed

    Xu, Yong; Han, Ming; Wang, Anbo; Liu, Zhiwen; Heflin, James R

    2008-04-25

    We analyze second order parametric processes in a silica microsphere coated with radially aligned nonlinear optical molecules. In a high-Q nonlinear microsphere, we discover that it is possible to achieve ultralow threshold parametric oscillation that obeys the rule of angular momentum conservation. Based on symmetry considerations, one can also implement parametric processes that naturally generate quantum entangled photon pairs. Practical issues regarding implementation of the nonlinear microsphere are also discussed. PMID:18518201

  15. Second-order reconstruction of the inflationary potential

    NASA Technical Reports Server (NTRS)

    Liddle, Andrew R.; Turner, Michael S.

    1994-01-01

    To first order in the deviation from scale invariance the inflationary potential and its first two derivatives can be expressed in terms of the spectral indices of the scalar and tensor perturbations, n and n(sub T), and their contributions to the variance of the quadrupole CBR temperature anisotropy, S and T. In addition, there is a 'consistency relation' between these quantities: n(sub T) = (-1/ 7)(T/S). We derive the second-order expressions for the inflationary potential and its first two derivatives and the first-order expression for its third derivative, in terms, of n, n(sub T), S, T, and dn/d ln gamma. We also obtain the second-order consistency relation, n(sub T) = (-1/7)(T/S)(1 + 0.11(T/S) + 0.15(n-1)). As an example we consider the exponential potential, the only known case where exact analytic solutions for the perturbation spectra exist. We reconstruct the potential via Taylor expansion (with coefficients calculated at both first and second order), and introduce the Pade approximate as a greatly improved alternative.

  16. Free-Form Region Description with Second-Order Pooling.

    PubMed

    Carreira, João; Caseiro, Rui; Batista, Jorge; Sminchisescu, Cristian

    2015-06-01

    Semantic segmentation and object detection are nowadays dominated by methods operating on regions obtained as a result of a bottom-up grouping process (segmentation) but use feature extractors developed for recognition on fixed-form (e.g. rectangular) patches, with full images as a special case. This is most likely suboptimal. In this paper we focus on feature extraction and description over free-form regions and study the relationship with their fixed-form counterparts. Our main contributions are novel pooling techniques that capture the second-order statistics of local descriptors inside such free-form regions. We introduce second-order generalizations of average and max-pooling that together with appropriate non-linearities, derived from the mathematical structure of their embedding space, lead to state-of-the-art recognition performance in semantic segmentation experiments without any type of local feature coding. In contrast, we show that codebook-based local feature coding is more important when feature extraction is constrained to operate over regions that include both foreground and large portions of the background, as typical in image classification settings, whereas for high-accuracy localization setups, second-order pooling over free-form regions produces results superior to those of the winning systems in the contemporary semantic segmentation challenges, with models that are much faster in both training and testing. PMID:26357341

  17. Non-Gaussianity from the second-order cosmological perturbation

    NASA Astrophysics Data System (ADS)

    Lyth, David H.; Rodríguez, Yeinzon

    2005-06-01

    Several conserved and/or gauge-invariant quantities described as the second-order curvature perturbation have been given in the literature. We revisit various scenarios for the generation of second-order non-Gaussianity in the primordial curvature perturbation ζ, employing for the first time a unified notation and focusing on the normalization fNL of the bispectrum. When ζ first appears a few Hubble times after horizon exit, |fNL| is much less than 1 and is, therefore, negligible. Thereafter ζ (and hence fNL) is conserved as long as the pressure is a unique function of energy density (adiabatic pressure). Nonadiabatic pressure comes presumably only from the effect of fields, other than the one pointing along the inflationary trajectory, which are light during inflation (“light noninflaton fields”). During single-component inflation fNL is constant, but multicomponent inflation might generate |fNL|˜1 or bigger. Preheating can affect fNL only in atypical scenarios where it involves light noninflaton fields. The simplest curvaton scenario typically gives fNL≪-1 or fNL=+5/4. The inhomogeneous reheating scenario can give a wide range of values for fNL. Unless there is a detection, observation can eventually provide a limit |fNL|≲1, at which level it will be crucial to calculate the precise observational limit using second-order theory.

  18. Second-order parametrized-post-Newtonian Lagrangian

    SciTech Connect

    Benacquista, M.J. )

    1992-02-15

    A many-body Lagrangian to second post-Newtonian order using an extension of the parametrized-post-Newtonian (PPN) formalism is introduced and the properties of new parameters are explored. A parametrized gauge transformation is developed to permit comparison with theories of gravity in a variety of different coordinate systems. A procedure to impose Lorentz invariance on a general second-order post-Newtonian Lagrangian is developed. The Lagrangian is then constrained to possess Lorentz invariance and a Lorentz-invariant'' gauge is introduced. The constrained Lagrangian is found to be described by ten new second-order PPN parameters. When the Lagrangian is further constrained to describe theories of gravity for which test particles move along geodesics, one of the ten new parameters is given entirely in terms of first-order PPN parameters, leaving only nine PPN parameters to describe the second-order gravitational interaction. A metric'' gauge is introduced which allows the metric to be easily found from the Lagrangian and is shown to reduce to the gauge associated with the canonical formalism of Arnowitt, Deser, and Misner when the general-relativity values of the PPN parameters are used.

  19. Dressed four-wave mixing second-order Talbot effect

    NASA Astrophysics Data System (ADS)

    Chen, Haixia; Zhang, Xun; Zhu, Dayu; Yang, Chang; Jiang, Tao; Zheng, Huaibin; Zhang, Yanpeng

    2014-10-01

    We theoretically demonstrate second-order Talbot effect (SOTE) based on entangled photon pairs. The photon pairs are generated from the spontaneous parametric four-wave mixing (SPFWM) process in a cold atomic medium and can be taken as the imaging light in order to realize coincidence recording. A strong standing wave is used to create the electromagnetically induced grating in the entangled photon pairs channels. By changing the frequency detuning of the standing wave or the other optical fields participating in the process, we can manipulate the contrast of the second-order Talbot image. We use the second-order correlation function and the dressed-state picture to explain the SOTE occurring in the SPFWM process. Moreover, we demonstrate the scheme for SOTE based on the spatially correlated twin beams generated from the SPFWM process with injection. This scheme provides a convenient detection proposal for the SOTE at the cost of the image contrast. Compared to the previous self-imaging schemes, the present schemes have the characteristic of controllable image contrast and of nonlocal imaging, and thus, they might broaden their applications in imaging techniques and find applications in quantum lithography.

  20. NO sub x -char reactions: Kinetics and transport aspects

    SciTech Connect

    Calo, J.M.; Suuberg, E.M.

    1990-01-01

    The present project is motivated by the need to reduce NO{sub x} emissions from combustors, especially coal combustors. Reactions with carbon are known to be effective at reducing No to N{sub 2}, and remain interesting candidates in a wide variety of possible applications. These reactions are known to be important in reducing NO{sub x} emissions from fluidized bed coal combustors, in which the coal char itself serves as the reducing agent. The principal goal of this project is to develop a mechanistic understanding of the processes by which carbons reduce NO to N{sub 2}. The carbon was a char derived from phenol-formaldehyde resin. This material has been noted to be a reasonable model for coal chars in most respects, expect that its gasification behavior is not complicated by catalytic processes due to minerals. In the first phases of the project, the global kinetics of the process were established. In more recent work, attention has been turned to the individual steps in the mechanism. Recent quarterly reports have detailed the role of both chemisorption and desorption processes in determining the course and kinetics of the process. This report continues the reporting of results obtained along these lines, and draws an important new conclusion concerning the number of separate processes involved in determining the kinetics. 40 refs., 3 figs., 2 tabs.

  1. A study of switchgrass pyrolysis: Product variability and reaction kinetics

    NASA Astrophysics Data System (ADS)

    Bovee, Jonathan Matthew

    Samples of the same cultivar of cave-in-rock switchgrass were harvested from plots in Frankenmuth, Roger City, Cass County, and Grand Valley, Michigan. It was determined that variation exists, between locations, among the pyrolytic compounds which can lead to variability in bio-oil and increased processing costs at bio-refineries to make hydrocarbon fuels. Washed and extractives-free switchgrass samples, which contain a lower alkali and alkaline earth metals content than untreated samples, were shown to produce lower amounts of acids, esters, furans, ketones, phenolics, and saccharides and also larger amounts of aldehydes upon pyrolysis. Although the minerals catalyzed pyrolytic reactions, there was no evidence indicating their effect on reducing the production of anhydrosugars, specifically levoglucosan. To further link minerals present in the biomass to a catalytic pathway, mathematic models were employed to determine the kinetic parameters of the switchgrass. While the calculated activation energies of switchgrass, using the FWO and KAS methods, were 227.7 and 217.8 kJ/mol, correspondingly, it was concluded that the activation energies for the switchgrass hemicellulose and cellulose peaks were 115.5 and 158.2 kJ/mol, respectively, using a modified model-fitting method. The minerals that effect the production of small molecules and levoglucosan also have an observable catalytic effect on switchgrass reaction rate, which may be quantifiable through the use of reaction kinetics so as to determine activation energy.

  2. Classic reaction kinetics can explain complex patterns of antibiotic action.

    PubMed

    Abel Zur Wiesch, Pia; Abel, Sören; Gkotzis, Spyridon; Ocampo, Paolo; Engelstädter, Jan; Hinkley, Trevor; Magnus, Carsten; Waldor, Matthew K; Udekwu, Klas; Cohen, Ted

    2015-05-13

    Finding optimal dosing strategies for treating bacterial infections is extremely difficult, and improving therapy requires costly and time-intensive experiments. To date, an incomplete mechanistic understanding of drug effects has limited our ability to make accurate quantitative predictions of drug-mediated bacterial killing and impeded the rational design of antibiotic treatment strategies. Three poorly understood phenomena complicate predictions of antibiotic activity: post-antibiotic growth suppression, density-dependent antibiotic effects, and persister cell formation. We show that chemical binding kinetics alone are sufficient to explain these three phenomena, using single-cell data and time-kill curves of Escherichia coli and Vibrio cholerae exposed to a variety of antibiotics in combination with a theoretical model that links chemical reaction kinetics to bacterial population biology. Our model reproduces existing observations, has a high predictive power across different experimental setups (R(2) = 0.86), and makes several testable predictions, which we verified in new experiments and by analyzing published data from a clinical trial on tuberculosis therapy. Although a variety of biological mechanisms have previously been invoked to explain post-antibiotic growth suppression, density-dependent antibiotic effects, and especially persister cell formation, our findings reveal that a simple model that considers only binding kinetics provides a parsimonious and unifying explanation for these three complex, phenotypically distinct behaviours. Current antibiotic and other chemotherapeutic regimens are often based on trial and error or expert opinion. Our "chemical reaction kinetics"-based approach may inform new strategies, which are based on rational design. PMID:25972005

  3. Reaction of OH with CINO: kinetics and mechanisms

    SciTech Connect

    Finlayson-Pitts, B.J.; Ezell, M.J.; Wang, S.Z.; Grant, C.E.

    1987-04-23

    The kinetics and products of the gas-phase reaction of OH with CINO have been studied in a fast flow discharge system using the reaction of hydrogen atoms with NO/sub 2/ as the source of OH. The decay of OH in excess CINO at a total pressure of 1.05 +/- 0.05 Torr in He was followed by resonance fluorescence at 309.5 nm at temperatures from 262 to 373K. The stable products observed by mass spectrometry from 276 to 353 K and from 0.2 to 0.8 Torr total pressure were HOCl, HONO, and Cl/sub 2/. Molecular Cl/sub 2/ results from the reaction of Cl atoms with the excess CINO present. The ratio of the products HOCl/Cl/sub 2/ did not change significantly with temperature or total pressure. The Arrhenius expression for the rate constant k/sub 1/ (= k/sub 1a/ + k/sub 1b/) for the reaction of Oh with CINO is k/sub 1/ = (1.5/sub -0.1//sup +0.1/ x 10/sup -12/) exp(-(458 +/- 27)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/, with k/sub 1/ = (3.2 +/- 0.5) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 298 K, where all errors are two standard deviations. From these kinetic data, a typical tropospheric lifetime of CINO with respect to reaction with Oh is calculated to be approx.36 days, too slow to compete with CINO photolysis.

  4. Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

    SciTech Connect

    Lin, M.C.

    1993-12-01

    Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

  5. Kinetic studies of cascade reactions in high-throughput systems.

    PubMed

    Iron, David; Boelens, Hans F M; Westerhuis, Johan A; Rothenberg, Gadi

    2003-12-01

    The application of robotic systems to the study of complex reaction kinetics is considered, using the cascade reaction A --> B --> C as a working example. Practical problems in calculating the rate constants k1 and k2 for the reactions A --> B and B --> C from concentration measurements of CA, CB, or CC are discussed in the light of the symmetry and invertability of the rate equations. A D-optimal analysis is used to determine the points in time and the species that will give the best (i.e., most accurate) results. When exact data are used, the most robust solution results from measuring the pair of concentrations (CA, CC). The system's information function is computed using numeric methods. This function is then used to estimate the amount of information obtainable from a given cascade reaction at any given time. The theoretical findings are compared with experimental results from a set of two-stage cascade experiments monitored using UV-visible spectroscopy. Finally, the pros and cons of using a single reaction sample to estimate both k1 and k2 are discussed. PMID:16465720

  6. Influence of chemical kinetics on postcolumn reaction in a capillary Taylor reactor with catechol analytes and photoluminescence following electron transfer.

    PubMed

    Jung, Moon Chul; Weber, Stephen G

    2005-02-15

    Postcolumn derivatization reactions can enhance detector sensitivity and selectivity, but their successful combination with capillary liquid chromatography has been limited because of the small peak volumes in capillary chromatography. A capillary Taylor reactor (CTR), developed in our laboratory, provides simple and effective mixing and reaction in a 25-microm-radius postcolumn capillary. Homogenization of reactant streams occurs by radial diffusion, and a chemical reaction follows. Three characteristic times for a given reaction process can be predicted using simple physical and chemical parameters. Two of these times are the homogenization time, which governs how long it takes the molecules in the analyte and reagent streams to mix, and the reaction time, which governs how long the molecules in a homogeneous solution take to react. The third characteristic time is an adjustment to the reaction time called the start time, which represents an estimate of the average time the analyte stream spends without exposure to reagent. In this study, laser-induced fluorescence monitored the extent of the postcolumn reaction (reduction of Os(bpy)3(3+) by analyte to the photoluminescent Os(bpy)3(2+)) in a CTR. The reaction time depends on the reaction rates. Analysis of product versus time data yielded second-order reaction rate constants between the PFET reagent, tris(2,2'-bipyridine)osmium, and standards ((ferrocenylmethyl)trimethylammonium cation and p-hydroquinone) or catechols (dopamine, epinephrine, norepinephrine, 3, 4-dihydroxyphenylacetic acid. The extent of the reactions in a CTR were then predicted from initial reaction conditions and compared to experimental results. Both the theory and experimental results suggested the reactions of catechols were generally kinetically controlled, while those of the standards were controlled by mixing time (1-2 s). Thus, the extent of homogenization can be monitored in a CTR using the relatively fast reaction of the reagent and p

  7. Determination of robust stability margin for second-order systems

    NASA Technical Reports Server (NTRS)

    Chuang, C.-H.; Kau, C.-T.; Juang, Jer-Nan

    1992-01-01

    Robust stabilization of uncertain systems has been extensively investigated and the stability test for the whole set of uncertain parameters has been reduced to a finite number of test points, four points for the characteristic polynomial with independent coefficients. As a result the robust stability margin can be determined using a reasonable amount of computation. It is impossible to apply the results of the test to a practical system as the coefficients of the characteristic polynomial for a physical system are usually functions of uncertain parameters. However, many physical systems may be represented by a second-order mass-spring-damper system with a special multilinear form in its characteristic polynomial. This paper investigates second-order mass-spring-damper systems and the reduction of the number of test points. It is shown that such a system with arbritrary compensators always has a multilinear characteristic polynomial. It is also shown that a line in the two-dimensional parameter space forms the boundary after the mapping of a multilinear characteristic polynomial and this interior extreme line forms a conic curve in the complex plane. The boundary of uncertain domain for a multilinear polynomial with two uncertainty parameters can be determined analytically using this curve, and the four sides image of a square of the uncertain parameter. Therefore, the stability margin may be determined by checking the intersections of the boundary with the zero point. A similar procedure can be used for second-order systems with more than two uncertainty parameters when parameter optimization is used in determining the boundary.

  8. Superquadric glyphs for symmetric second-order tensors.

    PubMed

    Schultz, Thomas; Kindlmann, Gordon L

    2010-01-01

    Symmetric second-order tensor fields play a central role in scientific and biomedical studies as well as in image analysis and feature-extraction methods. The utility of displaying tensor field samples has driven the development of visualization techniques that encode the tensor shape and orientation into the geometry of a tensor glyph. With some exceptions, these methods work only for positive-definite tensors (i.e. having positive eigenvalues, such as diffusion tensors). We expand the scope of tensor glyphs to all symmetric second-order tensors in two and three dimensions, gracefully and unambiguously depicting any combination of positive and negative eigenvalues. We generalize a previous method of superquadric glyphs for positive-definite tensors by drawing upon a larger portion of the superquadric shape space, supplemented with a coloring that indicates the quadratic form (including eigenvalue sign). We show that encoding arbitrary eigenvalue magnitudes requires design choices that differ fundamentally from those in previous work on traceless tensors that arise in the study of liquid crystals. Our method starts with a design of 2-D tensor glyphs guided by principles of scale-preservation and symmetry, and creates 3-D glyphs that include the 2-D glyphs in their axis-aligned cross-sections. A key ingredient of our method is a novel way of mapping from the shape space of three-dimensional symmetric second-order tensors to the unit square. We apply our new glyphs to stress tensors from mechanics, geometry tensors and Hessians from image analysis, and rate-of-deformation tensors in computational fluid dynamics. PMID:20975202

  9. Detection of a diffusive cloak via second-order statistics

    NASA Astrophysics Data System (ADS)

    Koirala, Milan; Yamilov, Alexey

    2016-08-01

    We propose a scheme to detect the diffusive cloak proposed by Schittny et al [Science 345, 427 (2014)]. We exploit the fact that diffusion of light is an approximation that disregards wave interference. The long-range contribution to intensity correlation is sensitive to locations of paths crossings and the interference inside the medium, allowing one to detect the size and position, including the depth, of the diffusive cloak. Our results also suggest that it is possible to separately manipulate the first- and the second-order statistics of wave propagation in turbid media.

  10. Detection of a diffusive cloak via second-order statistics.

    PubMed

    Koirala, Milan; Yamilov, Alexey

    2016-08-15

    We propose a scheme to detect the diffusive cloak proposed by Schittny et al. [Science345, 427 (2014).SCIEAS0036-807510.1126/science.1254524]. We exploit the fact that diffusion of light is an approximation that disregards wave interference. The long-range contribution to intensity correlation is sensitive to the locations of path crossings and the interference inside the medium, allowing one to detect the size and position, including the depth, of the diffusive cloak. Our results also suggest that it is possible to separately manipulate the first- and the second-order statistics of wave propagation in turbid media. PMID:27519108

  11. Stochastic systems with delay: Perturbation theory for second order statistics

    NASA Astrophysics Data System (ADS)

    Frank, T. D.

    2016-03-01

    Within the framework of delay Fokker-Planck equations, a perturbation theoretical method is developed to determine second-order statistical quantities such as autocorrelation functions for stochastic systems with delay. Two variants of the perturbation theoretical approach are presented. The first variant is based on a non-local Fokker-Planck operator. The second variant requires to solve a Fokker-Planck equation with source term. It is shown that the two variants yield consistent results. The perturbation theoretical approaches are applied to study negative autocorrelations that are induced by feedback delays and mediated by the strength of the fluctuating forces that act on the feedback systems.

  12. Supersonic second order analysis and optimization program user's manual

    NASA Technical Reports Server (NTRS)

    Clever, W. C.

    1984-01-01

    Approximate nonlinear inviscid theoretical techniques for predicting aerodynamic characteristics and surface pressures for relatively slender vehicles at supersonic and moderate hypersonic speeds were developed. Emphasis was placed on approaches that would be responsive to conceptual configuration design level of effort. Second order small disturbance theory was utilized to meet this objective. Numerical codes were developed for analysis and design of relatively general three dimensional geometries. Results from the computations indicate good agreement with experimental results for a variety of wing, body, and wing-body shapes. Case computational time of one minute on a CDC 176 are typical for practical aircraft arrangement.

  13. P-stable boundary value methods for second order IVPs

    NASA Astrophysics Data System (ADS)

    Aceto, Lidia; Ghelardoni, Paolo; Magherini, Cecilia

    2012-09-01

    We introduce a family of Linear Multistep Methods used as Boundary Value Methods for the numerical solution of initial value problems for second order ordinary differential equations of special type. The aim is to obtain P-stable methods with arbitrary order of accuracy. This result allows to overcome the order barrier established by Lambert and Watson which limited to p = 2 the maximum order of a P-stable Linear Multistep Method. In addition, an extension of the methods in the Exponential Fitting framework is also considered.

  14. Entanglement in a second-order quantum phase transition

    SciTech Connect

    Vidal, Julien; Palacios, Guillaume; Mosseri, Remy

    2004-02-01

    We consider a system of mutually interacting spins 1/2 embedded in a transverse magnetic field which undergoes a second-order quantum phase transition. We analyze the entanglement properties and the spin squeezing of the ground state and show that, contrarily to the one-dimensional case, a cusplike singularity appears at the critical point {lambda}{sub c} in the thermodynamical limit. We also show that there exists a value {lambda}{sub 0}{>=}{lambda}{sub c} above which the ground state is not spin squeezed despite a nonvanishing concurrence.

  15. A second-order impact model for forest fire regimes.

    PubMed

    Maggi, Stefano; Rinaldi, Sergio

    2006-09-01

    We present a very simple "impact" model for the description of forest fires and show that it can mimic the known characteristics of wild fire regimes in savannas, boreal forests, and Mediterranean forests. Moreover, the distribution of burned biomasses in model generated fires resemble those of burned areas in numerous large forests around the world. The model has also the merits of being the first second-order model for forest fires and the first example of the use of impact models in the study of ecosystems. PMID:16723147

  16. Kinetics of the reaction of hydroxyl radicals with nitric acid

    NASA Technical Reports Server (NTRS)

    Margitan, J. J.; Watson, R. T.

    1982-01-01

    An extensive study was made of the reaction of hydroxyl radicals with nitric acid in a laser photolysis-resonance fluorescence system. A 266 nm laser was used to photolyze HNO3 in the temperature range 225-415 K at pressures of 20-300 torr. A temperature dependence was detected below room temperature, with a leveling off at 298 K and a wide spread in the rate constants. A pressure dependence was observed over the entire range and was more pronounced at lower temperatures. The results are noted to be in agreement with those of previous investigations. However, the wide range of rate constants are suggested to be a problem for stratospheric HO(x) modeling for anthropogenic effects. No explanation could be given of the varying results obtained by other investigators regarding the kinetics of the reactions.

  17. Thermochemical Kinetics for Multireference Systems: Addition Reactions of Ozone

    SciTech Connect

    Zhao, Yan; Tishchenko, Oksana; Gour, Jeffrey R.; Li, Wei; Lutz, Jesse; Piecuch, Piotr; Truhlar, Donald G.

    2009-05-14

    The 1,3-dipolar cycloadditions of ozone to ethyne and ethene provide extreme examples of multireference singlet-state chemistry, and they are examined here to test the applicability of several approaches to thermochemical kinetics of systems with large static correlation. Four different multireference diagnostics are applied to measure the multireference characters of the reactants, products, and transition states; all diagnostics indicate significant multireference character in the reactant portion of the potential energy surfaces. We make a more complete estimation of the effect of quadruple excitations than was previously available, and we use this with CCSDT/CBS estimation of Wheeler et al. (Wheeler, S. E.; Ess, D. H.; Houk, K. N. J. Phys. Chem. A 2008, 112, 1798.) to make new best estimates of the van der Waals association energy, the barrier height, and the reaction energy to form the cycloadduct for both reactions. Comparing with these best estimates, we present comprehensive mean unsigned errors for a variety of coupled cluster, multilevel, and density functional methods. Several computational aspects of multireference reactions are considered: (i) the applicability of multilevel theory, (ii) the convergence of coupled cluster theory for reaction barrier heights, (iii) the applicability of completely renormalized coupled cluster methods to multireference systems, (iv) the treatment by density functional theory, (v) the multireference perturbation theory for multireference reactions, and (vi) the relative accuracy of scaling-type multilevel methods as compared with additive ones. It is found that scaling-type multilevel methods do not perform better than the additive-type multilevel methods. Among the 48 tested density functionals, only M05 reproduces the best estimates within their uncertainty. Multireference perturbation theory based on the complete-active-space reference wave functions constructed using a small number of reaction-specific active orbitals

  18. Kinetics and toxicity of direct reaction between ozone and 1,2-dihydrobenzene in dilute aqueous solution.

    PubMed

    Zaror, C; Carrasco, V; Perez, L; Soto, G; Mondaca, M A; Mansilla, H

    2001-01-01

    The presence of toxic aromatic organic compounds in industrial wastewater affects the efficiency of conventional biological treatment. The oxidizing power of ozone represents an interesting pretreatment to reduce toxicity and increase biodegradability. At low pH, ozone is known to attack electron-rich structures by direct electrophilic reactions which open aromatic rings, and generate smaller oxidized compounds. This paper reports experimental results on kinetic and toxicity aspects of ozone direct reactions with 1,2-dihydrobenzene. This toxic compound is frequently found in cellulose bleaching effluents. Although the reaction pathway is rather complex, 4-carbon compounds, such as maleic acid, are readily formed during the first stage of ozonation. These 4-carbon compounds are further oxidized to form smaller molecules (mostly 2-carbon, such as oxalic acid). The apparent kinetics of 1,2-dihydrobenzene follows a second order law, with a rate constant around 0.36 (dm3 mmol-1s-1), at pH 2 and 20 degrees C. Results show that the BOD:COD ratio increase five-fold as ozonation progresses. Furthermore, the mutagenicity of 1,2-dihydrobenzene totally disappears as the aromatic compound is destroyed by ozonation. PMID:11380197

  19. Reaction kinetics and oxidation product formation in the degradation of acetaminophen by ferrate (VI).

    PubMed

    Wang, Hongyu; Liu, Yibing; Jiang, Jia-Qian

    2016-07-01

    This paper investigates the degradation of acetaminophen (AAP) in aqueous solutions by ferrate (VI), aiming to propose the kinetics, pathways and the oxidation products' formation in the AAP degradation. A series of jar tests were undertaken over ferrate (VI) dosages (molar ratios of ferrate (VI):AAP, 5:1 to 25:1) and pH values (4-11). The effects of co-existing ions (0.2-5 mM) and humic acid (10-50 mg l(-1)) on the AAP removal were investigated. Ferrate (VI) can remove 99.6% AAP (from 1000 μg l(-1)) in 60 min under study conditions when majority of the AAP reduction occurred in the first 5 min. The treatment performance depended on the ferrate(VI) dosage, pH and the type and strength of co-existing ions and humic acid. Raising ferrate (VI) dosage with optimal pH 7 improved the AAP degradation. In the presence of humic acid, the AAP degradation by ferrate (VI) was promoted in a short period (<30 min) but then inhibited with increasing in humic acid contents. The presence of Al(3+), CO3(2-) and PO4(3-) ions declined but the existence of K(+), Na(+), Mg(2+) and Ca(2+) ions can improve the AAP removal. The catalytic function of Al(3+) on the decomposition of ferrate (VI) in aqueous solution was found. The kinetics of the reaction between ferrate (VI) and AAP was pseudo first-order for ferrete (VI) and pseudo second-order for AAP. The pseudo rate constant of ferrate (VI) with AAP was 1.4 × 10(-5) L(2) mg(-2) min(-1). Three oxidation products (OPs) were identified and the AAP degradation pathways were proposed. PMID:27155474

  20. Kinetic studies of the hydroxyl radical reaction with PAHs

    NASA Astrophysics Data System (ADS)

    Ananthula, Rajeshwar

    An existing quartz optical reactor heating system was designed to permit higher temperature kinetic measurements more closely associated with post-combuston conditions (up to 1200 K). A pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique was then applied with this modified reactor to study the OH radical kinetics with polycyclic aromatic hydrocarbons (PAHs). The kinetics of the reaction of a surrogate three-ring PAH, anthracene (and its deuterated form) with hydroxyl (OH) radicals was investigated over the temperature range of 373 to 1200 K. This study represents the first examination of the OH kinetics for this class of reactions at elevated temperatures (>470 K). The results indicate a complex temperature dependence similar to that observed for simpler aromatic compounds, e.g., benzene. At low temperatures (373-498 K), the rate measurements exhibited Arrhenius behavior (1.82 x 10-11 exp(542.35/T) in units of cm3 molecule -1 s-1) and kinetic isotope effect (KIE) measurements were consistent with an OH addition mechanism. The low temperature results are extrapolated to atmospheric temperatures and compared with previous measurements. Rate measurements between 673 and 923 K exhibited a sharp decrease in the magnitude of the rate coefficients (a factor of 9). KIE measurements under these conditions were still consistent with an OH addition mechanism. The following modified Arrhenius equation is the best fit to our anthracene measurements between 373 and 923 K, 8.17 x 1014 T-8.3 exp(-3171.71/T) (in units of cm3 molecule-1 s-1). For a limited temperature range between 1000 and 1200 K, the rate measurements exhibited an apparent positive temperature dependence with the following Arrhenius equation the best fit to the data, 2.18 x 10-11*exp(-1734.11/T) (in units of cm3molecule-1s -1). KIE measurements above 999 K were slightly larger than unity, but inclusive regarding the mechanism of the reaction. Theoretical calculations of the KIE indicate

  1. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  2. A-posteriori error estimation for second order mechanical systems

    NASA Astrophysics Data System (ADS)

    Ruiner, Thomas; Fehr, Jörg; Haasdonk, Bernard; Eberhard, Peter

    2012-06-01

    One important issue for the simulation of flexible multibody systems is the reduction of the flexible bodies degrees of freedom. As far as safety questions are concerned knowledge about the error introduced by the reduction of the flexible degrees of freedom is helpful and very important. In this work, an a-posteriori error estimator for linear first order systems is extended for error estimation of mechanical second order systems. Due to the special second order structure of mechanical systems, an improvement of the a-posteriori error estimator is achieved. A major advantage of the a-posteriori error estimator is that the estimator is independent of the used reduction technique. Therefore, it can be used for moment-matching based, Gramian matrices based or modal based model reduction techniques. The capability of the proposed technique is demonstrated by the a-posteriori error estimation of a mechanical system, and a sensitivity analysis of the parameters involved in the error estimation process is conducted.

  3. Classic reaction kinetics can explain complex patterns of antibiotic action

    PubMed Central

    zur Wiesch, P. Abel; Abel, S.; Gkotzis, S.; Ocampo, P.; Engelstädter, J.; Hinkley, T.; Magnus, C.; Waldor, M. K.; Udekwu, K.; Cohen, T.

    2015-01-01

    Finding optimal dosing strategies for treating bacterial infections is extremely difficult, and improving therapy requires costly and time-intensive experiments. To date, an incomplete mechanistic understanding of drug effects has limited our ability to make accurate quantitative predictions of drug-mediated bacterial killing and impeded the rational design of antibiotic treatment strategies. Three poorly understood phenomena complicate predictions of antibiotic activity: post-antibiotic growth suppression, density-dependent antibiotic effects, and persister cell formation. Here, we show that chemical binding kinetics alone are sufficient to explain these three phenomena, using single cell data and time-kill curves of Escherichia coli and Vibrio cholerae exposed to a variety of antibiotics in combination with a theoretical model that links chemical reaction kinetics to bacterial population biology. Our model reproduces existing observations, has a high predictive power across different experimental setups (R2= 0.86), and makes several testable predictions, which we verified in new experiments and by analysing published data from a clinical trial on tuberculosis therapy. While a variety of biological mechanisms have previously been invoked to explain post-antibiotic growth suppression, density-dependent antibiotic effects, and especially persister cell formation, our findings reveal that a simple model which considers only binding kinetics provides a parsimonious and unifying explanation for these three complex, phenotypically distinct behaviours. Current antibiotic and other chemotherapeutic regimens are often based on trial-and-error or expert opinion. Our ‘chemical reaction kinetics’-based approach may inform new strategies, that are based on rational design. PMID:25972005

  4. Transport coefficients in second-order non-conformal viscous hydrodynamics

    NASA Astrophysics Data System (ADS)

    Ryblewski, Radoslaw

    2015-05-01

    Based on the exact solution of Boltzmann kinetic equation in the relaxation-time approximation, the precision of the two most recent formulations of relativistic second-order non-conformal viscous hydrodynamics (14-moment approximation and causal Chapman-Enskog method), standard Israel-Stewart theory, and anisotropic hydrodynamics framework, in the simple case of one-dimensional Bjorken expansion, is tested. It is demonstrated that the failure of Israel-Stewart theory in reproducing exact solutions of the Boltzmann kinetic equation occurs due to neglecting and/or choosing wrong forms of some of the second-order transport coefficients. In particular, the importance of shear-bulk couplings in the evolution equations for dissipative quantities is shown. One finds that, in the case of the bulk viscous pressure correction, such coupling terms are as important as the corresponding first-order Navier-Stokes term and must be included in order to obtain, at least qualitative, overall agreement with the kinetic theory.

  5. Solvent effects on kinetics of an heteroatomic nucleophilic substitution reaction in ionic liquid and molecular solvents mixtures

    NASA Astrophysics Data System (ADS)

    Salari, Hadi; Pedervand, Mohsen; Sadeghzadeh-Darabi, Faramarz; Gholami, Mohammad Reza

    2013-12-01

    Rate constants, k A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]) with dimethyl sulfoxide at 25°C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO4]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the effects of the solvents on a chemical process. The influence of solvent parameters including normalized polarity ( E {/T N }), dipolarity/polarizability (π*), hydrogen bond donor acidity (α), and hydrogen bond acceptor basicity (β) on the second-order rate constants were investigated and multiple linear regressions gave much better results with regard to single parameter regressions. The dipolarity/polarizability of media has a positive effect in all mixtures regarding zwitterionic character of the reaction intermediate and the hydrogen bond acceptor basicity of the solvent by stabilizing of activated complex increases the reaction rate.

  6. Communication: Explicitly correlated four-component relativistic second-order Møller-Plesset perturbation theory.

    PubMed

    Ten-no, Seiichiro; Yamaki, Daisuke

    2012-10-01

    We propose explicitly correlated Ansatz for four-component relativistic methods within the framework of the no-pair approximation. Kinetically balanced geminal basis is derived to satisfy the cusp conditions in the non-relativistic limit based on the Lévy-Leblend-like equation. Relativistic variants of strong-orthogonality projection operator (Ansätze 2α and 2β) suitable for practical calculations are introduced by exploiting the orthogonal complement of the large-component basis. A pilot implementation is performed for the second order Møller-Plesset perturbation theory. PMID:23039576

  7. Magnetic Compensation for Second-Order Doppler Shift in LITS

    NASA Technical Reports Server (NTRS)

    Burt, Eric; Tjoelker, Robert

    2008-01-01

    The uncertainty in the frequency of a linear-ion-trap frequency standard (LITS) can be reduced substantially by use of a very small magnetic inhomogeneity tailored to compensate for the residual second-order Doppler shift. An effect associated with the relativistic time dilatation, one cause of the second-order Doppler shift, is ion motion that is attributable to the trapping radio-frequency (RF)electromagnetic field used to trap ions. The second-order Doppler shift is reduced by using a multi-pole trap; however it is still the largest source of systematic frequency shift in the latest generation of LITSs, which are among the most stable clocks in the world. The present compensation scheme reduces the frequency instability of the affected LITS to about a tenth of its previous value. The basic principles of prior generation LITSs were discussed in several prior NASA Tech Briefs articles. Below are recapitulated only those items of basic information necessary to place the present development in context. A LITS includes a microwave local oscillator, the frequency of which is stabilized by comparison with the frequency of the ground state hyperfine transition of 199Hg+ ions. The comparison involves a combination of optical and microwave excitation and interrogation of the ions in a linear ion trap in the presence of a nominally uniform magnetic field. In the current version of the LITS, there are two connected traps (see figure): (1) a quadrupole trap wherein the optical excitation and measurement take place and (2) a 12-pole trap (denoted the resonance trap), wherein the microwave interrogation takes place. The ions are initially loaded into the quadrupole trap and are thereafter shuttled between the two traps. Shuttling ions into the resonance trap allows sensitive microwave interrogation to take place well away from loading interference. The axial magnetic field for the resonance trap is generated by an electric current in a finely wound wire coil surrounded by

  8. The Reaction Kinetics of LiD with Water Vapor

    SciTech Connect

    Balooch, M; Dinh, L N; Calef, D F

    2003-04-01

    The interaction of LiD with water vapor in the partial pressure range of 10{sup -7} Torr to 20 Torr has been investigated. The reaction probability of water with pure LiD cleaved in an ultra high vacuum environment was obtained using the modulated molecular beam technique. This probability was 0.11 and independent of LiD surface temperature suggesting a negligible activation energy for the reaction in agreement with quantum chemical calculations. The value gradually reduced, however, to .007 as the surface concentration of oxygen containing product (LiOH), which was monitored in-situ by Auger electron spectroscopy on the reaction zone, approached full coverage. As the hydroxide film grew beyond a monolayer, the phase lag of hydrogen product increased from zero to 20 degrees and the reaction probability reduced further until it approached our detection limit ({approx} 10{sup -4}). This phase lag was attributed to a diffusion limited process in this regime. In separate experiments, the film growth has been studied in nitrogen atmosphere with 100% relative humidity using thermogravimetric analysis (TGA) and in air with 50% relative humidity utilizing scanning electron microscopy (SEM). For exposures to environment with high water concentrations and for micrometer thick films, the reaction probability reduced to 4 x 10{sup -7} and was independent of exposure time, The lattice diffusion through the film was no longer controlling the transport of water to the LiD/LiOH interface. Microcracks generated in the film to release stress provided easier pathways to the interface. A modified microscope, capable of both atomic force microscopy (AFM) and nanoindentation, was employed to investigate the surface morphology of LiOH.H{sub 2}O grown on LiOH at high water vapor partial pressures and the kinetics of this growth.

  9. A new approach for second-order perturbation theory.

    PubMed

    Tomlinson, David G; Asadchev, Andrey; Gordon, Mark S

    2016-05-30

    A new second-order perturbation theory (MP2) approach is presented for closed shell energy evaluations. The new algorithm has a significantly lower memory footprint, a lower FLOP (floating point operations) count, and a lower time to solution compared to previously implemented parallel MP2 methods in the GAMESS software package. Additionally, this algorithm features an adaptive approach for the disk/distributed memory storage of the MP2 amplitudes. The algorithm works well on a single workstation, small cluster, and large Cray cluster, and it allows one to perform large calculations with thousands of basis functions in a matter of hours on a single workstation. The same algorithm has been adapted for graphical processing unit (GPU) architecture. The performance of the new GPU algorithm is also discussed. © 2016 Wiley Periodicals, Inc. PMID:26940648

  10. Absorbing boundary conditions for second-order hyperbolic equations

    NASA Technical Reports Server (NTRS)

    Jiang, Hong; Wong, Yau Shu

    1989-01-01

    A uniform approach to construct absorbing artificial boundary conditions for second-order linear hyperbolic equations is proposed. The nonlocal boundary condition is given by a pseudodifferential operator that annihilates travelling waves. It is obtained through the dispersion relation of the differential equation by requiring that the initial-boundary value problem admits the wave solutions travelling in one direction only. Local approximation of this global boundary condition yields an nth-order differential operator. It is shown that the best approximations must be in the canonical forms which can be factorized into first-order operators. These boundary conditions are perfectly absorbing for wave packets propagating at certain group velocities. A hierarchy of absorbing boundary conditions is derived for transonic small perturbation equations of unsteady flows. These examples illustrate that the absorbing boundary conditions are easy to derive, and the effectiveness is demonstrated by the numerical experiments.

  11. Compact Two-State-Variable Second-Order Memristor Model.

    PubMed

    Kim, Sungho; Kim, Hee-Dong; Choi, Sung-Jin

    2016-06-01

    A key requirement for using memristors in functional circuits is a predictive physical model to capture the resistive switching behavior, which shall be compact enough to be implemented using a circuit simulator. Although a number of memristor models have been developed, most of these models (i.e., first-order memristor models) have utilized only a one-state-variable. However, such simplification is not adequate for accurate modeling because multiple mechanisms are involved in resistive switching. Here, a two-state-variable based second-order memristor model is presented, which considers the axial drift of the charged vacancies in an applied electric field and the radial vacancy motion caused by the thermophoresis and diffusion. In particular, this model emulates the details of the intrinsic short-term dynamics, such as decay and temporal heat summation, and therefore, it accurately predicts the resistive switching characteristics for both DC and AC input signals. PMID:27152649

  12. K-inflationary power spectra at second order

    SciTech Connect

    Martin, Jérôme; Vennin, Vincent; Ringeval, Christophe E-mail: christophe.ringeval@uclouvain.be

    2013-06-01

    Within the class of inflationary models, k-inflation represents the most general single field framework that can be associated with an effective quadratic action for the curvature perturbations and a varying speed of sound. The incoming flow of high-precision cosmological data, such as those from the Planck satellite and small scale Cosmic Microwave Background (CMB) experiments, calls for greater accuracy in the inflationary predictions. In this work, we calculate for the first time the next-to-next-to-leading order scalar and tensor primordial power spectra in k-inflation needed in order to obtain robust constraints on the inflationary theory. The method used is the uniform approximation together with a second order expansion in the Hubble and sound flow functions. Our result is checked in various limits in which it reduces to already known situations.

  13. Absorbing boundary conditions for second-order hyperbolic equations

    NASA Technical Reports Server (NTRS)

    Jiang, Hong; Wong, Yau Shu

    1990-01-01

    A uniform approach to construct absorbing artificial boundary conditions for second-order linear hyperbolic equations is proposed. The nonlocal boundary condition is given by a pseudodifferential operator that annihilates travelling waves. It is obtained through the dispersion relation of the differential equation by requiring that the initial-boundary value problem admits the wave solutions travelling in one direction only. Local approximation of this global boundary condition yields an nth-order differential operator. It is shown that the best approximations must be in the canonical forms which can be factorized into first-order operators. These boundary conditions are perfectly absorbing for wave packets propagating at certain group velocities. A hierarchy of absorbing boundary conditions is derived for transonic small perturbation equations of unsteady flows. These examples illustrate that the absorbing boundary conditions are easy to derive, and the effectiveness is demonstrated by the numerical experiments.

  14. Analysis of implicit second-order upwind-biased stencils

    NASA Technical Reports Server (NTRS)

    Roberts, Thomas W.; Warren, Gary P.

    1993-01-01

    Truncation error and stability properties of several implicit upwind schemes for the two-dimensional Euler equations are examined. The schemes use linear data reconstruction methods to achieve second-order flux integrations where the implicit Jacobian operators are first order. The stability properties of the schemes are examined by a Von Neumann analysis of the linearized, constant-coefficient Euler equations. The choice of the data reconstruction method used to evaluate the flux integral has a dramatic effect on the convergence properties of the implicit solution method. In particular, the typical one-dimensional data reconstruction methods used with structured grids exhibit poor convergence properties compared to the unstructured grid method considered. Of the schemes examined, the one with the superior convergence properties is well-suited for both unstructured and structured grids, which has important implications for the design of implicit methods.

  15. Second-Order Fermi Acceleration and Emission in Blazar Jets

    NASA Astrophysics Data System (ADS)

    Asano, Katsuaki; Takahara, Fumio; Toma, Kenji; Kusunose, Masaaki; Kakuwa, Jun

    The second-order Fermi acceleration (Fermi-II) driven by turbulence may be responsible for the electron acceleration in blazar jets. We test this model with time-dependent simulations, adopt it for 1ES 1101-232, and Mrk 421. The Fermi-II model with radial evolution of the electron injection rate and/or diffusion coefficient can reproduce the spectra from the radio to the gamma-ray regime. For Mrk 421, an external radio photon field with a luminosity of 4.9 begin{math} {times} 10 (38) erg s (-1) is required to agree with the observed GeV flux. The temporal variability of the diffusion coefficient or injection rate causes flare emission. The observed synchronicity of X-ray and TeV flares implies a decrease of the magnetic field in the flaring source region.

  16. New implicitly solvable potential produced by second order shape invariance

    SciTech Connect

    Cannata, F.; Ioffe, M.V.; Kolevatova, E.V.; Nishnianidze, D.N.

    2015-05-15

    The procedure proposed recently by Bougie et al. (2010) to study the general form of shape invariant potentials in one-dimensional Supersymmetric Quantum Mechanics (SUSY QM) is generalized to the case of Higher Order SUSY QM with supercharges of second order in momentum. A new shape invariant potential is constructed by this method. It is singular at the origin, it grows at infinity, and its spectrum depends on the choice of connection conditions in the singular point. The corresponding Schrödinger equation is solved explicitly: the wave functions are constructed analytically, and the energy spectrum is defined implicitly via the transcendental equation which involves Confluent Hypergeometric functions. - Highlights: • New potential with 2nd order irreducible shape invariance was constructed. • The connection conditions at the singularity of potential were obtained. • The explicit expressions for all wave functions were derived. • The implicit equation for the energy spectrum was obtained.

  17. Pump power dependence of second order correlation in nondegenerate SPDC

    NASA Astrophysics Data System (ADS)

    Kim, Charles; Kanner, Gary

    2009-08-01

    We observed the second order correlation peak for nondegenerate spontaneous parametric down conversion (SPDC) of a pulsed pump at 532 nm into 810 nm and 1550 nm entangled beams. We used a Si avalanche photodiode (APD) to detect the 810 nm photons, and an InGaAs APD to detect those at 1550 nm. We defined both a visibility and signal-to-noise ratio (SNR) based on the data, which were obtained at various pump powers. In contrast to classical imaging systems, for which SNR increases monotonically with transmitted power, the SNR for the correlation peak in our setup exhibited a gradual decay as the pump power increased. We derived an empirical relation for the SNR, which was inversely proportional to the square root of pump power.

  18. Second-order UV contamination in astronomical spectra

    NASA Astrophysics Data System (ADS)

    Gutierrez-Moreno, A.; Heathcote, S.; Moreno, H.; Hamuy, M.

    1994-11-01

    Observations of the planetary nebula Me 2-1 are used to discuss some effects of contamination produced by the second-order ultraviolet spectrum in the first-order red, longer than approximately 6200 A. It is found that this contamination is present with some instrumental setups, and that the contaminating lines are displaced in wavelength with respect to the predictions from diffraction theory by an amount which varies slightly for different setups. From the theoretical and empirical analysis of these displacements, it is concluded that the shift in wavelength is due to the presence of chromatic difference in magnification in spectrograph cameras including any transmission element, as in the case in the semi-solid Schmidt-Cassegrain cameras used in our observations.

  19. Relativistic quantum transport coefficients for second-order viscous hydrodynamics

    NASA Astrophysics Data System (ADS)

    Florkowski, Wojciech; Jaiswal, Amaresh; Maksymiuk, Ewa; Ryblewski, Radoslaw; Strickland, Michael

    2015-05-01

    We express the transport coefficients appearing in the second-order evolution equations for bulk viscous pressure and shear stress tensor using Bose-Einstein, Boltzmann, and Fermi-Dirac statistics for the equilibrium distribution function and Grad's 14-moment approximation as well as the method of Chapman-Enskog expansion for the nonequilibrium part. Focusing on the case of transversally homogeneous and boost-invariant longitudinal expansion of the viscous medium, we compare the results obtained using the above methods with those obtained from the exact solution of the massive 0+1 d relativistic Boltzmann equation in the relaxation-time approximation. We show that compared to the 14-moment approximation, the hydrodynamic transport coefficients obtained by employing the Chapman-Enskog method lead to better agreement with the exact solution of the relativistic Boltzmann equation.

  20. Gravitational Microlensing by Ellis Wormhole: Second Order Effects

    NASA Astrophysics Data System (ADS)

    Lukmanova, Regina; Kulbakova, Aliya; Izmailov, Ramil; Potapov, Alexander A.

    2016-07-01

    Gravitational lensing is the effect of light bending in a gravitational field. It can be used as a possible observational method to detect or exclude the existence of wormholes. In this work, we extend the work by Abe on gravitational microlensing by Ellis wormhole by including the second order deflection term. Using the lens equation and definition of Einstein radius, we find the angular locations of the physical image inside and outside Einstein ring. The work contains a comparative analysis of light curves between the Schwarzschild black hole and the Ellis wormhole that can be used to distinguish such objects though such distinctions are too minute to be observable even in the near future. We also tabulate the optical depth and event rate for lensing by bulge and Large Magellanic Cloud (LMC) stars.

  1. Invariant classification of second-order conformally flat superintegrable systems

    NASA Astrophysics Data System (ADS)

    Capel, J. J.; Kress, J. M.

    2014-12-01

    In this paper we continue the work of Kalnins et al in classifying all second-order conformally-superintegrable (Laplace-type) systems over conformally flat spaces, using tools from algebraic geometry and classical invariant theory. The results obtained show, through Stäckel equivalence, that the list of known nondegenerate superintegrable systems over three-dimensional conformally flat spaces is complete. In particular, a seven-dimensional manifold is determined such that each point corresponds to a conformal class of superintegrable systems. This manifold is foliated by the nonlinear action of the conformal group in three dimensions. Two systems lie in the same conformal class if and only if they lie in the same leaf of the foliation. This foliation is explicitly described using algebraic varieties formed from representations of the conformal group. The proof of these results rely heavily on Gröbner basis calculations using the computer algebra software packages Maple and Singular.

  2. Simultaneous determination of kinetic and thermodynamic parameters from fast-reaction kinetic measurements.

    PubMed

    Trimm, H H; Ushio, H; Patel, R C

    1981-10-01

    A combined stopped-flow temperature-jump apparatus interfaced with a dedicated microcomputer has been used to study the complexation reaction of iron(III) with thiocyanate in aqueous solution. Kinetic rate-constants (k(f) = 143 l.mole(-1) .sec(-1) from T-jump, k(f) = 150 l.mole(-1) .sec(-1) from stopped flow), equilibrium constants (K = 143 from T-jump, K = 150 from stopped flow) and the thermodynamic enthalpy change (DeltaH(c) = -6.7 kJ/mole) could be independently determined from the simultaneous application of the two techniques. PMID:18962997

  3. WEAK GALERKIN METHODS FOR SECOND ORDER ELLIPTIC INTERFACE PROBLEMS.

    PubMed

    Mu, Lin; Wang, Junping; Wei, Guowei; Ye, Xiu; Zhao, Shan

    2013-10-01

    Weak Galerkin methods refer to general finite element methods for partial differential equations (PDEs) in which differential operators are approximated by their weak forms as distributions. Such weak forms give rise to desirable flexibilities in enforcing boundary and interface conditions. A weak Galerkin finite element method (WG-FEM) is developed in this paper for solving elliptic PDEs with discontinuous coefficients and interfaces. Theoretically, it is proved that high order numerical schemes can be designed by using the WG-FEM with polynomials of high order on each element. Extensive numerical experiments have been carried to validate the WG-FEM for solving second order elliptic interface problems. High order of convergence is numerically confirmed in both L 2 and L ∞ norms for the piecewise linear WG-FEM. Special attention is paid to solve many interface problems, in which the solution possesses a certain singularity due to the nonsmoothness of the interface. A challenge in research is to design nearly second order numerical methods that work well for problems with low regularity in the solution. The best known numerical scheme in the literature is of order [Formula: see text] to [Formula: see text] for the solution itself in L ∞ norm. It is demonstrated that the WG-FEM of the lowest order, i.e., the piecewise constant WG-FEM, is capable of delivering numerical approximations that are of order [Formula: see text] to [Formula: see text] in the L ∞ norm for C (1) or Lipschitz continuous interfaces associated with a C (1) or H (2) continuous solution. PMID:24072935

  4. Second order closure modeling of turbulent buoyant wall plumes

    NASA Technical Reports Server (NTRS)

    Zhu, Gang; Lai, Ming-Chia; Shih, Tsan-Hsing

    1992-01-01

    Non-intrusive measurements of scalar and momentum transport in turbulent wall plumes, using a combined technique of laser Doppler anemometry and laser-induced fluorescence, has shown some interesting features not present in the free jet or plumes. First, buoyancy-generation of turbulence is shown to be important throughout the flow field. Combined with low-Reynolds-number turbulence and near-wall effect, this may raise the anisotropic turbulence structure beyond the prediction of eddy-viscosity models. Second, the transverse scalar fluxes do not correspond only to the mean scalar gradients, as would be expected from gradient-diffusion modeling. Third, higher-order velocity-scalar correlations which describe turbulent transport phenomena could not be predicted using simple turbulence models. A second-order closure simulation of turbulent adiabatic wall plumes, taking into account the recent progress in scalar transport, near-wall effect and buoyancy, is reported in the current study to compare with the non-intrusive measurements. In spite of the small velocity scale of the wall plumes, the results showed that low-Reynolds-number correction is not critically important to predict the adiabatic cases tested and cannot be applied beyond the maximum velocity location. The mean and turbulent velocity profiles are very closely predicted by the second-order closure models. but the scalar field is less satisfactory, with the scalar fluctuation level underpredicted. Strong intermittency of the low-Reynolds-number flow field is suspected of these discrepancies. The trends in second- and third-order velocity-scalar correlations, which describe turbulent transport phenomena, are also predicted in general, with the cross-streamwise correlations better than the streamwise one. Buoyancy terms modeling the pressure-correlation are shown to improve the prediction slightly. The effects of equilibrium time-scale ratio and boundary condition are also discussed.

  5. Kinetics of enol formation from reaction of OH with propene.

    PubMed

    Huynh, Lam K; Zhang, Hongzhi R; Zhang, Shaowen; Eddings, Eric; Sarofim, Adel; Law, Matthew E; Westmoreland, Phillip R; Truong, Thanh N

    2009-04-01

    Kinetics of enol generation from propene has been predicted in an effort to understand the presence of enols in flames. A potential energy surface for reaction of OH with propene was computed by CCSD(T)/cc-pVDZ//B3LYP/cc-pVTZ calculations. Rate constants of different product channels and branching ratios were then calculated using the Master Equation formulation (J. Phys. Chem. A 2006, 110, 10528). Of the two enol products, ethenol is dominant over propenol, and its pathway is also the dominant pathway for the OH + propene addition reactions to form bimolecular products. In the temperature range considered, hydrogen abstraction dominated propene + OH consumption by a branching ratio of more than 90%. Calculated rate constants of enol formation were included in the Utah Surrogate Mechanism to model the enol profile in a cyclohexane premixed flame. The extended model shows consistency with experimental data and gives 5% contribution of ethenol formation from OH + propene reaction, the rest coming from ethene + OH. PMID:19271758

  6. Kinetics of the Self Reaction of Cyclopentadienyl Radicals.

    PubMed

    Knyazev, Vadim D; Popov, Konstantin V

    2015-07-16

    The kinetics of the self-reaction of cyclopentadienyl radicals (c-C5H5) was studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 304-600 K and at bath gas densities of (3.00-12.0) × 10(16) molecules cm(-3). The room-temperature value of the rate constant, (3.98 ± 0.41) × 10(-10) cm(3) molecule(-1) s(-1), is significantly higher than the rate constants for most hydrocarbon radical-radical reactions and coincides with the estimated collision rate. The observed overall c-C5H5 + c-C5H5 rate constant demonstrates an unprecedented strong negative temperature dependence: k1 = 2.9 × 10(-12) exp(+1489 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainty increasing with temperature, from 13% at 304 to 32% at 600 K. Formation of C10H10 as the primary product of cyclopentadienyl self-reaction was observed. In additional experiments performed at the temperature of 800 K, formation of C10H10, C10H9, and C10H8 was observed. Final product analysis by gas chromatography/mass spectrometry detected two isomers of C10H8 at 800 K: naphthalene (major) and azulene (minor). PMID:25760686

  7. A second-order closure analysis of turbulent diffusion flames. [combustion physics

    NASA Technical Reports Server (NTRS)

    Varma, A. K.; Fishburne, E. S.; Beddini, R. A.

    1977-01-01

    A complete second-order closure computer program for the investigation of compressible, turbulent, reacting shear layers was developed. The equations for the means and the second order correlations were derived from the time-averaged Navier-Stokes equations and contain third order and higher order correlations, which have to be modeled in terms of the lower-order correlations to close the system of equations. In addition to fluid mechanical turbulence models and parameters used in previous studies of a variety of incompressible and compressible shear flows, a number of additional scalar correlations were modeled for chemically reacting flows, and a typical eddy model developed for the joint probability density function for all the scalars. The program which is capable of handling multi-species, multistep chemical reactions, was used to calculate nonreacting and reacting flows in a hydrogen-air diffusion flame.

  8. Spectator Ions ARE Important! A Kinetic Study of the Copper-Aluminum Displacement Reaction

    ERIC Educational Resources Information Center

    Sobel, Sabrina G.; Cohen, Skyler

    2010-01-01

    Surprisingly, spectator ions are responsible for unexpected kinetics in the biphasic copper(II)-aluminum displacement reaction, with the rate of reaction dependent on the identity of the otherwise ignored spectator ions. Application of a published kinetic analysis developed for a reaction between a rotating Al disk and a Cu(II) ion solution to the…

  9. Manifestation of macroscopic correlations in elementary reaction kinetics. I. Irreversible reaction A+A-->product.

    PubMed

    Doktorov, Alexander B; Kipriyanov, Alexander A; Kipriyanov, Alexey A

    2010-05-28

    Using an modern many-particle method for the derivation of non-Markovian binary kinetic equations, we have treated theoretically the applicability of the encounter theory (ET) (the prototype of the collision theory) concepts to the widely known diffusion assisted irreversible bulk reaction A+A-->product (for example, radical reaction) in dilute solutions. The method shows that the agreement with the ET is observed when the familiar integral ET is employed which in this method is just a step in the derivation of kinetic equations. It allows for two-particle correlations only, but fails to take account of correlation of reactant simultaneously with the partner of the encounter and the reactant in the bulk. However, the next step leading to the modified ET under transformation of equations to the regular form both extends the time range of the applicability of ET rate equation (as it was for reactions proceeding with one of the reactants in excess), and gives the equation of the generalized ET. In full agreement with physical considerations, this theory reveals macroscopic correlations induced by the encounters in the reservoir of free walks. This means that the encounters of reactants in solution are correlated on a rather large time interval of the reaction. Though any nonstationary (non-Markovian) effects manifest themselves rather weakly in the kinetics of the bimolecular reaction in question, just the existence of the revealed macroscopic correlations in the binary theory is of primary importance. In particular, it means that the well-known phenomena which are generally considered to be associated solely with correlation of particles on the encounter (for example, chemically induced dynamic nuclear polarization) may be induced by correlation in the reservoir of free random walks of radicals in solution. PMID:20515095

  10. Reaction Kinetics of Meteoric Sodium Reservoirs in the Upper Atmosphere.

    PubMed

    Gómez Martín, J C; Garraway, S A; Plane, J M C

    2016-03-10

    The gas-phase reactions of a selection of sodium-containing species with atmospheric constituents, relevant to the chemistry of meteor-ablated Na in the upper atmosphere, were studied in a fast flow tube using multiphoton ionization time-of-flight mass spectrometry. For the first time, unambiguous observations of NaO and NaOH in the gas phase under atmospheric conditions have been achieved. This enabled the direct measurement of the rate constants for the reactions of NaO with H2, H2O, and CO, and of NaOH with CO2, which at 300-310 K were found to be (at 2σ confidence level): k(NaO + H2O) = (2.4 ± 0.6) × 10(-10) cm(3) molecule (-1) s(-1), k(NaO + H2) = (4.9 ± 1.2) × 10(-12) cm(3) molecule (-1) s(-1), k(NaO + CO) = (9 ± 4) × 10(-11) cm(3) molecule (-1) s(-1), and k(NaOH + CO2 + M) = (7.6 ± 1.6) × 10(-29) cm(6) molecule (-2) s(-1) (P = 1-4 Torr). The NaO + H2 reaction was found to make NaOH with a branching ratio ≥ 99%. A combination of quantum chemistry and statistical rate theory calculations are used to interpret the reaction kinetics and extrapolate the atmospherically relevant experimental results to mesospheric temperatures and pressures. The NaO + H2O and NaOH + CO2 reactions act sequentially to provide the major atmospheric sink of meteoric Na and therefore have a significant impact on the underside of the Na layer in the terrestrial mesosphere: the newly determined rate constants shift the modeled peak to about 93 km, i.e., 2 km higher than observed by ground-based lidars. This highlights further uncertainties in the Na chemistry cycle such as the unknown rate constant of the NaOH + H reaction. The fast Na-recycling reaction between NaO and CO and a re-evaluated rate constant of the NaO + CO2 sink should be now considered in chemical models of the Martian Na layer. PMID:25723735

  11. Understanding intramembrane proteolysis: from protein dynamics to reaction kinetics.

    PubMed

    Langosch, D; Scharnagl, C; Steiner, H; Lemberg, M K

    2015-06-01

    Intramembrane proteolysis - cleavage of proteins within the plane of a membrane - is a widespread phenomenon that can contribute to the functional activation of substrates and is involved in several diseases. Although different families of intramembrane proteases have been discovered and characterized, we currently do not know how these enzymes discriminate between substrates and non-substrates, how site-specific cleavage is achieved, or which factors determine the rate of proteolysis. Focusing on γ-secretase and rhomboid proteases, we argue that answers to these questions may emerge from connecting experimental readouts, such as reaction kinetics and the determination of cleavage sites, to the structures and the conformational dynamics of substrates and enzymes. PMID:25941170

  12. Nuclear quantum effects and kinetic isotope effects in enzyme reactions.

    PubMed

    Vardi-Kilshtain, Alexandra; Nitoker, Neta; Major, Dan Thomas

    2015-09-15

    Enzymes are extraordinarily effective catalysts evolved to perform well-defined and highly specific chemical transformations. Studying the nature of rate enhancements and the mechanistic strategies in enzymes is very important, both from a basic scientific point of view, as well as in order to improve rational design of biomimetics. Kinetic isotope effect (KIE) is a very important tool in the study of chemical reactions and has been used extensively in the field of enzymology. Theoretically, the prediction of KIEs in condensed phase environments such as enzymes is challenging due to the need to include nuclear quantum effects (NQEs). Herein we describe recent progress in our group in the development of multi-scale simulation methods for the calculation of NQEs and accurate computation of KIEs. We also describe their application to several enzyme systems. In particular we describe the use of combined quantum mechanics/molecular mechanics (QM/MM) methods in classical and quantum simulations. The development of various novel path-integral methods is reviewed. These methods are tailor suited to enzyme systems, where only a few degrees of freedom involved in the chemistry need to be quantized. The application of the hybrid QM/MM quantum-classical simulation approach to three case studies is presented. The first case involves the proton transfer in alanine racemase. The second case presented involves orotidine 5'-monophosphate decarboxylase where multidimensional free energy simulations together with kinetic isotope effects are combined in the study of the reaction mechanism. Finally, we discuss the proton transfer in nitroalkane oxidase, where the enzyme employs tunneling as a catalytic fine-tuning tool. PMID:25769515

  13. Kinetics Of Isomerisation Reaction Of Oriented Polyacetylene Induced By Laser

    SciTech Connect

    Mammeri, S.; Belloum, M.; Tabacik, V.

    2008-09-23

    The impact of a laser's photons ({lambda} = 514.5 nm) on the surface of polyacetylene films (PA), composed of macromolecules PAcis and PAtrans produces simultaneously thermal and Raman diffusion [1]. The thermal effect initializes the isomerization of macromolecules PAcis to PAtrans [2]; this reaction is exothermic. Samples are polyacetylene oriented films synthesized horizontally or vertically in cis configuration and are subject to different laser powers during intervals of time which vary between 20 s and 250 s. The power (P ({lambda}), mW) of the laser is equivalent to the temperature T, of isomerization [3]. Isotherms are constructed and are characterized by the laser power applied. We have established theoretical models calculations with the aim of determining the kinetic parameters of the reaction of isomerization: the activation energy (Ea), the frequency factor of Arrhenius (A), and the rate constant (k). We concluded that even in the field of seconds, the isomerization is a complex process different from a reaction of order: 1, 7/10, 2/3, 3/5, 1/2, 2/5 and 1/4. The order 2/3 being the most suitable. The study determined, among others, the rate constants k 2/3 (T)(of the order 2/3 of the isomerization reaction)= 0.003337244, 0.0052149, 0.0209636, 0.043727 s-1 respectively for Laser powers 30, 120, 200 and 300 mW; activation energy 17.7844 kcal/mol and a factor of collision 19.066816 10{sup 6} s{sup -1}. These results are found to be close to the experimental results studied.

  14. Kinetic study of hydrated lime reaction with HCl.

    PubMed

    Yan, Rong; Chin, Terence; Liang, David Tee; Laursen, Karin; Ong, Wan Yean; Yao, Kaiwen; Tay, Joo Hwa

    2003-06-01

    Hydrochloride (HCl) is an acidic pollutant present in the flue gas of most municipal or hazardous waste incinerators. Hydrated lime (Ca(OH)2) is often used as a dry sorbent for injection in a spray reactor to remove HCI. However, due to the short residence time encountered, this control method has generally been found to have low conversion efficiencies which results in the high lime usage and generates large amount of fly ash as solid wastes. A fundamental study was carried outto investigate the kinetics of HCl-lime reaction under simulated flue gas conditions in order to better understand the process thereby providing a basis for an optimized lime usage and reduced fly ash production. The initial reaction rate and conversion of three limes were studied using a thermogravimetric analyzer by varying the gas flow rate, temperature (170-400 degrees C), and HCI concentrations (600-1200 mg/m3) as well as the associated particle size and surface area of the limes. The initial lime conversions were found to rely mostly on the residence time, while the ultimate lime conversions were strongly influenced by temperature and the reaction products. CaOHCI was found to be the primary product in most cases, while for one specific lime, CaCl2 was the ultimate conversion product after an extended time period. The true utilization of lime in flue gas cleanup is thus higher when CaOHCl is considered as the final product than those based on CaCl2 as the final product, which has been commonly used in previous studies. The initial reaction was controlled by diffusion of HCl in gas phase and the subsequent reaction by gaseous diffusion through the developing product layer. Increasing the HCI concentration raised the initial rate as well as conversion. However, overloading the lime with excessive HCI caused clogging at its surface and a drop in the ultimate conversion. Limes with smaller particle diameters and higher surface areas were found to be more reactive. The effect of gas

  15. A novel second-order flux splitting for ideal magnetohydrodynamics

    NASA Astrophysics Data System (ADS)

    Borah, Kalpajyoti; Natarajan, Ganesh; Dass, Anoop K.

    2016-05-01

    A new flux splitting scheme based on wave-particle behaviour is developed for one-dimensional ideal magnetohydrodynamics. We exploit the idea that while ideal magnetohydrodynamics equations are non-convex with non-homogeneous fluxes as opposed to their hydrodynamic counterparts, they exhibit an overall wave-like structure. The proposed approach splits the flux vector into three distinct parts: the particle-like transport part and the wave-like pressure and magnetic parts, with the latter vanishing for pure hydrodynamics. The pressure part of the fluxes satisfy homogeneity property and the split flux Jacobians are constructed with a provision to regulate the numerical dissipation. The magnetic part of the fluxes however is non-homogeneous and is treated using a central scheme with artificial viscosity. This disparate treatment of the individual components of the total flux vector results in a scheme with a central-upwind character that can be implemented with low computational effort. Referred to as Magneto-acoustic Wave Particle Splitting (MWPS) scheme, it is extended to second-order accuracy by using slope limiters incorporated through the solution-dependent weighted least squares approach for gradient calculations. Several one-dimensional MHD problems are numerically solved to highlight the accuracy, positivity preservation and robustness of the MWPS scheme and comparative studies show that MWPS performs at least as well as the Advection Upstream Splitting Method (AUSM) and even outperforms it for some test cases.

  16. Cavity-Enhanced Second-Order Nonlinear Photonic Logic Circuits

    NASA Astrophysics Data System (ADS)

    Trivedi, Rahul; Khankhoje, Uday K.; Majumdar, Arka

    2016-05-01

    A large obstacle for realizing photonic logic is the weak optical nonlinearity of available materials, which results in large power consumption. In this paper, we present the theoretical design of all-optical logic with second-order (χ(2 )) nonlinear bimodal cavities and their networks. Using semiclassical models derived from the Wigner quasiprobability distribution function, we analyze the power consumption and signal-to-noise ratio (SNR) of networks implementing an optical and gate and an optical latch. A comparison between the second- and third-order (χ(3 )) optical logic reveals that, while the χ(3 ) design outperforms the χ(2 ) design in terms of the SNR for the same input power, employing the χ(3 ) nonlinearity necessitates the use of cavities with ultrahigh-quality factors (Q ˜106) to achieve a gate power consumption comparable to that of the χ(2 ) design at significantly smaller quality factors (Q ˜104). Using realistic estimates of the χ(2 ) and χ(3 ) nonlinear susceptibilities of available materials, we show that, at achievable quality factors (Q ˜104), the χ(2 ) design is an order of magnitude more energy efficient than the corresponding χ(3 ) design.

  17. Second order sliding mode control for a quadrotor UAV.

    PubMed

    Zheng, En-Hui; Xiong, Jing-Jing; Luo, Ji-Liang

    2014-07-01

    A method based on second order sliding mode control (2-SMC) is proposed to design controllers for a small quadrotor UAV. For the switching sliding manifold design, the selection of the coefficients of the switching sliding manifold is in general a sophisticated issue because the coefficients are nonlinear. In this work, in order to perform the position and attitude tracking control of the quadrotor perfectly, the dynamical model of the quadrotor is divided into two subsystems, i.e., a fully actuated subsystem and an underactuated subsystem. For the former, a sliding manifold is defined by combining the position and velocity tracking errors of one state variable, i.e., the sliding manifold has two coefficients. For the latter, a sliding manifold is constructed via a linear combination of position and velocity tracking errors of two state variables, i.e., the sliding manifold has four coefficients. In order to further obtain the nonlinear coefficients of the sliding manifold, Hurwitz stability analysis is used to the solving process. In addition, the flight controllers are derived by using Lyapunov theory, which guarantees that all system state trajectories reach and stay on the sliding surfaces. Extensive simulation results are given to illustrate the effectiveness of the proposed control method. PMID:24751475

  18. The motion of ellipsoids in a second order fluid

    NASA Astrophysics Data System (ADS)

    Kim, S.

    1985-09-01

    The rigid body motion of an ellipsoid in a second order fluid (SOF) under the action of specified (time independent) external forces and torques have been obtained to first order in the Weissenberg number by inverting the resistance relations for the force an torque under specified rigid body motions. The reciprocal theorem of Lorentz was used to bypass the calculation of the O(W) velocity field. The results agree with known analytic solutions for SOF with the secondary to primary normal stress ratio of -1/2. The solution procedure was also tested by computing the torque on a translating prolate spheroid with aspect ratios ranging from slender bodies to near-spheres. One result is that for a SOF with zero secondary normal stress (Weissenberg fluid), previous asymptotic results for near-spheres were found to be accurate even at fairly large aspect ratios. New results of nondegenerate ellipsoids suggest that the orientation (as monitored by Euler angles) and trajectory of sedimenting, nonaxisymmetric particles such as ellipsoids provide useful information on the rheology of the suspending fluid.

  19. Modal cost analysis for linear matrix-second-order systems

    NASA Technical Reports Server (NTRS)

    Skelton, R. E.; Hughes, P. C.

    1980-01-01

    Reduced models and reduced controllers for systems governed by matrix-second-order differential equations are obtained by retaining those modes which make the largest contributions to quadratic control objectives. Such contributions, expressed in terms of modal data, used as mode truncation criteria, allow the statement of the specific control objectives to influence the early model reduction from very high order models which are available, for example, from finite element methods. The relative importance of damping, frequency, and eigenvector in the mode truncation decisions are made explicit for each of these control objectives: attitude control, vibration suppression and figure control. The paper also shows that using modal cost analysis (MCA) on the closed loop modes of the optimally controlled system allows the construction of reduced control policies which feedback only those closed loop modal coordinates which are most critical to the quadratic control performance criterion. In this way, the modes which should be controlled (and hence the modes which must be observable by choice of measurements), are deduced from truncations of the optimal controller.

  20. Superconvergent discontinuous Galerkin methods for second-order elliptic problems

    NASA Astrophysics Data System (ADS)

    Cockburn, Bernardo; Guzman, Johnny; Wang, Haiying

    2009-03-01

    We identify discontinuous Galerkin methods for second-order elliptic problems in several space dimensions having superconvergence properties similar to those of the Raviart-Thomas and the Brezzi-Douglas-Marini mixed methods. These methods use polynomials of degree kge0 for both the potential as well as the flux. We show that the approximate flux converges in L^2 with the optimal order of k+1 , and that the approximate potential and its numerical trace superconverge, in L^2 -like norms, to suitably chosen projections of the potential, with order k+2 . We also apply element-by-element postprocessing of the approximate solution to obtain new approximations of the flux and the potential. The new approximate flux is proven to have normal components continuous across inter-element boundaries, to converge in L^2 with order k+1 , and to have a divergence converging in L^2 also with order k+1 . The new approximate potential is proven to converge with order k+2 in L^2 . Numerical experiments validating these theoretical results are presented.

  1. Second order anisotropy contribution in perpendicular magnetic tunnel junctions

    PubMed Central

    Timopheev, A. A.; Sousa, R.; Chshiev, M.; Nguyen, H. T.; Dieny, B.

    2016-01-01

    Hard-axis magnetoresistance loops were measured on perpendicular magnetic tunnel junction pillars of diameter ranging from 50 to 150 nm. By fitting these loops to an analytical model, the effective anisotropy fields in both free and reference layers were derived and their variations in temperature range between 340 K and 5 K were determined. It is found that a second-order anisotropy term of the form −K2cos4θ must be added to the conventional uniaxial –K1cos2θ term to explain the experimental data. This higher order contribution exists both in the free and reference layers. At T = 300 K, the estimated −K2/K1 ratios are 0.1 and 0.24 for the free and reference layers, respectively. The ratio is more than doubled at low temperatures changing the ground state of the reference layer from “easy-axis” to “easy-cone” regime. The easy-cone regime has clear signatures in the shape of the hard-axis magnetoresistance loops. The existence of this higher order anisotropy was also confirmed by ferromagnetic resonance experiments on FeCoB/MgO sheet films. It is of interfacial nature and is believed to be due to spatial fluctuations at the nanoscale of the first order anisotropy parameter at the FeCoB/MgO interface. PMID:27246631

  2. Second order anisotropy contribution in perpendicular magnetic tunnel junctions.

    PubMed

    Timopheev, A A; Sousa, R; Chshiev, M; Nguyen, H T; Dieny, B

    2016-01-01

    Hard-axis magnetoresistance loops were measured on perpendicular magnetic tunnel junction pillars of diameter ranging from 50 to 150 nm. By fitting these loops to an analytical model, the effective anisotropy fields in both free and reference layers were derived and their variations in temperature range between 340 K and 5 K were determined. It is found that a second-order anisotropy term of the form -K2cos(4)θ must be added to the conventional uniaxial -K1cos(2)θ term to explain the experimental data. This higher order contribution exists both in the free and reference layers. At T = 300 K, the estimated -K2/K1 ratios are 0.1 and 0.24 for the free and reference layers, respectively. The ratio is more than doubled at low temperatures changing the ground state of the reference layer from "easy-axis" to "easy-cone" regime. The easy-cone regime has clear signatures in the shape of the hard-axis magnetoresistance loops. The existence of this higher order anisotropy was also confirmed by ferromagnetic resonance experiments on FeCoB/MgO sheet films. It is of interfacial nature and is believed to be due to spatial fluctuations at the nanoscale of the first order anisotropy parameter at the FeCoB/MgO interface. PMID:27246631

  3. Correction of the Chromaticity up to Second Order for MEIC

    SciTech Connect

    H. K. Sayed, S.A. Bogacz, P. Chevtsov

    2010-03-01

    The proposed electron collider lattice exhibits low β- functions at the Interaction Point (IP) (βx*100mm - βy* 20 mm) and rather large equilibrium momentum spread of the collider ring (δp/p = 0.00158). Both features make the chromatic corrections of paramount importance. Here the chromatic effects of the final focus quadruples are cor- rected both locally and globally. Local correction features symmetric sextupole families around the IP, the betatron phase advances from the IP to the sextupoles are chosen to eliminate the second order chromatic aberration. Global interleaved families of sextupoles are placed in the figure-8 arc sections, and non-interleaved families at straight sec- tion making use of the freely propagated dispersion wave from the arcs. This strategy minimizes the required sex- tupole strength and eventually leads to larger dynamic aper- ture of the collider. The resulting spherical aberrations induced by the sextupoles are mitigated by design; the straight and arc sections optics features an inverse identity transformation between sextupoles in each pair.

  4. Photonic second-order duty-cycle modulator

    NASA Astrophysics Data System (ADS)

    Costanzo-Caso, Pablo A.; Reeves, Erin; Jin, Yiye; Granieri, Sergio; Siahmakoun, Azad

    2011-09-01

    The delta sigma modulator (DSM) is a device which transforms the amplitude information of an analog input signal to the duty cycle and frequency of a binary output. This device, typically employed in oversampled analog-to-digital converters, is based on a feedback loop which includes at least one integrator and one quantizer in the forward path. In this paper, a novel photonic second-order DSM is proposed and experimentally demonstrated. The system is composed of two inverted leaky integrator and one electro-optic quantizer. The maximum input frequency is around 2 MHz, limited by the fiber length of the accumulator and feedback loops, and the quantizer rise/fall times. The system is characterized at different input frequencies and waveforms (sinusoidal and saw tooth) to analyze the modulator performance and linearity. The binary output is acquired, processed and demodulated using a personal computer, in order to reconstruct the input analog signal. The reported fiber-optic DSM is very promising for future integration increasing the operation frequency up to GHz range.

  5. A planar second-order DC SQUID gradiometer.

    PubMed

    Carelli, P; Chiaventi, L; Leoni, R; Pullano, M; Schirripa Spagnolo, G

    1991-01-01

    In this work we describe a DC SQUID gradiometer, sensitive to the second spatial derivative of the magnetic field. The sensitive area of the gradiometer is the inductive body of the DC SQUID itself. The isoflux line distribution generated by a dipolar source, obtained by performing magnetic measurements with an array of such detectors, is relatively complicated, but its localisation capability is similar to that one usually achieves with axial detector arrays. Planar gradiometers also show a better resolution for near sources and a stronger rejection of far disturbances. The final device is expected to have an inductance of a few hundreds of pH in order to obtain performances typical of a low noise DC SQUID. The pick-up coils will be the combination of four square holes of 500 microns side with a 1.05 cm baseline. Due to the magnetic field concentration (in the final device it can be a factor 10) the gradiometer will have a sensitivity of 10(-11) T m-2 Hz-1/2 and a field sensitivity of about 2 fT Hz-1/2. Some preliminary results, obtained on detectors with an intermediate area between the prototype and final device, are reported here. The process used to fabricate this second-order gradiometer is based on Nb-NbO chi-PbAuIn Josephson tunnel junctions. Some possible improvements will also be described. PMID:1807874

  6. Second-order perturbation theory: Problems on large scales

    NASA Astrophysics Data System (ADS)

    Pound, Adam

    2015-11-01

    In general-relativistic perturbation theory, a point mass accelerates away from geodesic motion due to its gravitational self-force. Because the self-force is small, one can often approximate the motion as geodesic. However, it is well known that self-force effects accumulate over time, making the geodesic approximation fail on long time scales. It is less well known that this failure at large times translates to a failure at large distances as well. At second perturbative order, two large-distance pathologies arise: spurious secular growth and infrared-divergent retarded integrals. Both stand in the way of practical computations of second-order self-force effects. Utilizing a simple flat-space scalar toy model, I develop methods to overcome these obstacles. The secular growth is tamed with a multiscale expansion that captures the system's slow evolution. The divergent integrals are eliminated by matching to the correct retarded solution at large distances. I also show how to extract conservative self-force effects by taking local-in-time "snapshots" of the global solution. These methods are readily adaptable to the physically relevant case of a point mass orbiting a black hole.

  7. Second order gyrokinetic theory for particle-in-cell codes

    NASA Astrophysics Data System (ADS)

    Tronko, Natalia; Bottino, Alberto; Sonnendrücker, Eric

    2016-08-01

    The main idea of the gyrokinetic dynamical reduction consists in a systematical removal of the fast scale motion (the gyromotion) from the dynamics of the plasma, resulting in a considerable simplification and a significant gain of computational time. The gyrokinetic Maxwell-Vlasov equations are nowadays implemented in for modeling (both laboratory and astrophysical) strongly magnetized plasmas. Different versions of the reduced set of equations exist, depending on the construction of the gyrokinetic reduction procedure and the approximations performed in the derivation. The purpose of this article is to explicitly show the connection between the general second order gyrokinetic Maxwell-Vlasov system issued from the modern gyrokinetic theory and the model currently implemented in the global electromagnetic Particle-in-Cell code ORB5. Necessary information about the modern gyrokinetic formalism is given together with the consistent derivation of the gyrokinetic Maxwell-Vlasov equations from first principles. The variational formulation of the dynamics is used to obtain the corresponding energy conservation law, which in turn is used for the verification of energy conservation diagnostics currently implemented in ORB5. This work fits within the context of the code verification project VeriGyro currently run at IPP Max-Planck Institut in collaboration with others European institutions.

  8. Second order anisotropy contribution in perpendicular magnetic tunnel junctions

    NASA Astrophysics Data System (ADS)

    Timopheev, A. A.; Sousa, R.; Chshiev, M.; Nguyen, H. T.; Dieny, B.

    2016-06-01

    Hard-axis magnetoresistance loops were measured on perpendicular magnetic tunnel junction pillars of diameter ranging from 50 to 150 nm. By fitting these loops to an analytical model, the effective anisotropy fields in both free and reference layers were derived and their variations in temperature range between 340 K and 5 K were determined. It is found that a second-order anisotropy term of the form ‑K2cos4θ must be added to the conventional uniaxial –K1cos2θ term to explain the experimental data. This higher order contribution exists both in the free and reference layers. At T = 300 K, the estimated ‑K2/K1 ratios are 0.1 and 0.24 for the free and reference layers, respectively. The ratio is more than doubled at low temperatures changing the ground state of the reference layer from “easy-axis” to “easy-cone” regime. The easy-cone regime has clear signatures in the shape of the hard-axis magnetoresistance loops. The existence of this higher order anisotropy was also confirmed by ferromagnetic resonance experiments on FeCoB/MgO sheet films. It is of interfacial nature and is believed to be due to spatial fluctuations at the nanoscale of the first order anisotropy parameter at the FeCoB/MgO interface.

  9. Effect of ADP on Na+-Na+ Exchange Reaction Kinetics of Na,K-ATPase

    PubMed Central

    Peluffo, R. Daniel

    2004-01-01

    The whole-cell voltage-clamp technique was used in rat cardiac myocytes to investigate the kinetics of ADP binding to phosphorylated states of Na,K-ATPase and its effects on presteady-state Na+-dependent charge movements by this enzyme. Ouabain-sensitive transient currents generated by Na,K-ATPase functioning in electroneutral Na+-Na+ exchange mode were measured at 23°C with pipette ADP concentrations ([ADP]) of up to 4.3 mM and extracellular Na+ concentrations ([Na]o) between 36 and 145 mM at membrane potentials (VM) from −160 to +80 mV. Analysis of charge-VM curves showed that the midpoint potential of charge distribution was shifted toward more positive VM both by increasing [ADP] at constant Na+o and by increasing [Na]o at constant ADP. The total quantity of mobile charge, on the other hand, was found to be independent of changes in [ADP] or [Na]o. The presence of ADP increased the apparent rate constant for current relaxation at hyperpolarizing VM but decreased it at depolarizing VM as compared to control (no added ADP), an indication that ADP binding facilitates backward reaction steps during Na+-Na+ exchange while slowing forward reactions. Data analysis using a pseudo three-state model yielded an apparent Kd of ∼6 mM for ADP binding to and release from the Na,K-ATPase phosphoenzyme; a value of 130 s−1 for k2, a rate constant that groups Na+ deocclusion/release and the enzyme conformational transition E1∼P → E2-P; a value of 162 s−1M−1 for k−2, a lumped second-order VM-independent rate constant describing the reverse reactions; and a Hill coefficient of ∼1 for Na+o binding to E2-P. The results are consistent with electroneutral release of ADP before Na+ is deoccluded and released through an ion well. The same approach can be used to study additional charge-moving reactions and associated electrically silent steps of the Na,K-pump and other transporters. PMID:15298896

  10. Combustion reaction kinetics of guarana seed residue applying isoconversional methods and consecutive reaction scheme.

    PubMed

    Lopes, Fernanda Cristina Rezende; Tannous, Katia; Rueda-Ordóñez, Yesid Javier

    2016-11-01

    This work aims the study of decomposition kinetics of guarana seed residue using thermogravimetric analyzer under synthetic air atmosphere applying heating rates of 5, 10, and 15°C/min, from room temperature to 900°C. Three thermal decomposition stages were identified: dehydration (25.1-160°C), oxidative pyrolysis (240-370°C), and combustion (350-650°C). The activation energies, reaction model, and pre-exponential factor were determined through four isoconversional methods, master plots, and linearization of the conversion rate equation, respectively. A scheme of two-consecutive reactions was applied validating the kinetic parameters of first-order reaction and two-dimensional diffusion models for the oxidative pyrolysis stage (149.57kJ/mol, 6.97×10(10)1/s) and for combustion stage (77.98kJ/mol, 98.611/s), respectively. The comparison between theoretical and experimental conversion and conversion rate showed good agreement with average deviation lower than 2%, indicating that these results could be used for modeling of guarana seed residue. PMID:27513645

  11. Reaction kinetics of dual setting α-tricalcium phosphate cements.

    PubMed

    Hurle, Katrin; Christel, Theresa; Gbureck, Uwe; Moseke, Claus; Neubauer, Juergen; Goetz-Neunhoeffer, Friedlinde

    2016-01-01

    Addition of ductile polymers to calcium-deficient hydroxyapatite (CDHA)-forming bone cements based on α-tricalcium phosphate (α-TCP) is a promising approach to improve the mechanical performance of α-TCP cements and extend their application to load-bearing defects, which is else impeded by the brittleness of the hardened cement. One suitable polymer is poly-(2-hydroxyethylmethacrylate) (p-HEMA), which forms during cement setting by radical polymerisation of the monomer. In this study the hydration kinetics and the mechanical performance of α-TCP cements modified with addition of different HEMA concentrations (0-50 wt% in the cement liquid) was investigated by quantitative in situ XRD and four-point bending tests. Morphology of CDHA crystals was monitored by scanning electron microscopy. The hydration of α-TCP to CDHA was increasingly impeded and the visible crystal size of CDHA increasingly reduced with increasing HEMA concentration. Modification of the cements by adding 50 wt% HEMA to the cement liquid changed the brittle performance of the hardened cement to a pseudoplastic behaviour, reduced the flexural modulus and increased the work of fracture, while lower HEMA concentrations had no significant effect on these parameters. In such a composite, the extent of CDHA formation was considerably reduced (34.0 ± 1.8 wt% CDHA with 50 % HEMA compared to 54.1 ± 2.4 wt% CDHA in the reference formed after 48 h), while the general reaction kinetics were not changed. In conclusion, while the extent of CDHA formation was decreased, the mechanical properties were noticeably improved by addition of HEMA. Hence, α-TCP/HEMA composites might be suitable for application in some load-bearing defects and have adequate properties for mechanical treatment after implantation, like insertion of screws. PMID:26610924

  12. Second order multidimensional sign-preserving remapping for ALE methods

    SciTech Connect

    Hill, Ryan N; Szmelter, J.

    2010-12-15

    A second-order conservative sign-preserving remapping scheme for Arbitrary Lagrangian-Eulerian (ALE) methods is developed utilising concepts of the Multidimensional Positive Definite Advection Transport Algorithm (MPDATA). The algorithm is inherently multidimensional, and so does not introduce splitting errors. The remapping is implemented in a two-dimensional, finite element ALE solver employing staggered quadrilateral meshes. The MPDATA remapping uses a finite volume discretization developed for volume coordinates. It is applied for the remapping of density and internal energy arranged as cell centered, and velocity as nodal, dependent variables. In the paper, the advection of scalar fields is examined first for test cases with prescribed mesh movement. A direct comparison of MPDATA with the performance of the van Leer MUSCL scheme indicates advantages of a multidimensional approach. Furthermore, distinctly different performance between basic MPDATA and the infinite gauge option is illustrated using benchmarks involving transport of a sign changing velocity field. Further development extends the application of MPDATA remapping to the full ALE solver with a staggered mesh arrangement for density, internal energy and momentum using volume coordinates. At present, two options of the algorithm - basic and infinite gauge - are implemented. To ensure a meaningful assessment, an identical Lagrangian solver and computational mesh update routines are used with either MPDATA or van Leer MUSCL remapping. The evaluation places particular focus on the abilities of both schemes to accurately model multidimensional problems. Theoretical considerations are supported with numerical examples. In addition to the prescribed mesh movement cases for advection of scalars, the demonstrations include two-dimensional Eulerian and ALE flow simulations on quadrilateral meshes with both fixed and variable timestep control. The key comparisons include the standard test cases of Sod and Noh

  13. General chemical kinetics computer program for static and flow reactions, with application to combustion and shock-tube kinetics

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Scullin, V. J.

    1972-01-01

    A general chemical kinetics program is described for complex, homogeneous ideal-gas reactions in any chemical system. Its main features are flexibility and convenience in treating many different reaction conditions. The program solves numerically the differential equations describing complex reaction in either a static system or one-dimensional inviscid flow. Applications include ignition and combustion, shock wave reactions, and general reactions in a flowing or static system. An implicit numerical solution method is used which works efficiently for the extreme conditions of a very slow or a very fast reaction. The theory is described, and the computer program and users' manual are included.

  14. Kinetics of the self reaction of cyclohexyl radicals.

    PubMed

    Loginova, Ksenia A; Knyazev, Vadim D

    2011-08-11

    The kinetics of the self-reaction of cyclohexyl radicals was studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 303-520 K and at bath gas (helium with up to 5% of radical precursors) densities (3.00-12.0) × 10(16) molecules cm(-3). Cyclohexyl radicals were produced by a combination of the 193 nm photolysis of oxalyl chloride ((CClO)(2)) with the subsequent fast reaction of Cl atoms with cyclohexane, and their initial concentrations were determined from real-time profiles of HCl. The observed overall c-C(6)H(11) + c-C(6)H(11) rate constants demonstrate negative temperature dependence, which can be described by the following expressions: k(1) = 4.8 × 10(-12) exp(+542 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainty of 16% over the 303-520 K temperature range. The fraction of disproportionation equal to 41 ± 7% was determined at 305 K; analysis of earlier experimental determinations of the disproportionation-to-recombination branching ratio leads to recommending this room-temperature value for other temperatures. The corresponding temperature dependences of the recombination (1a, bicyclohexyl product) and the disproportionation (1b, cyclohexene and cyclohexane products) channels are k(1a) = 2.8 × 10(-12) exp(+542 K/T) and k(1b) = 2.0 × 10(-12) exp(+542 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainties of 20% and 29%, respectively. PMID:21702489

  15. Constraining kinetic rates of mineral reactions using reactive transport models

    NASA Astrophysics Data System (ADS)

    Bolton, E. W.; Wang, Z.; Ague, J.; Bercovici, D.; Cai, Z.; Karato, S.; Oristaglio, M. L.; Qiu, L.

    2012-12-01

    We use a reactive transport model to better understand results of experiments to obtain kinetic rates of mineral reactions in closed systems. Closed system experiments pose special challenges in that secondary minerals may form that modify the fluid composition evolution and may grow on the dissolving minerals thus armoring the surface. Even so, such closed system experiments provide critical data for what minerals would actually form in field applications and how coupled dissolution and precipitation mineral reactions are strongly linked. Comparing to experimental observations can test the reactive transport model, and the experimental observations can be better understood by comparing the results to the modeling. We apply a 0D end member of the model to understand the dissolution of single crystals of forsterite in a variety of settings (low pH, high pH, or NaHCO3 initial fluids, at 100 C and 1 bar, or 200 C and 150 bar). Depending on the initial conditions, we observe the precipitation of talc, brucite, amorphous silica, chrysotile, or magnesite, in various combinations. We compare simulation results to fluid compositions and the presence of secondary minerals experimentally sampled at various times. Insight from the simulations helped create an inverse model to extract the rates of forsterite dissolution and to create a simple forward model useful for exploring the influence of system size, secondary mineral surface areas, etc. Our reactive transport model allows secondary minerals to armor the forsterite surface, which can strongly decrease the dissolution rate as the system evolves. Tuning our model with experimentally derived rates and assuring relevant processes are included so as to reproduce experimental observations is necessary before upscaling to heterogeneous field conditions. The reactive transport model will be used for field-scale sequestration simulations and coupled with a geomechanical model that includes the influence of deformation.

  16. Evaluating the interfacial reaction kinetics of the bipolar membrane interface in the bipolar membrane fuel cell.

    PubMed

    Peng, Sikan; Lu, Shanfu; Zhang, Jin; Sui, Pang-Chieh; Xiang, Yan

    2013-07-21

    A reaction kinetic model of the bipolar membrane interface in the bipolar membrane fuel cell (BPMFC) was proposed based on the p-n junction theory and chemical reaction kinetics. It verified the self-humidification feasibility of the BPMFC successfully. PMID:23744271

  17. Kinetics of the ClO + NO2 + M reaction

    NASA Technical Reports Server (NTRS)

    Molina, M. J.; Molina, L. T.; Ishiwata, T.

    1980-01-01

    The ClO + NO2 + M reaction has been studied with two techniques: Fourier transform infrared spectroscopy of the products, and flash photolysis-ultraviolet absorption to monitor the decay of ClO in excess NO2. The measured third-order rate constant is 1.5 x 10 to the -31st cm to the 6th/molecule-squared per sec at 298 K with M = N2, in good agreement with previous literature values, but the rate constant appears to decrease by up to a factor of three in the presence of increasing amounts of OClO. For the infrared studies a stoichiometric mixture of ClO and NO2 was prepared in a flow system by mixing NO with OClO; at least as much NO2 as ClONO2 was produced under a variety of experimental conditions. These two sets of results are incompatible with the assumption made in previous kinetic studies that ClONO2 is the only recombination product; other isomers such as OClONO or ClOONO are likely to be formed three to four times faster. These results imply that potential stratospheric ozone depletion due to chlorofluoromethanes may be even larger than previously thought.

  18. Cell population kinetic parameters for acute epidermal reactions in man

    SciTech Connect

    Cohen, L.

    1986-11-01

    Cell population kinetic parameters for acute reactions in squamous epithelium were estimated using available data on skin tolerance doses. Roughly equivalent doses for kilovoltage radiation delivered in equal daily fractions, as reported by F. Ellis (Br. J. Radiol. 15, 348-350 (1942)) and by R. Paterson (The Treatment of Malignant Disease by Radium and X-Rays. Edward Arnold, London, 1948), were combined with data for nonstandard fractionation at longer intervals of 1 or 2 weeks. By analyzing the combined data set, well-determined parameters could be derived. The data show that repopulation, with a potential cell doubling time of about 7 days, must occur in irradiated human skin, though this may possibly be limited to no more than seven doublings. The parameters derived are distinctly different from those associated with late-reacting dose-limiting tissues. The main difference is the steeper initial slope of the computed survival curve, that is a larger J parameter (multitarget model) or a larger alpha component (linear-quadratic model).

  19. Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach

    ERIC Educational Resources Information Center

    Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

    2008-01-01

    A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

  20. Reaction of Phenyl Radical with O2: Thermodynamic Properties, Important Reaction Paths and Kinetics

    SciTech Connect

    Bozzelli, J; Sebbar, N; Pitz, W; Bockhorn, H

    2001-04-12

    The Phenyl + O{sub 2} association results in a chemically activated phenyl-peroxy radical which can dissociate to phenoxy radical + O, undergo intramolecular addition of the peroxy radical to several unsaturated carbon sites or react back to phenyl + O{sub 2}. The intramolecular addition channels further react through several paths to ring opening (unsaturated + carbonyl moieties) as well as cyclopentadieny radical + CO{sub 2}. Enthalpy ({Delta}H{sub f(298)}{sup o}), Entropy (S{sub 298}), and heat capacities Cp(T) for species in the decomposition of the ring are evaluated using density functional and ab initio calculations and by comparisons to vinyl + O{sub 2} data of Mebel et al, and phenyl + O{sub 2} data of Hadad et al. Isodesmic reaction analysis is used to estimate enthalpy values of the intermediates and well depths of the adducts. High Pressure limit kinetic parameters are obtained from the calculation results using canonical Transition State Theory. Quantum RRK analysis is utilized to obtain k(E) and modified strong collision or master equation analysis is used for evaluation of pressure fall-off in this complex bimolecular, chemical activation, reaction system. Uncertainty in key barriers is discussed, resulting variations in important reaction product ratios are illustrated, and changes in these branching ratios are evaluated with a detailed reaction mechanism.

  1. Theoretical Analysis of Kinetic Isotope Effects on Proton Transfer Reactions between Substituted α-Methoxystyrenes and Substituted Acetic Acids

    PubMed Central

    Wong, Kin Yiu; Richard, John P.; Gao, Jiali

    2009-01-01

    Primary kinetic isotope effects (KIEs) on a series of carboxylic acid-catalyzed protonation reactions of aryl-substituted α-methoxystyrenes (X-1) to form oxocarbenium ions have been computed using the Kleinert variational second-order perturbation theory (KP2) in the framework of Feynman path integrals (PI) along with the potential energy surface obtained at the B3LYP/6-31+G(d,p) level. Good agreement with the experimental data was obtained, demonstrating that this novel computational approach for computing KIEs of organic reactions is a viable alternative to the traditional method employing Bigeleisen equation and harmonic vibrational frequencies. Although tunneling makes relative small contributions to the lowering of the free energy barriers for the carboxylic acid catalyzed protonation reaction, it is necessary to include tunneling contributions to obtain quantitative estimates of the KIEs. Consideration of anharmonicity can further improve the calculated KIEs for the protonation of substituted α-methoxystyrenes by chloroacetic acid, but for the reactions of the parent and 4-NO2 substituted α-methoxystyrene with substituted carboxylic acids, the correction of anharmonicity overestimates the computed KIEs for strong acid catalysts. In agreement with experimental findings, the largest KIEs are found in nearly ergoneutral reactions, ΔGo ≈ 0, where the transition structures are nearly symmetric and the reaction barriers are relatively low. Furthermore, the optimized transition structures are strongly dependent on the free energy for the formation of the carbocation intermediate, i.e., the driving force ΔGo, along with a good correlation of Hammond shift in the transition state structure. PMID:19754046

  2. Reassessing the dissolution of marine carbonates: II. Reaction kinetics

    NASA Astrophysics Data System (ADS)

    Gehlen, M.; Bassinot, F. C.; Chou, L.; McCorkle, D.

    2005-08-01

    We studied dissolution kinetics of the carbonate fraction >150 μm of sediments sampled along two bathymetric transects in the eastern tropical Atlantic: the Sierra Leone Rise (SLR) and the Cape Verde Plateau (CVP). The reaction was followed by monitoring solution pH during freedrift experiments lasting between 46 and 50 h (20 °C, pCO 2≈3100 ppm and 1 atm pressure). The alkalinity reached at the end of the dissolution experiments ranged between 2.444 and 2.798 meq/kg sw. The dissolution time series was extrapolated to equilibrium by fitting an empirical relation to the data. The estimated asymptotic concentration products ([Ca 2+] ∞×[CO 32-] ∞, for t→∞ and dA/dt=0) range from 4.27×10 -7 to 6.77×10 -7 mol 2/kg sw2. These asymptotic concentration products are comparable with the stoichiometric concentration product of aragonite (6.56×10 -7 mol 2/kg sw2) and calcite (4.37 (±0.22)×10 -7 mol 2/kg sw2) derived for the same sediment material during long-term equilibration experiments. They are indicative of the presence of trace amounts of a higher solubility carbonate phase in sediments of the shallow stations (SLR station A, 2637 m; CVP station M, 3104 m). While it is likely that this phase is aragonite, the presence of authigenic carbonate precipitated in contact with supersaturated bottom waters cannot be excluded. Calcite is the main dissolving carbonate mineral in sediments from deeper stations. The order of reaction is always greater than unity. It varies between 1.4 (SLR station C) and 2.8 (CVP station M2), with an average n=2.3±0.4. The higher order reaction is explained in terms of a multiphase system. Specific rate constants range from 0.09 to 0.53 meq/m 2/d.

  3. First- and second-order elliptic conditional moment closure calculations of piloted methane diffusion flames

    SciTech Connect

    Fairweather, M.; Woolley, R.M.

    2007-07-15

    Presented are results obtained from the application of a first- and higher-order conditional moment closure (CMC) approach to the modeling of three methane diffusion flames at differing levels of local extinction. In addition to the analysis of higher-order chemistry applications, the results obtained from an elliptic formulation of the CMC equation are considered next to parabolic results presented in previous work. All predictions are based upon second-moment turbulence and scalar-flux closures, and the chemistry applied to represent mean production rates of species is a 16-step reduced mechanism. A second-order chemistry is implemented on the basis of a two-step kinetic representation of methane combustion, used to correct first-order rates. In general, predictions obtained using the second-order model improve significantly upon first-order results for both major and minor species under fuel-rich conditions. The simplified chemistry employed does not however fully capture the effects of local extinction, and suggestions are made regarding the further developments required to permit the accurate prediction of highly strained flames using CMC methods. (author)

  4. Second-order dispersion interactions in π-conjugated polymers

    NASA Astrophysics Data System (ADS)

    Barford, William; Paiboonvorachat, Nattapong; Yaron, David

    2011-06-01

    We calculate the ground state and excited state second-order dispersion interactions between parallel π-conjugated polymers. The unperturbed eigenstates and energies are calculated from the Pariser-Parr-Pople model using CI-singles theory. Based on large-scale calculations using the molecular structure of trans-polyacetylene as a model system and by exploiting dimensional analysis, we find that: (1) For inter-chain separations, R, greater than a few lattice spacings, the ground-state dispersion interaction, Δ E_{GS}, satisfies, Δ E_{GS} ˜ L^2/R^6 for L ≪ R and Δ E_{GS} ˜ L/R^5 for R ≪ L, where L is the chain length. The former is the London fluctuating dipole-dipole interaction while the latter is a fluctuating line dipole-line dipole interaction. (2) The excited state screening interaction exhibits a crossover from fluctuating monopole-line dipole interactions to either fluctuating dipole-dipole or fluctuating line dipole-line dipole interactions when R exceeds a threshold Rc, where Rc is related to the root-mean-square separation of the electron-hole excitation. Specifically, the excited state screening interaction, ΔEn, satisfies, ΔEn ˜ L/R6 for Rc < L ≪ R and ΔEn ˜ L0/R5 for Rc < R ≪ L. For R < Rc < L, ΔEn ˜ R-ν, where ν ≃ 3. We also investigate the relative screening of the primary excited states in conjugated polymers, namely the n = 1, 2, and 3 excitons. We find that a larger value of n corresponds to a larger value of ΔEn. For example, for poly(para-phenylene), ΔEn = 1 ≃ 0.1 eV, ΔEn = 2 ≃ 0.6 eV, and ΔEn = 3 ≃ 1.2 eV (where n = 1 is the 11B1 state, n = 2 is the m1A state, and n = 3 is the n1B1 state). Finally, we find that the strong dependence of ΔEn on inter-chain separation implies a strong dependency of ΔEn on density fluctuations. In particular, a 10% density fluctuation implies a fluctuation of 13 meV, 66 meV, and 120 meV for the 11B1, m1A state, and n1B1 states of poly(para-phenylene), respectively. Our results

  5. Dinitrosyl iron complexes with cysteine. Kinetics studies of the formation and reactions of DNICs in aqueous solution.

    PubMed

    Pereira, José Clayston Melo; Iretskii, Alexei V; Han, Rui-Min; Ford, Peter C

    2015-01-14

    Kinetics studies provide mechanistic insight regarding the formation of dinitrosyl iron complexes (DNICs) now viewed as playing important roles in the mammalian chemical biology of the ubiquitous bioregulator nitric oxide (NO). Reactions in deaerated aqueous solutions containing FeSO4, cysteine (CysSH), and NO demonstrate that both the rates and the outcomes are markedly pH dependent. The dinuclear DNIC Fe2(μ-CysS)2(NO)4, a Roussin's red salt ester (Cys-RSE), is formed at pH 5.0 as well as at lower concentrations of cysteine in neutral pH solutions. The mononuclear DNIC Fe(NO)2(CysS)2(-) (Cys-DNIC) is produced from the same three components at pH 10.0 and at higher cysteine concentrations at neutral pH. The kinetics studies suggest that both Cys-RSE and Cys-DNIC are formed via a common intermediate Fe(NO)(CysS)2(-). Cys-DNIC and Cys-RSE interconvert, and the rates of this process depend on the cysteine concentration and on the pH. Flash photolysis of the Cys-RSE formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 5.0 solution led to reversible NO dissociation and a rapid, second-order back reaction with a rate constant kNO = 6.9 × 10(7) M(-1) s(-1). In contrast, photolysis of the mononuclear-DNIC species Cys-DNIC formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 10.0 solution did not labilize NO but instead apparently led to release of the CysS(•) radical. These studies illustrate the complicated reaction dynamics interconnecting the DNIC species and offer a mechanistic model for the key steps leading to these non-heme iron nitrosyl complexes. PMID:25479566

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

    SciTech Connect

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

    2007-01-01

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

  7. Further development and testing of a second-order bulk boundary layer model. Master's thesis

    SciTech Connect

    Krasner, R.D.

    1993-05-03

    A one-layer bulk boundary layer model is developed. The model predicts the mixed layer values of the potential temperature, mixing ratio, and u- and v-momentum. The model also predicts the depth of the boundary layer and the vertically integrated turbulence kinetic energy (TKE). The TKE is determined using a second-order closure that relates the rate of dissipation to the TKE. The fractional area covered by rising motion sigma and the entrainment rate (E) are diagnostically determined. The model is used to study the clear convective boundary layer (CBL) using data from the Wangara, Australia boundary layer experiment. The Wangara data is also used as an observation base to validate model results. A further study is accomplished by simulating the planetary boundary layer (PBL) over an ocean surface. This study is designed to find the steady-state solutions of the prognostic variable.

  8. Growth kinetics of forsterite reaction rims at high-pressure

    NASA Astrophysics Data System (ADS)

    Nishihara, Yu; Maruyama, Genta; Nishi, Masayuki

    2016-08-01

    Growth kinetics of forsterite (Fo) reaction rims between periclase (Per) and enstatite (En) were studied experimentally at pressure (P) and temperature (T) conditions of 3.0-11.1 GPa and 1473-1873 K, respectively. Pt markers originally placed at the Per-En interface were always observed at the Per-Fo interface, which indicates that Mg and O are the diffusing species in Fo rim growth (Mg-O coupled diffusion). The presence of some En inclusions in Fo grains and the growth rate of the Fo rim suggests that grain boundary diffusion is dominant rather than lattice diffusion. Considering the very fast grain boundary diffusion of O in olivine, the Mg-O coupled grain boundary diffusion in Fo is deduced to be rate-limited by the diffusivity of Mg. Based on an analysis of data collected under dry conditions, the product of the Mg grain boundary diffusion coefficient (Dgb) and the effective grain boundary width (δ) was determined to be δDgb = δDgb,0exp[-(E∗ + PV∗)/RT] with δDgb,0 = 10-9.68 ± 1.51 m3/s, E∗ = 379 ± 44 kJ/mol and V∗ = -1.9 ± 1.4 cm3/mol. Our results, combined with previously reported data on Mg lattice diffusion in Fo, suggest that for Mg, the significance of grain boundary diffusion increases with depth in the Earth's upper mantle, although lattice diffusion is still dominant for typical mantle grain sizes of 1-10 mm.

  9. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products.

    PubMed

    Ji, Yuefei; Kong, Deyang; Lu, Junhe; Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo

    2016-08-01

    Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO4(-)) with TBBPA was determined to be 5.27×10(10)M(-1)s(-1). Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO4(-). Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6-10h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health. PMID:27107323

  10. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    SciTech Connect

    Fedorenko, S. G.; Burshtein, A. I.

    2014-09-21

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  11. Renormalized second-order perturbation theory for the electron correlation energy: Concept, implementation, and benchmarks

    NASA Astrophysics Data System (ADS)

    Ren, Xinguo; Rinke, Patrick; Scuseria, Gustavo E.; Scheffler, Matthias

    2013-07-01

    We present a renormalized second-order perturbation theory (rPT2), based on a Kohn-Sham (KS) reference state, for the electron correlation energy that includes the random-phase approximation (RPA), second-order screened exchange (SOSEX), and renormalized single excitations (rSE). These three terms all involve a summation of certain types of diagrams to infinite order, and can be viewed as ``renormalization'' of the second-order direct, exchange, and single-excitation (SE) terms of Rayleigh-Schrödinger perturbation theory based on a KS reference. In this work, we establish the concept of rPT2 and present the numerical details of our SOSEX and rSE implementations. A preliminary version of rPT2, in which the renormalized SE (rSE) contribution was treated approximately, has already been benchmarked for molecular atomization energies and chemical reaction barrier heights and shows a well-balanced performance [J. Paier , New J. Phys.1367-263010.1088/1367-2630/14/4/043002 14, 043002 (2012)]. In this work, we present a refined version of rPT2, in which we evaluate the rSE series of diagrams rigorously. We then extend the benchmark studies to noncovalent interactions, including the rare-gas dimers, and the S22 and S66 test sets, as well as the cohesive energy of small copper clusters, and the equilibrium geometry of 10 diatomic molecules. Despite some remaining shortcomings, we conclude that rPT2 gives an overall satisfactory performance across different electronic situations, and is a promising step towards a generally applicable electronic-structure approach.

  12. Ab initio study of the kinetics of hydrogen abstraction reactions on toluene and tetralin

    SciTech Connect

    Beste, Ariana; Britt, Phillip F; Buchanan III, A C; Harrison, Robert J; Hathorn, Bryan C

    2008-01-01

    Hydrogen abstraction reactions play a key role in many thermal and catalytic processes involved in the production of fuels and chemicals. In this paper, the reaction barriers and rate constants for the hydrogen abstraction reactions on toluene and tetralin by the benzyl radical are calculated by ab initio methods. These reactions are representatives of similar reactions occurring in the thermolysis of lignin model compounds containing the phenethyl phenyl ether (PPE) structural moiety. Thermolysis of PPE occurs by a free radical chain mechanism in which the product selectivity arises from competitive hydrogen abstraction at the benzylic and nonbenzylic methylen sites by chain carrying benzyl and phenoxyl radicals. The title reactions serve to calibrate the theoretical methods to be used in the study of PPE through comparison of the rate constants and the reaction enthalpies with reliable experimental values. In this study, we used two different hybrid density functionals (BHandHLYP, B3LYP) and second-order perturbation theory to obtain equilibrium and transition state geometries. Multiple transition states were found for both reactions. BHandHLYP underestimates and second-order perturbation theory overestimates the reaction barriers; B3LYP energy barriers agree well with experiment. Absolute and relative rate constants were calculated using transition state theory. We found that the relative rate constant using the B3LYP functional agrees within a factor of 2.0 with experiment at the experimental temperature of 333 K, indicating that the B3LYP functional will be successful in predicting relative rate constants for hydrogen abstraction reactions participating in the pyrolysis of PPE.

  13. Biosynthesis reaction mechanism and kinetics of deoxynucleoside triphosphates, dATP and dGTP.

    PubMed

    Bao, Jie; Ryu, Dewey D Y

    2005-02-20

    The enzyme reaction mechanism and kinetics for biosyntheses of deoxyadenosine triphosphate (dATP) and deoxyguanosine triphosphate (dGTP) from the corresponding deoxyadenosine diphosphate (dADP) and deoxyguanosine diphosphate (dGDP) catalyzed by pyruvate kinase were studied. A kinetic model for this synthetic reaction was developed based on a Bi-Bi random rapid equilibrium mechanism. Kinetic constants involved in this pyruvate kinase catalyzed phosphorylation reactions of deoxynucleoside diphosphates including the maximum reaction velocity, Michaelis-Menten constants, and inhibition constants for dATP and dGTP biosyntheses were experimentally determined. These kinetic constants for dATP and dGTP biosyntheses are of the same order of magnitude but significantly different between the two reactions. Kinetic constants involved in ATP and GTP biosyntheses as reported in literature are about one order of magnitude different from those involved in dATP and dGTP biosyntheses. This enzyme reaction requires Mg2+ ion and the optimal Mg2+ concentration was also determined. The experimental results showed a very good agreement with the simulation results obtained from the kinetic model developed. This kinetic model can be applied to the practical application of a pyruvate kinase reaction system for production of dATP and dGTP. There is a significant advantage of using enzymatic biosyntheses of dATP and dGTP as compared to the chemical method that has been in commercial use. PMID:15643625

  14. Radical Recombination Kinetics: An Experiment in Physical Organic Chemistry.

    ERIC Educational Resources Information Center

    Pickering, Miles

    1980-01-01

    Describes a student kinetic experiment involving second order kinetics as well as displaying photochromism using a wide variety of techniques from both physical and organic chemistry. Describes measurement of (1) the rate of the recombination reaction; (2) the extinction coefficient; and (3) the ESR spectrometer signal. (Author/JN)

  15. A Pore Scale Evaluation of the Kinetics of Mineral Dissolution and Precipitation Reactions (EMSI)

    SciTech Connect

    Steefel, Carl I.

    2006-06-01

    The chief goals for CEKA are to (1) collect and synthesize molecular-level kinetic data into a coherent framework that can be used to predict time evolution of environmental processes over a range of temporal and spatial scales; (2) train a cohort of talented and diverse students to work on kinetic problems at multiple scales; (3) develop and promote the use of new experimental techniques in environmental kinetics; (4) develop and promote the use of new modeling tools to conceptualize reaction kinetics in environmental systems; and (5) communicate our understanding of issues related to environmental kinetics and issues of scale to the broader scientific community and to the public.

  16. ENZO: A Web Tool for Derivation and Evaluation of Kinetic Models of Enzyme Catalyzed Reactions

    PubMed Central

    Bevc, Staš; Konc, Janez; Stojan, Jure; Hodošček, Milan; Penca, Matej; Praprotnik, Matej; Janežič, Dušanka

    2011-01-01

    We describe a web tool ENZO (Enzyme Kinetics), a graphical interface for building kinetic models of enzyme catalyzed reactions. ENZO automatically generates the corresponding differential equations from a stipulated enzyme reaction scheme. These differential equations are processed by a numerical solver and a regression algorithm which fits the coefficients of differential equations to experimentally observed time course curves. ENZO allows rapid evaluation of rival reaction schemes and can be used for routine tests in enzyme kinetics. It is freely available as a web tool, at http://enzo.cmm.ki.si. PMID:21818304

  17. Model for reaction kinetics in pyrolysis of wood

    SciTech Connect

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kumar, S.

    1996-12-31

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

  18. Effects of Deception on Children's Understanding of Second-Order False Belief

    ERIC Educational Resources Information Center

    Miller, Scott A.

    2013-01-01

    This research examined two questions: effects of deception on children's understanding of second-order false belief, and possible effects of number of siblings on second-order performance. Kindergarten children responded to 3 second-order problems that varied in the presence and the nature of deception. Performance was better on the problems…

  19. Linear-noise approximation and the chemical master equation agree up to second-order moments for a class of chemical systems

    NASA Astrophysics Data System (ADS)

    Grima, Ramon

    2015-10-01

    It is well known that the linear-noise approximation (LNA) agrees with the chemical master equation, up to second-order moments, for chemical systems composed of zero and first-order reactions. Here we show that this is also a property of the LNA for a subset of chemical systems with second-order reactions. This agreement is independent of the number of interacting molecules.

  20. DIRECT COMPARISON OF KINETIC AND LOCAL EQUILIBRIUM FORMULATIONS FOR SOLUTE TRANSPORT AFFECTED BY SURFACE REACTIONS.

    USGS Publications Warehouse

    Bahr, Jean M.; Rubin, Jacob

    1987-01-01

    Modeling transport of reacting solutes in porous media often requires a choice between models based on the local equilibrium assumption (LEA) and models involving reaction kinetics. Direct comparison of the mathematical formulations for these two types of transport models can aid in this choice. For cases of transport affected by surface reaction, such a comparison is made possible by a new derivation procedure. This procedure yields a kinetics-based formulation that is the sum of the LEA formulation and one or more kinetically influenced terms. The dimensionless form of the new kinetics-based formulation facilitates identification of critical parameter groupings which control the approach to transport behavior consistent with LEA model predictions. Results of numerical experiments demonstrate that criteria for LEA applicability can be expressed conveniently in terms of these parameter groupings. The derivation procedure is demonstrated for examples of surface reactions including first-order reversible sorption, Langmuir-type kinetics and binary, homovalent ion exchange.

  1. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification.

    PubMed

    Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang

    2016-06-01

    This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H2O2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H2O2 concentration, while the optimal pH and H2O2 concentration were 7.0 and 8μM, respectively. 98% TCS was removed with only 0.1UmL(-1) SBP in 30min reaction time, while an HRP dose of 0.3UmL(-1) was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (KCAT) and catalytic efficiency (KCAT/KM) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via CC and CO coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment. PMID:26921508

  2. Microscopic molecular dynamics characterization of the second-order non-Navier-Fourier constitutive laws in the Poiseuille gas flow

    NASA Astrophysics Data System (ADS)

    Rana, A.; Ravichandran, R.; Park, J. H.; Myong, R. S.

    2016-08-01

    The second-order non-Navier-Fourier constitutive laws, expressed in a compact algebraic mathematical form, were validated for the force-driven Poiseuille gas flow by the deterministic atomic-level microscopic molecular dynamics (MD). Emphasis is placed on how completely different methods (a second-order continuum macroscopic theory based on the kinetic Boltzmann equation, the probabilistic mesoscopic direct simulation Monte Carlo, and, in particular, the deterministic microscopic MD) describe the non-classical physics, and whether the second-order non-Navier-Fourier constitutive laws derived from the continuum theory can be validated using MD solutions for the viscous stress and heat flux calculated directly from the molecular data using the statistical method. Peculiar behaviors (non-uniform tangent pressure profile and exotic instantaneous heat conduction from cold to hot [R. S. Myong, "A full analytical solution for the force-driven compressible Poiseuille gas flow based on a nonlinear coupled constitutive relation," Phys. Fluids 23(1), 012002 (2011)]) were re-examined using atomic-level MD results. It was shown that all three results were in strong qualitative agreement with each other, implying that the second-order non-Navier-Fourier laws are indeed physically legitimate in the transition regime. Furthermore, it was shown that the non-Navier-Fourier constitutive laws are essential for describing non-zero normal stress and tangential heat flux, while the classical and non-classical laws remain similar for shear stress and normal heat flux.

  3. Detailed Chemical Kinetic Reaction Mechanisms for Incineration of Organophosphorus and Fluoro-Organophosphorus Compounds

    SciTech Connect

    Glaude, P A; Melius, C; Pitz, W J; Westbrook, C K

    2001-12-13

    A detailed chemical kinetic reaction mechanism is developed to describe incineration of the chemical warfare nerve agent sarin (GB), based on commonly used principles of bond additivity and hierarchical reaction mechanisms. The mechanism is based on previous kinetic models of organophosphorus compounds such as TMP, DMMP and DIMP that are often used as surrogates to predict incineration of GB. Kinetic models of the three surrogates and GB are then used to predict their consumption in a perfectly stirred reactor fueled by natural gas to simulate incineration of these chemicals. Computed results indicate that DIMP is the only one of these surrogates that adequately describes combustion of GB under comparable conditions. The kinetic pathways responsible for these differences in reactivity are identified and discussed. The most important reaction in GB and DIMP that makes them more reactive than TMP or DMMP is found to be a six-center molecular elimination reaction producing propene.

  4. Kinetics and thermodynamics of chemical reactions in Li/SOCl2 cells

    NASA Technical Reports Server (NTRS)

    Hansen, Lee D.; Frank, Harvey

    1987-01-01

    Work is described that was designed to determine the kinetic constants necessary to extrapolate kinetic data on Li/SOCl2 cells over the temperature range from 25 to 75 C. A second objective was to characterize as far as possible the chemical reactions that occur in the cells since these reactions may be important in understanding the potential hazards of these cells. The kinetics of the corrosion processes in undischarged Li/SOCl2 cells were determined and separated according to their occurrence at the anode and cathode; the effects that switching the current on and off has on the corrosion reactions was determined; and the effects of discharge state on the kinetics of the corrosion process were found. A thermodynamic analysis of the current-producing reactions in the cell was done and is included.

  5. Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

    ERIC Educational Resources Information Center

    Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

    2014-01-01

    An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

  6. Utilization of the Recycle Reactor in Determining Kinetics of Gas-Solid Catalytic Reactions.

    ERIC Educational Resources Information Center

    Paspek, Stephen C.; And Others

    1980-01-01

    Describes a laboratory scale reactor that determines the kinetics of a gas-solid catalytic reaction. The external recycle reactor construction is detailed with accompanying diagrams. Experimental details, application of the reactor to CO oxidation kinetics, interphase gradients, and intraphase gradients are discussed. (CS)

  7. Detailed Chemical Kinetic Reaction Mechanism for Biodiesel Components Methyl Stearate and Methyl Oleate

    SciTech Connect

    Naik, C; Westbrook, C K; Herbinet, O; Pitz, W J; Mehl, M

    2010-01-22

    New chemical kinetic reaction mechanisms are developed for two of the five major components of biodiesel fuel, methyl stearate and methyl oleate. The mechanisms are produced using existing reaction classes and rules for reaction rates, with additional reaction classes to describe other reactions unique to methyl ester species. Mechanism capabilities were examined by computing fuel/air autoignition delay times and comparing the results with more conventional hydrocarbon fuels for which experimental results are available. Additional comparisons were carried out with measured results taken from jet-stirred reactor experiments for rapeseed methyl ester fuels. In both sets of computational tests, methyl oleate was found to be slightly less reactive than methyl stearate, and an explanation of this observation is made showing that the double bond in methyl oleate inhibits certain low temperature chain branching reaction pathways important in methyl stearate. The resulting detailed chemical kinetic reaction mechanism includes more approximately 3500 chemical species and more than 17,000 chemical reactions.

  8. A second-order closure prediction of premixed turbulent combustion in jets

    NASA Astrophysics Data System (ADS)

    Davé, N.; Kollmann, W.

    1987-02-01

    In this paper, a numerical prediction is reported involving second-order closure of a turbulent flow of a vertically burning, lean mixture of premixed combustible gases discharging from a pipe and developing into a turbulent combusting roundjet. Classical closures are used where available. Expressions for the chemical reaction rate term and other unclosed terms related to variable density flow in the Favre-averaged turbulent transport equations are based on the Bray-Moss-Libby aerothermochemistry for premixed turbulent combustion, extended to variable enthalpy systems. Mixing of hot burned and cool ambient gases and the attendant buoyancy effects are found to be significant physical phenomena in the behavior of such lean premixed combusting jets. Results of the simulation are compared with experimental data of Yoshida [Proceedings of the Eighteenth International Symposium on Combustion (The Combustion Institute, Pittsburgh, 1981), p. 931] with which reasonable numerical agreement is obtained. Reasons for discrepancies and possible lines for future research are discussed.

  9. Second Order Catalytic Quasispecies Yields Discontinuous Mean Fitness at Error Threshold

    NASA Astrophysics Data System (ADS)

    Wagner, Nathaniel; Tannenbaum, Emmanuel; Ashkenasy, Gonen

    2010-05-01

    The quasispecies model describes processes related to the origin of life and viral evolutionary dynamics. We discuss how the error catastrophe that reflects the transition from localized to delocalized quasispecies population is affected by catalytic replication of different reaction orders. Specifically, we find that second order mechanisms lead to a discontinuity in the mean fitness of the population at the error threshold. This is in contrast to the behavior of the first order, autocatalytic replication mechanism considered in the standard quasispecies model. This suggests that quasispecies models with higher order replication mechanisms produce discontinuities in the mean fitness, and hence the viable population fraction as well, at the error threshold, while lower order replication mechanisms yield a continuous mean fitness function. We discuss potential implications for understanding replication in the RNA world and in virology.

  10. Incorporation of aqueous reaction and sorption kinetics andbiodegradation into TOUGHREACT

    SciTech Connect

    Xu, Tianfu

    2006-04-17

    The needs for considering aqueous and sorption kinetics and microbiological processes arises in many subsurface problems, such as environmental and acid mine remediation. A general rate expression has been implemented into TOUGHREACT, which considers multiple mechanisms(pathways) and includes multiple product, Monod, and inhibition terms. In this paper, the formulation for incorporating kinetic rates among primary species into the mass balance equations is presented. A batch sulfide oxidation problem is simulated. The resulting concentrations are consistent with simple hand calculations. A 1-D reactive transport problem with kinetic biodegradation and sorption was investigated, which models the processes when a pulse of water containing NTA (nitrylotriacetate) and cobalt is injected into a column. The problem has several interacting chemical processes that are common to many environmental problems: biologically-mediated degradation of an organic substrate, bacterial cell growth and decay, metal sorption and aqueous speciation including metal-ligand complexation. The TOUGHREACT simulation results agree very well with those obtained with other simulators.

  11. Linear free energy relationship and deuterium kinetic isotope effect observed on phospho and thiophosphoryl transfer reactions in some organophosphorous compounds

    NASA Astrophysics Data System (ADS)

    Lumbiny, B. J.; Hui, Z.; Islam, M. A.; Quader, M. A.; Rahman, M.

    2014-04-01

    Tetracoordinated organophosphorous compounds were synthesized, characterized and nucleophilic substitution reaction were investigated by varying substituents around phosphorous centre or in nucleophile considering its utility in biological and environmental system. The reactivity is expressed in terms of second-order rate constant, k2 and measured conductometrically. Linear Free Energy Relationship (LFER) tools mainly Hammett (ρ), Brönsted (β) LFER coefficients and deuterium kinetic isotope effects (KIEs) being determined for the pyridinolysis of 4 - chlorophenyl 4 - methoxy phenyl chlorophosphate, 1 in acetonitrile at 5.0 °C. The experimental data's were compared with those of structurally similar organophosphorous compounds reported earlier in quest for the mechanistic information. Nice linear correlation being found for Hammett (logk2 vs σx), having negative value of the ρX = -5.85 and Brönsted (logk2 vs pKa(x)) plots having large positive value for βX = 1.18 for 1 can be interpreted as SN2 process with greater extent of bond formation in transition state (TS) of 1. The observed kH/kD values of 1 is 1.00 ± 0.05 and net KIE, 1.32 suggests the primary KIE and indicates frontside nucleophilic attack through the partial deprotonation of pyridine occurs by the hydrogen bonding in the rate-determining step.

  12. Kinetics, mechanisms and products of reactions of Criegee intermediates

    NASA Astrophysics Data System (ADS)

    Orr-Ewing, Andrew

    The atmospheric ozonolysis of alkenes such as isoprene produces Criegee intermediates which are increasingly recognized as important contributors to oxidation chemistry in the Earth's troposphere. Stabilized Criegee intermediates are conveniently produced in the laboratory by ultraviolet photolysis of diiodoalkanes in the presence of O2, and can be detected by absorption spectroscopy using their strong electronic bands in the near ultraviolet region. We have used these techniques to study a wide range of reactions of Criegee intermediates, including their self-reactions, and reactions with carboxylic acids and various other trace atmospheric constituents. In collaboration with the Sandia National Laboratory group led by Drs C.A. Taatjes and D.L. Osborn, we have used photoionization and mass spectrometry methods, combined with electronic structure calculations, to characterize the products of several of these reactions. Our laboratory studies determine rate coefficients for the Criegee intermediate reactions, many of which prove to be fast. In the case of reactions with carboxylic acids, a correlation between the dipole moments of the reactants and the reaction rate coefficients suggests a dipole-capture controlled reaction and allows us to propose a structure-activity relationship to predict the rates of related processes. The contributions of these various Criegee intermediate reactions to the chemistry of the troposphere have been assessed using the STOCHEM-CRI global atmospheric chemistry model. This work was supported by NERC grant NE/K004905/1.

  13. Kinetics of Reactions of Monomeric Nitrosomethane Induced by Flash Photolysis.

    ERIC Educational Resources Information Center

    Kozubek, H.; And Others

    1984-01-01

    Describes an experiment in which the kinetics of dimerization of nitrosamine induced by a flash of light is measured. The experiment can be performed with a commercial ultraviolet-VIS spetrophotometer with easy to make modifications. The experiment demonstrates a flash photolysis system not always available in university chemistry laboratories.…

  14. New Direction in Hydrogeochemical Transport Modeling: Incorporating Multiple Kinetic and Equilibrium Reaction Pathways

    SciTech Connect

    Steefel, C.I.

    2000-02-02

    At least two distinct kinds of hydrogeochemical models have evolved historically for use in analyzing contaminant transport, but each has important limitations. One kind, focusing on organic contaminants, treats biodegradation reactions as parts of relatively simple kinetic reaction networks with no or limited coupling to aqueous and surface complexation and mineral dissolution/precipitation reactions. A second kind, evolving out of the speciation and reaction path codes, is capable of handling a comprehensive suite of multicomponent complexation (aqueous and surface) and mineral precipitation and dissolution reactions, but has not been able to treat reaction networks characterized by partial redox disequilibrium and multiple kinetic pathways. More recently, various investigators have begun to consider biodegradation reactions in the context of comprehensive equilibrium and kinetic reaction networks (e.g. Hunter et al. 1998, Mayer 1999). Here we explore two examples of multiple equilibrium and kinetic reaction pathways using the reactive transport code GIMRT98 (Steefel, in prep.): (1) a computational example involving the generation of acid mine drainage due to oxidation of pyrite, and (2) a computational/field example where the rates of chlorinated VOC degradation are linked to the rates of major redox processes occurring in organic-rich wetland sediments overlying a contaminated aerobic aquifer.

  15. Probing Aluminum Reactions in Combustion and Explosion Via the Kinetic Isotope Effect

    NASA Astrophysics Data System (ADS)

    Tappan, Bryce

    2015-06-01

    The mechanism that controls the reaction speed of aluminum in explosion and combustion is poorly understood, and experimentally difficult to measure. Recently, work in our laboratory has demonstrated that during the combustion of nanoparticulate aluminum with H2O or D2O, different reaction rates due to the kinetic isotope effect are observed. This result is the first-ever observed kinetic isotope effect in a metal combustion reaction and verifies that chemical reaction kinetics play a major role in determining the global burning rate. During or shortly after a detonation, however, the reaction rates are dramatically faster and the physical mechanism controlling Al reaction is likely different than during combustion events. To utilize the kinetic isotope effect to probe Al reactions in detonation, formulations were produced that contain powdered Al in deuterated high explosives and high-fidelity detonation velocity were determined along with PDV measurements to observe early wall velocity expansion measurements. The JWL equation of state was solved to determine temperature, pressure and energies at specific time periods, in addition of Gurney energies, which enables the elucidation of Al reaction extent. By comparison of the Al oxidation with LiF, data indicate that Al oxidation occurs on an extremely fast time scale and isotope effects in both the HE detonation and post-detonation Al reactions are discussed.

  16. The maintenance of the second-order advantage: second-order calibration of excitation-emission matrix fluorescence for quantitative analysis of herbicide napropamide in various environmental samples.

    PubMed

    Li, Yuan-Na; Wu, Hai-Long; Qing, Xiang-Dong; Nie, Chong-Chong; Li, Shu-Fang; Yu, Yong-Jie; Zhang, Shu-Rong; Yu, Ru-Qin

    2011-07-15

    A rapid non-separative spectrofluorometric method based on the second-order calibration of excitation-emission matrix (EEM) fluorescence was proposed for the determination of napropamide (NAP) in soil, river sediment, and wastewater as well as river water samples. With 0.10 mol L(-1) sodium citrate-hydrochloric acid (HCl) buffer solution of pH 2.2, the system of NAP has a large increase in fluorescence intensity. To handle the intrinsic fluorescence interferences of environmental samples, the alternating penalty trilinear decomposition (APTLD) algorithm as an efficient second-order calibration method was employed. Satisfactory results have been achieved for NAP in complex environmental samples. The limit of detection obtained for NAP in soil, river sediment, wastewater and river water samples were 0.80, 0.24, 0.12, 0.071 ng mL(-1), respectively. Furthermore, in order to fully investigate the performance of second-order calibration method, we test the second-order calibration method using different calibration approaches including the single matrix model, the intra-day various matrices model and the global model based on the APTLD algorithm with nature environmental datasets. The results showed the second-order calibration methods also enable one or more analyte(s) of interest to be determined simultaneously in the samples with various types of matrices. The maintenance of second-order advantage has been demonstrated in simultaneous determinations of the analyte of interests in the environmental samples of various matrices. PMID:21645706

  17. Kinetically influenced terms for solute transport affected by heterogeneous and homogeneous classical reactions

    USGS Publications Warehouse

    Bahr, J.M.

    1990-01-01

    This paper extends a four-step derivation procedure, previously presented for cases of transport affected by surface reactions, to transport problems involving homogeneous reactions. Derivations for these classes of reactions are used to illustrate the manner in which mathematical differences between reaction classes are reflected in the mathematical derivation procedures required to identify kinetically influenced terms. Simulation results for a case of transport affected by a single solution phase complexation reaction and for a case of transport affected by a precipitation-dissolution reaction are used to demonstrate the nature of departures from equilibrium-controlled transport as well as the use of kinetically influenced terms in determining criteria for the applicability of the local equilibrium assumption. A final derivation for a multireaction problem demonstrates the application of the generalized procedure to a case of transport affected by reactions of several classes. -from Author

  18. Kinetics of a Substitution Reaction of Sulfitopentaaminecobalt(III).

    ERIC Educational Resources Information Center

    Richards, Lynne

    1988-01-01

    Describes a laboratory experiment to determine the rate law for a substitution reaction of a transition metal. Derives the corresponding rate law from the accepted mechanism for the reaction using the steady state approximation and determines the conditions under which the two agree. (CW)

  19. Implementing the Second-Order Fermi Process in a Kinetic Monte-Carlo Simulation

    NASA Technical Reports Server (NTRS)

    Summerlin, Errol J.

    2010-01-01

    Radio JOVE is an education and outreach project intended to give students and other interested individuals hands-on experience in learning radio astronomy. They can do this through building a radio telescope from a relatively inexpensive kit that includes the parts for a receiver and an antenna as well as software for a computer chart recorder emulator (Radio Skypipe) and other reference materials

  20. 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...

  1. High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1975-01-01

    An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

  2. Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

    SciTech Connect

    Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

    2011-05-20

    A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

  3. Atmospheric chemistry: Laboratory studies of kinetics of important reactions

    NASA Astrophysics Data System (ADS)

    Smith, S. J.

    Experiments to measure the rate constants for some reactions of the atmospherically important nitrate radical (NO3) are described using the discharge-flow technique. The nitrate radical was monitored by optical absorption at lambda = 662 nm. The reactions of NO3 with some stable organic and inorganic substrates are reported. The temperature dependences of some of the rate constants were also determined (298 less than T less than 523 K). In most cases, computer simulation was used to extract the rate constant for the primary process because the time-dependent behavior of (NO3) was affected by secondary reactions of NO3 with products of the primary interaction. The Arrhenius parameter for the reactions of NO3 with CH3CH3, CH2CH2, CH3OH, CHCl3, and HCl were determined. The activation energies for the reactions studied between NO3 and some alkynes are presented along with the corresponding pre-exponential factors. Some reactions were studied at room temperature (298 plus or minus 2 K) only and the rate constants found (in units of cubic cm/molecule sec) are: buta-1,3-diene (1.8 x 10 (exp -13), isobutene (2.8 x 10 (exp -13), HBr (1.3 x 10 (exp -15) and hex-2-yne (3.0 x 10 (exp -14). Non-Arrhenius behavior was found in the reactions of NO3 with n-butane, isobutane and propene. The empirical variation of these rate constants with temperature is presented. The curvature of the Arrhenius plots is discussed in terms of (1) a temperature-dependent pre-exponential factor, and (2) the possibility that two competing channels, possessing differing activation energies, exist for each reaction. The atmospheric implications of these reactions are discussed with reference to the nighttime production of nitric acid and the importance of the these reactions as loss processes for NO3.

  4. Reaction progress kinetic analysis of a copper-catalyzed aerobic oxidative coupling reaction with N-phenyl tetrahydroisoquinoline.

    PubMed

    Scott, Martin; Sud, Abhishek; Boess, Esther; Klussmann, Martin

    2014-12-19

    The results from a kinetic investigation of a Cu-catalyzed oxidative coupling reaction between N-phenyl tetrahydroisoquinoline and a silyl enol ether using elemental oxygen as oxidant are presented. By using reaction progress kinetic analysis as an evaluation method for the obtained data, we discovered information regarding the reaction order of the substrates and catalysts. Based on this information and some additional experiments, a refined model for the initial oxidative activation of the amine substrate and the activation of the nucleophile by the catalyst was developed. The mechanistic information also helped to understand why silyl nucleophiles have previously failed in a related Cu-catalyzed reaction using tert-butyl hydroperoxide as oxidant and how to overcome this limitation. PMID:25203932

  5. Kinetic Studies of the Solvolysis of Two Organic Halides

    ERIC Educational Resources Information Center

    Duncan, J. A.; Pasto, D. J.

    1975-01-01

    Describes an undergraduate organic chemistry laboratory experiment which utilizes the solvolysis of organic halides to demonstrate first and second order reaction kinetics. The experiment also investigates the effect of a change of solvent polarity on reaction rate, common-ion and noncommon-ion salt effects, and the activation parameters of a…

  6. Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

    ERIC Educational Resources Information Center

    Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

    2011-01-01

    A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

  7. Kinetics of sunflower oil methanolysis at low temperatures.

    PubMed

    Stamenković, Olivera S; Todorović, Zoran B; Lazić, Miodrag L; Veljković, Vlada B; Skala, Dejan U

    2008-03-01

    The kinetics of the sunflower oil methanolysis process was studied at lower temperatures (10-30 degrees C). The sigmoidal kinetics of the process was explained by the mass transfer controlled region in the initial heterogenous regime, followed by the chemical reaction controlled region in the pseudo-homogenous regime. A simple kinetic model, which did not require complex computation of the kinetic constants, was used for simulation of the TG conversion and the FAME formation in the latter regime: the fast irreversible second-order reaction was followed by the slow reversible second-order reaction close to the completion of the methanolysis reaction. The mass transfer was related to the drop size of the dispersed (methanol) phase, which reduced rapidly with the progress of the methanolysis reaction. This was attributed to the formation of the emulsifying agents stabilizing the emulsion of methanol drops into the oil. PMID:17434728

  8. Accurately Predicting Complex Reaction Kinetics from First Principles

    NASA Astrophysics Data System (ADS)

    Green, William

    Many important systems contain a multitude of reactive chemical species, some of which react on a timescale faster than collisional thermalization, i.e. they never achieve a Boltzmann energy distribution. Usually it is impossible to fully elucidate the processes by experiments alone. Here we report recent progress toward predicting the time-evolving composition of these systems a priori: how unexpected reactions can be discovered on the computer, how reaction rates are computed from first principles, and how the many individual reactions are efficiently combined into a predictive simulation for the whole system. Some experimental tests of the a priori predictions are also presented.

  9. Kinetics of liquid-solid reactions in naphthenic acid conversion and Kraft pulping

    NASA Astrophysics Data System (ADS)

    Yang, Ling

    Two liquid-solid reactions, in which the morphology of the solid changes as the reactions proceeds, were examined. One is the NA conversion in oil by decarboxylation on metal oxides and carbonates, and the other is the Kraft pulping in which lignin removal by delignification reaction. In the study of the NA conversion, CaO was chosen as the catalyst for the kinetic study from the tested catalysts based on NA conversion. Two reaction mixtures, carrier oil plus commercial naphthenic acids and heavy vacuum gas oil (HVGO) from Athabasca bitumen, were applied in the kinetic study. The influence of TAN, temperature, and catalyst loading on the NA conversion and decarboxylation were studied systematically. The results showed that the removal rate of TAN and the decarboxylation of NA were both independent of the concentration of NA over the range studied, and significantly dependent on reaction temperature. The data from analyzing the spent catalyst demonstrated that calcium naphthenate was an intermediate of the decarboxylation reaction of NA, and the decomposition of calcium naphthenate was a rate-determining step. In the study on the delignification of the Kraft pulping, a new mechanism was proposed for the heterogeneous delignification reaction during the Kraft pulping process. In particular, the chemical reaction mechanism took into account the heterogeneous nature of Kraft pulping. Lignin reacted in parallel with sodium hydroxide and sodium sulfide. The mechanism consists of three key kinetic steps: (1) adsorption of hydroxide and hydrosulfide ions on lignin; (2) surface reaction on the solid surface to produce degraded lignin products; and (3) desorption of degradation products from the solid surface. The most important step for the delignification process is the surface reaction, rather than the reactions occurring in the liquid phase. A kinetic model has, thus, been developed based on the proposed mechanism. The derived kinetic model showed that the mechanism

  10. A simultaneous one pot synthesis of two fractal structures via swapping two fractal reaction kinetic states.

    PubMed

    Ghosh, Subrata; Dutta, Mrinal; Ray, Kanad; Fujita, Daisuke; Bandyopadhyay, Anirban

    2016-06-01

    We introduce a new class of fractal reaction kinetics wherein two or more distinct fractal structures are synthesized as parts of a singular cascade reaction in a single chemical beaker. Two examples: sphere ↔ spiral & triangle ↔ square fractals, grow 10(6) orders from a single dendrimer (8 nm) to the visible scale. PMID:27166589

  11. Reactions between beta-lactoglobulin and genipin: kinetics and characterization of the products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this paper, we present the first detailed report of the reaction kinetics studies and the characterization of the products from the endothermic reactions between beta-lactoglobulin and genipin. The effects of concentration, temperature, and pH were examined. In the temperature range studied, th...

  12. Using temperature-programmed reaction for kinetic analysis of reactions in dilute aqueous solutions at high pressure

    SciTech Connect

    Brown, L.F.; Robinson, B.A.

    1986-01-01

    The technique of temperature-programmed reaction (TPR) is shown to be a practical experimental method for determining reaction-rate expressions and kinetics parameters for reactions in dilute aqueous solutions under high ambient pressure. By sampling and measuring the extent of reaction during a rise in temperature, information normally obtained from a series of isothermal batch kinetics experiments can be found in a single TPR test. The use of nonlinear least-squares regression eliminates the need to achieve a constant rate of temperature rise, simplifies the experimental requirements for TPR results, and gives more accurate answers than does a linear analysis of TPR results. Numerical simulations of TPR tests in the presence of random concentration-measurement error is used to assess the accuracy of the technique and to identify the best values of crucial operating parameters. The results of two TPR experiments measuring the alkaline hydrolysis of ethyl acetate demonstrate the applicability of the technique to reactions in dilute aqueous solutions at high pressure. These preliminary experimental results, along with numerical simulations, allow us to chart a course for future TPR kinetics experiments on a large number of similar reactions. 16 refs., 6 figs., 8 tabs.

  13. Kinetics and mechanism of the IO + IO reaction

    NASA Technical Reports Server (NTRS)

    Sander, S. P.

    1986-01-01

    The flash photolysis-absorption technique has been used to measure the rate constant for the reaction IO + IO over the temperature range 250-373 K and pressure range 20-700 torr of N2. The rate constant for the overall reaction was found to be independent of pressure and equal to 1.73 x 10 to the -12th exp (1020 + or - 200)/T cu cm/molecule s. Branching ratios for the reaction channels forming 2I + O2, I2 + O2, and I2O2, were found to be pressure dependent, with the I2 channel accounting for less than 5 percent of the total reaction over the observed pressure range. A stable reaction product was observed between 230 and 300 nm which was formed on a long time scale compared to IO disappearance. The rate constant for the reaction I + O3 + yields to IO + O2 was measured at 298 K and found to be (9.5 + or - 1.5) x 10 to the -13th cu cm/molecule s.

  14. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    SciTech Connect

    Yeh, G.T.; Iskra, G.A.; Szecsody, J.E.; Zachara, J.M.; Streile, G.P.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength.

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

    SciTech Connect

    Tully, F.P.

    1993-12-01

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

  16. General theory of multistage geminate reactions of isolated pairs of reactants. I. Kinetic equations

    SciTech Connect

    Doktorov, Alexander B.; Kipriyanov, Alexey A.

    2014-05-14

    General matrix approach to the consideration of multistage geminate reactions of isolated pairs of reactants depending on reactant mobility is formulated on the basis of the concept of “effective” particles. Various elementary reactions (stages of multistage reaction including physicochemical processes of internal quantum state changes) proceeding with the participation of isolated pairs of reactants (or isolated reactants) are taken into account. Investigation has been made in terms of kinetic approach implying the derivation of general (matrix) kinetic equations for local and mean probabilities of finding any of the reaction species in the sample under study (or for local and mean concentrations). The recipes for the calculation of kinetic coefficients of the equations for mean quantities in terms of relative coordinates of reactants have been formulated in the general case of inhomogeneous reacting systems. Important specific case of homogeneous reacting systems is considered.

  17. Differential effects of exogenous and endogenous attention on second-order texture contrast sensitivity

    PubMed Central

    Barbot, Antoine; Landy, Michael S.; Carrasco, Marisa

    2012-01-01

    The visual system can use a rich variety of contours to segment visual scenes into distinct perceptually coherent regions. However, successfully segmenting an image is a computationally expensive process. Previously we have shown that exogenous attention—the more automatic, stimulus-driven component of spatial attention—helps extract contours by enhancing contrast sensitivity for second-order, texture-defined patterns at the attended location, while reducing sensitivity at unattended locations, relative to a neutral condition. Interestingly, the effects of exogenous attention depended on the second-order spatial frequency of the stimulus. At parafoveal locations, attention enhanced second-order contrast sensitivity to relatively high, but not to low second-order spatial frequencies. In the present study we investigated whether endogenous attention—the more voluntary, conceptually-driven component of spatial attention—affects second-order contrast sensitivity, and if so, whether its effects are similar to those of exogenous attention. To that end, we compared the effects of exogenous and endogenous attention on the sensitivity to second-order, orientation-defined, texture patterns of either high or low second-order spatial frequencies. The results show that, like exogenous attention, endogenous attention enhances second-order contrast sensitivity at the attended location and reduces it at unattended locations. However, whereas the effects of exogenous attention are a function of the second-order spatial frequency content, endogenous attention affected second-order contrast sensitivity independent of the second-order spatial frequency content. This finding supports the notion that both exogenous and endogenous attention can affect second-order contrast sensitivity, but that endogenous attention is more flexible, benefitting performance under different conditions. PMID:22895879

  18. Density Functional Theory and Reaction Kinetics Studies of the Water–Gas Shift Reaction on Pt–Re Catalysts

    SciTech Connect

    Carrasquillo-Flores, Ronald; Gallo, Jean Marcel R.; Hahn, Konstanze; Dumesic, James A.; Mavrikakis, Manos

    2013-11-05

    Periodic, self-consistent density functional theory calculations (DFT-GGA-PW91) on Pt(111) and Pt3Re(111) surfaces, reaction kinetics measurements, and microkinetic modeling are employed to study the mechanism of the water–gas shift (WGS) reaction over Pt and Pt–Re catalysts. The values of the reaction rates and reaction orders predicted by the model are in agreement with the ones experimentally determined; the calculated apparent activation energies are matched to within 6% of the experimental values. The primary reaction pathway is predicted to take place through adsorbed carboxyl (COOH) species, whereas formate (HCOO) is predicted to be a spectator species. We conclude that the clean Pt(111) is a good representation of the active site for the WGS reaction on Pt catalysts, whereas the active sites on the Pt–Re alloy catalyst likely contain partially oxidized metal ensembles.

  19. Explaining the atypical reaction profiles of heme enzymes with a novel mechanistic hypothesis and kinetic treatment.

    PubMed

    Manoj, Kelath Murali; Baburaj, Arun; Ephraim, Binoy; Pappachan, Febin; Maviliparambathu, Pravitha Parapurathu; Vijayan, Umesh K; Narayanan, Sivaprasad Valiyaveettil; Periasamy, Kalaiselvi; George, Ebi Ashley; Mathew, Lazar T

    2010-01-01

    Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO) characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP), uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation) of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model) was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the "steady state kinetics" of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates) is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s) affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of "the product of interest" in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of "substrate concentration at maximum observed rate". The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes. PMID:20498847

  20. Kinetic studies of the infrared-induced reaction between atomic chlorine and solid parahydrogen

    NASA Astrophysics Data System (ADS)

    Raston, Paul L.; Kettwich, Sharon C.; Anderson, David T.

    2015-04-01

    We present Fourier-transform infrared (FTIR) spectroscopic studies of the IR-induced Cl + H2(v = 1) → HCl + H reaction in a parahydrogen (pH2) matrix aimed at distinguishing between two proposed reactions mechanisms; direct-IR and vibron-mediated. The Cl atom reactants are produced via 355 nm in situ photolysis of a Cl2 doped pH2 matrix. After photolysis is complete, a long-pass IR filter in the FTIR beam is removed and we measure the ensuing IR-induced reaction kinetics using rapid scan FTIR spectroscopy. We follow both the decay of the Cl atom reactant and growth of the HCl product using the Cl spin-orbit (SO) + Q1(0) and HCl R1(0) transitions, respectively. We show the IR-induced reaction mechanism depends on the spectral profile of the IR radiation; for IR spectral profiles that have significant IR intensities between 4000 and 5000 cm-1 we observe first-order kinetics that are assigned to a vibron-mediated mechanism and for spectral profiles that have significant IR intensities that include the Cl SO + Q1(0) transition near 5094 cm-1 we observe bi-exponential kinetics that are dominated by the direct-IR mechanism at early reaction times. We can distinguish between the two mechanisms using the observed kinetics. We investigate the reaction kinetics for different FTIR optical setups, for a range of sample conditions, and start and stop the IR-induced reaction to investigate the importance of secondary H atom reactions. We also study the IR-induced reaction in Br/Cl co-doped pH2 samples and show the presence of the Br atom quenches the vibron-mediated reaction kinetics presumably because the Br-atoms serve as efficient vibron traps. This paper indicates that in a highly enriched pH2 matrix the H atoms that are produced by the IR-induced Cl atom reaction likely do not play a significant role in the measured reaction kinetics which implies these secondary H atom reactions are highly selective.

  1. Linear matrix inequalities for analysis and control of linear vector second-order systems

    SciTech Connect

    Adegas, Fabiano D.; Stoustrup, Jakob

    2014-10-06

    Many dynamical systems are modeled as vector second-order differential equations. This paper presents analysis and synthesis conditions in terms of LMI with explicit dependence in the coefficient matrices of vector second-order systems. These conditions benefit from the separation between the Lyapunov matrix and the system matrices by introducing matrix multipliers, which potentially reduce conservativeness in hard control problems. Multipliers facilitate the usage of parameter-dependent Lyapunov functions as certificates of stability of uncertain and time-varying vector second-order systems. The conditions introduced in this work have the potential to increase the practice of analyzing and controlling systems directly in vector second-order form.

  2. Simulation of hydrodynamics using large eddy simulation-second-order moment model in circulating fluidized beds

    NASA Astrophysics Data System (ADS)

    Juhui, Chen; Yanjia, Tang; Dan, Li; Pengfei, Xu; Huilin, Lu

    2013-07-01

    Flow behavior of gas and particles is predicted by the large eddy simulation of gas-second order moment of solid model (LES-SOM model) in the simulation of flow behavior in CFB. This study shows that the simulated solid volume fractions along height using a two-dimensional model are in agreement with experiments. The velocity, volume fraction and second-order moments of particles are computed. The second-order moments of clusters are calculated. The solid volume fraction, velocity and second order moments are compared at the three different model constants.

  3. Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

    SciTech Connect

    Creighton, J.R.; Coltrin, M.E.

    1994-03-01

    This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

  4. Kinetics and Mechanism of the Chlorate-Bromide Reaction.

    PubMed

    Sant'Anna, Rafaela T P; Faria, Roberto B

    2015-11-01

    The chlorate-bromide reaction, ClO3(-) + 6Br(-) + 6H(+) → 3Br2 + Cl(-) + 3H2O, was followed at the Br3(-)/Br2 isosbestic point (446 nm). A fifth-order rate law was found: (1)/3 d[Br2]/dt = k[ClO3(-)][Br(-)][H(+)](3) (k = 5.10 × 10(-6) s(-1) L(4) mol(-4)) at 25 °C and I = 2.4 mol L(-1). At high bromide concentrations, the bromide order becomes close to zero, indicating a saturation profile on bromide concentration, similar to the chloride saturation profile observed in the chlorate-chloride reaction. A mechanism is proposed that considers the formation of the intermediate BrOClO2(2-), similar to the intermediate ClOClO2(2-) proposed in the mechanism of the chlorate-chloride reaction. PMID:26467822

  5. Ab initio chemical kinetics for the HCCO + OH reaction

    NASA Astrophysics Data System (ADS)

    Mai, Tam V.-T.; Raghunath, P.; Le, Xuan T.; Huynh, Lam K.; Nam, Pham-Cam; Lin, M. C.

    2014-01-01

    The mechanism for the reaction of HCCO and OH has been investigated at different high-levels of theory. The reaction was found to occur on singlet and triplet potential energy surfaces with multiple accessible paths. Rate constants predicted by variational RRKM/ME calculations show that the reaction on both surfaces occurs primarily by barrierless OH attack at both C atoms producing excited intermediates which fragment to produce predominantly CO and 1,3HCOH with kS = 3.12 × 10-8T-0.59exp[-73.0/T] and kT = 6.29 × 10-11T0.13exp[108/T] cm3 molecule-1 s-1 at T = 300-2000 K, independent of pressure at P < 76 000 Torr.

  6. ACKS2: Atom-condensed Kohn-Sham DFT approximated to second order

    NASA Astrophysics Data System (ADS)

    Verstraelen, T.; Ayers, P. W.; Van Speybroeck, V.; Waroquier, M.

    2013-02-01

    A new polarizable force field (PFF), namely atom-condensed Kohn-Sham density functional theory approximated to second order (ACKS2), is proposed for the efficient computation of atomic charges and linear response properties of extended molecular systems. It is derived from Kohn-Sham density functional theory (KS-DFT), making use of two novel ingredients in the context of PFFs: (i) constrained atomic populations and (ii) the Legendre transform of the Kohn-Sham kinetic energy. ACKS2 is essentially an extension of the Electronegativity Equalization Method (EEM) [W. J. Mortier, S. K. Ghosh, and S. Shankar, J. Am. Chem. Soc. 108, 4315 (1986)], 10.1021/ja00275a013 in which two major EEM shortcomings are fixed: ACKS2 predicts a linear size-dependence of the dipole polarizability in the macroscopic limit and correctly describes the charge distribution when a molecule dissociates. All ACKS2 parameters are defined as atoms-in-molecules expectation values. The implementation of ACKS2 is very similar to that of EEM, with only a small increase in computational cost.

  7. An efficient second-order accurate and continuous interpolation for block-adaptive grids

    NASA Astrophysics Data System (ADS)

    Borovikov, Dmitry; Sokolov, Igor V.; Tóth, Gábor

    2015-09-01

    In this paper we present a second-order and continuous interpolation algorithm for cell-centered adaptive-mesh-refinement (AMR) grids. Continuity requirement poses a non-trivial problem at resolution changes. We develop a classification of the resolution changes, which allows us to employ efficient and simple linear interpolation in the majority of the computational domain. The algorithm is well suited for massively parallel computations. Our interpolation algorithm allows extracting jump-free interpolated data distribution along lines and surfaces within the computational domain. This capability is important for various applications, including kinetic particles tracking in three dimensional vector fields, visualization (i.e. surface extraction) and extracting variables along one-dimensional curves such as field lines, streamlines and satellite trajectories, etc. Particular examples are models for acceleration of solar energetic particles (SEPs) along magnetic field-lines. As such models are sensitive to sharp gradients and discontinuities the capability to interpolate the data from the AMR grid to be passed to the SEP model without producing false gradients numerically becomes crucial. We provide a complete description of the algorithm and make the code publicly available as a Fortran 90 library.

  8. Kinetic transitions in diffusion-reaction space. II. Geometrical effects

    NASA Astrophysics Data System (ADS)

    Kozak, John J.

    1999-02-01

    We extend the stochastic master equation approach described earlier [J. J. Kozak and R. Davidson, J. Chem. Phys. 101, 6101 (1994)] to examine the influence on reaction efficiency of multipolar correlations between a fixed target molecule and a diffusing coreactant, the latter constrained to move on the surface of a host medium (e.g., a colloidal catalyst or molecular organizate) modeled as a Cartesian shell [Euler characteristic, χ=2]. Our most comprehensive results are for processes involving ion pairs, and we find that there exists a transition between two qualitatively different types of behavior in diffusion-reaction space, viz., a regime where the coreactant's motion is totally correlated with respect to the target ion, and a regime where the coreactant's motion is effectively uncorrelated. This behavior emerges both in the situation where correlations between the ion pair are strictly confined to the surface of the host medium or where correlations can be propagated through the host medium. The effects of system size are also examined and comparisons with diffusion-reaction processes taking place on surfaces characterized by Euler characteristic χ=0 are made. In all cases studied, the most dramatic effects on the reaction efficiency are uncovered in the regime where the Onsager (thermalization) length is comparable to the mean displacement of the coreactant, a conclusion consistent with results reported in earlier work.

  9. Atmospheric Chemistry: Laboratory Studies of Kinetics of Important Reactions.

    NASA Astrophysics Data System (ADS)

    Smith, S. J.

    Available from UMI in association with The British Library. Requires signed TDF. This thesis describes the experiments to measure the rate constants for some reactions of the atmospherically important nitrate radical (NO_3) using the discharge-flow technique. The nitrate radical was monitored by optical absorption at lambda = 662 nm. The reactions of NO_3 with some stable organic and inorganic substrates are reported. The temperature dependences of some of the rate constants have also been determined (298 < T < 523 K). In most cases, computer simulation was used to extract the rate constant for the primary process because the time-dependent behaviour of (NO_3) was affected by secondary reactions of NO_3 with products of the primary interaction. The Arrhenius parameter in parentheses (E _{rm a}/kJ mol^ {-1}, A/cm^3 molecule ^{-1}s^ {-1} respectively) for the following reactions have been determined: ethane (37, 6.7 times 10^{-12}), ethylene (25.8, 6.3 times 10^ {-12}), CH_3OH (21.3, 1.2 times 10^ {-12}), CHCiota_3 (23.4, 8.6 times 10 ^{-13}) and HCl (27.7, 4 times 10^{-12}). The activation energies for the reactions studied between NO_3 and some alkynes are represented well by the value 25 +/- 3 kJ mol^{-1} and the corresponding pre-exponential factors (expressed as ln(10 ^{13}A/cm^3 molecule^{-1}s ^{-1}) are as follows: C_2H_2 (1.6 +/- 1.4), C_3H _4 (5.0 +/- 1.4), 1-C_4H_6 (5.8 +/- 1.0), 1-C_5 H_8 (5.7 +/- 0.6) and 1-C_6H _{10} (4.5 +/- 0.4). Some reactions were studied at room temperature _3(298 +/- 2 K) only and the rate constants found (in units of cm ^3 molecule^{ -1}s^{-1}) are: buta-1,3-diene (1.8 times 10 ^{-13}), isobutene (2.8 times 10^{-13 }), HBr (1.3 times 10 ^{-15}) and hex-2-yne (3.0 times 10^{-14 }). Non-Arrhenius behaviour was found in the reactions of NO_3 with n-butane, isobutane and propene. The empirical variation of these rate constants with temperature is well represented by the three parameter expressions:. k(T) = 1.2 times 10 ^{-46}T^{11

  10. Kinetic study for phenol degradation by ZVI-assisted Fenton reaction and related iron corrosion investigated by X-ray absorption spectroscopy.

    PubMed

    Yoon, In-Ho; Yoo, Gursong; Hong, Hye-Jin; Kim, Jungmin; Kim, Min Gyu; Choi, Wang-Kyu; Yang, Ji-Won

    2016-02-01

    In this study, we investigated phenol degradation via zero-valent iron (ZVI)-assisted Fenton reaction through kinetic and spectroscopic analysis. In batch experiments, 100 mg/L of phenol was completely degraded, and 75% of TOC was removed within 3 min under an optimal hydrogen peroxide (H2O2) concentration (50 mM) via the Fenton reaction. In the absence of H2O2, oxygen (O2) was dissolved into the solution and produced H2O2, which resulted in phenol degradation. However, phenol removal efficiency was not very high compared to external H2O2 input. The Fenton reaction rapidly occurred at the surface of ZVI, and then phenol mobility from the solution to the ZVI surface was the rate determining step of the whole reaction. The pseudo-second order adsorption kinetic model well describes phenol removal, and its rate increased according to the H2O2 concentration. X-ray absorption spectroscopic analysis revealed that iron oxide (Fe-O bonding) was formed on ZVI with [H2O2] > 50 mM. A high concentration of H2O2 led to rapid degradation of phenol and caused corrosion on the ZVI surface, indicating that Fe(2+) ions were rapidly oxidized to Fe(3+) ions due to the Fenton reaction and that Fe(3+) was precipitated as iron oxide on the ZVI surface. However, ZVI did not show corroded characteristics in the absence of H2O2 due to the insufficient ZVI-assisted Fenton reaction and oxidation of Fe(2+) to Fe(3+). PMID:26692518

  11. Oxygen Diffusion and Reaction Kinetics in Continuous Fiber Ceramic Matrix Composites

    NASA Technical Reports Server (NTRS)

    Halbig, Michael C.; Eckel, Andrew J.; Cawley, James D.

    1999-01-01

    Previous stressed oxidation tests of C/SiC composites at elevated temperatures (350 C to 1500 C) and sustained stresses (69 MPa and 172 MPa) have led to the development of a finite difference cracked matrix model. The times to failure in the samples suggest oxidation occurred in two kinetic regimes defined by the rate controlling mechanisms (i.e. diffusion controlled and reaction controlled kinetics). Microstructural analysis revealed preferential oxidation along as-fabricated, matrix microcracks and also suggested two regimes of oxidation kinetics dependent on the oxidation temperature. Based on experimental results, observation, and theory, a finite difference model was developed. The model simulates the diffusion of oxygen into a matrix crack bridged by carbon fibers. The model facilitates the study of the relative importance of temperature, the reaction rate constant, and the diffusion coefficient on the overall oxidation kinetics.

  12. Kinetic characterization of the photosynthetic reaction centres in microalgae by means of fluorescence methodology.

    PubMed

    Gargano, Immacolata; Olivieri, Giuseppe; Spasiano, Danilo; Andreozzi, Roberto; Pollio, Antonino; Marotta, Raffaele; D'Ambrosio, Nicola; Marzocchella, Antonio

    2015-10-20

    The kinetic characterization of the photosynthetic activity in autotrophic microalgae plays a key role in the design of optimized photobioreactors. This paper presents a procedure to assess kinetic parameters of a three-state photosynthetic reaction centres model. Four kinetic parameters of the model were assessed by processing the time-series measurements of pulse-amplitude modulation fluorimetry. The kinetic parameters were assessed for several microalgal strains (Stichococcus bacillaris, Scenedesmus vacuolatus, Chlamydomonas reinhardtii, Chlorella vulgaris) growth in vertical and inclined bubble columns and irradiated by white-light or red/blue light. The procedure was successfully applied to the investigated strains. The assessed parameters allow identifying the irradiance range under which: the photochemical process is controlled by the photons capture; the photoinhibition competes with the photochemical quenching. The analysis of the time-scale of the photosynthetic reaction centres as a function of the irradiance allows interpreting the performances of photobioreactors characterized by non-homogeneous irradiance. PMID:26216180

  13. LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, Krishnan; Bittker, David A.

    1993-01-01

    A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

  14. Kinetics of the reactions of trichlorosilane with alkyl chlorides in the gas phase

    SciTech Connect

    Chernishev, E.A.; Bykovchenko, V.G.; Kisileva, T.S.; Silkina, N.N.

    1987-04-01

    The kinetics of vapor phase reactions of trichlorosilane (TCS) with alkyl chlorides, namely, CCl/sub 4/, HCCl/sub 3/, and H/sub 2/CCl/sub 2/, have been studied. The indicated reactions have been found to be first order with respect to TCS and half-order with respect to alkyl chlorides. The Arrhenius kinetic parameters for these reactions have also been determined. Within the temperature range 400-580/sup 0/C, the reactivity of alkyl chlorides with TCS has been shown to decrease in the order: CCl/sub 4/ > HCCl/sub 3/ > H/sub 2/CCl/sub 2/. A radical chain mechanism, which is assumed to operate in the reactions of TCS with alkyl chlorides, is examined in the case of the reaction of TCS with CCl/sub 4/.

  15. The Gaseous Explosive Reaction : A Study of the Kinetics of Composite Fuels

    NASA Technical Reports Server (NTRS)

    Stevens, F W

    1929-01-01

    This report deals with the results of a series of studies of the kinetics of gaseous explosive reactions where the fuel under observation, instead of being a simple gas, is a known mixture of simple gases. In the practical application of the gaseous explosive reaction as a source of power in the gas engine, the fuels employed are composite, with characteristics that are apt to be due to the characteristics of their components and hence may be somewhat complex. The simplest problem that could be proposed in an investigation either of the thermodynamics or kinetics of the gaseous explosive reaction of a composite fuel would seem to be a separate study of the reaction characteristics of each component of the fuel and then a study of the reaction characteristics of the various known mixtures of those components forming composite fuels more and more complex. (author)

  16. Anomalous kinetics in diffusion limited reactions linked to non-Gaussian concentration probability distribution function.

    PubMed

    de Anna, Pietro; Le Borgne, Tanguy; Dentz, Marco; Bolster, Diogo; Davy, Philippe

    2011-11-01

    We investigate anomalous reaction kinetics related to segregation in the one-dimensional reaction-diffusion system A + B → C. It is well known that spatial fluctuations in the species concentrations cause a breakdown of the mean-field behavior at low concentration values. The scaling of the average concentration with time changes from the mean-field t(-1) to the anomalous t(-1/4) behavior. Using a stochastic modeling approach, the reaction-diffusion system can be fully characterized by the multi-point probability distribution function (PDF) of the species concentrations. Its evolution is governed by a Fokker-Planck equation with moving boundaries, which are determined by the positivity of the species concentrations. The concentration PDF is in general non-Gaussian. As long as the concentration fluctuations are small compared to the mean, the PDF can be approximated by a Gaussian distribution. This behavior breaks down in the fluctuation dominated regime, for which anomalous reaction kinetics are observed. We show that the transition from mean field to anomalous reaction kinetics is intimately linked to the evolution of the concentration PDF from a Gaussian to non-Gaussian shape. This establishes a direct relationship between anomalous reaction kinetics, incomplete mixing and the non-Gaussian nature of the concentration PDF. PMID:22070289

  17. Complex Cure Kinetics of the Hydroxyl-Epoxide Reaction in DGEBA Epoxy Hardened with Diethanolamine

    NASA Astrophysics Data System (ADS)

    Ancipink, Windy; McCoy, John; Kropka, Jamie; Celina, Mathias

    The curing of a diglycidyl ether of bisphenol-A Epoxy (Epon 828) with diethanolamine (DEA) involves a fast amine-epoxide reaction followed by a slower hydroxyl-epoxide reaction. At curing temperatures below 100°C, the time scales of these two reactions are well separated, and the hydroxyl addition can be studied as an ''isolated'' reaction. The hydroxyl-epoxide reaction is of great interest due to the complex kinetics involved, which are brought about by competing reactions. The reaction kinetics are believed to be tertiary amine catalyzed and are well fit to a modified form of the Kamal-type equation. Here we study the complex long term reaction kinetics at various temperatures, by using isothermal modulated differential scanning calorimetry, micro calorimetry, and infrared spectroscopy. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  18. Reaction Mechanism and Kinetics of Enargite Oxidation at Roasting Temperatures

    NASA Astrophysics Data System (ADS)

    Padilla, Rafael; Aracena, Alvaro; Ruiz, Maria C.

    2012-10-01

    Roasting of enargite (Cu3AsS4) in the temperature range of 648 K to 898 K (375 °C to 625 °C) in atmospheres containing variable amounts of oxygen has been studied by thermogravimetric methods. From the experimental results of weight loss/gain data and X-ray diffraction (XRD) analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was determined, which occurred in three sequential stages:

  19. Reaction kinetics of resveratrol with tert-butoxyl radicals

    NASA Astrophysics Data System (ADS)

    Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

    2012-09-01

    The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×108 M-1s-1. This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol.

  20. Operator Factorization and the Solution of Second-Order Linear Ordinary Differential Equations

    ERIC Educational Resources Information Center

    Robin, W.

    2007-01-01

    The theory and application of second-order linear ordinary differential equations is reviewed from the standpoint of the operator factorization approach to the solution of ordinary differential equations (ODE). Using the operator factorization approach, the general second-order linear ODE is solved, exactly, in quadratures and the resulting…

  1. Explanation of Second-Order Asymptotic Theory Via Information Spectrum Method

    NASA Astrophysics Data System (ADS)

    Hayashi, Masahito

    We explain second-order asymptotic theory via the information spectrum method. From a unified viewpoint based on the generality of the information spectrum method, we consider second-order asymptotic theory for use in fixed-length data compression, uniform random number generation, and channel coding. Additionally, we discuss its application to quantum cryptography, folklore in source coding, and security analysis.

  2. Second-order theory of the rotation of an artificial satellite

    NASA Astrophysics Data System (ADS)

    Bois, Eric

    The attitude evolution of the motion of a satellite subjected to specified torques is investigated analytically, extending the theory of Bois (1986) to second order. The formulation and reduction of the second-order differential equations are outlined, and the derivation of the solutions is given in detail. Numerical results for the ESA Hipparcos astrometric satellite are presented in graphs and briefly characterized.

  3. The Second Order Approximation to Sample Influence Curve in Canonical Correlation Analysis.

    ERIC Educational Resources Information Center

    Fung, Wing K.; Gu, Hong

    1998-01-01

    A second order approximation to the sample influence curve (SIC) has been derived in the literature. This paper presents a more accurate second order approximation, which is exact for the SIC of the squared multiple correction coefficient. An example is presented. (SLD)

  4. Simplifying Second-Order Belief Attribution: What Facilitates Children's Performance on Measures of Conceptual Understanding?

    ERIC Educational Resources Information Center

    Coull, Greig J.; Leekam, Susan R.; Bennett, Mark

    2006-01-01

    This study investigated how 4- to 7-year-old children's second-order belief attribution might be facilitated by either reducing information processing or varying the sequence of task questions. In Experiment 1, compared with Perner and Wimmer's (1985) original second-order false-belief task, a new task with reduced information-processing demands…

  5. The similarity rules for second-order subsonic and supersonic flow

    NASA Technical Reports Server (NTRS)

    Van Dyke, Milton D

    1958-01-01

    The similarity rules for linearized compressible flow theory (Gothert's rule and its supersonic counterpart) are extended to second order. It is shown that any second-order subsonic flow can be related to "nearly incompressible" flow past the same body, which can be calculated by the Janzen-Rayleigh method.

  6. On group classification of normal systems of linear second-order ordinary differential equations

    NASA Astrophysics Data System (ADS)

    Meleshko, S. V.; Moyo, S.

    2015-05-01

    In this paper we study the general group classification of systems of linear second-order ordinary differential equations inspired from earlier works and recent results on the group classification of such systems. Some interesting results and subsequent theorem arising from this particular study are discussed here. This paper considers the study of irreducible systems of second-order ordinary differential equations.

  7. Post processing with first- and second-order hidden Markov models

    NASA Astrophysics Data System (ADS)

    Taghva, Kazem; Poudel, Srijana; Malreddy, Spandana

    2013-01-01

    In this paper, we present the implementation and evaluation of first order and second order Hidden Markov Models to identify and correct OCR errors in the post processing of books. Our experiments show that the first order model approximately corrects 10% of the errors with 100% precision, while the second order model corrects a higher percentage of errors with much lower precision.

  8. Teacher's Corner: Testing Measurement Invariance of Second-Order Factor Models

    ERIC Educational Resources Information Center

    Chen, Fang Fang; Sousa, Karen H.; West, Stephen G.

    2005-01-01

    We illustrate testing measurement invariance in a second-order factor model using a quality of life dataset (n = 924). Measurement invariance was tested across 2 groups at a set of hierarchically structured levels: (a) configural invariance, (b) first-order factor loadings, (c) second-order factor loadings, (d) intercepts of measured variables,…

  9. Low Temperature Kinetics of the CH3OH + OH Reaction

    PubMed Central

    Martín, J. C. Gómez; Caravan, R. L.; Blitz, M. A.; Heard, D. E.; Plane, J. M. C.

    2014-01-01

    The rate constant of the reaction between methanol and the hydroxyl radical has been studied in the temperature range 56-202 K by pulsed laser photolysis-laser induced fluorescence in two separate experiments using either a low temperature flow tube coupled to a time of flight mass spectrometer or a pulsed Laval nozzle apparatus. The two independent techniques yield rate constants which are in mutual agreement and consistent with the results reported previously below 82 K [Shannon et al., Nature Chemistry, 2013, 5, 745-749] and above 210 K [Dillon et al., Phys. Chem. Chem. 2005, 7, 349-355], showing a very sharp increase with decreasing temperature with an onset around 180 K. This onset is also signalled by strong chemiluminescence tentatively assigned to formaldehyde, which is consistent with the formation of the methoxy radical at low temperature by quantum tunnelling, and its subsequent reaction with H and OH. Our results add confidence to the previous low temperature rate constant measurements and consolidate the experimental reference dataset for further theoretical work required to describe quantitatively the tunnelling mechanism operating in this reaction. An additional measurement of the rate constant at 56 K yielded a value of (4.9 ± 0.8) × 10−11 cm3 molecule−1 s−1 (2σ), showing that the rate constant is increasing less rapidly at temperatures below 70 K. PMID:24669816

  10. Kinetics of the reaction of nitric oxide with hydrogen

    NASA Technical Reports Server (NTRS)

    Flower, W. L.; Hanson, R. K.; Kruger, C. H.

    1975-01-01

    The reaction of nitric oxide with hydrogen has been studied in the temperature range 2400-4500 K using a shock-tube technique. Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principal result of the study was the determination of the rate constant k1 for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k1 were obtained for each test through comparisons of measured and numerically predicted NO profiles. The data are fit closely by the expression k1 = 1.34 times 10 to the fourteenth power exp(-49 200/RT) cu cm/mole-sec. These data appear to be the first available for this rate constant.

  11. Kinetic of antigent-antibody reactions with scattering method

    NASA Astrophysics Data System (ADS)

    Bilyi, Olexander I.; Kiselyov, Yevgen M.; Novikov, Volodymyr P.

    2001-07-01

    The immune reactions of interaction antigen-antibody represent specific effect of an antigene with an antibody, which outcome are the complex immune aggregates forming precipitate in case of a soluble antigene, or agglutinate in case of a corpuscular antigene. Immunological methods which uses in the quality of carrier protein latex's polymeric microspheresis, gained name and method latex agglutination. Polymeric microspheresis have the array of advantages before biological carries, which consist in the opportunity of the variation of attributes surface and size microspheresis in the broad band of meanings with the preservation of narrow distribution particles behind measurements, the putting of functional groups, necessary for bunch with ligand on stage their synthesis, in ragidity at storage. The quantitative evaluation of parameters of a response of interaction antigen-antibody in immunology is possible by optical methods on a measurement of a modification of intensity of a light stream of a solution in an outcome of a course of a reaction. Concentration of immune complexes determine both on slacking a taking place stream of light, and on a modification of intensity of a stream of light scattering suspended particles in a solution. The process light scattering by colloidal aggregates are formed from suspension microspheresis with adsorbed on their surface protein is described. In report the physics principle of registration immune reaction by light scattering methods is concerned. The results of the effectiveness latex's preparation created on basis of the polymeric carries is described.

  12. Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system.

    PubMed

    Kocadağlı, Tolgahan; Gökmen, Vural

    2016-11-15

    The study describes the kinetics of the formation and degradation of α-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants. PMID:27283710

  13. Explaining the Atypical Reaction Profiles of Heme Enzymes with a Novel Mechanistic Hypothesis and Kinetic Treatment

    PubMed Central

    Manoj, Kelath Murali; Baburaj, Arun; Ephraim, Binoy; Pappachan, Febin; Maviliparambathu, Pravitha Parapurathu; Vijayan, Umesh K.; Narayanan, Sivaprasad Valiyaveettil; Periasamy, Kalaiselvi; George, Ebi Ashley; Mathew, Lazar T.

    2010-01-01

    Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO) characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP), uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation) of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model) was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the “steady state kinetics” of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates) is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s) affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of “the product of interest” in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of “substrate concentration at maximum observed rate”. The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes. PMID:20498847

  14. Second order gravitational effects on CMB temperature anisotropy in {lambda} dominated flat universes

    SciTech Connect

    Tomita, Kenji; Inoue, Kaiki Taro

    2008-05-15

    We study second order gravitational effects of local inhomogeneities on the cosmic microwave background radiation in flat universes with matter and a cosmological constant {lambda}. We find that the general relativistic correction to the Newtonian approximation is negligible at second order provided that the size of the inhomogeneous region is sufficiently smaller than the horizon scale. For a spherically symmetric top-hat type quasilinear perturbation, the first order temperature fluctuation corresponding to the linear integrated Sachs-Wolfe effect is enhanced (suppressed) by the second order one for a compensated void (lump). As a function of redshift of the local inhomogeneity, the second order temperature fluctuations due to evolution of the gravitational potential have a peak before the matter-{lambda} equality epoch for a fixed comoving size and a density contrast. The second order gravitational effects from local quasilinear inhomogeneities at a redshift z{approx}1 may significantly affect the cosmic microwave background.

  15. Effects of Second-Order Hydrodynamics on a Semisubmersible Floating Offshore Wind Turbine: Preprint

    SciTech Connect

    Bayati, I.; Jonkman, J.; Robertson, A.; Platt, A.

    2014-07-01

    The objective of this paper is to assess the second-order hydrodynamic effects on a semisubmersible floating offshore wind turbine. Second-order hydrodynamics induce loads and motions at the sum- and difference-frequencies of the incident waves. These effects have often been ignored in offshore wind analysis, under the assumption that they are significantly smaller than first-order effects. The sum- and difference-frequency loads can, however, excite eigenfrequencies of the system, leading to large oscillations that strain the mooring system or vibrations that cause fatigue damage to the structure. Observations of supposed second-order responses in wave-tank tests performed by the DeepCwind consortium at the MARIN offshore basin suggest that these effects might be more important than originally expected. These observations inspired interest in investigating how second-order excitation affects floating offshore wind turbines and whether second-order hydrodynamics should be included in offshore wind simulation tools like FAST in the future. In this work, the effects of second-order hydrodynamics on a floating semisubmersible offshore wind turbine are investigated. Because FAST is currently unable to account for second-order effects, a method to assess these effects was applied in which linearized properties of the floating wind system derived from FAST (including the 6x6 mass and stiffness matrices) are used by WAMIT to solve the first- and second-order hydrodynamics problems in the frequency domain. The method has been applied to the OC4-DeepCwind semisubmersible platform, supporting the NREL 5-MW baseline wind turbine. The loads and response of the system due to the second-order hydrodynamics are analysed and compared to first-order hydrodynamic loads and induced motions in the frequency domain. Further, the second-order loads and induced response data are compared to the loads and motions induced by aerodynamic loading as solved by FAST.

  16. The kinetics of electron transfer reaction of methylene green and titanium trichloride in different solvents

    NASA Astrophysics Data System (ADS)

    Saeed, Rehana; Nadeem, Syed Muhammad Saqib

    2016-06-01

    The kinetics of the electron transfer reaction of methylene green and titanium trichloride was investigated in different solvents by spectrophotometry at different temperatures. The the reaction rate was determined by monitoring the absorbance as a function of time at λmax 655 nm. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at a fixed concentration of methylene green. The effect of an aqueous alcoholic solvent was studied in the acidic range of pH from 4 to 7. It was observed that the reaction rate increased with an increase in polarity of the reaction medium. The the reaction rate was high in acidic conditions and decreased with a further increase in acidity. The increase in temperature increased the rate of the electron transfer reaction of methylene green and titanium trichloride. The activation energy ( E a) was calculated by the Arrhenius relation. The absence of any reaction intermediate was confirmed by spectroscopic and kinetic investigations. A plausible mechanism for the reaction in line with outer-sphere reaction pathway has been proposed. Thermodynamic parameters such as the activation energy ( E a), enthalpy change (Δ H), free energy change (Δ G), and entropy change (Δ S) were also evaluated

  17. Reaction kinetics and product distributions in photoelectrochemical cells

    SciTech Connect

    Koval, C.A.

    1992-01-01

    Hot electron reaction studies at p-InP/CH[sub 3]CN interface revealed essential/desirable features for redox systems used to investigate hot carriers in photoelectrocehmical cells. Reduction of dibromoethylbenzene (DBEB) in presence of metallocene couples is being studied using rotating rink disk electrodes of n-and p-InP disks and Pt rings. At highly doped p-InP electrodes, reduction of DBEB can be very efficient (>30%). A minielectrochemical cell was used to investigate electron transfer at nonilluminated n-WSe[sub 2]/dimethylferrocene[sup +/0] interfaces.

  18. Characterization of reaction kinetics in a porous electrode

    NASA Technical Reports Server (NTRS)

    Fedkiw, Peter S.

    1990-01-01

    A continuum-model approach, analogous to porous electrode theory, was applied to a thin-layer cell of rectangular and cylindrical geometry. A reversible redox couple is assumed, and the local reaction current density is related to the potential through the formula of Hubbard and Anson for a uniformily accessible thin-layer cell. The placement of the reference electrode is also accounted for in the analysis. Primary emphasis is placed on the effect of the solution-phase ohmic potential drop on the voltammogram characteristics. Correlation equations for the peak-potential displacement from E(sup 0 prime) and the peak current are presented in terms of two dimensionless parameters.

  19. Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.

    PubMed

    Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C

    2013-02-01

    The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⁻¹s⁻¹ and k(1,DiOxY) = 154 ± 76 M⁻¹s⁻¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10⁶ M⁻¹s⁻¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10⁵ M⁻¹s⁻¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⁻¹s⁻¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent

  20. Kinetics of the reaction Cl + NO2 + M

    NASA Technical Reports Server (NTRS)

    Leu, M.-T.

    1984-01-01

    Using atomic chlorine resonance fluorescence at 140 nm to detect the decay of atomic chlorine in the presence of an excess of NO2, the rate constant for the reaction Cl + NO2 + M, where M is the total gas concentration, is measured over the temperature range 264 to 417 K and at a pressure 1 to 7 torr in a discharge flow system. The rate constants for M= He and M= N2 are measured and the results are summarized in a table. The systematic error of the rate constants is estimated to be about 15 percent. A static photolysis system coupled with an FTIR spectrophotometer is used to determine the branching ratio for the formation of two possible isomers. The ratio is concluded to be ClONO (greater than or equal 75 percent) and ClNO2 (less than or equal 25 percent) which is in agreement with the results of Niki et al. (1978).

  1. Low pressure UV/H2O2 treatment for the degradation of the pesticides metaldehyde, clopyralid and mecoprop - Kinetics and reaction product formation.

    PubMed

    Semitsoglou-Tsiapou, Sofia; Templeton, Michael R; Graham, Nigel J D; Hernández Leal, Lucía; Martijn, Bram J; Royce, Alan; Kruithof, Joop C

    2016-03-15

    The degradation kinetics of three pesticides - metaldehyde, clopyralid and mecoprop - by ultraviolet photolysis and hydroxyl radical oxidation by low pressure ultraviolet hydrogen peroxide (LP-UV/H2O2) advanced oxidation was determined. Mecoprop was susceptible to both LP-UV photolysis and hydroxyl radical oxidation, and exhibited the fastest degradation kinetics, achieving 99.6% (2.4-log) degradation with a UV fluence of 800 mJ/cm(2) and 5 mg/L hydrogen peroxide. Metaldehyde was poorly degraded by LP-UV photolysis while 97.7% (1.6-log) degradation was achieved with LP-UV/H2O2 treatment at the maximum tested UV fluence of 1000 mJ/cm(2) and 15 mg/L hydrogen peroxide. Clopyralid was hardly susceptible to LP-UV photolysis and exhibited the lowest degradation by LP-UV/H2O2 among the three pesticides. The second-order reaction rate constants for the reactions between the pesticides and OH-radicals were calculated applying a kinetic model for LP-UV/H2O2 treatment to be 3.6 × 10(8), 2.0 × 10(8) and 1.1 × 10(9) M(-1) s(-1) for metaldehyde, clopyralid and mecoprop, respectively. The main LP-UV photolysis reaction product from mecoprop was 2-(4-hydroxy-2-methylphenoxy) propanoic acid, while photo-oxidation by LP-UV/H2O2 treatment formed several oxidation products. The photo-oxidation of clopyralid involved either hydroxylation or dechlorination of the ring, while metaldehyde underwent hydroxylation and produced acetic acid as a major end product. Based on the findings, degradation pathways for the three pesticides by LP-UV/H2O2 treatment were proposed. PMID:26803264

  2. Theoretical study of the kinetics of reactions of the monohalogenated methanes with atomic chlorine.

    PubMed

    Brudnik, Katarzyna; Twarda, Maria; Sarzyński, Dariusz; Jodkowski, Jerzy T

    2013-04-01

    Ab initio calculations at the G2 level were used in a theoretical description of the kinetics and mechanism of the hydrogen abstraction reactions from fluoro-, chloro- and bromomethane by chlorine atoms. The profiles of the potential energy surfaces show that mechanism of the reactions under investigation is complex and consists of two - in the case of CH3F+Cl - and of three elementary steps for CH3Cl+Cl and CH3Br+Cl. The heights of the energy barrier related to the H-abstraction are of 8-10 kJ mol(-1), the lowest value corresponds to CH3Cl+Cl and the highest one to CH3F+Cl. The rate constants were calculated using the theoretical method based on the RRKM theory and the simplified version of the statistical adiabatic channel model. The kinetic equations derived in this study[Formula: see text]and[Formula: see text]allow a description of the kinetics of the reactions under investigation in the temperature range of 200-3000 K. The kinetics of reactions of the entirely deuterated reactants were also included in the kinetic analysis. Results of ab initio calculations show that D-abstraction process is related with the energy barrier of 5 kJ mol(-1) higher than the H-abstraction from the corresponding non-deuterated reactant molecule. The derived analytical equations for the reactions, CD3X+Cl, CH2X+HCl and CD2X+DCl (X = F, Cl and Br) are a substantial supplement of the kinetic data necessary for the description and modeling of the processes of importance in the atmospheric chemistry. PMID:23239396

  3. a Second-Order Closure Prediction of Premixed Turbulent Combustion in Jets

    NASA Astrophysics Data System (ADS)

    Dave, Nikhil

    1985-12-01

    This thesis is a report on work carried out and results obtained in the prediction of a turbulent flow of premixed combustible gases discharging from a pipe and developing into a turbulent, combusting roundjet. The expressions for the chemical reaction rate term and other unclosed terms in the Favre averaged turbulent transport equations at the level of second-order closure are based on the Bray-Moss-Libby aerothermochemistry for premixed turbulent combustion, extended to variable enthalpy systems as in Bray, Champion, Dave, Libby (referenced herein). The numerical technique used is a parabolic solver developed by Kollmann from the GENMIX program due to Patankar and Spalding. Various test cases such as constant density and variable density jets are calculated using the program and the results are compared herein with experimentally observed values. Results for premixed turbulent combusting jets are compared with experimental data of Yoshida and of Shepherd and Moss. Buoyancy is found to play an important role in the behavior of these primixed combusting jets. Reasonable numerical agreement is obtained with the results of Yoshida, and good qualitative agreement is obtained with the data of Shepherd and Moss. Reasons for the discrepancies and limitations of the numerical simulation are discussed.

  4. In unison: First- and second-order information combine for integration of shape information.

    PubMed

    Tan, Ken W S; Dickinson, J Edwin; Badcock, David R

    2016-09-01

    The modulation of orientation around radial frequency (RF) patterns and RF textures is globally processed in both cases. This psychophysical study investigates whether the combination-a textured RF path obtained by applying an RF texture to an RF contour-is processed like a texture or a contour when making judgements about shape. Unlike RF textures, the impression of a closed flow was not required for global integration of textured RF paths, suggesting that these paths were processed as second-order, or contrast-defined contours. Luminance-defined (LD) RF paths were shown to globally integrate but with thresholds approximately half of those for the proposed second-order textured paths. The next experiment investigated whether this benefit was due to LD stimuli possessing double the amount of information (first- and second-order information). A mixed three-part contour composed of two different second-order texture components and an LD component was then employed to determine how the different cues combined. The mixed path thresholds matched predictions derived from a linear combination of first- and second-order cues. The conclusion is that the shape of isolated contours is processed using both first- and second-order information equally and that the contribution of texture is to carry additional second-order signal. PMID:27618513

  5. Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.

    1997-01-01

    The purpose of this project was to experimentally measure the rates of several thermochemical gas-solid reactions between sulfur gases in the Venus atmosphere and reactive minerals on the hot Venus surface. Despite the great importance of these reactions for the maintenance of significant amounts of sulfur gases (and thus for the maintenance of the global cloud cover) in the atmosphere of Venus, essentially no kinetic data are currently available for them.

  6. Kinetics and reaction mechanism of iodination of diolefins with a bycyclo (3. 3. 1) nonane structure

    SciTech Connect

    Serguchev, Y.A.; Barabash, V.B.; Khotkevich, A.B.; Krasutskii, P.A.; Yurchenko, A.G.

    1985-05-01

    To investigate the kinetics and reaction mechanism of iodination of diolefins with a bycyclo (3.3.1) nonane structure, the authors perform spectrophotometric analysis. They conclude that the transannular addition of iodine to these compounds in slightly polar and nonpolar media proceeds with the participation of donor-acceptor compounds of different composition. The charge separation in the intermediate complex, directly proceding the transitional state, should reach a minimal value necessary and sufficient for the effective intermolecular nucleophilic stage of the reaction.

  7. Studies of Reaction Kinetics of Methane Hydrate Dissocation in Porous Media

    SciTech Connect

    Moridis, George J.; Seol, Yongkoo; Kneafsey, Timothy J.

    2005-03-10

    The objective of this study is the description of the kinetic dissociation of CH4-hydrates in porous media, and the determination of the corresponding kinetic parameters. Knowledge of the kinetic dissociation behavior of hydrates can play a critical role in the evaluation of gas production potential of gas hydrate accumulations in geologic media. We analyzed data from a sequence of tests of CH4-hydrate dissociation by means of thermal stimulation. These tests had been conducted on sand cores partially saturated with water, hydrate and CH4 gas, and contained in an x-ray-transparent aluminum pressure vessel. The pressure, volume of released gas, and temperature (at several locations within the cores) were measured. To avoid misinterpreting local changes as global processes, x-ray computed tomography scans provided accurate images of the location and movement of the reaction interface during the course of the experiments. Analysis of the data by means of inverse modeling (history matching ) provided estimates of the thermal properties and of the kinetic parameters of the hydration reaction in porous media. Comparison of the results from the hydrate-bearing porous media cores to those from pure CH4-hydrate samples provided a measure of the effect of the porous medium on the kinetic reaction. A tentative model of composite thermal conductivity of hydrate-bearing media was also developed.

  8. Kinetics of Single-Enzyme Reactions on Vesicles: Role of Substrate Aggregation

    NASA Astrophysics Data System (ADS)

    Zhdanov, Vladimir P.

    2015-03-01

    Enzymatic reactions occurring in vivo on lipid membranes can be influenced by various factors including macromolecular crowding in general and substrate aggregation in particular. In academic studies, the role of these factors can experimentally be clarified by tracking single-enzyme kinetics occurring on individual lipid vesicles. To extend the conceptual basis for such experiments, we analyze herein the corresponding kinetics mathematically with emphasis on the role of substrate aggregation. In general, the aggregation may occur on different length scales. Small aggregates may e.g. contain a few proteins or peptides while large aggregates may be mesoscopic as in the case of lipid domains which can be formed in the membranes composed of different lipids. We present a kinetic model describing comprehensively the effect of aggregation of the former type on the dependence of the reaction rate on substrate membrane concentration. The results obtained with physically reasonable parameters indicate that the aggregation-related deviations from the conventional Michaelis-Menten kinetics may be appreciable. Special Issue Comments: This theoretical article is focused on single-enzyme reactions occurring in parallel with substrate aggregation on individual vesicles. This subject is related to a few Special Issue articles concerning enzyme dynamics6,7 and function8 and mathematical aspects of stochastic kinetics.9

  9. Kinetic Modeling and Fitting Software for Inter-connected Reaction Schemes: VisKin

    PubMed Central

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

    2007-01-01

    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. In order to determine rate constants from experimental data, fitting algorithms using the Levenberg-Marquardt algorithm or using Broyden-Fletcher-Goldfarb-Shanno (BFGS) methods were implemented that adjust rate constants to fit the model to imported data. 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. PMID:17207764

  10. 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. PMID:17207764

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

    SciTech Connect

    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 free and open source PyNE library. (authors)

  12. First and Second Order Necessary Conditions for Stochastic Optimal Control Problems

    SciTech Connect

    Bonnans, J. Frederic; Silva, Francisco J.

    2012-06-15

    In this work we consider a stochastic optimal control problem with either convex control constraints or finitely many equality and inequality constraints over the final state. Using the variational approach, we are able to obtain first and second order expansions for the state and cost function, around a local minimum. This fact allows us to prove general first order necessary condition and, under a geometrical assumption over the constraint set, second order necessary conditions are also established. We end by giving second order optimality conditions for problems with constraints on expectations of the final state.

  13. Orientation-selective adaptation to first- and second-order patterns in human visual cortex

    PubMed Central

    Larsson, Jonas; Landy, Michael S.; Heeger, David J.

    2006-01-01

    Second-order textures – patterns that cannot be detected by mechanisms sensitive only to luminance changes – are ubiquitous in visual scenes, but the neuronal mechanisms mediating perception of such stimuli are not well understood. We used an adaptation protocol to measure neural activity in the human brain selective for the orientation of second-order textures. FMRI responses were measured in three subjects to presentations of first- and second-order probe gratings after adapting to a high-contrast first- or second-order grating that was either parallel or orthogonal to the probe gratings. First-order (LM) stimuli were generated by modulating the stimulus luminance. Second-order stimuli were generated by modulating the contrast (CM) or orientation (OM) of a first-order carrier. We used four combinations of adapter and probe stimuli: LM:LM, CM:CM, OM:OM, and LM:OM. The fourth condition tested for cross-modal adaptation with first-order adapter and second-order probe stimuli. Attention was diverted from the stimulus by a demanding task at fixation. Both first- and second-order stimuli elicited orientation-selective adaptation in multiple cortical visual areas, including V1, V2, V3, V3A/B, a newly identified visual area anterior to dorsal V3 which we have termed LO1, hV4, and VO1. For first-order stimuli (condition LM:LM), the adaptation was no larger in extrastriate areas than in V1, implying that the orientation-selective first-order (luminance) adaptation originated in V1. For second-order stimuli (conditions CM:CM and OM:OM), the magnitude of adaptation, relative to the absolute response magnitude, was significantly larger in VO1 (and for condition CM:CM, also in V3A/B and LO1) than in V1, suggesting that second-order stimulus orientation was extracted by additional processing after V1. There was little difference in the amplitude of adaptation between the second-order conditions. No consistent effect of adaptation was found in the cross-modal condition LM

  14. Second order finite volume scheme for Maxwell's equations with discontinuous electromagnetic properties on unstructured meshes

    SciTech Connect

    Ismagilov, Timur Z.

    2015-02-01

    This paper presents a second order finite volume scheme for numerical solution of Maxwell's equations with discontinuous dielectric permittivity and magnetic permeability on unstructured meshes. The scheme is based on Godunov scheme and employs approaches of Van Leer and Lax–Wendroff to increase the order of approximation. To keep the second order of approximation near dielectric permittivity and magnetic permeability discontinuities a novel technique for gradient calculation and limitation is applied near discontinuities. Results of test computations for problems with linear and curvilinear discontinuities confirm second order of approximation. The scheme was applied to modelling propagation of electromagnetic waves inside photonic crystal waveguides with a bend.

  15. The making of an Alfvenic fluctuation: The resolution of a second-order analysis

    NASA Technical Reports Server (NTRS)

    Vasquez, Bernard J.; Hollweg, Joseph V.

    1995-01-01

    Ulysses observations of the high speed polar streams show that they are largely occupied by very large amplitude Alfvenic fluctuations accompanied by many rotational discontinuities. These fluctuations have a nearly constant magnetic intensity or amplitude, and the magnetic field direction per wave cycle sweeps only through a limited arc, much as a car wiperblade would do. Barnes and Hollweg (JGR, 79, 2302, 1974) suggested that this unusual waveform could arise from an obliquely propagating and linearly polarized Alfven wave of finite amplitude. From a second-order analysis, they showed that the existence of a particular solution with a constant amplitude but could not resolve the outcome of the homogeneous solution which consisted of fast waves. They suggested that Landau damping of these fast waves may be needed to get the observed waveform. We present a 1 1/2 D hybrid simulation which is fully nonlinear and correctly describes the ion kinetics for an initially monochromatic and linearly polarized Alfven wave propagating obliquely to the background magnetic field. The wave has a large amplitude and a wavelength so long that it can be considered dispersionless for simulation times. At early times, the second harmonic in density and in magnetic field transverse to the initial wave magnetic field are generated and have more power than other harmonics. Steepening is observed with a weak fast shock emerging, but no rotational discontinuity is left behind, and instead a constant amplitude and an arc-shaped waveform is made. The compressional component which develops after the shocks have dissipated is to zeroth order better described as a pure acoustic wave than as a fast wave. This might be explained by the relaxing of the Alfven wave to a state where its ponderomotive force vanishes so that the compressional component can travel almost independently of it.

  16. Excluded volume effects on the intrachain reaction kinetics.

    PubMed

    Kim, Ji-Hyun; Lee, Woojin; Sung, Jaeyoung; Lee, Sangyoub

    2008-05-15

    On the basis of the recently developed optimized Rouse-Zimm theory of chain polymers with excluded volume interactions, we calculate the long-time first-order rate constant k(1) for end-to-end cyclization of linear chain polymers. We first find that the optimized Rouse-Zimm theory provides the longest chain relaxation times tau(1) of excluded volume chains that are in excellent agreement with the available Brownian dynamics simulation results. In the free-draining limit, the cyclization rate is diffusion-controlled and k(1) is inversely proportional to tau(1), and the k(1) values calculated using the Wilemski-Fixman rate theory are in good agreement with Brownian dynamics simulation results. However, when hydrodynamic interactions are included, noticeable deviations are found. The main sources of errors are fluctuating hydrodynamic interaction and correlation hole effects as well as the non-Markovian reaction dynamic effect. The physical natures of these factors are discussed, and estimates for the magnitudes of required corrections are given. When the corrections are included, the present theory allows the prediction of accurate k(1) values for the cyclization of finite-length chains in good solvents as well as the correct scaling exponent in the long-chain limit. PMID:18419166

  17. Thermodynamics and kinetics of reactions in protective coating systems

    NASA Technical Reports Server (NTRS)

    Gupta, B.; Sarkhel, A.; Sivakumar, R.; Seigle, L.

    1974-01-01

    Investigations of fluoride activated packs with Al:Ni ratios greater than 50 a/o prove that the specimen surface is not in equilibrium with the pack at high Al:Ni ratios but that an activity gradient exists between pack and specimen. Therefore, gaseous diffusion and possibly surface reactions play a role in determining the overall rate of Al deposition in such packs. Noticeable differences in coating behavior have been obtained in packs activated with chloride and iodide, and it appears that poorest results are obtained with iodides, better with chlorides, and best with fluorides. A numerical method has been perfected for calculating rates of solid-state diffusion controlled coating formation, allowing for the variation of diffusivity with composition in the NiAl phase. Layer growth rates can now be accurately predicted from a knowledge of the surface and substrate compositions. Furthermore, the correct diffusion profiles are obtained by this method. These differ substantially from the profile obtained when the diffusivity is assumed constant.

  18. Employing Magnetic Levitation to Monitor Reaction Kinetics and Measure Activation Energy

    ERIC Educational Resources Information Center

    Benz, Lauren; Cesafsky, Karen E.; Le, Tran; Park, Aileen; Malicky, David

    2012-01-01

    This article describes a simple and inexpensive undergraduate-level kinetics experiment that uses magnetic levitation to monitor the progress and determine the activation energy of a condensation reaction on a polymeric solid support. The method employs a cuvette filled with a paramagnetic solution positioned between two strong magnets. The…

  19. Pulsed laser photolysis kinetics study of the O(3P) + ClO reaction

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Wine, P. H.; Ravishankara, A. R.

    1988-01-01

    A pulsed laser photolysis technique was used to investigate the kinetics of the important stratospheric reaction O + ClO yields Cl + O2 in buffer gas over the temperature and pressure ranges of 231-367 K and 25-500 torr. The results indicate a lack of pressure dependence at 298 K over the 25-500 torr range.

  20. Stereochemically Rich Polycyclic Amines from the Kinetic Resolution of Indolines through Intramolecular Povarov Reactions.

    PubMed

    Min, Chang; Seidel, Daniel

    2016-07-25

    Under control of a chiral Brønsted acid catalyst, racemic indolines undergo intramolecular Povarov reactions with achiral aromatic aldehydes bearing a pendent dienophile. One enantiomer of the indoline reacts preferentially, resulting in the highly enantio- and diastereoselective formation of polycyclic heterocycles with four stereogenic centers. This kinetic resolution approach exploits the differential formation/reactivity of diastereomeric ion pairs. PMID:27346876

  1. Interfacial reaction kinetics of coated SiC fibers with various titanium alloys

    NASA Technical Reports Server (NTRS)

    Gundel, D. B.; Wawner, F. E.

    1991-01-01

    The kinetics of the reaction between the silicon carbide fibers and the titanium-based alloy matrix was investigated at temperatures from 800 to 1000 C for several titanium-based alloys (including Ti-1100 alloy and BETA 21S) and unalloyed Ti, reinforced with coated silicon carbide fiber SCS-6. The reaction zone growth kinetics was studied by exposing vacuum encapsulated samples to temperatures from 700 to 1000 C for times up to 150 hrs, followed by SAM observations of samples which were polished perpendicular to the fiber axis and etched. It was found that the reaction zone growth kinetics of the alpha (hcp) and beta (bcc) phases of unalloyed titanium reacting with SCS-6 fibers exhibited different values of the apparent activation energy and of the preexponential factor. Additions of other metals to Ti was found to slow down the reaction kinetics. Among the alloys studied, the Ti-1100 was the slowest reacting conventional alloy and the Ti-14Al-21Nb (in wt pct) was the slowest overall.

  2. An Inexpensive Kinetic Study: The Reaction of FD&C Red #3 (Erythrosin B) with Hypochlorite

    ERIC Educational Resources Information Center

    Henary, Maher M.; Russell, Arlene A.

    2007-01-01

    Kinetics constitutes a core topic in both the lecture and laboratory components of lower- level chemistry courses. While textbook examples can ignore issues of time, temperature and safety, the laboratory can not. Reactions must occur slowly enough to be detected by students, occur rapidly enough for data collection in the few hours assigned to a…

  3. Studies of NO-char reaction kinetics obtained from drop-tube furnace and thermogravimetric experiments

    SciTech Connect

    Shaozeng Sun; Juwei Zhang; Xidong Hu; Shaohua Wu; Jiancheng Yang; Yang Wang; Yukun Qin

    2009-01-15

    Four coal chars were prepared in a flat flame flow reactor (FFR), which can simulate the temperature and gas composition of a real pulverized coal combustion environment. The pore structure of chars was measured by mercury porosimetry and nitrogen adsorption, and the Hg and Brunauer-Emmett-Teller (BET) surface areas were obtained. The kinetics of NO-char was studied in a drop-tube furnace (DTF) and thermogravimetric analyzer (TGA). In the TGA experiments, the random pore model (RPM) was applied to describe the NO-char reactions and obtain the intrinsic kinetics. By presenting the data of DTF and TGA experiments on the same Arrhenius plot, it can be concluded that TGA is an available tool to study the kinetics of a high-temperature NO-char reaction. With respect to the DTF experiments, in comparison to the BET surface area, the Hg surface area is a better basis for normalizing the reactivity of different coal chars because of less scatter in the measured values, better agreement with TGA experimental data, and more stable values during the process of reaction. Moreover, by comparing the Hg surface area of chars before and after reactions, it is believed that the Hg surface area basis is more appropriate for high-rank coal chars. The determined kinetic rate constants are in good agreement with other data in the literature, and a new rate constant expression is proposed. 30 refs., 8 figs., 7 tabs.

  4. A Molecular Reaction Cycle with a Solvatochromic Merocyanine Dye: An Experiment in Photochemistry, Kinetics, and Catalysis.

    ERIC Educational Resources Information Center

    Abdel-Kader, M. H.; Steiner, U.

    1983-01-01

    Three experiments using merocyanine M suitable as an integrated laboratory experience for undergraduates are described. Experiments demonstrate: complete molecular cycle composed of photochemical, thermal, and protolytic reaction steps; kinetics of cis-trans isomerization of the dye; and mechanism of base catalysis for thermal isomerization of the…

  5. Marcus Theory: Thermodynamics CAN Control the Kinetics of Electron Transfer Reactions

    ERIC Educational Resources Information Center

    Silverstein, Todd P.

    2012-01-01

    Although it is generally true that thermodynamics do not influence kinetics, this is NOT the case for electron transfer reactions in solution. Marcus Theory explains why this is so, using straightforward physical chemical principles such as transition state theory, Arrhenius' Law, and the Franck-Condon Principle. Here the background and…

  6. Kinetic evaluation of the Na-K pump reaction mechanism.

    PubMed Central

    Sachs, J R

    1977-01-01

    1. The ouabain-sensitive K influx was measured at varying external K concentrations ([K]o) and at several fixed internal Na concentrations ([Na]c). The cells were nominally K-free and the solutions Na-free. Both the apparent maximal velocity (VM) and the apparent Michaelis constant for K (KK) increased as Nac increased. The ratio app. VM/app. KK increased with increasing Nac. 2. The ouabain-sensitive Cs influx was measured at varying external Cs concentrations and at several fixed Nac in K-free cells and Na-free solutions. Both app. VM and app. Kcs increased as Nac increased and the ratio app. VM/app. Kcs increased with increasing Nac. 3. The data were evaluated in terms of ping-pong model and a simultaneous model for the pump reaction mechanism. The simultaneous model described the data adequately and the ping-pong models did not. 4. The K influx was measured at varying external K concentrations in solutions containing Na and at a low and high Nac; the cells contained K. The relation between the pump rate and the external K concentration was sigmoid. A Hill equation was fitted to the data. KK was higher in the high Nac cells, but the Hill coefficient (n) was not altered as Nac increased. 5. The K influx was measured at varying internal Na concentrations and two fixed external K concentrations; the cells contained K. The relation between the pump rate and Nac was sigmoid. When a Hill equation was fitted to the data, it was found that KNac was higher at the high external K concentration, but n was the same at both K concentrations. PMID:599454

  7. Macroscopic Kinetic Effect of Cell-to-Cell Variation in Biochemical Reactions

    NASA Astrophysics Data System (ADS)

    Kim, Pan-Jun; Price, Nathan D.

    2010-04-01

    Genetically identical cells under the same environmental conditions can show strong variations in protein copy numbers due to inherently stochastic events in individual cells. We here develop a theoretical framework to address how variations in enzyme abundance affect the collective kinetics of metabolic reactions observed within a population of cells. Kinetic parameters measured at the cell population level are shown to be systematically deviated from those of single cells, even within populations of homogeneous parameters. Because of these considerations, Michaelis-Menten kinetics can even be inappropriate to apply at the population level. Our findings elucidate a novel origin of discrepancy between in vivo and in vitro kinetics, and offer potential utility for analysis of single-cell metabolomic data.

  8. A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction

    NASA Technical Reports Server (NTRS)

    Lian, Yongsheng; Xu, Kun

    1999-01-01

    This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

  9. Laboratory support for in situ gasification: reaction kinetics. Annual report October 1977-September 1978

    SciTech Connect

    Young, J.E.; Wong, S.H.; Johnson, J.E.; Sikand, N.; Jonke, A.A.

    1980-02-01

    This work is directed toward support studies for the national program for the development and demonstration of in situ coal gasification processes. The objective of this work is to determine the reaction-controlling variables and reaction kinetics for the gasification of chars obtained by pyrolyzing coal in simulated underground gasification conditions. The reactions being studied and to be studied include steam-char, CO/sub 2/-char, H/sub 2/-char, the water-gas shift reaction, and the methanation reaction. In this report are presented data regarding the kinetics of the reaction of steam with chars prepared from Pittsburgh seam high-volatile bituminous coal. In addition, a reaction model is described correlating the steam-char reaction rates measured earlier for Hanna subbituminous coal with operating conditions including temperature, partial pressures of steam and hydrogen, and extent of carbon gasification. Partial results are presented and discussed for an investigation of structural parameters of Hanna char as a function of pyrolysis conditions and extent of carbon gasified.

  10. SurfKin: an ab initio kinetic code for modeling surface reactions.

    PubMed

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-01

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. PMID:25111729

  11. Bench-scale Kinetics Study of Mercury Reactions in FGD Liquors

    SciTech Connect

    Gary Blythe; John Currie; David DeBerry

    2008-03-31

    This document is the final report for Cooperative Agreement DE-FC26-04NT42314, 'Kinetics Study of Mercury Reactions in FGD Liquors'. The project was co-funded by the U.S. DOE National Energy Technology Laboratory and EPRI. The objective of the project has been to determine the mechanisms and kinetics of the aqueous reactions of mercury absorbed by wet flue gas desulfurization (FGD) systems, and develop a kinetics model to predict mercury reactions in wet FGD systems. The model may be used to determine optimum wet FGD design and operating conditions to maximize mercury capture in wet FGD systems. Initially, a series of bench-top, liquid-phase reactor tests were conducted and mercury species concentrations were measured by UV/visible light spectroscopy to determine reactant and byproduct concentrations over time. Other measurement methods, such as atomic absorption, were used to measure concentrations of vapor-phase elemental mercury, that cannot be measured by UV/visible light spectroscopy. Next, a series of bench-scale wet FGD simulation tests were conducted. Because of the significant effects of sulfite concentration on mercury re-emission rates, new methods were developed for operating and controlling the bench-scale FGD experiments. Approximately 140 bench-scale wet FGD tests were conducted and several unusual and pertinent effects of process chemistry on mercury re-emissions were identified and characterized. These data have been used to develop an empirically adjusted, theoretically based kinetics model to predict mercury species reactions in wet FGD systems. The model has been verified in tests conducted with the bench-scale wet FGD system, where both gas-phase and liquid-phase mercury concentrations were measured to determine if the model accurately predicts the tendency for mercury re-emissions. This report presents and discusses results from the initial laboratory kinetics measurements, the bench-scale wet FGD tests, and the kinetics modeling efforts.

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

    PubMed

    Cerar, Janez

    2015-01-01

    Widely cited and accepted explanation of reaction mechanism of the case study reaction of chemical kinetics between Cr(III) ions and ethylenediaminetetraacetic acid (EDTA) contradicts modern chromium(III) coordination chemistry data. Absorption UV and visible light spectra were recorded during the reaction between aqueous solution of Cr(NO(3))(3) and EDTA in order to obtain new information about this reaction. Analysis of the spectra showed that only very small fraction of intermediates may be present in solution during the course of the reaction. The reaction scheme was established and according to it calculations based on a simplified model were carried out. Literature data for constants were used if known, otherwise, adjusted values of their sound estimates were applied. Reasonable agreement of the model calculations with the experimental data was obtained for pH values 3.8 and 4.5 but the model failed to reproduce measured rate of reaction at pH 5.5, probably due to the use of the oversimplified model. PMID:26454587

  13. Trigonometrically fitted two step hybrid method for the numerical integration of second order IVPs

    NASA Astrophysics Data System (ADS)

    Monovasilis, Th.; Kalogiratou, Z.; Simos, T. E.

    2016-06-01

    In this work we consider the numerical integration of second order ODEs where the first derivative is missing. We construct trigonometrically fitted two step hybrid methods. We apply the new methods on the numerical integration of several test problems.

  14. A second order accurate embedded boundary method for the wave equation with Dirichlet data

    SciTech Connect

    Kreiss, H O; Petersson, N A

    2004-03-02

    The accuracy of Cartesian embedded boundary methods for the second order wave equation in general two-dimensional domains subject to Dirichlet boundary conditions is analyzed. Based on the analysis, we develop a numerical method where both the solution and its gradient are second order accurate. We avoid the small-cell stiffness problem without sacrificing the second order accuracy by adding a small artificial term to the Dirichlet boundary condition. Long-time stability of the method is obtained by adding a small fourth order dissipative term. Several numerical examples are provided to demonstrate the accuracy and stability of the method. The method is also used to solve the two-dimensional TM{sub z} problem for Maxwell's equations posed as a second order wave equation for the electric field coupled to ordinary differential equations for the magnetic field.

  15. Evaluation of decay curves of a chemical species undergoing simultaneous first- and second-order decay

    NASA Technical Reports Server (NTRS)

    Schmidt, K. H.

    1970-01-01

    IBM 1620 computer prepares tables to enable fast calculation of the first- and second-order rate constants from two half-lives and the corresponding initial concentrations, obtained from either one or two decay curves.

  16. Second-order curved boundary treatments of the lattice Boltzmann method for convection-diffusion equations

    NASA Astrophysics Data System (ADS)

    Huang, Juntao; Hu, Zexi; Yong, Wen-An

    2016-04-01

    In this paper, we present a kind of second-order curved boundary treatments for the lattice Boltzmann method solving two-dimensional convection-diffusion equations with general nonlinear Robin boundary conditions. The key idea is to derive approximate boundary values or normal derivatives on computational boundaries, with second-order accuracy, by using the prescribed boundary condition. Once the approximate information is known, the second-order bounce-back schemes can be perfectly adopted. Our boundary treatments are validated with a number of numerical examples. The results show the utility of our boundary treatments and very well support our theoretical predications on the second-order accuracy thereof. The idea is quite universal. It can be directly generalized to 3-dimensional problems, multiple-relaxation-time models, and the Navier-Stokes equations.

  17. Completeness of first and second order ODE flows and of Euler-Lagrange equations

    NASA Astrophysics Data System (ADS)

    Minguzzi, Ettore

    2015-11-01

    Two results on the completeness of maximal solutions to first and second order ordinary differential equations (or inclusions) over complete Riemannian manifolds, with possibly time-dependent metrics, are obtained. Applications to Lagrangian mechanics and gravitational waves are given.

  18. Comparison of Second-Order Loads on a Tension-Leg Platform for Wind Turbines: Preprint

    SciTech Connect

    Gueydon, S.; Wuillaume, P.; Jonkman, J.; Robertson, A.; Platt, A.

    2015-03-01

    The first objective of this work is to compare the two floating offshore wind turbine simulation packages {DIFFRAC+aNySIM} and {WAMIT+FAST}. The focus is on second-order wave loads, and so first- and second-order wave loads are applied to a structure sequentially for a detailed comparison and a more precise analysis of the effects of the second-order loads. aNySIM does not have the capability to model flexible bodies, and so the simulations performed in this tool are done assuming a rigid body. FAST also assumes that the platform is rigid, but can account for the flexibility of the tower. The second objective is to study the effects of the second-order loads on the response of a TLP floating wind turbine. The flexibility of the tower must be considered for this investigation, and therefore only FAST is used.

  19. Multiple Positive Solutions in the Second Order Autonomous Nonlinear Boundary Value Problems

    NASA Astrophysics Data System (ADS)

    Atslega, Svetlana; Sadyrbaev, Felix

    2009-09-01

    We construct the second order autonomous equations with arbitrarily large number of positive solutions satisfying homogeneous Dirichlet boundary conditions. Phase plane approach and bifurcation of solutions are the main tools.

  20. Oxygen exchange reaction kinetics for cerium(IV) oxide at 1000 °C

    SciTech Connect

    Whiting, Christofer E. Douglas, John M.; Cremeans, Bethany M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2014-10-15

    Bulk oxygen exchange rate kinetics on CeO{sub 2} at 1000 °C were observed to have a first order dependence on the fraction of reaction remaining and to be independent of oxygen partial pressure, total pressure, particle size, and specific surface area. This suggests that the exchange reaction is dominated by an internal chemical reaction that is occurring throughout the bulk of the material, and not at the material surface. Oxygen exchange rates were limited by this internal chemical reaction for all CeO{sub 2} powders studied (15 nm to −325 mesh), and had a rate constant of 1.19×10{sup −2} s{sup −1} with a time to completion of 617 s. These results are similar to the exchange rates observed previously on PuO{sub 2}, suggesting that oxygen exchange on PuO{sub 2} may also be dominated by an internal chemical reaction under similar conditions. This work will help guide future experiments on {sup 238}PuO{sub 2} oxygen exchange reactions. - Graphical abstract: Oxygen exchange kinetics on CeO{sub 2} at 1000 °C are independent of a wide range of experimental conditions and exhibit first-order chemical reaction kinetics. - Highlights: • Stable oxygen exchange rates obtained on a variety of CeO{sub 2} powders at 1000 °C. • Exchange rates are independent of atmospheric composition and specific surface area. • Exchange rates are limited by an internal chemical reaction, not a surface reaction. • CeO{sub 2} exchange rates appear similar to the rates observed on PuO{sub 2} at 1000 °C.

  1. Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs

    NASA Astrophysics Data System (ADS)

    Chia, A.; Tan, K. C.; Pawela, Ł.; Kurzyński, P.; Paterek, T.; Kaszlikowski, D.

    2016-03-01

    Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013), 10.1063/1.4844355], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010), 10.1016/j.cplett.2010.01.063]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.

  2. Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids

    NASA Astrophysics Data System (ADS)

    Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian

    2015-05-01

    The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2]3+ (1), cis-[Co(dp)2(C12H25NH2)2]3+ (2), cis-[Co(trien)(C12H25NH2)2]3+ (3), cis-[Co(bpy)2(C12H25NH2)2]3+ (4) and cis-[Co(phen)2(C12H25NH2)2]3+ (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2‧-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe2+ ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323 K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ΔH‡ and entropy of activation ΔS‡) of the reaction have been calculated which substantiate the kinetics of the reaction.

  3. Second Order Duality in Multiobjective Fractional Programming with Square Root Term under Generalized Univex Function

    PubMed Central

    Tripathy, Arun Kumar

    2014-01-01

    Three approaches of second order mixed type duality are introduced for a nondifferentiable multiobjective fractional programming problem in which the numerator and denominator of objective function contain square root of positive semidefinite quadratic form. Also, the necessary and sufficient conditions of efficient solution for fractional programming are established and a parameterization technique is used to establish duality results under generalized second order ρ-univexity assumption. PMID:27379308

  4. Comments on the present state of second-order closure models for incompressible flows

    NASA Technical Reports Server (NTRS)

    Speziale, Charles G.

    1992-01-01

    Second-order closure models account for history and nonlocal effects of the mean velocity gradients on the Reynolds stress tensor. Turbulent flows involving body forces or curvature, Reynolds stress relaxational effects, and counter-gradient transport are usually better described. The topics are presented in viewgraph form and include: (1) the Reynolds stress transport equation; (2) issues in second-order closure modeling; and (3) near wall models.

  5. Parallel coding of first- and second-order stimulus attributes by midbrain electrosensory neurons.

    PubMed

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

    2012-04-18

    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

  6. Second-order contributions to relativistic time delay in the parametrized post-Newtonian formalism

    SciTech Connect

    Richter, G.W.; Matzner, R.A.

    1983-12-15

    Using a parametrized expansion of the solar metric to second order in the Newtonian potential, we calculate the relativistic delay in the round-trip travel time of a radar signal reflected from a nearby planet. We find that one second-order contribution to the delay is on the order of ten nanoseconds, which is comparable to the uncertainties in present-day experiments involving the Viking spacecraft.

  7. Reaction kinetics for the oxygen hydrogenation process on Pt(111) derived from temperature-programmed XPS

    NASA Astrophysics Data System (ADS)

    Näslund, Lars-Åke

    2013-12-01

    Oxygen hydrogenation under ultra high vacuum conditions at the platinum surface was explored using temperature-programmed X-ray photoelectron spectroscopy. Through modeling of the oxygen consumption, information on the reaction kinetics was obtained indicating that the reaction rate of the oxygen hydrogenation process depends on the hydrogen diffusion and on the lifetime of hydroxyl intermediates. The reaction rate is, however, enhanced when an autocatalytic process stabilizes the hydroxyl intermediates through hydrogen bonding to neighboring water molecules. The overall activation energy for the hydrogenation of atomic oxygen to form water was determined to be 0.20 eV with a frequency factor of only 103 s- 1.

  8. Kinetics of the ferrous/ferric electrode reaction in the absence of chloride catalysis

    SciTech Connect

    Hung, N.C.; Nagy, Z.

    1987-09-01

    The kinetics of the ferrous ferric redox electrode reaction has been investigated by many workers as a simple, uncomplicated charge transfer reaction which seems ideal for testing experimental techniques and charge transfer theories. However, it has only recently been understood that very small traces of chloride can have a considerable effect on the reaction rate. The relation between the chloride content of the solution and the rate constant of the ferrous/ferric reaction on a gold electrode in perchloric acid solutions is confirmed in this work. The chloride effect free apparent standard rate constant is found to be 2.2 x 10/sup -5/ cm s/sup -1/, which is two to three orders of magnitude smaller than the rate constants normally reported for this reaction if the chloride content of the solution is not scrupulously controlled. Measurements were carried out by using two different in situ methods for cleaning the working electrode surface rather than employing extensive solution purification. In the first method the measuring electrode was potentiostated at sufficiently negative potentials to desorb the chloride from the surface followed by a potential step to the equilibrium potential and a pulse measurement of the kinetics. In the second method chloride ions were removed from the surface before and during the kinetic measurement by continuous oxidation of chromous ions added in small concentration to the test solution. Good agreement was found among the rate constants determined by these methods and a reported rate constant determined in ultraclean solution.

  9. Carbon kinetic isotope effect in the reaction of CH4 with HO

    NASA Technical Reports Server (NTRS)

    Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.

    1987-01-01

    The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

  10. Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Shackelford, C. J.; Wine, P. H.

    1997-01-01

    Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

  11. A hydrodynamics-reaction kinetics coupled model for evaluating bioreactors derived from CFD simulation.

    PubMed

    Wang, Xu; Ding, Jie; Guo, Wan-Qian; Ren, Nan-Qi

    2010-12-01

    Investigating how a bioreactor functions is a necessary precursor for successful reactor design and operation. Traditional methods used to investigate flow-field cannot meet this challenge accurately and economically. Hydrodynamics model can solve this problem, but to understand a bioreactor in sufficient depth, it is often insufficient. In this paper, a coupled hydrodynamics-reaction kinetics model was formulated from computational fluid dynamics (CFD) code to simulate a gas-liquid-solid three-phase biotreatment system for the first time. The hydrodynamics model is used to formulate prediction of the flow field and the reaction kinetics model then portrays the reaction conversion process. The coupled model is verified and used to simulate the behavior of an expanded granular sludge bed (EGSB) reactor for biohydrogen production. The flow patterns were visualized and analyzed. The coupled model also demonstrates a qualitative relationship between hydrodynamics and biohydrogen production. The advantages and limitations of applying this coupled model are discussed. PMID:20727741

  12. Kinetics of phyllosemiquinone oxidation in the Photosystem I reaction centre of Acaryochloris marina.

    PubMed

    Santabarbara, Stefano; Bailleul, Benjamin; Redding, Kevin; Barber, James; Rappaport, Fabrice; Telfer, Alison

    2012-02-01

    Light-induced electron transfer reactions in the chlorophyll a/d-binding Photosystem I reaction centre of Acaryochloris marina were investigated in whole cells by pump-probe optical spectroscopy with a temporal resolution of ~5ns at room temperature. It is shown that phyllosemiquinone, the secondary electron transfer acceptor anion, is oxidised with bi-phasic kinetics characterised by lifetimes of 88±6ns and 345±10ns. These lifetimes, particularly the former, are significantly slower than those reported for chlorophyll a-binding Photosystem I, which typically range in the 5-30ns and 200-300ns intervals. The possible mechanism of electron transfer reactions in the chlorophyll a/d-binding Photosystem I and the slower oxidation kinetics of the secondary acceptors are discussed. PMID:22037394

  13. Hydrolysis of Surfactants Containing Ester Bonds: Modulation of Reaction Kinetics and Important Aspects of Surfactant Self-Assembly

    ERIC Educational Resources Information Center

    Lundberg, Dan; Stjerndahl, Maria

    2011-01-01

    The effects of self-assembly on the hydrolysis kinetics of surfactants that contain ester bonds are discussed. A number of examples on how reaction rates and apparent reaction orders can be modulated by changes in the conditions, including an instance of apparent zero-order kinetics, are presented. Furthermore, it is shown that the examples on…

  14. The kinetic model for slow photoinduced electron transport in the reaction centers of purple bacteria.

    PubMed

    Serdenko, T V; Barabash, Y M; Knox, P P; Seifullina, N Kh

    2016-12-01

    The present work is related to the investigation of slow kinetics of electron transport in the reaction centers (RCs) of Rhodobacter sphaeroides. Experimental data on the absorption kinetics of aqueous solutions of reaction centers at different modes of photoexcitation are given. It is shown that the kinetics of oxidation and reduction of RCs are well described by the sum of three exponential functions. This allows to suggest a two-level kinetic model for electron transport in the RC as a system of four electron-conformational states which correspond to three balance differential equations combined with state equation. The solution of inverse problem made it possible to obtain the rate constant values in kinetic equations for different times and intensities of exciting light. Analysis of rate constant values in different modes of RC excitation allowed to suggest that two mechanisms of structural changes are involved in RC photo-oxidation. One mechanism leads to the increment of the rate of electron return, another one-to its drop. Structural changes were found out to occur in the RCs under incident light. After light was turned off, the reduction of RCs was determined by the second mechanism. PMID:27271854

  15. The kinetic model for slow photoinduced electron transport in the reaction centers of purple bacteria

    NASA Astrophysics Data System (ADS)

    Serdenko, T. V.; Barabash, Y. M.; Knox, P. P.; Seifullina, N. Kh.

    2016-06-01

    The present work is related to the investigation of slow kinetics of electron transport in the reaction centers (RCs) of Rhodobacter sphaeroides. Experimental data on the absorption kinetics of aqueous solutions of reaction centers at different modes of photoexcitation are given. It is shown that the kinetics of oxidation and reduction of RCs are well described by the sum of three exponential functions. This allows to suggest a two-level kinetic model for electron transport in the RC as a system of four electron-conformational states which correspond to three balance differential equations combined with state equation. The solution of inverse problem made it possible to obtain the rate constant values in kinetic equations for different times and intensities of exciting light. Analysis of rate constant values in different modes of RC excitation allowed to suggest that two mechanisms of structural changes are involved in RC photo-oxidation. One mechanism leads to the increment of the rate of electron return, another one—to its drop. Structural changes were found out to occur in the RCs under incident light. After light was turned off, the reduction of RCs was determined by the second mechanism.

  16. Methods for studying reaction kinetics in gas chromatography, exemplified by using the 1-chloro-2,2-dimethylaziridine interconversion reaction.

    PubMed

    Krupcík, J; Mydlová, J; Májek, P; Simon, P; Armstrong, D W

    2008-04-01

    In this paper, methods are described that are used for studying first-order reaction kinetics by gas chromatography. Basic theory is summarized and illustrated using the interconversion of 1-chloro-2,2-dimethylaziridine enantiomers as a representative example. For the determination of the kinetic and thermodynamic activation data of interconversion the following methods are reviewed: (i) classical kinetic methods where samples of batch-wise kinetic studies are analyzed by enantioselective gas chromatography, (ii) stopped-flow methods performed on one chiral column, (iii) stopped-flow methods performed on an achiral column or empty capillary coupled in series with two chiral columns, (iv) on-flow method performed on an achiral column coupled in series with two chiral columns, and (v) reaction gas chromatography, known as a dynamic gas chromatography, where the interconversion is performed on chiral column during the separation process. The determination of kinetic and thermodynamic activation data by methods (i) through (iv) is straightforward as the experimental data needed for the evaluation (particularly the concentration of reaction constituents) are accessible from the chromatograms. The evaluation of experiments from reaction chromatography method (v) is complex as the concentration bands of reaction constituents are overlapped. The following procedures have been developed to determination peak areas of reaction constituents in such complex chromatograms: (i) methods based on computer-assisted simulations of chromatograms where the kinetic activation parameters for the interconversion of enantiomers are obtained by iterative comparison of experimental and simulated chromatograms, (ii) stochastic methods based on the simulation of Gaussian distribution functions and using a time-dependent probability density function, (iii) approximation function and unified equation, (iv) computer-assisted peak deconvolution methods. Evaluation of the experimental data permits

  17. Kinetic characterization of the first step of the ribozyme-catalyzed trans excision-splicing reaction.

    PubMed

    Dotson, P Patrick; Sinha, Joy; Testa, Stephen M

    2008-06-01

    Group I introns catalyze the self-splicing reaction, and their derived ribozymes are frequently used as model systems for the study of RNA folding and catalysis, as well as for the development of non-native catalytic reactions. Utilizing a group I intron-derived ribozyme from Pneumocystis carinii, we previously reported a non-native reaction termed trans excision-splicing (TES). In this reaction, an internal segment of RNA is excised from an RNA substrate, resulting in the covalent reattachment of the flanking regions. TES proceeds through two consecutive phosphotransesterification reactions, which are similar to the reaction steps of self-splicing. One key difference is that TES utilizes the 3'-terminal guanosine of the ribozyme as the first-step nucleophile, whereas self-splicing utilizes an exogenous guanosine. To further aid in our understanding of ribozyme reactions, a kinetic framework for the first reaction step (substrate cleavage) was established. The results demonstrate that the substrate binds to the ribozyme at a rate expected for simple helix formation. In addition, the rate constant for the first step of the TES reaction is more than one order of magnitude lower than the analogous step in self-splicing. Results also suggest that a conformational change, likely similar to that in self-splicing, exists between the two reaction steps of TES. Finally, multiple turnover is curtailed because dissociation of the cleavage product is slower than the rate of chemistry. PMID:18479464

  18. Dynamics of a lamellar system with diffusion and reaction: Scaling analysis and global kinetics

    NASA Astrophysics Data System (ADS)

    Muzzio, F. J.; Ottino, J. M.

    1989-12-01

    The evolution of a one-dimensional array of reactive lamellae with distributed striation thickness is studied by means of simulations, scaling analysis, and space-averaged kinetics. An infinitely fast, diffusion-controlled reaction A+B-->2P occurs at the interfaces between striations. As time increases, thin striations are eaten by thicker neighbors resulting in a modification of the striation thickness distribution (STD). Scaling analysis suggests that the STD evolves into a universal form and that the behavior of the system at short and long times is characterized by two different kinetic regimes. These predictions are confirmed by means of a novel numerical algorithm.

  19. Oxazines: A New Class of Second-Order Nonlinear Optical Switches.

    PubMed

    Beaujean, Pierre; Bondu, Flavie; Plaquet, Aurélie; Garcia-Amorós, Jaume; Cusido, Janet; Raymo, Françisco M; Castet, Frédéric; Rodriguez, Vincent; Champagne, Benoît

    2016-04-20

    A combined experimental-theoretical investigation has revealed that oxazine-based compounds are multiaddressable, multistate, and multifunctional molecular switches exhibiting contrasts of both linear and second-order nonlinear optical properties. The switching properties are particularly large when the substituent is a donor group. In this study, the cleavage of the C-O bond at the junction of the indole and oxazine cycles (of the closed a forms) is acido-triggered, leading to an open form (b(+)) characterized by larger first hyperpolarizabilities (βHRS) and smaller excitation energies than in the closed form. These results are confirmed and interpreted utilizing ab initio calculations that have been carried out on a broad set of compounds to unravel the role of the substituent. With respect to acceptor groups, oxazines bearing donor groups are characterized not only by larger βHRS and βHRS contrast ratios but also by smaller excitation energies, larger opening-induced charge transfer, and reduction of the bond length alternation, as well as smaller Gibbs energies of the opening reaction. Compared to protonated open forms (b(+)), calculations on the zwitterionic open forms (b) have pointed out similarities in the long-wavelength UV/vis absorption spectra, whereas their βHRS values might differ strongly as a function of the substituent. Indeed, the open forms present two NLOphores, the indoleninium-substituent entity and the nitrophenol (present in the protonated open form, b(+)) or nitrophenolate (present in the zwitterionic open form, b) moiety. Then, nitrophenolate displays a larger first hyperpolarizability than nitrophenol and the β tensor of the two entities might reinforce or cancel each other. PMID:26996994

  20. Second-Order Inference for the Mean of a Variable Missing at Random.

    PubMed

    Díaz, Iván; Carone, Marco; van der Laan, Mark J

    2016-05-01

    We present a second-order estimator of the mean of a variable subject to missingness, under the missing at random assumption. The estimator improves upon existing methods by using an approximate second-order expansion of the parameter functional, in addition to the first-order expansion employed by standard doubly robust methods. This results in weaker assumptions about the convergence rates necessary to establish consistency, local efficiency, and asymptotic linearity. The general estimation strategy is developed under the targeted minimum loss-based estimation (TMLE) framework. We present a simulation comparing the sensitivity of the first and second-order estimators to the convergence rate of the initial estimators of the outcome regression and missingness score. In our simulation, the second-order TMLE always had a coverage probability equal or closer to the nominal value 0.95, compared to its first-order counterpart. In the best-case scenario, the proposed second-order TMLE had a coverage probability of 0.86 when the first-order TMLE had a coverage probability of zero. We also present a novel first-order estimator inspired by a second-order expansion of the parameter functional. This estimator only requires one-dimensional smoothing, whereas implementation of the second-order TMLE generally requires kernel smoothing on the covariate space. The first-order estimator proposed is expected to have improved finite sample performance compared to existing first-order estimators. In the best-case scenario of our simulation study, the novel first-order TMLE improved the coverage probability from 0 to 0.90. We provide an illustration of our methods using a publicly available dataset to determine the effect of an anticoagulant on health outcomes of patients undergoing percutaneous coronary intervention. We provide R code implementing the proposed estimator. PMID:27227727

  1. Co-Ordinate Transformations for Second Order Systems. Part II: Elementary Structure-Preserving Transformations

    NASA Astrophysics Data System (ADS)

    Garvey, S. D.; Friswell, M. I.; Prells, U.

    2002-12-01

    It has been shown in a previous paper that there is a real-valued transformation from the general N -degree-of-freedom second order system to a second order system characterized by diagonal matrices. An immediate extension of this fact is that for any second order system, there is a set of real-valued transformations (the structure-preserving transformations) which transform this system to a different second order system having identical characteristic behaviour. There are several possible reasons why it may be very useful to achieve a particular structure in the transformed system. It is obvious that a diagonal structure is extremely useful and a method has been devised for determining the diagonalizing transformation from the solution of the usual (complex) eigenvalue-eigenvector problem. This paper begins by outlining the usefulness of some other structures. Then it defines a class of elementary structure-preserving co-ordinate transformations that transform from one N -degree-of-freedom second order system to another. The term elementary is applied because any one of these transformations is the minimum-rank modification of the identity transformation. The changes occurring in the system matrices as a result of the application of one such elementary transformation transpire to be very simple in form, they are low rank, and they can be computed very efficiently. This paper provides the fundamental tools to enable the design of structure-preserving co-ordinate transformations which transform a second order system originally characterized by three general matrices in stages into a mathematically similar second order system characterized by three diagonal matrices. The procedure by which the individual elementary transformations are obtained is still under development and it is not discussed in this paper. However, an illustration is given of a five-degree-of-freedom self-adjoint system being transformed into tridiagonal form.

  2. Development and application of a numerical model of kinetic and equilibrium microbiological and geochemical reactions (BIOKEMOD)

    NASA Astrophysics Data System (ADS)

    Salvage, Karen M.; Yeh, Gour-Tsyh

    1998-08-01

    This paper presents the conceptual and mathematical development of the numerical model titled BIOKEMOD, and verification simulations performed using the model. BIOKEMOD is a general computer model for simulation of geochemical and microbiological reactions in batch aqueous solutions. BIOKEMOD may be coupled with hydrologic transport codes for simulation of chemically and biologically reactive transport. The chemical systems simulated may include any mixture of kinetic and equilibrium reactions. The pH, pe, and ionic strength may be specified or simulated. Chemical processes included are aqueous complexation, adsorption, ion-exchange and precipitation/dissolution. Microbiological reactions address growth of biomass and degradation of chemicals by microbial metabolism of substrates, nutrients, and electron acceptors. Inhibition or facilitation of growth due to the presence of specific chemicals and a lag period for microbial acclimation to new substrates may be simulated if significant in the system of interest. Chemical reactions controlled by equilibrium are solved using the law of mass action relating the thermodynamic equilibrium constant to the activities of the products and reactants. Kinetic chemical reactions are solved using reaction rate equations based on collision theory. Microbiologically mediated reactions for substrate removal and biomass growth are assumed to follow Monod kinetics modified for the potentially limiting effects of substrate, nutrient, and electron acceptor availability. BIOKEMOD solves the ordinary differential and algebraic equations of mixed geochemical and biogeochemical reactions using the Newton-Raphson method with full matrix pivoting. Simulations may be either steady state or transient. Input to the program includes the stoichiometry and parameters describing the relevant chemical and microbiological reactions, initial conditions, and sources/sinks for each chemical species. Output includes the chemical and biomass concentrations

  3. Thermal decomposition of sugarcane straw, kinetics and heat of reaction in synthetic air.

    PubMed

    Rueda-Ordóñez, Yesid Javier; Tannous, Katia

    2016-07-01

    The aim of this work was to analyze the thermal decomposition, kinetics and heat of reaction of sugarcane straw in synthetic air by thermogravimetry (TG) and differential scanning calorimetry (DSC). The TG and DSC experiments were carried out using heating rates of 2.5°C/min, 5°C/min, and 10°C/min, and particle diameter of 0.250mm. In the study of the smoldering reaction were identified three consecutive stages, drying, oxidative pyrolysis, and combustion. Thus, the kinetic pathway was composed by six independent parallel reactions, three for each stage after drying, in which the activation energies were 176, 313, 150, 80, 150, and 100kJ/mol. The heat of reaction in synthetic air was completely exothermic releasing 8MJ/kg. The modeled curves of thermal decomposition of sugarcane straw presented good agreement with experimental data. Then, the kinetic parameters obtained could be used to analyze different processes involving smoldering. PMID:27019126

  4. The filamentary structure of mixing fronts and its control on reaction kinetics in porous media flows

    NASA Astrophysics Data System (ADS)

    de Anna, Pietro; Dentz, Marco; Tartakovsky, Alexandre; Le Borgne, Tanguy

    2014-07-01

    The mixing dynamics resulting from the combined action of diffusion, dispersion, and advective stretching of a reaction front in heterogeneous flows leads to reaction kinetics that can differ by orders of magnitude from those measured in well-mixed batch reactors. The reactive fluid invading a porous medium develops a filamentary or lamellar front structure. Fluid deformation leads to an increase of the front length by stretching and consequently a decrease of its width by compression. This advective front deformation, which sharpens concentration gradients across the interface, is in competition with diffusion, which tends to increase the interface width and thus smooth concentration gradients. The lamella scale dynamics eventually develop into a collective behavior through diffusive coalescence, which leads to a disperse interface whose width is controlled by advective dispersion. We derive a new approach that quantifies the impact of these filament scale processes on the global mixing and reaction kinetics. The proposed reactive filament model, based on the elementary processes of stretching, coalescence, and fluid particle dispersion, provides a new framework for predicting reaction front kinetics in heterogeneous flows.

  5. Solvation effect on kinetic rate constant of reactions in supercritical solvents

    SciTech Connect

    Chialvo, A.A.; Cummings, P.T. |; Kalyuzhnyi, Yu.V.

    1998-03-01

    A statistical mechanical analysis of the solvation effects on the kinetic rate constants of reactions in near and supercritical solvents is presented to understand the experimental findings regarding the thermodynamic pressure effects. This is an extension of the solvation formalism of Chialvo and Cummings to the analysis of the microscopic basis for the macroscopic pressure and temperature effects on the kinetic rate constants of reactions conducted in the compressible region of the solvent phase diagram. This analysis is illustrated with integral equations calculations involving Lennard-Jones infinitely dilute quaternary systems to describe the species in solution during the reaction of triplet benzophenone ({sup 3}BP) with a cosolvent (either O{sub 2} or 1,4-cyclohexadiene) in supercritical CO{sub 2} along the supercritical isotherms T{sub r} = 1.01 and 1.06. The role of the species molecular asymmetries and consequently their solvation behavior in determining the thermodynamic pressure and temperature effects on the kinetic rate constant of reactions at near-critical conditions are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  7. Study on the kinetics of homogeneous enzyme reactions in a micro/nanofluidics device.

    PubMed

    Wang, Chen; Li, Su-Juan; Wu, Zeng-Qiang; Xu, Jing-Juan; Chen, Hong-Yuan; Xia, Xing-Hua

    2010-03-01

    In this paper, a micro/nanofluidic preconcentration device integrated with an electrochemical detector has been used to study the enrichment of enzymes and homogeneous enzyme reaction kinetics. The enzymes are first concentrated in front of a nanochannel via an exclusion-enrichment effect (EEE) mechanism of the nanochannel integrated in a microfluidics device. If a substrate is electrokinetically transported to the concentrated enzymes, homogeneous enzymatic reaction occurs. The enzymatic reaction product can penetrate through the nanochannel to be detected electrochemically. In this device, the enriched enzymes can be well retained and repeatedly used, thus, the enzymatic reaction occurs in a continuous-flow mode. For demonstration, Glucose oxidase (GOx) was chosen as the model enzyme to study the influence of enzyme concentration on its reaction kinetics. The different concentration of GOx in front of the nanochannel was simply achieved by using different enrichment time. When substrate glucose was introduced electrokinetically, a rapid electrochemical steady-state response could be obtained. It was found that the electrochemical response to a constant glucose concentration increased with the increase of enzyme enrichment time, which is expected for homogeneous enzymatic reactions. Under proper conditions, the electrochemical responds linearly to the glucose concentration ranging from 0 to 15 mM, and the Michaelis constants (K(m)) are relatively low, which indicates a more efficient complex formation between enzyme and substrate. These results suggest that the present micro/nanofluidics device is promising for the study of enzymatic reaction kinetics and other bioassays such as cell assays, drug discovery, and clinical diagnosis. PMID:20162240

  8. Chemical kinetic analysis of hydrogen-air ignition and reaction times

    NASA Technical Reports Server (NTRS)

    Rogers, R. C.; Schexnayder, C. J., Jr.

    1981-01-01

    An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

  9. Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics

    NASA Technical Reports Server (NTRS)

    Kawa, S. Randolph; Stolarksi, Richard S.; Douglass, Anne R.; Newman, Paul A.

    2008-01-01

    Several recent observational and laboratory studies of processes involved in polar stratospheric ozone loss have prompted a reexamination of aspects of our understanding for this key indicator of global change. To a large extent, our confidence in understanding and projecting changes in polar and global ozone is based on our ability to simulate these processes in numerical models of chemistry and transport. The fidelity of the models is assessed in comparison with a wide range of observations. These models depend on laboratory-measured kinetic reaction rates and photolysis cross sections to simulate molecular interactions. A typical stratospheric chemistry mechanism has on the order of 50- 100 species undergoing over a hundred intermolecular reactions and several tens of photolysis reactions. The rates of all of these reactions are subject to uncertainty, some substantial. Given the complexity of the models, however, it is difficult to quantify uncertainties in many aspects of system. In this study we use a simple box-model scenario for Antarctic ozone to estimate the uncertainty in loss attributable to known reaction kinetic uncertainties. Following the method of earlier work, rates and uncertainties from the latest laboratory evaluations are applied in random combinations. We determine the key reactions and rates contributing the largest potential errors and compare the results to observations to evaluate which combinations are consistent with atmospheric data. Implications for our theoretical and practical understanding of polar ozone loss will be assessed.

  10. Lattice based Kinetic Monte Carlo Simulations of a complex chemical reaction network

    NASA Astrophysics Data System (ADS)

    Danielson, Thomas; Savara, Aditya; Hin, Celine

    Lattice Kinetic Monte Carlo (KMC) simulations offer a powerful alternative to using ordinary differential equations for the simulation of complex chemical reaction networks. Lattice KMC provides the ability to account for local spatial configurations of species in the reaction network, resulting in a more detailed description of the reaction pathway. In KMC simulations with a large number of reactions, the range of transition probabilities can span many orders of magnitude, creating subsets of processes that occur more frequently or more rarely. Consequently, processes that have a high probability of occurring may be selected repeatedly without actually progressing the system (i.e. the forward and reverse process for the same reaction). In order to avoid the repeated occurrence of fast frivolous processes, it is necessary to throttle the transition probabilities in such a way that avoids altering the overall selectivity. Likewise, as the reaction progresses, new frequently occurring species and reactions may be introduced, making a dynamic throttling algorithm a necessity. We present a dynamic steady-state detection scheme with the goal of accurately throttling rate constants in order to optimize the KMC run time without compromising the selectivity of the reaction network. The algorithm has been applied to a large catalytic chemical reaction network, specifically that of methanol oxidative dehydrogenation, as well as additional pathways on CeO2(111) resulting in formaldehyde, CO, methanol, CO2, H2 and H2O as gas products.

  11. A second order operator splitting method for Allen-Cahn type equations with nonlinear source terms

    NASA Astrophysics Data System (ADS)

    Lee, Hyun Geun; Lee, June-Yub

    2015-08-01

    Allen-Cahn (AC) type equations with nonlinear source terms have been applied to a wide range of problems, for example, the vector-valued AC equation for phase separation and the phase-field equation for dendritic crystal growth. In contrast to the well developed first and second order methods for the AC equation, not many second order methods are suggested for the AC type equations with nonlinear source terms due to the difficulties in dealing with the nonlinear source term numerically. In this paper, we propose a simple and stable second order operator splitting method. A core idea of the method is to decompose the original equation into three subequations with the free-energy evolution term, the heat evolution term, and a nonlinear source term, respectively. It is important to combine these three subequations in proper order to achieve the second order accuracy and stability. We propose a method with a half-time free-energy evolution solver, a half-time heat evolution solver, a full-time midpoint solver for the nonlinear source term, and a half-time heat evolution solver followed by a final half-time free-energy evolution solver. We numerically demonstrate the second order accuracy of the new numerical method through the simulations of the phase separation and the dendritic crystal growth.

  12. Assessing Stability and Change in a Second-Order Confirmatory Factor Model of Meaning in Life

    PubMed Central

    Hayward, R. David

    2013-01-01

    Research indicates that meaning in life is an important correlate of health and well-being. However, relatively little is known about the way a sense of meaning may change over time. The purpose of this study is to explore two ways of assessing change in meaning within a second-order confirmatory factor analysis framework. First, tests are conducted to see if the first and second-order factor loadings and measurement error terms are invariant over time. Second, a largely overlooked technique is used to assess change and stability in meaning at the second-order level. Findings from a nationwide survey reveal that the first and second-order factor loadings are invariant of time. Moreover, the second-order measurement error terms, but not the first-order measurement error terms, are invariant, as well. The results further reveal that standard ways of assessing stability mask significant change in meaning that is due largely to regression to the mean. PMID:24778574

  13. A critical perspective on second-order empathy in understanding psychopathology: phenomenology and ethics.

    PubMed

    Rashed, Mohammed Abouelleil

    2015-04-01

    The centenary of Karl Jaspers' General Psychopathology was recognised in 2013 with the publication of a volume of essays dedicated to his work (edited by Stanghellini and Fuchs). Leading phenomenological-psychopathologists and philosophers of psychiatry examined Jaspers notion of empathic understanding and his declaration that certain schizophrenic phenomena are 'un-understandable'. The consensus reached by the authors was that Jaspers operated with a narrow conception of phenomenology and empathy and that schizophrenic phenomena can be understood through what they variously called second-order and radical empathy. This article offers a critical examination of the second-order empathic stance along phenomenological and ethical lines. It asks: (1) Is second-order empathy (phenomenologically) possible? (2) Is the second-order empathic stance an ethically acceptable attitude towards persons diagnosed with schizophrenia? I argue that second-order empathy is an incoherent method that cannot be realised. Further, the attitude promoted by this method is ethically problematic insofar as the emphasis placed on radical otherness disinvests persons diagnosed with schizophrenia from a fair chance to participate in the public construction of their identity and, hence, to redress traditional symbolic injustices. PMID:25820144

  14. First estimates of the second-order ionospheric effect on radio occultation observations

    NASA Astrophysics Data System (ADS)

    Vergados, Panagiotis; Pagiatakis, Spiros D.

    2010-07-01

    This study examines the impact of the second-order ionospheric effect on radio occultation (RO) data products. We propose a new linear combination between dual frequency GPS observables, which retrieves slant total electron content free from the second-order ionospheric effect. Our STEC values differ from those obtained by independent techniques by a maximum of 3 total electron content units (TECU), depending on the geographic location and geomagnetic activity. Additionally, we suggest an alternative method of computing the second-order ionospheric delay in RO experiments, which does not require the use of geomagnetic and ionospheric models. First estimates show that the second-order ionospheric delay for the RO experiments falls within the range [-10, -8] mm, which is of the same order of magnitude with second-order ionospheric delay estimates from ground-based experiments. Finally, as a by-product of our model, we retrieve weighted mean geomagnetic field values, which we compare with theoretical estimates computed by the International Geomagnetic Reference Field-10 (IGRF-10) model. Our estimations agree with the IGRF-10 model between 0.23% and 7.0%.

  15. Revisiting Hartle's model using perturbed matching theory to second order: amending the change in mass

    NASA Astrophysics Data System (ADS)

    Reina, Borja; Vera, Raül

    2015-08-01

    Hartle's model describes the equilibrium configuration of a rotating isolated compact body in perturbation theory up to second order in general relativity. The interior of the body is a perfect fluid with a barotropic equation of state, no convective motions and rigid rotation. That interior is matched across its surface to an asymptotically flat vacuum exterior. Perturbations are taken to second order around a static and spherically symmetric background configuration. Apart from the explicit assumptions, the perturbed configuration is constructed upon some implicit premises, in particular the continuity of the functions describing the perturbation in terms of some background radial coordinate. In this work we revisit the model within a modern general and consistent theory of perturbative matchings to second order, which is independent of the coordinates and gauges used to describe the two regions to be joined. We explore the matching conditions up to second order in full. The main particular result we present is that the radial function m0 (in the setting of the original work) of the second order perturbation tensor, contrary to the original assumption, presents a jump at the surface of the star, which is proportional to the value of the energy density of the background configuration there. As a consequence, the change in mass δ M needed by the perturbed configuration to keep the value of the central energy density unchanged must be amended. We also discuss some subtleties that arise when studying the deformation of the star.

  16. Democratic decisions establish stable authorities that overcome the paradox of second-order punishment

    PubMed Central

    Hilbe, Christian; Traulsen, Arne; Röhl, Torsten; Milinski, Manfred

    2014-01-01

    Individuals usually punish free riders but refuse to sanction those who cooperate but do not punish. This missing second-order peer punishment is a fundamental problem for the stabilization of cooperation. To solve this problem, most societies today have implemented central authorities that punish free riders and tax evaders alike, such that second-order punishment is fully established. The emergence of such stable authorities from individual decisions, however, creates a new paradox: it seems absurd to expect individuals who do not engage in second-order punishment to strive for an authority that does. Herein, we provide a mathematical model and experimental results from a public goods game where subjects can choose between a community with and without second-order punishment in two different ways. When subjects can migrate continuously to either community, we identify a bias toward institutions that do not punish tax evaders. When subjects have to vote once for all rounds of the game and have to accept the decision of the majority, they prefer a society with second-order punishment. These findings uncover the existence of a democracy premium. The majority-voting rule allows subjects to commit themselves and to implement institutions that eventually lead to a higher welfare for all. PMID:24367116

  17. Kinetic and thermochemical studies of the ClO + ClO + M ↔ Cl2O2 + M reaction

    NASA Astrophysics Data System (ADS)

    Ferracci, V.; Rowley, D. M.

    2009-12-01

    Chlorine monoxide (ClO) radicals play a crucial role in polar ozone destruction events and the ClO dimer cycle has been identified as one of the most effective ozone-depleting catalytic cycles operating in the polar winter. A recent paper by von Hobe et al.1 highlighted significant inconsistencies between laboratory results, theoretical calculations and field observations concerning the ClO dimer ozone destruction cycle. This work has investigated the temperature dependence of the equilibrium constant of one of the key reactions in this cycle, ClO + ClO + M ↔ Cl2O2 + M (1, -1), by means of laser flash photolysis coupled with time-resolved UV absorption spectroscopy. ClO radicals were generated via laser flash photolysis of Cl2/Cl2O mixtures in synthetic air. The concentration of radicals was monitored via UV absorption spectroscopy: the use of a Charge Coupled Device (CCD) detector allowed time resolution over a broad range of wavelengths. The equilibrium constant Keq was determined as the ratio of the rate constants of the forward and reverse reaction (1, -1) over the T range 256 - 312 K. Second Law and Third Law analytical methods were employed to determine the standard enthalpy and entropy changes of reaction 1, ΔrH° and ΔrS°, from the measured equilibrium constants. The values obtained from the Second Law analysis (ΔrH° = - 80.8 ± 2.2 kJ mol-1; ΔrS° = - 168.4 ± 7.9 J K-1 mol-1) are in good agreement with previous work 2 but greater in magnitude than current NASA recommendations 3. It was also found that, under typical laboratory conditions employed in this work, [ClO] decay exhibits pure second order kinetics at T ≤ 250 K. A higher rate constant for the ClO recombination reaction (1) was also observed in this work (compared to the NASA evaluation 3), implying a higher Keq and a different partitioning between ClO and Cl2O2, shifting towards the dimer. 1. M. Von Hobe, R. J. Salawitch, T. Canty, H. Keller-Rudek, G. K. Moortgat, J.-U. Grooss, R. M

  18. CP: AN INVESTIGATION OF COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS, AND REACTION TO VARIOUS STIMULI

    SciTech Connect

    Weese, R K; Burnham, A K; Fontes, A T

    2005-03-23

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear heating rates, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Using differential scanning calorimetry, DSC, CP was decomposed at linear heating rates of 1, 3, and 7 C/min and the kinetic triplet calculated using the LLNL code Kinetics05. Values are also reported for spark, friction, and impact sensitivity.

  19. The kinetics and mechanisms of aromatic nucleophilic substitution reactions in liquid ammonia.

    PubMed

    Ji, Pengju; Atherton, John H; Page, Michael I

    2011-05-01

    The rates of aromatic nucleophilic substitution reactions in liquid ammonia are much faster than those in protic solvents indicating that liquid ammonia behaves like a typical dipolar aprotic solvent in its solvent effects on organic reactions. Nitrofluorobenzenes (NFBs) readily undergo solvolysis in liquid ammonia and 2-nitrofluorobenzene is about 30 times more reactive than the 4-substituted isomer. Oxygen nucleophiles, such as alkoxide and phenoxide ions, readily displace fluorine of 4-NFB in liquid ammonia to give the corresponding substitution product with little or no competing solvolysis product. Using the pK(a) of the substituted phenols in liquid ammonia, the Brønsted β(nuc) for the reaction of 4-NFB with para-substituted phenoxides is 0.91, indicative of the removal of most of the negative charge on the oxygen anion and complete bond formation in the transition state and therefore suggests that the decomposition of the Meisenheimer σ-intermediate is rate limiting. The aminolysis of 4-NFB occurs without general base catalysis by the amine and the second-order rate constants generate a Brønsted β(nuc) of 0.36 using either the pK(a) of aminium ion in acetonitrile or in water, which is also interpreted in terms of rate limiting breakdown of the Meisenheimer σ-intermediate. Nitrobenzene and diazene are formed as unusual products from the reaction between sodium azide and 4-NFB, which may be due to the initially formed 4-nitroazidobenzene decomposing to give a nitrene intermediate, which may then give diazene or be trapped by ammonia to give the unstable hydrazine which then yields nitrobenzene. PMID:21417418

  20. Temperature-dependences of the kinetics of reactions of papain and actinidin with a series of reactivity probes differing in key molecular recognition features

    PubMed Central

    Gul, Sheraz; Mellor, Geoffrey W.; Thomas, Emrys W.; Brocklehurst, Keith

    2006-01-01

    The temperature-dependences of the second-order rate constants (k) of the reactions of the catalytic site thiol groups of two cysteine peptidases papain (EC 3.4.22.2) and actinidin (EC 3.4.22.14) with a series of seven 2-pyridyl disulphide reactivity probes (R-S-S-2-Py, in which R provides variation in recognition features) were determined at pH 6.7 at temperatures in the range 4–30 °C by stopped-flow methodology and were used to calculate values of ΔS‡, ΔH‡ and ΔG‡. The marked changes in ΔS‡ from negative to positive in the papain reactions consequent on provision of increase in the opportunities for key non-covalent recognition interactions may implicate microsite desolvation in binding site–catalytic site signalling to provide a catalytically relevant transition state. The substantially different behaviour of actinidin including apparent masking of changes in ΔH‡ by an endothermic conformational change suggests a difference in mechanism involving kinetically significant conformational change. PMID:16445383

  1. Kinetics of the Reaction of O((sup 3)P) with CF3NO

    NASA Technical Reports Server (NTRS)

    Thorn, R. P.; Nicovich, J. M.; Cronkhite, J. M.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of O((sup 3)P) with CF3NO (k(2)) as a function of temperature. Our results are described by the Arrhenius expression k(2)(T) = (4.54 +/- 0.70) x 10(exp -l2)exp[(-560 +/- 46)/T] cu cm/molecule.s (243 K is less than or equal to T is less than or equal to 424 K); errors are 2 sigma and represent precision only. The O((sup 3)P) + CF3NO reaction is sufficiently rapid that CF3NO cannot be employed as a selective quencher for O2(alpha(1) Delta-g) in laboratory systems where O((sup 3)P) and O2(alpha 1 Delta g) coexist, and where O((sup 3)P) kinetics are being investigated.

  2. Chemical Kinetic Reaction Mechanisms for Combustion of Hydrocarbon and Other Types of Chemical Fuels

    DOE Data Explorer

    The central feature of the Combustion Chemistry project at LLNL is the development, validation, and application of detailed chemical kinetic reaction mechanisms for the combustion of hydrocarbon and other types of chemical fuels. For the past 30 years, LLNL's Chemical Sciences Division has built hydrocarbon mechanisms for fuels from hydrogen and methane through much larger fuels including heptanes and octanes. Other classes of fuels for which models have been developed include flame suppressants such as halons and organophosphates, and air pollutants such as soot and oxides of nitrogen and sulfur. Reaction mechanisms have been tested and validated extensively through comparisons between computed results and measured data from laboratory experiments (e.g., shock tubes, laminar flames, rapid compression machines, flow reactors, stirred reactors) and from practical systems (e.g., diesel engines, spark-ignition engines, homogeneous charge, compression ignition (HCCI) engines). These kinetic models are used to examine a wide range of combustion systems.

  3. Reaction kinetic parameters for ion transport from steady-state current-voltage curves.

    PubMed Central

    Gradmann, D; Klieber, H G; Hansen, U P

    1987-01-01

    This study demonstrates possible ways to estimate the rate constants of reaction kinetic models for ion transport from steady-state current-voltage data as measured at various substrate concentrations. This issue is treated theoretically by algebraic reduction and extension of a reaction kinetic four-state model for uniport. Furthermore, an example for application is given; current-voltage data from an open K+ selective channel (Schroeder, J.I., R. Hedrich, and J.M. Fernandez, 1984, Nature (Lond.), 312:361-362) supplemented by some new data have been evaluated. The analysis yields absolute numerical estimates of the 14 rate constants of a six-state model, which is discussed in a wider context. PMID:2437973

  4. Revisiting the Kinetics and Mechanism of the Tetrathionate-Hypochlorous Acid Reaction in Nearly Neutral Medium

    NASA Astrophysics Data System (ADS)

    Varga, Dénes; Horváth, Attila K.

    2009-11-01

    The tetrathionate-hypochlorous acid reaction has been investigated in nearly neutral medium at I = 0.5 M ionic strength and T = 25.0 ± 0.1 °C in dihydrogen-phosphate-hydrogen-phosphate buffer by UV-vis spectrophotometry. In excess of hypochlorous acid, the stoichiometry was found to be S4O62- + 7HOCl + 3H2O → 4SO42- + 7Cl- + 13H+, but in excess of tetrathionate colloidal sulfur precipitates. On the basis of the simultaneous evaluation of the kinetic curves, a nine-step kinetic model with four fitted and five fixed rate coefficients is proposed. Analogous oxidation reactions of tetrathionate are also compared and discussed.

  5. Encoding and estimation of first- and second-order binocular disparity in natural images

    PubMed Central

    Hibbard, Paul B.; Goutcher, Ross; Hunter, David W.

    2016-01-01

    The first stage of processing of binocular information in the visual cortex is performed by mechanisms that are bandpass-tuned for spatial frequency and orientation. Psychophysical and physiological evidence have also demonstrated the existence of second-order mechanisms in binocular processing, which can encode disparities that are not directly accessible to first-order mechanisms. We compared the responses of first- and second-order binocular filters to natural images. We found that the responses of the second-order mechanisms are to some extent correlated with the responses of the first-order mechanisms, and that they can contribute to increasing both the accuracy, and depth range, of binocular stereopsis. PMID:26731646

  6. Use of the particle swarm optimization algorithm for second order design of levelling networks

    NASA Astrophysics Data System (ADS)

    Yetkin, Mevlut; Inal, Cevat; Yigit, Cemal Ozer

    2009-08-01

    The weight problem in geodetic networks can be dealt with as an optimization procedure. This classic problem of geodetic network optimization is also known as second-order design. The basic principles of geodetic network optimization are reviewed. Then the particle swarm optimization (PSO) algorithm is applied to a geodetic levelling network in order to solve the second-order design problem. PSO, which is an iterative-stochastic search algorithm in swarm intelligence, emulates the collective behaviour of bird flocking, fish schooling or bee swarming, to converge probabilistically to the global optimum. Furthermore, it is a powerful method because it is easy to implement and computationally efficient. Second-order design of a geodetic levelling network using PSO yields a practically realizable solution. It is also suitable for non-linear matrix functions that are very often encountered in geodetic network optimization. The fundamentals of the method and a numeric example are given.

  7. Theoretical study of second-order hyperpolarizability for nitrogen radical cation

    NASA Astrophysics Data System (ADS)

    Tarazkar, Maryam; Romanov, Dmitri A.; Levis, Robert J.

    2015-05-01

    We report calculations of the static and dynamic hyperpolarizabilities of the nitrogen radical cation in doublet state. The electronic contributions were computed analytically using density functional theory and multi-configurational self-consistent field method with extended basis sets for non-resonant excitation. The open-shell electronic system of nitrogen radical cation provides negative second-order optical nonlinearity, suggesting that the hyperpolarizability coefficient, {{γ }(2)}, in the non-resonant regime is mainly composed of combinations of virtual one-photon transitions rather than two-photon transitions. The second-order optical properties of nitrogen radical cation have been calculated as a function of bond length starting with the neutral molecular geometry (S0 minimum) and stretching the N-N triple bond, reaching the ionic D0 relaxed geometry all the way toward dissociation limit, to investigate the effect of internuclear bond distance on second-order hyperpolarizability.

  8. New second order Mumford-Shah model based on Γ-convergence approximation for image processing

    NASA Astrophysics Data System (ADS)

    Duan, Jinming; Lu, Wenqi; Pan, Zhenkuan; Bai, Li

    2016-05-01

    In this paper, a second order variational model named the Mumford-Shah total generalized variation (MSTGV) is proposed for simultaneously image denoising and segmentation, which combines the original Γ-convergence approximated Mumford-Shah model with the second order total generalized variation (TGV). For image denoising, the proposed MSTGV can eliminate both the staircase artefact associated with the first order total variation and the edge blurring effect associated with the quadratic H1 regularization or the second order bounded Hessian regularization. For image segmentation, the MSTGV can obtain clear and continuous boundaries of objects in the image. To improve computational efficiency, the implementation of the MSTGV does not directly solve its high order nonlinear partial differential equations and instead exploits the efficient split Bregman algorithm. The algorithm benefits from the fast Fourier transform, analytical generalized soft thresholding equation, and Gauss-Seidel iteration. Extensive experiments are conducted to demonstrate the effectiveness and efficiency of the proposed model.

  9. An efficient second-order projection method for viscous incompressible flow

    NASA Astrophysics Data System (ADS)

    Bell, J. B.; Howell, L. H.; Colella, P.

    1991-04-01

    In this paper we describe a second-order projection method for the time-dependent, incompressible Navier-Stokes equations. The method is a second-order fractional step scheme in which one first solves diffusion-convection equations to determine intermediate velocities which are then projected onto the space of divergence-free vector fields. The diffusion-convection step uses a specialized second-order Godunov method for differencing the nonlinear convective terms that is conservative and free-stream preserving and provides a robust treatment of the nonlinearities at high Reynolds number. The projection is based on cell-centered centered difference approximations to divergence and gradient operators with the resulting linear system solved using a multigrid relaxation scheme. We apply the method to vortex spindown in a box to validate the numerical convergence of the method and to measure its overall performance.

  10. Encoding and estimation of first- and second-order binocular disparity in natural images.

    PubMed

    Hibbard, Paul B; Goutcher, Ross; Hunter, David W

    2016-03-01

    The first stage of processing of binocular information in the visual cortex is performed by mechanisms that are bandpass-tuned for spatial frequency and orientation. Psychophysical and physiological evidence have also demonstrated the existence of second-order mechanisms in binocular processing, which can encode disparities that are not directly accessible to first-order mechanisms. We compared the responses of first- and second-order binocular filters to natural images. We found that the responses of the second-order mechanisms are to some extent correlated with the responses of the first-order mechanisms, and that they can contribute to increasing both the accuracy, and depth range, of binocular stereopsis. PMID:26731646

  11. Consistency of Equations in the Second-Order Gauge-Invariant Cosmological Perturbation Theory

    NASA Astrophysics Data System (ADS)

    Nakamura, K.

    2009-06-01

    Along the general framework of the gauge-invariant perturbation theory developed in the papers [K.~Nakamura, Prog.~Theor.~Phys. 110 (2003), 723; Prog.~Theor.~Phys. 113 (2005), 481], we rederive the second-order Einstein equation on four-dimensional homogeneous isotropic background universe in a gauge-invariant manner without ignoring any mode of perturbations. We consider the perturbations both in the universe dominated by the single perfect fluid and in that dominated by the single scalar field. We also confirmed the consistency of all the equations of the second-order Einstein equation and the equations of motion for matter fields, which are derived in the paper [K.~Nakamura, arXiv:0804.3840]. This confirmation implies that all the derived equations of the second order are self-consistent and these equations are correct in this sense.

  12. Finite element method combined with second-order time discrete scheme for nonlinear fractional Cable equation

    NASA Astrophysics Data System (ADS)

    Wang, Yajun; Liu, Yang; Li, Hong; Wang, Jinfeng

    2016-03-01

    In this article, a Galerkin finite element method combined with second-order time discrete scheme for finding the numerical solution of nonlinear time fractional Cable equation is studied and discussed. At time t_{k-α/2} , a second-order two step scheme with α -parameter is proposed to approximate the first-order derivative, and a weighted discrete scheme covering second-order approximation is used to approximate the Riemann-Liouville fractional derivative, where the approximate order is higher than the obtained results by the L1-approximation with order (2-α in the existing references. For the spatial direction, Galerkin finite element approximation is presented. The stability of scheme and the rate of convergence in L^2 -norm with O(Δ t^2+(1+Δ t^{-α})h^{m+1}) are derived in detail. Moreover, some numerical tests are shown to support our theoretical results.

  13. Time-dependent Second Order Scattering Theory for Weather Radar with a Finite Beam Width

    NASA Technical Reports Server (NTRS)

    Kobayashi, Satoru; Tanelli, Simone; Im, Eastwood; Ito, Shigeo; Oguchi, Tomohiro

    2006-01-01

    Multiple scattering effects from spherical water particles of uniform diameter are studied for a W-band pulsed radar. The Gaussian transverse beam-profile and the rectangular pulse-duration are used for calculation. An second-order analytical solution is derived for a single layer structure, based on a time-dependent radiative transfer theory as described in the authors' companion paper. When the range resolution is fixed, increase in footprint radius leads to increase in the second order reflectivity that is defined as the ratio of the second order return to the first order one. This feature becomes more serious as the range increases. Since the spaceborne millimeter-wavelength radar has a large footprint radius that is competitive to the mean free path, the multiple scattering effect must be taken into account for analysis.

  14. A Quasi-Lie Schemes Approach to Second-Order Gambier Equations

    NASA Astrophysics Data System (ADS)

    Cariñena, José F.; Guha, Partha; de Lucas, Javier

    2013-03-01

    A quasi-Lie scheme is a geometric structure that provides t-dependent changes of variables transforming members of an associated family of systems of first-order differential equations into members of the same family. In this note we introduce two quasi-Lie schemes for studying second-order Gambier equations in a geometric way. This allows us to study the transformation of these equations into simpler canonical forms, which solves a gap in the previous literature, and other relevant differential equations, which leads to derive new constants of motion for families of second-order Gambier equations. Additionally, we describe general solutions of certain second-order Gambier equations in terms of particular solutions of Riccati equations, linear systems, and t-dependent frequency harmonic oscillators.

  15. Second-order systematic errors in Mueller matrix dual rotating compensator ellipsometry.

    PubMed

    Broch, Laurent; En Naciri, Aotmane; Johann, Luc

    2010-06-10

    We investigate the systematic errors at the second order for a Mueller matrix ellipsometer in the dual rotating compensator configuration. Starting from a general formalism, we derive explicit second-order errors in the Mueller matrix coefficients of a given sample. We present the errors caused by the azimuthal inaccuracy of the optical components and their influences on the measurements. We demonstrate that the methods based on four-zone or two-zone averaging measurement are effective to vanish the errors due to the compensators. For the other elements, it is shown that the systematic errors at the second order can be canceled only for some coefficients of the Mueller matrix. The calibration step for the analyzer and the polarizer is developed. This important step is necessary to avoid the azimuthal inaccuracy in such elements. Numerical simulations and experimental measurements are presented and discussed. PMID:20539341

  16. BOTDA sensors enhanced using high-efficiency second-order distributed Brillouin amplification.

    PubMed

    Jia, Xin-Hong; Chang, Han-Qing; Ao, Lei; Ji, Xiao-Ling; Xu, Cong; Zhang, Wei-Li

    2016-06-27

    A novel approach for long-distance sensing through Brillouin optical time-domain analysis (BOTDA) assisted by second-order distributed Brillouin amplification (DBA) was proposed and experimentally demonstrated. To the best of our knowledge, this is the first BOTDA study that used second-order DBA. Compared with BOTDA assisted by first-order DBA, the proposed approach enhanced the signal-to-noise ratio of the Brillouin trace by ~3 dB for a range featuring minimum sensing intensity. Long-distance sensing with ~5 m spatial resolution and ± 1.6°C measurement uncertainty over ~99 km fiber was successfully realized by employing high-efficiency pumping using ~6 dBm second-order and ~1.5 dBm first-order pumps. PMID:27410568

  17. Shot-Noise Seeded Microbunching Instability: Second-Order Correction to the Gain Function

    SciTech Connect

    Venturini, Marco

    2008-06-30

    We determine the second-order correction to the gain function of the microbunching instability in single-pass systems of interest for the next generation of light sources. The calculation applies to the case where the instability is seeded by shot noise. We examine an analytically treatable model of beam dynamics where collective forces are active only in non-dispersive sections of the linac. We find that the second order term can augment the linear gain significantly while affecting the spectrum of the overall gain only marginally. The weight of the second-order correction relative to the linear gain is found to scale quadratically with respect to R56. The qualitative behavior predicted by the model is consistent with exact numerical solutions of the Vlasov equations for realistic lattices.

  18. Feasibility of a second-order gravitational red-shift experiment

    NASA Technical Reports Server (NTRS)

    Jaffe, J.; Vessot, R. F. C.

    1976-01-01

    The number of gravitation experiments undertaken since the advent of Einstein's theory of gravitation is quite small, with, so far, only the famous perihelion-advance experiment and a recent lunar-laser-ranging experiment being capable of measuring a nonlinear, second-order effect. It now appears that another distinct test of the second-order term may be feasible through the use of very stable atomic clocks. This experiment, which would measure the second-order gravitational red-shift, is a bona fide test of the field equations of gravity, not just a test of the underlying principle of equivalence. The nature of such an experiment, the basic equations, model-orbit calculations, and some tracking-accuracy requirements are presented. It is concluded that current space-probe tracking capabilities cannot determine all the necessary orbital parameters with sufficient accuracy for this experiment at the present time.

  19. A novel second order fast decoupled load flow method in polar coordinates

    SciTech Connect

    Nanda, J.; Kothari, D.P.; Srivastava, S.C. )

    1988-01-01

    This paper presents a novel and effective second order fast decoupled load flow model in polar co-ordinates employing a totally different approach than used in existing second order methods in polar co-ordinates. This work eliminates the need for storing and computing repeatedly the second order terms by prudently injecting the elements of the Hessian matrix into the Jacobian. This results in a memory requirement at par with the usual fast decoupled load flow method. Investigations reveal that for well-behaved systems, the new method and the fast decoupled load flow method have practically the same convergence properties, whereas for certain ill-conditioned systems, the new method shows distinctly better convergence properties.

  20. The stability of numerical methods for second order ordinary differential equations

    NASA Technical Reports Server (NTRS)

    Gear, C. W.

    1978-01-01

    An important characterization of a numerical method for first order ODE's is the region of absolute stability. If all eigenvalues of the linear problem dy/dt = Ay are inside this region, the numerical method is stable. If the second order system d/dt(dy/dt) = 2Ady/dt - By is solved as a first order system, the same result applies to the eigenvalues of the generalized eigenvalue problem (lambda-squared)I 2(lambda)A + B. No such region exists for general methods for second order equations, but in some cases a region of absolute stability can be defined for methods for the single second order equation d/dt(dy/dt) = 2ady/dt - by. The absence of a region of absolute stability can occur when different members of a system of first order equations are solved by different methods.